LI NI U

Cun sch i cng ha hu c c bin son theo ni dung ca chng

trnh o to h chnh quy mn hc ny bc i hc v cao ng oc ging
dy trong nhiu nm trng i hc S phm i hc Nng.
Ni dung cun sch gm c 6 chng: M u; Cu trc khng gian phn
t hp cht hu c; Lin kt trong ha hc hu c; Hiu ng cu trc phn t hp
cht hu c; Cc axit baz hu c; Phn ng hu c. Sau mi chng c mt s
cu hi, bi tp cho sinh vin t gii nhm cng c thm cc kin thc v l
thuyt.
Cun sch l ti liu hc tp cho sinh vin cc chuyn ngnh ha hc s
phm, ha dc, ha sinh mi trng; lm ti liu tham kho cho cn b lm
cng tc ging dy, nghin cu khoa hc, cho cc hc vin cao hc, nghin cu
sinh cc chuyn ngnh ha hc.
Trong qu trnh bin son chc chn cn nhiu thiu st cha tht lm hi
lng bn c; Chng ti rt mong nhn c nhng kin ng gp hon thin
hn.

Tc gi

CHNG 1: M U
1.1. i tng ca ho hc hu c
Ho hc hu c l mn khoa hc nghin cu thnh phn v tnh cht cc
hp cht ca cacbon.Trong thnh phn ca cc hp cht hu c, ngoi cacbon cn
cha nhiu nguyn t khc nh: H, O, N, S, P, halogen Nhng cacbon c coi
l nguyn t c bn cu to nn cc hp cht hu c.
Ho hc hu c nhanh chng tr thnh mt ngnh khoa hc ring v cc
nguyn nhn di y:
- S lng cc hp cht hu c tng ln nhanh chng v t ti con s
khng l khong trn 5 triu cht, trong c nhng cht ng vai tr v cng
quan trng i vi s sng nh protein, axit nucleoic, hocmon
- Nguyn nhn dn n s tn ti mt s lng rt ln cc hp cht hu c
l ch cc nguyn t cacbon c kh nng c bit l va c th lin kt vi cc
nguyn t ca cc nguyn t khc v va c th lin kt vi nhau thnh mch
cacbon cc kiu khc nhau. Do , cc hp cht hu c xut hin cc hin tng
ng ng, ng phn, h bin v nhng biu hin phong ph v ho lp th.
- Cc lin kt ch yu trong ho hu c l lin kt cng ho tr nn c tnh
cht l hc v ho hc khc cc hp cht v c. Cc hp cht hu c mn cm vi
nhit hn, khng bn nhit cao, a s chy c, t tan trong nc, s tan
c thng t hoc khng phn li thnh ion. Cc phn ng thng chm, thun
nghch v theo nhiu hng.
1.2. S lc lch s pht trin ca ho hc hu c
T thi xa xa, ngi ta bit iu ch v s dng mt s cht hu c
trong i sng nh gim, mt s cht mu hu c, ru etylic, Thi k gi kim
thut, cc nh ho hc bit iu ch mt s cht hu c nh ete etylic, ur
Vo khong cui th k XVIII, u th k XIX, cc nh ho hc chit
tch c t ng thc vt nhiu axit hu c nh axit oxalic, axit xitric, axit
lactic v mt s baz hu c. Nm 1806, ln u tin Berzelius dng danh t
ho hc hu c ch ngnh ho hc nghin cu cc hp cht c ngun gc ng
thc vt. Thi im ny c th xem l im mc nh du s ra i ca mn ho
hc hu c.
Nm 1815, Berzelius a ra thuyt lc sng, mt lun thuyt duy tm,
cho rng cc hp cht hu c ch c th to ra trong c th ng, thc vt nh mt
lc sng c bit m bn tay con ngi khng th iu ch c trong cc bnh,
l, ng nghim nh i vi cc cht v c. Thuyt lc sng thng tr ho hc
hu c trong nhiu nm. Sau thuyt ny dn dn b nh nh cc cng trnh
tng hp cc cht hu c t cc cht v c. Nm 1824, Wohler tng hp c
axit oxalic, mt axit hu c in hnh (bng cch thu phn dixian l mt cht v

c). Nm 1828, cng chnh Wohler tng hp c ure (vn c trong nc tiu
ng vt) t amoni xyanat, cng l mt cht v c:
NH4CNO H2N CO NH2
Chnh pht minh ny lm sp bc tng ngn cch trc gia ho
hc v c v ho hc hu c, lm cho cc nh ha hc tin rng c th t tng hp
c cc cht hu c trong phng th nghim m khng cn c s tham gia ca
mt lc sng no c. Tip theo , Bectl tng hp c cht bo nm 1854
v Bulerp tng hp c ng glucoza t formalin nm 1861. Cho n nay,
hng triu cht hu c c tng hp trong cc phng th nghim v trong cng
nghip. Khng nhng con ngi bt chc c thin nhin trong nhiu lnh
vc m con ngi cn sng to ra c nhiu vt liu hu c, nhiu cht hu c
cc k quan trng, qu gi khng c trong t nhin.
Tuy nhin, tn gi hp cht hu c vn c duy tr, nhng khng phi
vi ngha nh trc y l cc cht c ngun gc ng, thc vt m n mang
mt ni dung mi, l cc hp cht ca cacbon.
1.3. Nhng quan im v cu to ca hp cht hu c
Cu to ca hp cht hu c l s phn b ca cc nguyn t hoc nhm
nguyn t trong khng gian ca mt phn t.
1.3.1. Thuyt gc (Radial, k hiu R)
Thuyt cu to ho hc ca cc hp cht hu c c pht trin mnh
u th k XIX. T nhng cng trnh ho hc ca Lavoisier, Berzelius, Wohler,
Liebig cho thy trong nhng phn ng hu c c nhng phn cht c cu trc
khng thay i chuyn t cht u sang cht cui gi l gc. Quan nim ny
cho ra i thuyt cu to ho hc u tin l thuyt gc. Thuyt gc cho rng:
phn t hu c gm 2 phn:
- Gc l phn khng bin i trong cc qu trnh chuyn ha ha hc
V d: Gc axetyl: CH3COGc benzoyl: C6H5CO- Phn kt hp vi gc l cc nguyn t hay nhm nguyn t khc nhau
u im: Phn loi c mt s cc hp cht ha hc hu c theo gc cu
to, t c th d on c tnh cht ca cc nhm hu c.
Nhc im: Ch phn bit c nhng hp cht n gin, khng c
ngha i vi cc hp cht phc tp do phm vi ng dng b.
1.3.2. Thuyt kiu
Thuyt kiu ca Dumas ra i chia ra lm hai dng:

- Dng ho hc: gm nhng cht c tnh cht ho hc ging nhau nh axit

axetic v axit cloaxetic.
- Dng c hc: gm nhng cht c cng s nguyn t nh nhau nhng tnh
cht khc nhau nh axit axetic v ru etylic.
Theo thuyt kiu ny, ngi ta thit lp c nhiu kiu hp cht
hu c nh:
-

Kiu nc ca Williamson:
H
H

CH3

CH3
CH3

- Kiu amin ca Wurtz v Hofmanm:

H
H

Kiu clorua hiro ca Gerhardt:

H

C2H5

CH3

Cl
Cl
Cl
hyrclorua m tylclorua tylclorua

C2H3O
Cl
ax tylclorua

Trong quan trng nht l kiu metan ca Kkul:

H
H
C
H
H

Ngi ta xc nh c rng, cc hp cht hu c c c trng bng

nhng phn ng kiu xc nh.
u im:
+ Thuyt kiu c ng gp to ln vo vic phn loi cc hp cht hu
c, thun li cho vic tm kim.

+ Nghin cu nhng phn khng thay i trong cc chuyn ho ho hc v

cng gii thch c phn no s thay i .
Nhc im:
+ Do s kiu nhiu nn rt phc tp trong vn phn loi, hn ch trong
vic s dng.
+ C nhng hp cht hu c khng th sp xp theo mt kiu no c.
1.3.3. Thuyt Butlerop
Ni dung ca thuyt cu to ho hc ca Butlerop bao gm cc lun im:
- Tt c cc nguyn t trong hp cht hu c kt hp vi nhau theo mt trt
t xc nh. Trong vic kt hp , cc nguyn t tiu ph mt phn i lc ho
hc ca mnh. Trt t kt hp ca cc nguyn t v c tnh ca cc lin kt trong
phn t l cu to ho hc.
- Nguyn t ca cc nguyn t to nn phn t lin kt vi nhau theo ng
ho tr ca mnh. Trong phn t cht hu c, cacbon bao gi cng c ho tr 4.
Cc nguyn t cacbon chng nhng c th lin kt vi cc nguyn t ca cc
nguyn t khc m cn c th lin kt vi nhau thnh mch.
- Tnh cht ca cc cht khng ch ph thuc vo thnh phn v s lng
nguyn t ca cc nguyn t m cn ph thuc vo cu to ho hc ca hp cht.
- Cu to ho hc ca cc cht c th xc nh c khi nghin cu tnh
cht ca chng. Cu to ho hc ca mi cht c th biu din bng mt cng thc
xc nh l cng thc cu to. Cng thc cu to va phn nh cu to ho hc
ca phn t va th hin nhng tnh cht c bn ca hp cht.
- Tnh cht ho hc ca mi nguyn t v nhm nguyn t trong phn t
khng phi l bt bin m thay i tu thuc vo cc nguyn t v nhm nguyn
t lin kt trc tip vi nhau mnh hn nh hng gin tip.
Th thch qua thi gian, thuyt cu to ho hc t ra ng n v su sc.
T nhng lun im s gin y, ngy nay pht trin thnh nhng thuyt hin
i v cu to v lin kt, v hiu ng, v ho hc lp th,
1.4. Cch biu din cng thc cu to hp cht hu c
Cng thc cu to phng biu din cu trc ca phn t quy c trn mt
mt phng, thng l mt phng giy.
1.4.1. Cng thc Lewis
Cng thc Lewis biu din cc lin kt gia cc phn t hay s electron
ho tr ca mi nguyn t bng s electron. S electron l bng tng electron ca
cc nguyn t ng gp vo v cc nguyn t c xu hng to trng thi electron
ln nht c th c c vng electron bn vng ca kh tr.
V d:

H
H C
O

H
C
H

Cc cng thc c th mang in tch, thng gi l in tch hnh thc hay

quy c:
H
H C

H
H N+ H

Ion amoni

Ion metoxit

Khi nhng tiu phn khng c vng bt t th thng l nhng tiu

phn trung gian khng bn, c kh nng phn ng cao v trong phn ng c xu
hng nhanh to thnh cu trc electron bt t.
H
H C+ H

H
H C

Cation metyl

Gc metyl

u im: D k hiu, cho thy c bn cht ca qu trnh phn tch.

Nhc im: Phc tp cho qu trnh biu din, d gy sai st. Trong mt s
trng hp khng biu din c.
1.4.2. Cng thc Kekule
n gin trong cch biu din ca Lewis, ngi ta quy c biu din
cc lin kt trong phn t bng vch ngang thay cho cp electron lin kt.
V d:
H

H
H

Trong cc hp cht c mang in tch cng c th thay th kin kt bng

mi tn t cht cho ti cht nhn:

Hay

n gin trong cch biu din cng thc, c th n cc gch lin kt, n
mt phn hay ton phn tu thuc vo yu cu cch biu din, ng thi cng b
qua cc cp electron khng lin kt, gi l cng thc rt gn:
CH3CH2CH3 , CH3 CH2 CH3 , CH3CH2CH2 H
Ngoi ra, mt cht c th biu din di nhiu dng cng thc, chng hn:
CH3

CH3

CH2

CH3

CH3

CH2
CH3

CH2
CH3

u im: Khc phc nhc im ca cng thc Lewis, n gin v phn

nh tht bn cht ca lin kt.
Nhc im: Khng thy s gp chung electron. Trong trng hp phn
ct d ly th khng thy c hin tng.
Ch : Trong mt s trng hp c bit cc hp cht hu c mch vng,
ngi ta thng khng biu din k hiu ca cc nguyn t cacbon v hidro.
1.5. Danh php hp cht hu c
C 4 loi danh php ch yu:
1.5.1. Danh php thng thng
L tn c gi theo ngun gc thu nhn c cht , theo tn ca ngi
tm ra n hay mun ca ngi tm ra n, theo phng php thu nhn c cht
.
V d: Axit fomic: HCOOH (Fomica: Kin)
Axit axetic: CH3COOH (Acetus: Gim)
Mentol: C10H20O (Mentha piperita: Bc h)
1.5.2. Danh php hp l
Ly tn ca mt hp cht hu c lm tn gi u sau gi tn ca cc hp
cht hu c khc tng t theo tn ca cc cht hu c u.
7

V d:
H
H

H
OH

Cacbinol

H
OH

C6H5

CH3

OH

CH3

Metyl Cacbinol

Metyl Phenyl Cacbinol

Nhc im: i vi cc hp cht phc tp th khng th gi tn c.

1.5.3. Danh php thng mi
L tn ca cc hp cht ho hc hu c c s dng trn th trng do cc
hng sn xut t tn.
V d: Cc loi thuc nhm: Rongalit C (NaHSO2.CH2O.2H2O): dng in hoa
Rongal P ( Dn xut ca axit sunfonic): dng
nhum huyn ph.
1.5.4. Danh php IUPAC (Hip hi ho hc quc t: International Union Pine
And Applycation Chemistry)
1.5.4.1. Tn gc - chc
TN PHN GC

TN PHN NH CHC

V d:
CH3CH2 Cl
Etyl clorua

CH3CH2 O COCH3
Etyl axetat

CH3CH2 O CH3
Etyl metyl ete

1.5.4.2. Tn thay th
Tn khng y :
TN PHN TH
(c th khng c)

TN MCH CACBON CHNH

(bt buc phi c)

TN PHN NH CHC
(bt buc phi c)

V d:
H3C CH3
Etan

H3C CH2Cl
Cloetan

* Tn nhm th:

H2C = CH2
Etan

Cc nguyn t ca cc nguyn t th gi tn theo tng nguyn t

OH
: Hiroxyl
OR
: Ancoxyl
CH3O
: Metoxyl
C6H5O
: Phenolxyl
CH3CO : Axetyl
C6H5
: Phenyl
C6H5CH2 : Benzyl
NO2
: Nitro
NH2
: Anmino
CN
: Nitryl
SH
: Mecaptan
SO3H
: Sunfonic
R: Ankyl
- Chn mch chnh: Chn mch cacbon di nht cha cc nguyn t cacbon
lin kt cacbon lm mch chnh. Chn mt nhm chc c u tin nht lm
nhm chc chnh, cc chc cn li l phn th.
u tin nhm chc:
-COOH > -COO- > -CHO > -CO- >-OH >-NH2 > -O- nh s th t:
Ta nh s th t t bn phi sang bn tri hoc tri qua sao cho tng cc
ch s ca cc nhm th l nh nht. Trng hp khi nh s t u ny n u
kia m thu c mt s dy ch s ca cc nhm mch nhnh khc nhau th phi
sp xp chng li theo th t tng dn. Dy c tng cc ch s nh nht c xem
l dy c ch s u nh nht.
V d:
CH3

CH2

CH

CH2

CH3

CH 3

CH

CH 2

CH 2

CH 3
2-metylpentan

CH3
3-metylpentan

* Tn phn nh chc:An, en, in, ol, al, on, oic

Tn y : Cu hnh + du quang hot + tn gi khng y
gi tn hp cht hu c, cn thuc tn cc s m v tn mch cacbon
nh sau:

CH 3

S M
1: mono

MCH CACBON CHNH

C

met

2: i

CC

et

3: tri

CCC

prop

4: tetra

CCCC

but

5: penta

CCCCC

pent

6: hexa
7: hepta

C C C C C C
CCCCCCC

hex
hep

8: octa

CCCCCCCC

oct

9: nona

CCCCCCCCC

non

10: deca

CCCCCCCCCC

dek

1.6. Phn loi cc hp cht hu c

Hp cht hu c c phn thnh hidrocacbon v dn xut ca
hidrocacbon.
- Hidrocacbon l nhng hp cht c to thnh t hai nguyn t C v H.
Gm 3 loi:
+ Hidrocabon no (Ankan): CH4, C2H6
+ Hidrocacbon khng no gm anken: C2H4 v ankin: C2H2
+ Hidrocacbon thm (Aren): C6H6
- Dn xut ca hidrocacbon l nhng hp cht m trong phn t ngoi C, H
ra cn c mt hay nhiu nguyn t ca cc nguyn t khc nh O, N, S,
halogenbao gm: dn xut halogen nh CH3Cl, ancol nh: CH3OH, axit nh:
CH3COOH,

10

CU HI V BI TP
Bi 1. Hy nu nhng quan im v cu to ca hp cht hu c?
Bi 2. Hy trnh by cc cch biu din cng thc cu to hp cht hu c?
Bi 3. Gi tn thay th cc hirocacbon sau theo danh php IUPAC:
CH3 CH2 CH2 C CH2 (C)
CH3 C C CH CH2 CH CH2(D)
CH2 CH3

CH CH2

Bi 4. Gi tn thay th cc hirocacbon sau theo danh php IUPAC:

CH3
CH3

CH2

CH3 (E)

(F)

Bi 5. Gi tn thay th cc HCHC sau theo danh php IUPAC:

CH3 CH CH3 CH3 CH CH C CH2
NO2 CH3 CH3 (Y)
Cl (X)

NH2 CH2
(Z)
OH

CH2 CH2
OH (T)

Bi 6. Gi tn thay th cc HCHC sau theo danh php IUPAC:

CH2 CH C C C OH
CH3 CH CH CH C C CH3

NH2 CH3

OH CH3

Cl O

Bi 7. Vit CTCT ca cc hp cht hu c sau:

a. 5-etyl-3-metylhept-3-en-1-in
b. 2-metylxiclopenta-1,3-ien
c. 4-brombut-3-enal
d. 3-clo-2,4-imetylpentan-1-ol
Bi 8. Vit CTCT ca hp cht cacbonyl cha vng benzen c CTPT C8H8O?
Bi 9. Hy phn loi hp cht hu c?

11

TI LIU THAM KHO

1. Phan Tng Sn, Trn Quc Sn, ng Nh Ti, C s l thuyt ho hu c,
tp 1,2, NXB i hc v trung hc chuyn nghip H Ni, 1980
2. Trn Quc Sn, ng Vn Liu Gio trnh c s ha hc hu c, Tp 1, 2,
NXB i hc s phm, 2007.
3. Thi Don Tnh, C s ho hc hu c, Tp 1, 2, NXB Khoa hc v K thut,
H Ni, 2006.
4. Thi Don Tnh, C ch v phn ng ha hc hu c (tp 1,2,3), NXB Khoa
hc v k thut, H Ni, 2008.
5. ng Nh Ti, C s l thuyt ha lp th, NXB Gio dc, H Ni, 1998.
6. Hong Trng Ym, Ho hc hu c, NXB Khoa hc & K thut, H Ni,
2002.

12

CHNG 2: CU TRC KHNG GIAN PHN T HP CHT HU C

2.1. Chit tch v tinh ch hp cht hu c
Cc hp cht hu c khi mi iu ch c hoc tch t ng thc vt,
thng dng hn hp khng tinh khit. V vy mun nghin cu chng, mun
phn tch nh tnh hay nh lng chng th nhim v trc tin l phi tch
chng thnh tng cht ring bit, dng tng i nguyn cht.
2.1.1. Tinh ch cht rn
2.1.1.1. Phng php kt tinh
a. Khi nim
Kt tinh l mt qu trnh bin i pha ca mt cht t rn sang lng khi ho
tan cht rn trong mt dung dch bo ho, sau lm lnh dung dch bo ho
thu c cht rn kt tinh
b. C s l thuyt
Phng php kt tinh c dng tch v tinh ch cc cht hu c rn,
da trn nguyn tc l cc cht khc nhau c ho tan khc nhau trong cng mt
dung mi. Dung mi thch hp c la chn thng l dung mi trong ho
tan ca cht cn tinh ch tng kh nhanh theo nhit , tan km nhit thng;
khng tan trong tp cht, khng c lc tng tc v mt ho hc i vi cht kt
tinh v sau khi kt tinh li phi d bay hi. Dung mi la phi d kim, r tin.
Bng cch to dung dch bo ho nhit cao (thng l nhit si ca
dung mi), sau ngui dung dch thu c, cht cn tinh ch s lng xung
y bnh (hay y cc), cc tp cht s li trong dung dch. Bng cch kt tinh
li mt s ln trong cng mt dung mi, hoc trong cc dung mi khc nhau,
ngi ta c th thu c tinh th cht cn tinh ch dng kh tinh khit. Cng c
khi ngi ta dng mt dung mi c ho tan vi tp cht nhiu hn loi tp
cht khi cht rn cn tinh ch. Dung mi thng dng l nc, alcol etylic, ancol
metylic hay mt alcol thch hp khc, axeton, axit axetic, ete, benzen, cloroform,
etyl axetat....hoc i khi hn hp gia chng.
Khi cn tch hai hay nhiu cht c cha trong hn hp vi nhng lng
tng ng nhau, ngi ta dng phng php kt tinh phn on. Cht kt tinh
li c ht u v trng. Khi c cht rn kt tinh, ta cn xc nh nhit nng
chy ca n bng ng mao qun gn vi nhit k nhng trong mt dung mi c
nhi si cao, hoc cch khng kh, hoc nh mt my chuyn dng ri i
chiu vi hng s vt l ca cht cho, bit c cht tinh khit hon ton
cha.
2.1.1.2. Phng php thng hoa
a. Khi nim
13

Thng hoa l mt qu trnh bin i pha ca mt cht t trng thi rn sang

trng thi hi m khng thng qua trng thi lng.
b. C s l thuyt
Mt s cht nh it, long no, naphtalen, menton, clorua st (III),... c kh
nng thng hoa, v vy ngi ta c th dng phng php thng hoa p sut
thng hoc p sut thp tinh ch chng.
Phng php tin hnh: Gia nhit mt cht rn bay hi, lm lnh hi ca
cht rn th ta s thu c cht rn kt tinh c tinh khit cao, cn tp cht
khng thng hoa th nm li y bnh.
u im: n gin, thi gian ngn, tinh khit cao, gi thnh r.
Nhc im: Trong thc t khng c nhiu cht thng hoa.
2.1.2. Tinh ch cht lng
2.1.2.1. Phng php chng ct
a. Khi nim
Chng ct l qu trnh lm bay hi cht lng, sau lm lnh v thu cht
lng c tinh khit cao hn.
b. Cc phng php chng ct
- Chng ct n gin
Trong trng hp cn tinh ch mt cht lng, tch n ra khi tp cht rn
khng bay hi, ta ch cn tin hnh chng ct n gin ngha l chuyn n sang
pha hi trong mt bnh ct c nhnh ri ngng t hi ca n bng ng sinh hn
vo mt bnh hng khc.
- Chng ct phn on
Phng php chng ct phn on dng tch hai hay nhiu cht lng c
nhit si khc nhau tan ln hon ton trong nhau da trn nguyn tc c s
phn b khc nhau v thnh phn cc cu t gia pha lng v pha hi trng thi
cn bng ( cng nhit ). Nu hai cht lng khng tng tc vi nhau, c th
biu din s ph thuc ca nhit si ca cht lng v nhit ngng t ca hi
ph thuc vo thnh phn hn hp hai cht (hnh 2.1)
T0
T2
T0
T1
TA
A

X2

X1B

X1

Thnh
phn
Hnh 2.1

14

Qua hnh 2.1 nhn thy rng, bng cch lp i lp li nhiu ln qu trnh
bay hi - ngng t, bay hi - ngng t li,... ta dn dn c th thu c cu t A
c nhit si thp hn dng gn nh tinh khit. V vy, ngi ta dng phng
php tinh luyn bng cch lp trn bnh ngng mt ct cao c nhiu a gip cho
vic ti to qu trnh bay hi - ngng t trn. Nh vy, cht lng A d bay hi dn
dn thot ln trn trng thi ngy cng tinh khit, cn cht lng B c nhit si
cao hn, ngng t tr li bnh ct. C th dng loi ct lp y cc ng thu tinh
hay s thay cho ct ni trn v hiu qu ca ct c tnh bng s a l
thuyt.
Trong trng hp c tng tc yu gia hai cht lng (solvat ho hay t
hp) th thu c hai dng th biu din s ph thuc nhit si v ngng t
vo thnh phn hn hp: mt dng vi nhit si ca hn hp ng ph cctiu
(hnh 2.2a) v mt dng vi nhit si cc i (hnh 2.2b).

C
t

tB
t

tB

tA
tA

X0

Thnh phn

X0

Thnh phn

Hnh 2.2a

Hnh 2.2b

Trong trng hp hn hp ng ph c nhit si cc tiu (thp hn hai

cu t ban u), cng ln pha trn ca ct ct, hn hp hi v lng cng gn thnh
phn ca hn hp ng ph, trong bnh ct s cn li cht A hay B nguyn cht ty
theo ta xut pht t hn hp c thnh phn pha bn tri hay bn phi hnh 2.2a.
Trong hn hp ng ph c nhit si cc i, cng ln pha trn ca ct ct th
cng giu cu t A hoc B, cn li trong bnh s l hn hp cng gn vi thang
phn ca hn hp ng ph (hnh 2.2b).
15

- Chng ct chn khng (hay gim p)

Khi cn chng ct mt cht lng d b phn hu nhit cao, ngi ta
phi dng phng php ct chn khng, tc l dng bm ht gim p sut trn
b mt cht lng. V cht lng s si khi p sut hi ring phn t n p sut kh
quyn, nn bng phng php ny, ngi ta c th gim c nhit si ca n
mt cch ng k, trnh hin tng phn hu hay chy n. Nh phng trnh
Clapayron - Clausius, ngi ta c th tnh c s ph thuc ca p sut hi mt
cht vo nhit . Tuy nhin, c th p dng qui lut thc nghim gn ng nh
sau: khi p sut kh quyn trn b mt mt cht lng gim i mt na, nhit si
ca n b h thp i khong 150C.
- Chng ct li cun hi nc
Ta cng c th tinh ch mt cht lng khng ho tan trong nc, bng
phng php ct li cun theo hi nc h im si ca n.
Phng php ny da trn nguyn tc: Khi hai hay nhiu cht lng khng
trn ln vi nhau nm trong mt hn hp, p sut chung p ca chng bng tng p
sut ring phn p1 + p2, ngha l n lun lun ln hn p sut hi ring phn ca
tng cu t bt k no. Do , nhit si ca hn hp s thp hn nhit hn
nhit si ca cu t si thp nht. T l hi ct sang bnh ngng (v s mol) s
bng t l p sut hi ring phn ca chng nhit si ca hn hp. Nh vy ta
c th tnh ton c lng nc cn thit li cun ht cht cn tinh ch.
Sau khi dng phng php ct li cun theo hi nc, thng ta phi
chit tch cc cht cn tinh ch ra khi nc bng mt dung mi thch hp, ri li
tin hnh ct phn on tch dung mi. Cui cng chng ly cht tinh khit
bng bnh ct c gn nhit k di p sut thng hay gim p, vi s kim tra
nhit ca cht cn tinh ch.
- Phng php chit
Chit l dng mt dung mi thch hp c kh nng ho tan cht ang cn
tch v tinh ch tch cht ra khi mi trng rn hoc lng khc. Thng
ngi ta dng mt dung mi si thp v t tan trong nc nh ete, cloroform
chit tch cht hu c t mi trng nc (cc cht hu c cn tinh ch ny
thng tan t trong nc hoc dng nh tng ln vi nc). Sau khi lc dung
mi vi hn hp cht cn tinh ch v nc, cht s chuyn phn ln ln dung
mi v ta c th dng phu chit tch ring dung dch thu c khi nc.
Bng cch lp li vic chit mt s ln, ta c th tch c hon ton cht cn tinh
ch vo dung mi chn, sau ct loi dung mi v ct ly cht tinh khit
nhit v p sut thch hp.
Ngi ta cng thng chit mt cht t hn hp rn bng mt dung mi
hoc hn hp dung mi vi mt dng c chuyn dng c bit gi l bnh cha
Soxhlet. Dung mi c un nng, cho bay hi lin tc chy vo bnh cha hn
hp cn chit tch (thng c gi bng giy lc), n s ho tan cht rn cn tinh
ch v nh mt ng xiphng, dung dch chy xung bnh cu bn di, dung mi

16

nguyn cht li tip tc c ct ln. Qu trnh c tip tc cho n khi s chit

tch c hon ton.
Phng php ny tit kim c dung mi v t hiu qu tng i cao.
2.1.3. Phng php sc k
2.1.3.1. Khi nim
Phng php sc k c Xvt pht minh ra tch cc cht bng hp ph
t u th k ny (1903), n nay tr thnh mt phng php tinh ch, nh
tnh, nh lng rt quan trng trong ho hc hu c, c pht trin mnh m v
c s dng rng ri trong hu ht cc phng th nghim hin i.
Nguyn tc chung ca phng php sc k nh sau: hn hp cht nghin
cu pha lng (dung dch) hay pha kh c cho i qua b mt cht hp ph
pha rn hay pha lng kh bay hi. Do kh nng tng tc vi pha tnh khc nhau
nn cc cht khc nhau trong hn hp nghin cu chuyn ng vi vn tc khc
nhau v dn c phn tch ra tng cu t ring bit.
2.1.3.2. Sc k ct (sc k hp ph)
Trong phng php sc k ct, ngi ta dng cc ct thu tinh hay i khi
bng kim loi, c kch thc thng thng l 15x1; 25x2; 40x3 hoc 60x4 cm;
dng cc cht hp ph dng bt, thng l nhm oxyt, silicagel, tinh bt, bari
sunfat... hoc mt cht bt k khc khng tng tc vi cht nghin cu v dung
mi. Hn hp cht nghin cu c ho tan trong mt dung mi tr thch hp v
cho chy qua ct. Cc cht trong hn hp nghin cu dn dn tch khi nhau v
chng chim cc v tr khc nhau trn ct hp ph. V lc u ngi ta tin hnh
trn ct th nghim vi cc cht mu, khi chng ta tch ra to thnh cc khoanh
mu khc nhau trn ng hp ph nn phng php ny c gi l phng php
sc k. Sau ngi ta tch ring tng cht hoc bng cch ct ct hp ph thnh
tng on ng vi tng cht, hoc lin tc thm dung mi, cc cht s ln lt
c ra tri v thot ra bnh hng cc thi im khc nhau.
C th dng phng php ny tch cc cht khng c mu, nhng phi
dng cc cht ch th hay thuc th thch hp nhn bit khi no chng bt u
thot ra bnh hng.
2.1.3.3. Sc k giy
Sc k giy l mt dng c bit ca sc k phn b do Consden, Gordon
v Martin pht minh nm 1944. Pha tnh y l nc thm trn giy lc c bit
(xenluloza tinh khit). Dung dch cht nghin cu c chm trn mt u ca di
giy (cch mp giy chng 2,5cm) v mi git cch nhau chng 2cm. Ngi ta
thng nh ng thi c dung dch mu bit so snh. Sau u giy lc
c nhng trong mt dung mi hay hn hp dung mi thch hp bo ho
nc. Do lc mao dn, dung mi s thm dn ln giy sc k, ko theo cht
nghin cu chuyn ng ln pha trn v to vt trn giy m ngi ta c th nhn
17

bit c bng mt thng hoc bng cht ch th. T s Rt gia dch chuyn
ca cht nghin cu v dung mi c gi l hng s sc k, hng s ny l i
lng quan trng c trng cho tng cht.
thu c kt qu tch tt hn, ngi ta c th lp li thao tc trn vi
mt dung mi khc v theo chiu thng gc vi chiu chy ln trc (sc k phn
b hai chiu).
Sc k giy thng dng nh tch cc cht, nhng cng c th dng
nh lng s b da vo m v tit din ca vt cht nghin cu.
2.1.3.4. Sc k lp mng
Phng php ny c Izmailop v Schreiber ngh t nm 1938, c
Stan pht trin v hon thin (1955), khin n c ng dng rt rng ri.
Ngi ta trng mt lp mng cht hp ph (Al2O3, silicagen) ln mt tm
knh kch thc khong 10x12 cm hoc 20x20 cm, chm mt git cht nghin cu
ln mt u bn (cch mp khong 2cm) ri cho dung mi chy nh sc k giy.
Phng php sc k lp mng thng cho hiu qu tch cao, thi gian
ngn, lng cht t, thng c dng nh tnh v tch cc hp cht thin
nhin. N cng c cc nh ho hc tng hp s dng thng xuyn nhanh
chng phn tch cc cht thu c trong phn ng.
2.1.3.5. Sc k kh lng
Nhng nm gn y sc k kh lng c pht trin mnh m, m ra kh
nng ln trong phn tch v tch cc hp cht d bay hi. Phng php thng
thng l cho vi microlit cht lng phn tch vo thit b bay hi ri dng dng
kh mang (thng l He) li cun hi ca chng qua mt ng di nung nng np
y mt cht rn xp (gch chu la tn nh, nhm oxyt, silicagel, than hot
tnh...) c tm bng cht lng kh bay hi nh du silicon, polyetylen glycol,
cc este si cao...Khi xy ra s phn b cc cht gia pha lng v pha kh, ng
thi ch cn c s khc nhau nh trong s phn b ny gia cc cu t trong hn
hp cng phn tch hon ton cc cht lng trong hn hp, v n c lp i
lp li nhiu ln trong ng di. Ngi ta thng nhn bit tng cht thot ra cui
ng bng cch o s thay i dn nhit ca kh thot ra. Tuy nhin vic pht
hin mt pic trong s sc k kh mi l iu kin cn, nhng cha v tinh
khit ca mt cht, phng php sc k kh vn rt hu ch khi phn tch mt
lng nh hn hp cng nh tch v tinh ch cc cht.
Cn nhn mnh rng, trong phng php sc k, ni chung cu trc phn t
ca cc hp cht c nh hng ln n cn bng hp ph, cng nh h s phn b
ca chng gia cc pha, do lin quan cht ch n hng s Rt. V vy kt qu
phn tch sc k cng cho ta thy nhng thng tin b ch v cu trc ca hp cht.
Sau qu trnh tinh ch, ta cn kim tra tinh khit ca hp cht thu c
bng cch o nhit nng chy (i vi cht rn) hoc nhit si (i vi cht
lng) hoc o t khi, ch s khc x, chp ph...Mt cht c coi l tinh khit
nu qua nhiu ln tinh ch, cc hng s vt l ca n khng thay i.

18

2.2. Cng thc phn t hp cht hu c

xc nh c cng thc phn t cc cht hu c, ngi ta tin hnh
xc nh cc thnh phn nguyn t v khi lng phn t ca chng.
2.2.1. Phn tch nguyn t
Cc cht hu c ngoi cacbon cn thng c hydro, oxy, nit, halogen, lu
hunh,... xc nh s c mt v hm lng ca chng, ngi ta s dng cc
phng php nh tnh v nh lng ring.
2.2.1.1. Xc nh cacbon v hydro
S c mt ca cacbon v hydro trong mt hp cht thng c xc nh
bng cch t chy hp cht trong oxi, vi xc tc l CuO:
CxHyOz + (x + y/4 - z/2) O2 x CO2 + y/2 H2O
CO2 thot ra c nhn bit bng phn ng lm c nc vi trong:
Ca(OH)2 + CO2 CaCO3 + H2O
H2O c nhn bit bng cch ngng t trn phn lnh ca ng t hay
bng CuSO4 khan.
nh lng cacbon v hydro, ngi ta t chy mt lng cn chnh xc
cht nghin cu bng dng oxy c mt CuO trong ng thch anh, ri hp th hi
nc thot ra bng perclorat magie (MgClO4); CO2 hp th bng bng tm st
(NaOH). Cc cht hp th ny ng trong ng ch U v khi lng ca chng
c cn chnh xc trc v sau khi th nghim kt thc. Hiu s khi lng gia
hai ln cn cho ta bit khi lng H2O v CO2 b hp th.
Nu trong thnh phn cht nghin cu c halogen, lu hunh, nit, chng
c th to ra cc oxit ca nit, ca lu hunh, halogen v cc oxit halogen hydric
v chng c th nh hng n kt qu cn cc ng hp th. loi tr chng,
trong ng nung phn cui, ngi ta dng cc si bc gi halogen v oxit lu
hunh, dng P 2O5 phn hu oxit nit.
2.2.1.2. Xc nh nit
xc nh s c mt ca nit trong hp cht nghin cu, ta c th t
nng mu th vi natri kim loi, nit cng cacbon trong mu th s chuyn thnh
NaCN, ho tan sn phm to thnh trong nc ct, lc ly dung dch; thm ln
lt cc ion Fe2+, Fe3+, axit ho s to thnh kt ta mu xanh:
6CN- + Fe2+ [Fe(CN)6 ]44Fe3+ + 3[Fe(CN)6 ]4- Fe 4 [Fe(CN)6 ]3
mu xanh

19

 nh lng nit, ngi ta dng phng php Dumas hoc Kjeldahl.

Nguyn l ca phng php Dumus l oxy ho hp cht hu c bng CuO
ri li cun sn phm bng mt dng CO2 tinh khit. Nit trong cht hu c s
chuyn thnh N2 t do. Ta c th thu N2 thot ra bng mt buret p ngc trong
chu cha dunh dch KOH m c. H2O s ngng t trong dunh dch; CO2 hon
ton b hp th bi KOH; N2 thot ln c v ta c th o c th tch ca n
mt cch d dng.
Phng php Kjeldahl tuy khng ph bin bng phng php Dumus song
trong nhiu trng hp cng rt thun tin, n cho php xc nh nhanh hm
lng nit trong mu th. Bng cch v c ho hp cht nghin cu khi nung
nng trong H2SO4 m c c xc tc selen (khi cn c th thm cht oxy ho) ta
chuyn nit thnh mui amon sunfat, sau kim ho dung dch thu c ri li
cun NH3 theo hi nc sang mt bnh khc v chun lng NH3 to thnh.
2.2.1.3. Xc nh halogen
S c mt ca halogen trong hp cht hu c c xc nh bng cch tm
mu giy vo si dy ng ri t, nu hp cht c cha halogen s to ra ngn
la mu xanh lc.
Ngi ta nh lng halogen bng cch oxy ho mu cht trong bnh cha
oxy nguyn cht, c xc tc Pt, khi s to halogenua hydro, hp th bng dung
dch HNO3 v sau xc nh bng phn ng nitrat bc:
AgNO3 + HX AgX + HNO3
Bng cch so c hoc chun lng Ag+ d, ngi ta tnh c hm
lng halogen trong mu cht nghin cu.
2.2.1.4. Xc nh lu hunh
Khi un chy hp cht hu c vi kim loi, lu hunh s chuyn thnh
Na2S, sau ta c th d dng nhn bit c bng cch phn ng to kt ta PbS
hay Ag2S:
Pb(NO3)2+ Na2S PbS + 2NaNO3
nh lng lu hunh, ngi ta oxy ho mu cht hu c bng HNO3
bc khi trong ng hn kn 200 300oC, sau vi gi lu hunh trong mu cht
s chuyn ho thnh H2SO4, ta c th nh bng phn ng vi BaCl2, ri xc nh
lng BaSO4 bng phng php trng lng:
H2SO4 + BaCl2 = BaSO4 + 2HCl
2.2.1.5. Xc nh cc nguyn t khc

20

Ngoi cc nguyn t k trn, trong mt s trng hp chy hu c c th

cn cha P, Si, mt s kim loi khc...
Ta cng oxy ho hp cht hu c bng HNO3 bc khi trong ng hn kn
hoc nung chy n vi hn hp NaNO3 v Na 2CO3. Cc nguyn t ni trn s
chuyn ho thnh cc hp cht v c tng ng (thng vi ho tr dng cao
nht), sau ta nh lng chng bng cc phng php v c thng thng.
2.2.1.6. Xc nh oxy
Hm lng oxy trong cc hp cht thng c xc nh mt cch gin
tip, tc l ta ly khi lng mu em t tr i khi lng tng cc nguyn t
va xc nh theo cc phng php trn, hoc ly 100% tr i hp phn ca cc
nguyn t khc.
Ta cng c th xc nh mt cch trc tip bng cch chuyn oxy trong hp
cht hu c thnh CO ri oxy ho bng I2O5:
5CO +I2O5 5CO2 + I2
Chun lng I2, CO2 c gii phng ra hoc chun lng I2O5 d,
ta tnh c lng CO hnh thnh.
Tm li, nh nhng phn tch ch to cc k chnh xc, nh nhng thit b
phn tch ngy cng hon thin, ngi ta c th tin hnh phn tch vi lng hoc
bn vi lng, vi nhng cht nh (vi mg) cng cho ta kt qu ng tin cy. T
nhng nm 60, ngi ta pht hin v s dng cc phng php siu vi lng,
ch cn cn mu cht (trn cn in t t ng) cn cc sn phm t chy c
xc nh bng nhng thit b tinh vi trn c s o dn nhit ca cc cht kh
nh b pht in etect. Vi phng php ny, ngi ta c th xc nh ng
thi C, H, N hon ton t ng trong vng 10 pht, lng mu ch cn khong 1
mg.
2.2.2. Thit lp cng thc tng qut ca hp cht
Sau khi xc nh thnh phn khi lng (hoc thnh phn trm khi lng)
ca tng nguyn t trong cht nghin cu, bng cch chia cho nguyn t lng
ca cc nguyn t tng ng, ta s c t l gia s nguyn t tng nguyn t
trong phn t, t thit lp c cng thc tng qut ca cc cht cho di
dng (CxHyOzNt)n
V d:
t chy 1,5 mg mt cht A to thnh 0,9 mg H2O; 1,76 mg CO2 v 0,224
ml N2 (ktc). Ta tnh khi lng tng nguyn t trong mu cht nh sau:
0,9 mg H2O 0,0009/ 18 ptg (0,0009/18) x 2 = 0,0001g H = 0,1 mg H
1.76 mg CO2 0,00176/44 ptg (0,00176/44) x 12 = 0,00048 g C = 0,48
mg C
0,224 ml N2 0,224/22,4 ptg (0,224/22,4) x 28 = 0,28 mg N
21

Lng oxy: mO = 1,5 -(0,48+0,1+0,28) = 0,64 mg

Ta c:
CxHyOzNt + (x+y/4-z/2) O2 xCO2 +y/2 H2O + t/2 N2
V x : y : z : t = 0,48/12 : 0,1/1 : 0,64/16 : 0,28/14 = 2 : 5 : 2 : 1
Vy cng thc tng qut ca cht nghin cu l (C2H5O2N)n.
xc nh n ta phi xc nh khi lng phn t cht cho hoc i khi
khng thc hin c trong iu kin th phi bin lun.
2.2.3. Xc nh khi lng phn t ca mt cht
tm c cng thc nguyn (cng thc phn t) ca mt hp cht, ta
phi xc nh khi lng phn t, hay ni chnh xc hn l xc nh phn t gam
ca cht nghin cu. C nhiu phng php xc nh phn t lng.
a. Nu mu cht nghin cu l cht lng d bay hi, ta cho bay hi nhit
thch hp, o th tch hi iu kin ri tnh phn t lng ca n theo
phng trnh:
pV = nRT = (m/M)RT
M = mRT/pV
Trong :
p - p sut;
V - th tch hi cht nghin cu;
m - khi lng cht bay hi;
T - nhit tuyt i;
R - hng s kh.
b. Nu o c t khi hi ca cht cho i vi mt cht kh no , ta
c th tnh c phn t gam ca n mt cch d dng.
V d, hi cht A nng gp 25 ln H2 th phn t lng ca n phi l
M = 25 x 2 = 50.
c. Da vo nh lut Raoult
Dung dch mt cht kh bay hi trong mt dung mi no c lun c
nhit si cao hn, nhit ng c thp hn so vi dung mi nguyn cht v
tng im si hay h im kt tinh lun t l vi nng cht tan.
t = KC
K - h s t l, c gi l hng s nghim si hay nghim lnh, c trng
cho tng loi dung mi;
22

C - nng mol/l hay khi lng mol phn t/1000 g dung mi

Bng cch o mc tng nhit si (phng php nghim si) hoc mc
h im kt tinh (phng php nghim lnh) ca dung dch cht nghin cu trong
dung mi cht thch hp, ta d dng xc nh c nng cht tan v do xc
nh c phn t gam ca chng.
Ngi ta hay dng campho lm dung mi, v hng s nghim lnh ca n
kh cao (khi ho tan mt phn t gam cht tan trong 1000 g campho, im ng
c h i t =37,7oC.
d. Cc phng php khc
Bng cch tng t, ngi ta cng c th o p sut thm thu ca dung
dch cht tan, o nht ca dung dch hoc bng phng php khi ph, t
xc nh c khi lng phn t cht cho. Nu bit r s nhm chc trong
mt phn t cht nghin cu, bng cch xc nh s nhm chc cng cho php xc
nh phn t lng ca chng.
V d, 0,92 g mt alcol n chc tc dng vi mt lng d Na cho 0,224 l
H2 (ktc) th phn t lng ca alcol phi l:
0,92/ (0,224 x 2)/22,4 = 46
2.2.4. Thit lp cng thc nguyn ca mt hp cht
Sau khi xc nh c cng thc tng qut ca cht nghin cu khi lng
phn t ca n, ta d dng tm ra c tr s ca n v do thit lp cng thc
nguyn ca hp cht.
V d, lp c cng thc tng qut ca cht A di dng (C2H5O2N)n
nh v d trn, ng thi bng mt trong cc phng php va nu ta xc nh
c phn t lng ca cht A l 75, ta tnh c:
(2 x 12+5 x 1+2 x 16+1 x 14)n = 75
75n = 75 n = 1
Vy cng thc nguyn ca A phi l C2H5O2N.
Tuy vy, nhiu khi trong iu kin thc nghim khng cho php ta thc
hin tt c cc bc trn, c ngha l phi gii bi ton tm cng thc nguyn khi
s phng trnh ton hc lp c it hn s n s, trong khi trng hp ny ta
phi bin lun. Phng php bin lun phi da vo c im ca hp cht cho
xc nh tr s n trong cng thc tng qut, hoc da vo cc bt phng trnh
phn nh mi tng quan gia s nguyeen t ca cc nguyn t c bn.
V d, mt hydrocacbon c t khi i vi hydro l 21. Hy tm cng thc
ca n.
Ta c khi lng phn t l 21x2 = 42. Nu gi cng thc ca hydrocacbon
l CxHy, ta c:
23

12x + y = 42
Suy ra:
12x < 42
Hay :
x < 3,5
Mt khc CxHy l hydrocacbon nn s nguyn t H trong phn t khng
vt qu 2x + 2, ngha l:
y 2x + 2
42-12x 2x + 2
40 14x
2,8 x
Kt hp vi lp lun trn, ta c 2,8 x <3,5 m x ch tip nhn gi tr
nguyn, vy x = 3, suy ra y = 6.
Cht cho cng thc C3H6.
2.3. Cu trc phn t hp cht hu c
2.3.1. ng phn
2.3.1.1. Khi nim
ng phn l mt khi nim biu th s phn b khc nhau ca cc nguyn
t hoc l nhm nguyn t ca mt phn t trong khng gian; l nhng hp cht
hu c c cng cng thc phn t nhng khc nhau v cu trc, do tnh cht
vt l v ho hc khc nhau.
2.3.1.2. Phn loi
C 3 loi:
- ng phn cu to
- ng phn hnh hc
- ng phn khng gian
a. ng phn cu to (ng phn phng)
Khi nim: ng phn cu to l loi ng phn m trong cu to ca
chng c s khc nhau v th t lin kt gia cc nguyn t vi nhau. Ngi ta
cn gi ng phn ny l ng phn lin kt.
V d: Hp cht hyrocacbon C4H10 c th tn ti di hai dng ng phn
cu to sau y:

H v

H C H
H
H
H

Hyrocacbon C5H12 tn ti di 3 dng ng phn cu to:

24

H H H H H
H C C

H H H

C C C H

H C

H H H H H

C C

C H

CH3 H

H C

H H CH3 H

C H

CH3 H

Khi s lng ca nguyn t cacbon trong phn t hyrocacbon tng ln th

s lng cc ng phn cu to tng rt nhanh. V d C6 c 5 ng phn, C7-9, C818, C20-366 319, C40-62.491.178.805.831 ng phn.
Mt loi ng phn cu to khc xut hin khi phn t ca cc hp cht
hyrocacbon c cha cc lin kt bi. V d hp cht hyrocacbon C4H8 tn ti
di 2 dng ng phn sau:
H H H H
H

H H H H
H

H H

v H

Phn loi: Loi ng phn ny thng gp cc dng sau:

- ng phn v mch cacbon, ngha l ch khc nhau v cch sp xp mch
cacbon:
CH 3CHCH 2OH

CH 3CH 2 CH 2CH 2OH

CH 3

ancol n - butylic

ancol isobutylic

- ng phn v v tr ca nhm chc. Cc hp cht ny c cng nhm chc

nhng khc nhau v s phn b v tr ca nhm chc:
CH3CHCH2CH3

CH3CH2CH2CH2OH

OH

Butan-1-ol

Butan-2-ol

- ng phn v nhm chc:

CH 3 CH 2CH 2CH 2OH

CH 3CH 2-O-CH 3

ancol

ete

- ng phn v cch chia on mch ca nhm chc:

25

CH 3C-O-CH 2CH 2CH 3

CH 3-O-C-CH 2CH 2CH 3

butyrat metyl

axetat n - propyl

Hai cht u thuc este, nhng xut pht t hai cp axit v ancol khc nhau,
axetat n - propyl hnh thnh t CH3COOH + CH3CH2CH2OH, cn este butyrat
metyl hnh thnh t CH3CH2CH2COOH + CH3OH.
b. ng phn hnh hc
Khi nim: L ng phn cu hnh do s sp xp khc nhau ca cc nhm
th 2 bn ni i hay mt phng vng no. S sp xp cc nhm th hai bn ni
i thc cht l hai bn mt phng . Mt phng v mt phng vng l nhng
mt phng c nh. Nu hai nhm th ging nhau hay gn ging nhau cng pha
ca mt phng gi l ng phn cis, khc pha l ng phn trans.
V d:
CH3

H3C
C

H3C
C

CH3

trans-but-2-en

cis-but-2-en

Cl

Cl

Cl

H
H

Cl

H
H

cis-icloxyclopropan

trans-icloxyclopropan

Cch qui nh v tr hai nhm th ging nhau trn y ch l trng hp c

bit trong cch qui nh tng qut v v tr ca 2 nhm th trong mch chnh.
V d:
CH3 > H

C2H5

H 3C
C

C2H5 > CH3

C
H

iu kin cn v xut hin ng phn hnh hc

26

CH3

H3C

C
C2H5

- iu kin cn: Phn t phi c ni i hay vng no nm trn mt mt

phng.
- iu kin : 2 nhm th mi cacbon ni i hay vng no phi khc
nhau.
c

ab
C

cd
b

Phn loi: c 3 loi

- ng phn cis trans
+ ng phn cis-trans xut hin cc ni i C-C khi c hai nguyn t
hoc nhm nguyn t nm cng pha hoc khc pha ca mt phng .
H 3C

H 3C

CH 3

CH 3

trans-2-buten

cis-2-buten

+ Trng hp phn cng nhc ca phn t l mt ni n hoc mt phn

vng trong cc hp cht vng:
Dn xut c 2 ln th:
Xiclopropan c 2 ng phn hnh hc

Cl

Cl

Cl

Cl

cis

trans

CH3

CH3

HOOC

HOOC

cis

trans

Xiclobutan c 4 ng phn hnh hc

27

Cl

Cl

Cl

Cl

cis

Cl

trans

Cl

cis

trans
Cl

Cl

Xiclopentan c 5 cu trc

Trong b,c,d,e l ng phn hnh hc ng thi nu 2 nhm th ging

nhau th c, d l hot ng quang hc cn nu khc nhau th c b,c,d,e u hot
ng quang hc.
Xiclohexan: cis-trans ca 1,2; 1,3; 1,4

cis-1,2

trans-1,2

cis-1,3

trans-1,3
cis-1,4

trans-1,4

Nhng hp cht c nhiu cnh v khng phng c s ng phn hnh hc

tng ln nhiu v tng s ng phn v tr v s nhm th c th c. Quan trng l
loi hp cht hexacloxyclohexan v loi inosit c 8 ng phn cis-trans, tong
c 7 dng meso v mt dng nghch quang:

28

X
X

X X

X
X X

X
X

X X
X

cis-inosit

alloinosit

epiinosit

mesoinosit

X
X

X=OH; Cl

neoinosit

mucoinosit

X
X

D,L-inosit

spiloinosit

Cc d vng:
H

HOOC

COOH
NH

CO

CO

NH

HOOC

trans

H
NH

CO

CO

NH
COOH

cis

Cc hp cht vng ngng t

Vng 3 cnh ngng t vi vng 4,5,6 cnh ch c ng phn cis
1
1

cis-bixyclo(2,1,0)pentan

Vng 4 cnh ngng t vi vng 5,6 cnh ch c ng phn cis cn ngng t

vi vng 7 cnh th c ng phn cis-trans:

cis-bixyclo(4,2,0)octan

cis-bixyclo(5,2,0)nonan

trans-bixyclo(5,2,0)nonan

Vng 5 cnh ngng t vi vng 5 cnh, vng 5 cnh ngng t vi vng 6

cnh c ng phn cis-trans

29

cis-bixyclo(3,3,0)octan

trans-bixyclo(3,3,0)octan

cis-hidrindan

trans- hidrindan

Vng 6 cnh ngng t vi vng 6 cnh c dng phn cis-trans

Cis-ecalin

trans-ecalin

- ng phn syn anti

C

Danh php Syn-anti: Dng cho ni i

c mt cp in t khng
phn chia nh i vi loi hp cht andoxim, xetoxim khng i xng, hidrazon,
hp cht azo c lin kt C=N, N=N. (syn-: cng pha, anti-: khc pha).
..

V d: CH3 - CH = N - OH
OH

H 3C

H3 C

OH

anti-

SynC6H5

C6H5

C6H5

C6H5

syn

anti

- ng phn E - Z
Trong trng hp khng dng c danh php cis - trans th dng danh
php chung gi l danh php E-Z.
30

Danh php E-Z da trn tnh hn cp ca nguyn t nh vi cacbon. Nhm

th c nguyn t c s th t nguyn t cao hn (hay c khi lng nguyn t
hoc phn t ln hn) th c tnh hn cp cao hn. Nu hai nhm th c tnh hn
cp cng pha ca mt phng gi l ng phn Z, khc pha l ng phn E.
+ Nhm th c nguyn t nh vi C lai ha sp2 c s th t hay in tch
ht nhn ln hn s hn cp hn:
Br > Cl > S > P > F > O > N > C > H
+ Nu cc nguyn t lin kt trc tip ging nhau th xt lp th hai:
CH(CH3)2 > CH2CH3 > CH3
(RO)3C > (RO)2CH > ROCH2
+ Cc nguyn t c cha lin kt bi c tnh bi ln:
HC=O > CH2OH ; C6H5 > (CH3)2CH ; C N > CH2NH2
+ Trong s cc ng v, nguyn t c s khi ln hn l hn cp hn D > H
V d:
NO2

Br

Br

H3C

Br

H3C

>

CH3

(Z)-2-Brom-1-nitropropen

NO2 >

C
NO2

H
(E)-2-Brom-1-nitropropen

Tnh cht ca ng phn hnh hc

+ bn tng i ca ng phn hnh hc: tnh bn ca cc anken tng
theo mc ankyl ha ca etylen:
R2C=CR2 > R2C=CHR > R2C=CH2
RCH=CHR > RCH=CH2 >CH2=CH2
ng phn hnh hc ni chung th ng phn trans bn hn cis do ng
phn cis c s y ln ca cc nhm th gn nhau hn.
+ Cc ng phn hnh hc c nhiu tnh cht khc nhau r rt, v d 1,2icloetilen.

31

cis
3,7A0
1,89D
-80,5 0C
600C

Khong cch 2 Cl

t0nc
t0s

trans
4,7A0
0,0D
-500C
48 0C

+ S ng phn ha hay chuyn ha ln gia cis-trans

Phn ng c in chuyn ha gia ng phn cis-trans l phn ng
quang ha. Khi chiu sng, nng ng phn cis trng thi dng quang ha l
ln hn trng thi c bn. Nh vy, s chiu sng l phng php chuyn ng
phn trans thnh cis.
Phn ng chuyn ha cis-trans c th thc hin bng phn ng ha hc qua
nhiu giai on phn ng:
R

RCOOH
C
H

C
H

O
C

cis

CH

SN 2

PR3

CH

C
H

O-

PR3
H

R3PO-

R
O-

R
C

PR3

trans

Giai on u l phn ng epoxy ha, sau l phn ng th SN2 vi s tn

cng ca photphin. c phn ng tch cis, tc nhn th SN2 phi quay xung
quanh lin kt C-C.
Nu xut pht ban u t trans, qua qu trnh trn thu c cis. Nh vy
qu trnh trn dng chuyn ha cis trans ca anken. iu ny gii thch ti
sao c 2 nguyn t cacbon v hidro m to nn v s cc phn t hp cht hu c.
c. ng phn khng gian
- ng phn quang hc
32

Khi nim: Nhng hp cht c cu trc v tnh cht vt l, ho hc ging

nhau nhng khc nhau v kh nng quay mt phng nh sng phn cc gi l ng
phn quang hc.
nh sng l dao ng sng ca trng in v t. Khi mt electron tng
tc vi nh sng th c dao ng theo tn s ca nh sng theo hng ca trng
in. nh sng thng c vect trng in ca sng nh sng trong tt c cc
hng ca mt phng. nh sng phn cc c vect ca trng in ca tt c cc
sng nh sng trong cng mt mt phng, gi l mt phng phn cc.

nh sng thng

nh sng phn cc

nh sng phn cc thu c khi cho nh sng thng i qua lng knh
phn cc:

Phn cc k

nh sng thng

nh sng phn cc

C mt s cht hu c (v c mt s cht v c) c kh nng lm quay mt

phng phn cc khi cho nh sng phn cc i qua. Kh nng gi l tnh quang
hot, cn nhng cht c kh nng gi l cht quang hot. Trong s nhng cht
quang hot c mt s khng nhiu lm ch th hin kh nng lm quay mt phng
phn cc khi cn trng thi tinh th (tinh th bt i), v d: tinh th ca cc cht
NaCl, ZnSO4. Cn mt s ln cht khc li c tnh quang hot khi th hi hay

33

trong dung dch. loi cht quang hot va ni, tnh quang hot khng phi do
cu trc tinh th m do cu trc ca nhng phn t ring r.
o kh nng lm quay mt phng phn cc ( quay cc) ca cc cht
quang hot ngi ta dng phn cc k ghi ly gc quay . i vi mt cht
quang hot ngi ta thng dng i lng quay cc ring [ ]. quay cc
ring ca mt cht trong dung dch c tnh theo cng thc sau:
0

.V
L.a

Trong :
: Gc quay quan st c i vi mt dung dch c b dy nh sng i
qua l d (dm) cha a (g) cht quang hot trong V (ml) dung dch. Vic thc
hin t0, vi nh sng c di sng .
Gc quay ca mt cht quang hot khng nhng ph thuc vo bn cht
ho hc ca cht , bc sng ca nh sng phn cc, b dy ca dung dch cht
quang hot, nhit khi o, m cn ph thuc vo nng v bn cht dung mi.
Cho nn khi vit quay cc ring phi ghi c th. V d:

25D 180

(C = 15 nc)

Nh th c ngha l quay cc ring ca cht quay v bn tri 180, nng

15g trong 100 ml dung dch nc, nhit khi o l 250, b dy dung dch
1dm, nh sng c dng l nh sng D ca natri vi bc sng 589nm.
iu kin xut hin ng phn quang hc
+ iu kin cn: Phi c trung tm bt i (nguyn t bt i, phn t bt
i hay tinh th bt i)
+ iu kin : Phi c phn b theo cng thc chiu Fis.
iu kin cn v xut hin tnh quang hot l khi phn chiu m hnh
ca hp cht qua mt mt phng ta c m hnh khc khng ng nht vi n,
ngha l khng th ch bng chuyn ng tnh tin v quay m c th a c hai
m hnh lng kht vo nhau c. Ni cch khc, xut hin c hin tng
quang hot, phn t phi khng lng kht c vi nh gng ca n, tng t
nh quan h gia hai bn tay ca mt ngi bnh thng. Tnh cht c gi l
tnh khng trng vt - nh (chirality). Khi c hin tng ny, s xut hin hai dng
ng phn i xng nhau, khng lng kht vo nhau c nh hnh a.1

34

b
b
d

Mt phng gng

Hnh a.1: Hai dng ng phn i xng nhau

Hai ng phn ny c kh nng lm quay mt phng nh sng phn cc
nhng gc c tr s nh nhau nhng theo chiu ngc nhau. l hai cht i
quang.
Nguyn t cacbon bt i
Trong mt hnh t din u c mt tm i xng, bn trc i xng v su
mt phng i xng.
Nu ta thay th tt c bn nguyn t hydro trong phn t CH4 bng bn
nguyn t hay nhm nguyn t ging ht nhau th cc yu t i xng vn cn
nguyn vn. Nhng nu thay th mt hay nhiu nguyn t hydro trong CH4 bng
nhng nguyn t hay nhm nguyn t khc nhau th cc yu t i xng s b vi
phm.
V d: Th mt nguyn t H bng Br th ch cn mt trc i xng v ba
mt phng i xng, th 3 nguyn t H bng 3 nguyn t khc nhau th s khng
cn mt yu t i xng no c.
Khi trong phn t c nguyn t C nh vi 4 nguyn t hay nhm nguyn
t khc nhau Cabcd s xut hin hai dng ng phn i xng nhau qua mt
phng nh vt vi nh trong gung (hnh a.1) v c tnh quang hot. Nguyn t C
gi l nguyn t C bt i, phn t Cabcd l phn t bt i.
V d:
H

C*

H 3C

C*

COOH

OH

Cl

C*

SO 3 H

Cl

C*

Br

Trong trng hp hai nguyn t ng v nh vo mt nguyn t C cng

vi hai nhm nguyn t khc na, nguyn t C cng l C bt i, cho nn
nhng hp cht nh trong v d di y cng c th l nhng cht quang hot:

35

C*

C6H 5

CH 3

C*

H 3C

CD 3

OH

biu din nguyn t cacbon t din trong cc phn t kiu Cabcd ta c

th dng cc cng thc khc nhau hnh a.2. l cc cng thc t din (1), Fis
(2) v (3), phi cnh (4) v phi cnh kt hp vi Fis (5).
Trong cc cng thc , nt lin biu din lin kt nm trn mt phng
giy, nhng ng chm nh hoc ng gch ngn dn dng ch nhng lin
kt hay ng ni hng v pha di mt phng giy (i xa pha ngi quan st),
cn cc ng m hnh tam gic ch nhng lin kt hng t mt phng giy
v pha ngi quan st (i gn pha ngi quan st) :

c
a

d
(1)

(2)

(3)
c

(4)

(5)

Quy tc chiu Fis

+ Mch chnh biu din cnh nm dc.
+ Nguyn t hoc nhm nguyn t c s oxi ho cao th c biu din
pha trn, ngc li th biu din pha di.
+ Qui c: Cc nhm nguyn t ng k ngang (a v b) pha gn
ngi quan st, cn cc nhm nguyn t ng dc (c v d) pha xa hn.
Mun chuyn cng thc hnh t din sang cng thc Fis ta dng phng php
chiu cc nhm nguyn t ca t din ln mt phng giy. Khi y cn ch l t

36

din phi c phn b nh th no mt cnh nm ngang ca t din gn

ngi quan st.
c

c
b

a
d

-3

*
CHOH

V d: CH3

+1
CH2OH
CHO

CHO

OH

OH

CH3

CH3

+ Ta c th bin i cng thc Fis theo cc cch khc nhau, khi y tu

tng trng hp m cu hnh vn c bo ton hay b nghch o (quay cu
hnh).
i ch bt k hai nhm th no C cng lm quay cu hnh v nh vy
s sinh ra mt dng khc ca phn t ban u.
V d:
CHO
OH

CHO
H

OH

CH2OH
Dng D

CH2OH
Dng L

37

OH
H

OCH

CH2OH
Dng D

 Nu dch chuyn ng thi ba nhm th theo chiu kim ng h hoc

theo chiu ngc li th cng thc Fis vn gi nguyn ngha, tc l cu hnh
c bo ton.
V d:
CHO

CHO
H

OH

CH2OH

OH
H

CH2OH

Dng D

Dng D

Khng c a cng thc Fis ra khi mt phng giy, cng khng

c quay cng thc trn mt phng nhng gc 900 hay 2700 (v s quay cu hnh)
nhng c th quay 1800 (cu hnh khng i).
V d:
H

CHO
H

OH

Quay 900

HOCH2

CH2OH

CHO

CHO

HO

OH

CH2OH
Dng L

Dng D

CHO

CH2OH
Quay 1800

OH

HO

CH2OH

CHO

Dng D

Dng D

38

 biu din hai hay nhiu nguyn t cacbon t din k tip nhau ta cng
c dng cng thc t din hay cng thc Fis
V d: Vit ng phn quang hc ca : HOOC-CHOH-CHOH-COOH
COOH

COOH

COOH

OH

HO

OH

HO

HO

COOH

OH

COOH

HO

COOH

COOH

ng phn mz

OH

COOH

Hai ng phn i quang

Hai ng phn khng i quang

Phn loi ng phn quang hc

+ Cp i quang
V d: Andehit glixeric HOCH2-CHOH-CH=O
CHO
H

CHO

OH

OH

CH2OH

H
CH2OH

Andehit D (+) glixeric

Andehit L (-) glixeric

+ Tnh cht ca mt cp i quang

Ging nhau: Hai cht i quang c cc tnh cht vt l v ho hc bnh
thng ging ht nhau.
Khc nhau: Chng khc nhau du ca nng sut quay cc ( = +: quay
sang phi; = - : quay sang tri) v hot tnh sinh hc ( tng tc vi tc nhn

39

c tnh quang hot). Nhng s khc nhau ny bt ngun t s khc nhau v cu

hnh.
+ Tnh cht ca cp ng phn quang hc khng i quang (ng phn lp
th ia)
Ging nhau: C tnh cht vt l v ho hc bnh thng ging ht nhau.
Khc nhau: Gi tr gc quay cc khc nhau nhng c th giing nhau hoc
khc nhau v du.
- ng phn mz
L ng phn c yu t i xng ni phn t, c c im gc quay cc
ring = 0, l ng phn lp th khng quang hot (do s b tr ni phn t).
V d:
COOH

COOH

HO

HO

OH

OH

COOH
COOH
Axit mztactric

- Bin th Raxemic
V d:
CN

CN

OH

HO

CH3

H
CH3

Thng thng trong t nhin cng nh trong cc qu trnh ha hc, ngi

ta hay gp hai cht i quang ca mt cht tn ti dng tp hp ng phn t
(cu to ca tp hp cha tht r rng) gi l bin th raxemic, k hiu bng du
( ) hay ch D, L hoc d, l. V d : andehyt ( ) glyxric. Tt nhin phi hiu rng
khi nim bin th raxemic l mt khi nim c tnh cch thng k, khng dng
ch cc phn t ring r m ch mt tp hp ln cc phn t.
Bin th raxemic khng c tnh quang hot v y c s b tr nhau v
nng sut quay cc gia hai cht i quang ( = 0).

40

Thng thng cc trng thi kh, lng hay dung dch, bin th raxemic c
th c coi l hn hp ng phn t gn nh l tng ca hai cht i quang cho
nn n c tnh cht vt l ging nh cc cht i quang to nn n nh t0s, t khi,
chit sut, quang ph hng ngoi trng thi lng hay dung dch,...
Ch : H thng k hiu D-L c nhng hn ch nht nh nn hin nay
ngi ta dng ph bin h thng R-S ch cu hnh.
S ng phn quang hc ca mt hp cht l: N = 2n trong n l s
nguyn t C bt i. Tuy nhin i vi cc cht c s i xng ring trong phn t
th s ng phn lp th t hn 2n.
- ng phn cu dng
Khi nim
+ Cu dng l nhng dng cu trc khng gian sinh ra do s quay xung
quanh mt hay vi lin kt n m khng lm t nhng lin kt ny.
+ ng phn cu dng (ng phn quay) l nhng cu dng tng i bn
ca phn t.
iu kin c ng phn cu dng
+ iu kin cn: C lin kt n C - C.
+ iu kin : Phi c m t bng cng thc Niumen hoc biu din
di dng phi cnh.
Phn loi
+ Cu dng ca etan v cc hp cht kiu X3C - CX3
Dng che khut: Dng c th nng cao nht, cu dng ny khng bn.
H H

H
H
H

H
H

Dng xen k: Dng c th nng thp nht, cu dng ny bn.

H
H

H
H

H
H

H
H

S ng phn cu dng: N =

3600
vi n l gc quay. Nh vy ta s c
n

v vn dng hnh hc khc nhau, trong c hai dng ti hn l dng che khut v
dng xen k.

41

Biu din th nng theo gc nh din ( n = 600) ta s c gin th nng:

E (kcal/mol)
3

2
1

60

120

180

H
H H
H
H

H
H
H

H H
H
H

300

H
H

240

H H

H
H
H

H
H

Gc quay

H
H H

360

H
H

H
H
H

H H

H
H

H
H

H
H

Gin trn c dng hnh syn, vi 3 cc i bng nhau v 3 cc tiu bng

nhau ng vi chnh lch v nng lng l 2,8 kcal/mol.
Cu dng v gin th nng ca cc hp cht khc kiu X3C - CX3 tng
t etan.
+ Butan v cc hp cht kiu XCH2 CH2Y
i vi phn t n-butan CH3-CH2-CH2-CH3 khi quay quanh lin kt C-C
xut hin 2 cc i nng lng ng vi hai dng che khut: che khut ton phn
v che khut mt phn v 2 loi cc tiu nng lng ng vi 2 dng xen k. Ngi
ta phn bit 2 dng xen k: anti (hay transoit) v syn (cisoit). Dng anti tng i
bn hn dng syn, chnh lch nhau khong 0,7 kcal/mol. Tng tc gia 2 nhm
CH3- lm cho dng syn km bn, gi l tng tc syn. nhit thng, dng
anti chim t l gp i dng syn.
i vi dn xut 1,2-ihalogen ca etan nh: 1,2-icloetan; 1,2-ibrom
etan.ta cng thy hin tng tng t nh n-butan. Kt qu nghin cu cho thy
rng trong dung dch CCl4 250C, 1,2-iclo etan tn ti ti 70% dng anti v
30% dng syn.

42

CH3
H

CH3
H

CH3

Dng anti
H

Dng syn
H

CH3

Trong iu kin tng t 1,2-ibrom etan cha 89% dng anti v 11% dng
syn. Nu dng syn ca XCH2-CH2Y c lin kt hidro th s khc thm ch dng
syn bn hn dng anti. Cc cu dng tng i bn ca mt cht l nhng ng
phn cu dng ca nhau.
+ Cu dng ca hp cht khng no
Trong phn t nhng hp cht loi ny nguyn t hoc nhm nguyn t
mang ni i thng v tr che khut i vi nguyn t H hay cc nhm th nh
Cl, CH3
H

H
C

O
CH3

Axit fomic

Etyl fomiat

O
CH3

H 2C

Metyl vinyl ete

+ Cu dng bn ca mt s phn t c ni i
ng ch l cc hp cht c 2 ni i lin hp nh: buta-1,3-ien; 1,3icrolein c hai dng thng bn ch khc nhau v v tr nhm cha no so vi ni
n gia. V c s tng t vi ng phn hnh hc nn y ngi ta phn
bit nhng dng l -cis v -trans. i vi butadien-1,3, dng s-trans bn
hn dng s-cis l 2,3 kcal/mol
H2C

CH2
C

CH2
C

H2C

-trans

-cis

43

+ Cu dng ca cc hp cht vng no

Nhng yu t lm gim bn v bin dng vng no
) Sc cng Baye: (1885) l sc p hoc trng gc ho tr CC C so vi
gc ho t bnh thng 109028. Sc cng cng ln th vng cng km bn. Mc
sc cng l na hiu s gia gc ho tr ca vng phng v gc ho tr bnh
thng, tc l sai lch ca gc ho tr tiu chun.
n (s nguyn t cacbon ca vng)
( sai lch v gc)

3
24064

4
9 044

5
6
0
-5 16 -9033

7
-12046

Nh th, theo cc tr s c trng cho sc cng Baye th vng no bn nht

l xiclopentan cn nhng vng no km bn l xiclopropan v nhng vng ln.
Tuy vy, nhng ti liu tch lu cho n nay cho rng kt lun ca Baye ch
p dng ng cho nhng vng 5 cnh tr xung m thi. Ngi ta tng hp
nhng vng ln thy rng: nhng vng ny c bit l xiclohexan c bn ln
hn d kin ca Baye nhiu. Xt theo thiu nhit tnh cho mt n v mt xch
CH2 ca vng trong bng sau:
n
2*
3
4
5
6
7
8

H
168,7
166,6
164,0
158,7
157,4
158,3
158,6

H-157,4
11,3
9,2
6,5
1,3
0
0,9
1,2

n
9
10
11
12
13
16
17

H
158,8
158,6
157,4
157,7
157,4
157,5
157,2

H-157,4
1,4
1,2
1
0,3
0
0,1
0,2

Ngi ta cng thy nng lng ca cc vng ln t xiclopentan tr ln u

nh nhau, m theo quan im ca Baye th nng lng phi tng theo s cnh ca
vng.
) Sc cng Pitz: Thc ra cc vng no (tr xiclopropan) khng phi l
vng phng. Trong mt vng, ngoi sc cng Baye cn c sc cng do ch cc
nguyn t H trng thi che khut mt phn hay ton phn gy nn. Do , mt
vi nguyn t ca vng b lch ra khi mt phng ca vng. Sc cng gi l
sc cng Pitze.
Cu dng ca cc vng no
) Xiclopropan ch c th trn mt mt phng. Cc nguyn t H trng
thi che khut. Cn cc lin kt C-C b bin dng. Do vng ny t bn.
) Xiclobutan ch c th trn mt phng ca 3 nguyn t cn li. iu ny
c xc nh bi cc kt qu nghin cu quang ph cng nh phng php nhiu
x electron.

44

) Trong xiclopentan hu nh khng c sc cng gc nhng sc y li ln.

Do trong trng thi bn ca xiclopentan c mt nguyn t C b chch ra khi
o

mt phng ca vng 0,5 A :

H

H
H

H
H

H
H

H
H

xiclobutan

xiclopropan

xiclopentan

) Cu dng ca xiclohexan
Hnh dng ca vng xiclohexan
Xiclohexan cng c cu trc khng phng. m bo cho gc ho tr
bnh thng, xiclohexan cng c nhiu dng khc nhau: dng thuyn, dng xon,
dng gh:

Trn cc dng trn, dng gh l dng bn v vy tuyt ai a s cc hp

cht c vng xiclohexan cc phn t tn ti hu nh ch dng gh. nhit
phng, trong xiclohexan c ti 99,9% phn t tn ti dng gh.
Hai dng ng ch hn c l dng gh v dng thuyn.C 2 dng ny
khng c sc cng Baye v cc gc ho tr ca cacbon u bnh thng (109028).
dng gh khng c sc cng Pitze nn bn hn dng thuyn.
Tht vy, ta c th coi phn t xiclohexan nh t hp ca 6 h thng C-C
ging n-butan. dng gh tt c 6 h thng ny u theo cu dng xen k tng
t syn-butan khong cch gia cc nt H 2 nt C k nhau hay khng k nhau u
ln.
Trong khi , dng thuyn ch c 4 h thng: C1-C2; C3-C4; C4-C5; C6-C 1
c cu dng xen k cn 2 h thng cn li (C2-C3, C5-C6) c cu dng che khut
tng t cu dng che khut ca n-butan. Khng nhng th khong cch cc nt
0

C2-C4 ch cch nhau 1,81 A (so vi tng bn knh VanderWalls 2,4 A ) nn chng
y nhau, kt qu dng thuyn km bn hn dng gh khong 7 kcal/mol.
H

H
H
H

H
4H

2,49 A
6

H H

45

H
H3C
H3C

CH3

CH3

dng gh so snh vi cp syn-butan

Cu dng gh ca xiclohexan tn ti gia trng thi cn bng gia 2 dng

khc nhau:
H

H
H

H
H

H
H

H
H

Qu trnh chuyn ho xy ra rt nhanh (10 6 ln/s) phi i qua nhng dng

km bn l dng na gh, dng thuyn v dng xon. Dng xon bn hn dng
thuyn khong 1,4 kcal/mol, cn dng na gh km bn nht ( km dng thuyn
4 kcal/mol)
Lin kt trc v lin kt bin
dng gh 6 nguyn t cacbon c phn b trn hai mt phng song song
0

v cch nhau 0,5 A ( mi mt phng cha 3 nt cacbon v tr lun phin nhau.

Trc i xng bc ba ca nt thng gc vi mt phng . Su lin kt C-C song
song vi trc i xng c gi l lin kt trc, k hiu a; cn su lin kt C-C
hng ra ngoi bin ca phn t v to vi trc i xng nhng gc 109028, gi
l lin kt bin, k hiu e.
a
a
a

a
e

e
a

a
e

e
4

e
a

3
2

e
6a

e
Cc lin kt a v e trong xiclohexan (a: axial; e: equatorial)

46

) Dn xut th ca xiclohexan
V c 2 kiu lin kt a v e nn cc dn xut th mt ln ca xiclohexan
c 2 cu dng: dng a v dng e.

CH3

e
CH3

Hai dng a v e chuyn ho vi nhau rt nhanh nn khng th tch ring

chng vi nhau c, s c mt chng trong cn bng trn c chng minh
bng phng php vt l. Kt qu kho st l thuyt v thc nghim cho thy rng
cu to dng e bn hn dng a khong 1,7 kcal/mol. S km bn ca cu dng a so
vi dng e do c tng tc syn gia nhm th CH3 vi C6, mt khc nhm th CH3
tng tc y vi C3 v C5 (nhm th e khng gy hin tng ny).
3

3
2

2
4

4
6

CH3
Tng tc anti

Tng tc syn

47

CH3

Tng tc syn khng nhng a-metylxiclohexan m cn thy cc dng

axial mt ln th khc na. Tu theo bn cht v kch thc ca nhm th X trong
xiclohexan m s chnh lch v nng lng ca cu dng a v e khc nhau.
i vi dn xut th 2 ln ca xiclohexan, 2 nhm th c th v tr 1,1;
1,2; 1,3 hoc 1,4. Trong trng hp dn xut th 1,1, nu 2 nhm th ng nht th
ch c mt dng gh. Nu 2 nhm th khng ng nht s c 2 cu dng gh, trong
c mt cu dng u tin l cu dng c nhm th ln v tr e. V d:

CH 3

C2H5
CH 3

Cc cu dng 1,2; 1,3; 1,4 c th tn ti dng cis-trans. ng phn cis-1,2

c nhm th phn b theo kiu a,e hoc e,a cn ng phn trans-1,2 hai nhm th
l a,a hoc e,e.
6

R 1

2
2

3
4

cis-1,2

6
3

3
2
R

6
4

4
2

3
2
R

trans-1,2

Hai cu dng cis-1,2 (a,e) v (e,a) l ng nht nu 2 nhm R l ng nht.

Cu dng ny c 3 tng tc syn lm gim bn l: R-C1-C2-R; R-C1-C6-C5;
v R-C2-C3-C4. Cu dng trans-1,2 (a,a) c 4 tng tc syn cc h: R-C1-C2-C3;
R-C1-C6-C5; R-C2-C6-C4. Trong khi , cu dng trans-1,2 (e,e) ch c mt tng
tc h R-C1-C2-R, v vy cu dng ny bn hn c. nhit phng, trans-1,2imetylxiclohexan tn ti dng e ti 99%.

48

ng phn cis ca cc dn xut 1,3 hai ln th gm 2 dng a,a v e,e cn

ng phn trans tn ti di dng a,e v e,a (hai cu dng ny l ng nht vi 2
R
6
5
nhm th l ng nht).
1
6

5
4

R
3

2
R

cis-1,3

2
6

4
3

2
R

R
1

R
1

4
5

3
2

trans-1,3

S tng tc syn mi cu dng l cis-1,3 (a,a) l 2; cis-1,3 (e,e) l 0;

trans-1,3 (e,a) hoc trans-1,3 (a,e) l 2. V vy, cis-1,3 (e,e) l cu dng bn nht.
Quan h cu dng ca cc dn xut 2 ln th: ng phn trans-1,4 c 2 cu
dng a,a (4 tng tc syn) v e,e khng c tng tc syn, bn nht; ng phn cis1,4 c th l a,e hoc e,a (2 tng tc syn).
Trong nhng trng hp c 2 nhm R khng ng nht cc dn xut 1,4
cng nh dn xut 2 ln th khc, cc cn bng gia 2 cu dng a,e hoc e,a s
lch v pha cu dng no c nhm th c kch thc ln v tr e.
Trong nhng dn xut 6 ln th 6 cacbon khc nhau ca xiclohexan
C6H6X6 ng ch hn c l hexacloxiclohexxan (X=Cl), hexahidroxylxiclohexan
(inozit-X=OH). Nhng dn xut c th c 8 cu dng khc nhau:

cis ( )

allo ( )

pi
( )

muco ( )

(+)

milo ( )

Sillo ( )
neo ( )

(-)

d,l-()

49

Trong , c mt cu dng l bin th raxemic d,l. Mi cu dng c k hiu

ring bng ch ci Hi-Lp (cho C6H6Cl6) hoc ch ci La-tinh (cho inozit
C6H6(OH)6)
) Cu dng tetrahidropiran
Tng t xiclohexan, dng gh tetrahiropiran l dng bn. V c d t oxi
nn c 2 dng gh 1C v C1 ( C: chair); chng trng thi cn bng v i xng
nhau qua mt phng gng:

C1

1C

Cc hexopiranozo C6H12O6 c 16 ng phn quang hc mi ng phn

quang hc mi ng phn c th tn ti dng hay . Mi dng anome ny
li c hai dng bn l C1 v 1C. Th d -glucopinarozo gm 2 dng 1C v C1
nh sau:

HO

H2C OH

CH2OH
HO

OH
O
OH

HO

OH

C1

OH

OH

1C

i vi phn ln cc dng pinarozo dng C1 bn hn 1C. C nhiu yu t

lm monosaccarit chuyn t dng ny sang dng khc gi l cc yu t khng bn.
l s c mt ca nhm OH axial, nhm CH2OH axial v nhm OH axial cng
pha (hiu ng Hatxenotta); nhm OH axial C2 (hiu ng delta 2) nhm OH
equatorial C1 ( hiu ng anome).....
2.3.2. ng ng
2.3.2.1. Khi nim
Nhng hp cht c tnh cht vt l v ho hc gn ging nhau nhng khc
nhau mt hay nhiu nhm metylen (-CH2-) nm trong mt dy ng ng. Nhng

50

cht nm trong dy gi l cht ng ng. Mt dy ng ng c cng thc

tng qut chung.
2.3.2.2. Tnh cht
Cc hp cht trong dy ng ng c tnh cht vt l nh nhit si, nhit
nng chy tng khi tng s nhm metylen, ngha l tng khi lng phn t do
tng thm chiu di mch cacbon.
Khi nim ng ng thng dng d on s thay i tnh cht vt l
khi thay i thnh phn nhm metylen.
Cc cht trong dy ng ng cn phi c cng cu trc mch cacbon.
V d:
CH3CH2CH2CH3 v CH3CH2CH2CH2CH3 l hai ng ng ca nhau.
(CH3)2CHCH3 v (CH3)2CHCH2CH3 l hai ng ng ca nhau.
CH3CH2CH2CH3 v (CH3)2CHCH2CH3 khng phi l ng ng ca nhau
m nm trong hai dy ng ng n - ankan v isoankan.
Hin nay, thng ch ni n dy ng ng ca metan, etylen, axetylen v
nhng dy ng ng ca ancol metylic, andehit fomic, axit fomic,...ngha l
nhng hp cht c mch cacbon khng nhnh nh n-ankan, n-anken, n-ankin hay
n-ancol, n-axit,...
2.3.3. ng cp
2.3.3.1. Khi nim
L nhng hp cht c cng s nguyn t cacbon nhng khc nhau mt bi
2n nguyn t hidro.
V d:
CH CH, CH2=CH2, CH3-CH3: ng cp
2.3.3.2. Phn loi
- Cng v tr lin kt
V d:
CH3-CH2-CH2-CH3 , CH2=CH-CH2-CH3, CH C-CH2-CH3
- Khng cng v tr lin kt
V d:
CH2=CH-CH2-CH3, CH2-C CH-CH3
2.3.4. Cu hnh
2.3.4.1. Khi nim
L mt s qui c t c th bit c cch thc phn b ca cc
nguyn t hoc nhm nguyn t ca mt phn t trong khng gian.

51

2.3.4.2. Phn loi

- Cu hnh hnh hc
- Cu hnh quang hc
- Cu hnh cu dng
2.3.4.3. Cu hnh hnh hc
Gm 3 loi:
- Cu hnh cis-trans
- Cu hnh syn-anti
- Cu hnh E-Z
2.3.4.4. Cu hnh quang hc
Gm 2 loi:
- Cu hnh D-L
xt cu hnh D, L phi c nguyn t cacbon bt i v phi biu din
cng thc cu to ca n di dng Fis.
Nu nguyn t hoc nhm nguyn t d t ca nguyn t C* nm v pha
bn phi th l cu hnh D v ngc li.
V d:
CHO - CH2OH - CH2OH
CHO

CHO

OH

OH

CH2OH

CH2OH

Andehit D (+) glixeric

Andehit L (-) glixeric

Trong trng hp nhiu nguyn t C*, xt nguyn t C* no nm gn

nguyn t C c s oxi ho thp nht.
V d:
HOOC - CHCl - CHOH - CH3
COOH
H
H

Cl
OH
CH3
D

COOH
Cl
HO

COOH

H
H

Cl
H

CH3
L

H
OH
CH3
D

52

COOH
H

Cl
H

HO
CH3
L

- Cu hnh R-S: Do 3 nh bc hc pht minh ra l: Cahn - Ingold Prelog. Cu hnh R-S c xc nh theo tnh hn cp ca trung tm chiral (C*)
theo th t a > b > c > d, ch yu cn c vo s th t (hoc khi lng nguyn
t) ca cc nguyn t ni vi C*.
V d:
Br > Cl > SH > OH > NH2 > CH3 > H
OH > COOH > CHO > CH2OH > CH3
Nu cc nguyn t ni trc tip vi C* l ng nht th cn xt thm
nguyn t tip theo, khi y cn ch nhn i hoc ba i vi nguyn t mang ni
i hoc ni ba.
Biu din cng thc di dng cng thc phi cnh: t t din sao cho
lin kt vi nguyn t hoc nhm nguyn t tr nht (cp nh nht) i xa pha
ngi quan st th th t phn b ba nhm th cn li s nm trn mt mt phng
pha gn ngi quan st s xc nh cu hnh. Nu s gim tnh hn cp ca cc
nhm th theo chiu kim ng h th trung tm chiral c cu hnh R (rectus quay phi), nu theo chiu ngc kim ng h th trung tm c cu hnh S
(sinister - quay tri).
c

a
b

R
HOH2C

CH2OH

OH
CHO

HO
CHO

ANEHYT R-GLIXERIC

ANEHYT S-GLIXERIC

C th hnh dung cc nhm th a, b, c to nn hnh tam gic v nhm d nh

nht nm pha sau hnh tam gic :
a

c
b

53

Cu hnh R-S v Fischer khng c tng quan trc tip.

Trong cc hp cht loi andehit glyxeric c s trng hp cu hnh D andehit glyxeric l (R)-andehit glyxeric, cn L - andehit glyxeric l (S)-andehit
glyxeric.
CHO
OH

CH2OH

OH

CHO

OH

H
C
HOH 2 C

CH 2 OH

CHO

(R)

(D)
OH

CHO

OH

OHC

HO

H
CH2OH

HOH 2 C

CHO

CH 2 OH

(S)

(L)

Cu hnh cu dng: (a, e) ch c ngha i vi xiclohexan m thi.

54

CU HI V BI TP
Bi 1. Mt HCHC c CTPT C5H12O khi un nng vi axit axetic c mt mt
lng nh axit sunfuric lm xc tc cho hp cht c thnh phn C7H14O2, oxi ha
giai on th nht cho xeton thnh phn C5H10O, sau oxi ha mnh tip theo
s to thnh hn hp axit axetic v axit propionic. Hy suy ra CTCT ca cht
C5H12O v vit cc phng trnh phn ng xy ra?
Bi 2. Mt HCHC c CTPT C4H8O c kh nng phn ng vi natri bisunfit cho
hp cht cng bisunfit, tc dng vi hiroxylamin cho oxim, tc dng vi dung
dch bc nitrat trong amoniac cho phn ng trng gng v khi oxi ha cho axit
isobutyric. Hy suy ra CTCT ca cht C4H8O v vit cc phng trnh phn ng
xy ra?
Bi 3. Anken A C6H12 c ng phn hnh hc, tc dng vi dd Br2 cho hp cht
ibrom B. B tc dng vi KOH trong ancol un nng cho ien A v 1 ankin C. C
b oxi ho bi KMnO4 c, nng cho axit axetic A v CO2. Hy cho bit cu to
ca A
Bi 4. Hidrocacbon C7H12 khi oxi ho bng axit cromic to thnh axit
xiclopentancacboxylic, khi tc dng vi H2SO4 ri thu phn n chuyn thnh
ancol C7H14O. Ancol ny cho p iodoform. Xc nh CTCT ca hidrocacbon ?
Bi 5. Hp cht A (C7H14O2) phn ng vi (CH3CO)2O to ra B
(C7H13O(OCOCH3)). A khng phn ng vi hiroxylamin. Khi ch ha A bng
HIO4 thu c hp cht C (C7H12O2). C phn ng vi hiroxylamin to ra ioxim.
C kh c dung dch Felinh. 1 mol C phn ng vi 4 mol NaIO to ra ioofom
v mui ca axit aipic. Xc nh CTCT ca A v vit phng trnh phn ng?
Bi 6. Hp cht A c CTPT C3H7O2N c tnh cht lng tnh. A phn ng vi
HNO2 gii phng kh nit, vi etanol/HCl cho hp cht C5H11O2N. Khi un nng
A cho cht c cng thc C6H10O2N2. Xc nh CTCT ca A?
Bi 7. Hp cht A (C5H10O3) d tan trong baz long, c tnh quang hot; khi un
nhit cao thu c cht B (C5H8O2) khng cn tnh quang hot nhng vn
cn lm giy qu xanh. S ozon phn cht B cho etanal v axit 2-fomylaxetic.
A b oxi ha bng axit cromic cho cht C, cht ny cho 2,4-initrophenylhirazon
v phn ng halofom. Vit CTCT ca A, B, C?
Bi 8. Hp cht (A) C5H8O2 c th to ioxim, cho p iodoform, p vi bisunfit
v cng c kh nng chuyn thnh n-pentan. Xc inh A?
Bi 9. Hp cht C7H14O2 (A) p vi anhidrit axetic, to thnh C7H13O(OCOCH3)
(B) khng phn ng vi phenylhidrazin. Khi ch ho bng Pb(OCOCH3)4, hp
cht A chuyn thnh C7H12O2 (C)v C p vi NH2OH to thnh C7H12(=N-OH)2,
kh c dd Felinh v khi ch ho bng NaOI p vi 4 mol tc nhn to thnh
iooform v axit aipic. Gii thch ngn gn cc hin tng quan st thy trn v
a ra kt lun v cu to ca A?

55

Bi 10. Hp cht hu c A ch gm C, H,O. Ho tan 1,03 gam A trong 50 g

benzen ri xc nh nhit si ca dd th thy ts = 80,356oC, trong khi benzen
nguyn cht c nhit si ts = 80,1 oC. t chy hon ton 21 mg hp cht A th
thu c 0,0616 g CO2 v 9,0 mg H2O.
a, Xc nh CTPT A, bit hng s nghim si trong trng hp ny l 2,61.
b, Bit rng A c th l: hp cht ianehit, ixeton, iphenol, iancol v c kh
nng cho p iodoform. Vit CT cc ng phn tng ng ni trn?
Bi 11. Vit CTCT ca cc HCHC n chc mch h ng vi cc phn t:
a. C4H8O2
b. C5H10O.
Bi 12. Nhng cht no sau y c ng phn hnh hc. Biu din cc ng phn
v xc nh tn theo danh php ZE?
a. CH3 CH = CH CH3
(A)
d. CH3 CH = CH COOH (D)
b. CH2 = CH CH2 CH3
(B)
e. 1,1-imetylxiclopropan
(E)
f. 1,2-imetylxiclopropan
(F)
c. CH3 C C CH3
(C)
Bi 13. Nhng cht no sau y c ng phn quang hc. Ti sao? S ng phn
quang hc l bao nhiu?
CH3CHBrCH3
(A)
CH3CHBrCH2CH3
(B)
CH3CHBrCHBrCH3
(C)
CH3[CH(OH)]4 CH=O
(D)
HOOCCH(OH)CH(OH)COOH (E)
HOOC[CH(OH)]3COOH (F)
Bi 14. Vit cc cng thc ca cc ng phn lp th (nu c) ca cc cht sau y
v cho bit loi ng phn?
a. CH3 CH = CH CH = CH CH3
(A)
b. C2H5 CHBr CHBr C2H5
(B)
c. CH3 CH = CH CH(CH3) COOH
(C)
Bi 15. Vit cu to ca cc hp cht sau
a) (S)-1-brom-1-clopropan
b) (R,R)-1,2- diclobutan
c) (S)-bromcloflometan
d) (S)-1-deuterietanol
) (S)-2-brom-3-deuteri-2-metylpentan e) (R,S)-1,2-butadiol
Bi 16. Vit tt c cc ng phn lp th ca 1-brom-1,2-diclopropan bng cng
thc chiu Fischer v phi cnh. Ch r ng phn threo, erythro, i quang, meso
Bi 17. Vit hai cng thc chiu Newman hay phi cnh ca cu dng xen k ca
lin kt C2-C3 ca 2- methylbutan. So snh bn ca 2 cu dng v so vi
butan trn?
Bi 18. Vit hnh chiu Newman hay phi cnh ca 3 cu dng xen k c th c
ca 2,3-dimetylbutan, trong c 2 cu dng ging nhau, cn 2 cu dng c nng
lng khc nhau 0,9 kcal/mol. Cu dng no c nng lng thp nht. Tha nhn
Ho = Go, Tnh hng s cn bng nhit phng?

56

Bi 19. Phn tch ng phn lp th ca xyclohexan hai ln th 1,2 vi hai nhm

th ging nhau v khc nhau. Gii thch kt qu trn bng cu dng gh ca
xyclohexan?

57

TI LIU THAM KHO

1. Trn Quc Sn, ng Vn Liu Gio trnh c s ha hc hu c, Tp 1, 2,
NXB i hc s phm, 2007.
2. Chu Phm Ngc Sn, Nguyn Hu Tnh, Bi tp ha hc hu c, NXB Hn
Thuyn, Thnh ph H Ch Minh, 1995.
3. Trn Quc Sn, Trn Th Tu, Danh php hp cht hu c, NXB Gio dc,
H Ni, 2007.
4. Thi Don Tnh, C ch v phn ng ha hc hu c (tp 1,2,3), NXB Khoa
hc v k thut, H Ni, 2008.
5. Ng Th Thun Ho hc hu c phn bi tp (tp 1,2), NXB Khoa hc v k
thut, H Ni, 2006.
6. Hong Trng Ym, Ho hc hu c, NXB Khoa hc & K thut, H Ni,
2002.

58

CHNG 3: LIN KT TRONG HO HC HU C

Nu trong ho v c ta hay gp lin kt ion (cn gi l lin kt in ho tr)
th trong ho hu c, lin kt cng ho tr l lin kt bao trm v quan trng hn
c, sau l lin kt phi tr v lin kt hidro xut hin trong mt s trng hp.
3.1. Lin kt cng ho tr
3.1.1. Theo thuyt c in
Thuyt lin kt c in cho rng, khi hai nguyn t kt hp vi nhau, mi
nguyn t gp chung vo mt electron ho tr ca mnh. Cc electron ny chy
trn cng mt qu o vi cc electron c to nn lp v kh tr mi nguyn t.
V d:
H
H

Quan nim hin i thng nht vi quan nim c in l khi to nn lin kt

cng ho tr, 2 nguyn t gp chung in t, nhng khc v cch gp chung: do s
xen ph ca 2 obitan.
3.1.2. Quan nim hin i
3.1.2.1. Obitan nguyn t
Theo c hc lng t, cc ht c bn nh electron, proton c bn cht nh
nguyn: va c tnh cht ht, va c tnh cht sng.
Schroding thit lp phung trnh tng qut v quan h gia nng lng
ca electron v hm sng xc nh trng thi ca electron trong nguyn t:
H = E (H l ton t Haminton)
Khi phng trnh tho mn mt s iu kin nht nh th hm s sng
l nghim ca phng trnh v c gi l hm sng obitan nguyn t gi tt l
obitan nguyn t. Theo nhng kt qu tnh ton, cc obitan ca cc electron cc
mc c hnh dng rt khc nhau: obitan s lun lun c dng i xng cu. Cc
obitan p c dng hnh s 8 ni. Cc obitan p khc nhau v hng:
y
y

y
z
x

- Cu trc in t ca nguyn t cacbon v s lai ha

S phn b 6 in t theo obitan nguyn t cacbon c th biu din nh
sau: 1s22s22px2py2pz. Nh vy, nguyn t C, hai in t lp ngoi (2s 2) snh
59

i (c spin ngc nhau) v ch c hai in t c thn l 2px v 2p y nn nguyn

t cacbon c ha tr hai.
Trng hp cacbon c ha tr hai ch gp trong mt s t hp cht nh CO,
R-N=C. Cacbon c ha tr 4 hu ht cc hp cht hu c. C hc lng t cho
rng khi hnh thnh lin kt th cacbon trng thi kch thch: mt in t ca
obitan 2s nhn mc nng lng cao hn v nhy sang obitan 2p cn trng, do
cu hnh in t ca carbon tr thnh: 1s22s12px12py12p z1. C th biu din qua
trnh kch thch nh sau:
1s

2s

1s

2p

2s

2p

Nh vy, trng thi kch thch, cacbon c 4 in t khng ghp i: 1

in t 2s v 3 in t 2px, 2py, 2p z. S kch thch ny i hi nng lng ln
(97kcal/mol). Nng lng d gii phng ra trong s hnh thnh 4 lin kt ca
cacbon tha b cho nng lng kch thch . V vy, trong phn ln cc
cht hu c, cacbon c ha tr 4. Cacbon c ha tr 4 khng phi do s dng trc
tip 4 obitan trn to ra 4 lin kt vi s tham gia ca mt obitan 2s v 3 obitan
2p x, 2p y, 2p z. Nu bn obitan hnh thnh lin kt vi 4 obitan 1s ca bn
nguyn t hydro to ra phn t CH4 th ngi ta c th ngh rng ba trong bn
lin kt C-H phi khc vi lin kt th t (trong 4 lin kt c 1 lin kt to bi
obitan 1s ca C vi obitan 1s ca H to 1 ng thng, 3 lin kt to bi 3 obitan
1s ca H vi orital 2px, 2py, 2pz ca C, gc lin kt l 900).
y

900

z
CH

iu ny hon ton mu thun vi thc nghim ca ha hc hu c: bn

lin kt C-H trong phn t CH4 l hon ton ging ht nhau, khng c cch g
phn bit chng. gii quyt mu thun ny, Pauling gii thch bng s lai
ha cc obitan: khi hnh thnh lin kt th obitan 2s v obitan 2p c hin tng lai
ha vi nhau. Obitan 2s c th lai ha vi ba, hai, mt obitan 2p. C 3 kiu lai ha
sp 3, sp2, sp.

60

1800
120

109028

sp3

sp 2

sp

- Lai ha sp 3 (lai ha t din) l s t hp 1 obitan s vi 3 obitan p to

thnh 4
obitan sp 3 nh hng theo 4 nh ca mt t din u, gc lai ha 109028.
S lai ho sp 3 c th biu din nh sau:

sp3

y
lai ha
x
z s + 3p

sp3

Cc kt qu tnh ton cho thy rng nu coi kh nng xen ph ca obitan

s l 1 th obitan p l 3 v obitan lai ho sp3 l 2. Trong phn t mtan cng nh
cc ng ng ca n, obitan lai to sp3 ca cacbon xen ph vi obitan 1s ca
hyro to thnh lin kt (C-H). cc ng ng ca mtan 2 obitan sp3 ca hai
nguyn t cacbon bn cnh nhau to thnh lin kt (C-C). V gc ho tr ca
nguyn t cacbon sp3 l 109028 nn mch cacbon trong phn t ankan l ng
gp khc khc hnh ziczc.
H

H
H

H
H

CH4

CH CH CH2CH3
3 2

CH CH
3 3

61

Thc vy cc kt qu tnh ton cho thy rng:

+ Obitan lai to tt nht c hng xen ph cao hn obitan s hoc obitan p.
+ 4 obitan lai to tt nht c hng xen ph cao hn hon ton ng nht vi
nhau.
+ Cc obitan ny hng n gc ca mt t din u- tc l s sp xp m
trong cc obitan nm v tr cch xa nhau nht. S lai ho ny gi l lai ho t
din. Gc lai ho trong trng hp ny l 109 028 .
Lai ha sp2 l s t hp 1 obitan s vi 2 obitan p to thnh 3 obitan
sp2 (lai to tam gic hoc lai ho phng). Trc i xng ca 3
obitan sp2 nm trn mt mt phng to thnh gc 1200. Kh nng
xen ph tng i ca obitan sp2 l 1,99.

y
+
+

x
+
sp2

s + 2p
1s

2s

2p

lai ha sp
1s

sp

2p

Trong phn t etylen cc obitan sp2 tham gia xen ph to nn 5 lin kt

c trc nm trong mt mt phng. Cn li 2 obitan p thun khit cha lai to xen
ph bn nhau to thnh lin kt .

H
H

C
H

C
H

Lai ha sp: l t hp ca mt obitan s v mt obitan p gp trong cc

phn t c ni 3 vi kh nng xen ph l 1,93 v gc to bi trc
i xng ca 2 obitan l 1800 (kiu lai ho ng thng).

62

- -

sp

s+p
2

1s

2s

2p

Lai ha sp
2

sp

1s

2p

Trong phn t axetylen, cc obitan lai ho sp xen ph ln nhau v vi

obitan hyro (1s) to thnh 3 lin kt m trc lin kt cng nm trn mt ng
thng, cn li 4 obitan p thun khit chng s xen ph bn nhau tng i mt to
nn 2 lin kt .
Cc lin kt ca axetylen.
HC

CH

3.1.2.2. Obitan phn t lin kt

Theo phng php s ho tr cng nh theo phung php MO, lin kt
cng ho tr c hnh thnh do s xen ph cc obtian nguyn t thnh obitan
phn t lin kt. Khuynh hng ca s xen ph l tin ti cc i theo nguyn l
xen ph cc i. Mun cho cc obitan nguyn t tng tc c hiu lc vi nhau
thnh obitan phn t chng phi tho mn 3 iu kin sau y:
1- Nng lng ca chng gn bng nhau.
2- S xen ph mc ln.
3- Chng phi c cng mt kiu i xng vi trc ni hai nhn nguyn t.
Xt iu kin 3 ta c th xen ph:
- Hai obitan s
- Mt obitan s vi mt obitan p no c trc i xng trng vi trc ni
hai ht nhn.
- Hai obitan p c trc i xng song song vi nhau (cng px, py hoc pz).
S xen ph c th theo trc hay bn trc ni gia hai ht nhn nguyn t.Theo
trc:

63

+
s

Obitan lin kt c trc i xng l ng thng ni gia hai ht nhn v

c gi l obitan . Lin kt cng ho tr c hnh thnh gi l lin kt . S
xen ph xy ra tng t nh vy i vi trng hp obitan p + p.
-

+ -

+
-

S xen ph bn trc:
II

+
-

II *

+
-

+
II

S xen ph bn trc s to thnh obitan v lin kt .

V obitan khng c tnh i xng i vi trc hai ht nhn m ch i
xng vi mt phng nt cha 2 trc nn lin kt t bn, d phn cc ho. Mt
khc cn tr s quay t do ca nguyn t hay nhm nguyn t xung quanh trc
lin kt (do s quay s vi phm nguyn l cc i). l nguyn nhn lm xut
hin cc ng phn hnh hc.
- Lin kt
Trong s xen ph theo trc, obitan phn t lin kt c trc i xng l
ung thng ni hai ht nhn, gi l obitan . c im chung ca obitan l c
tnh i xng i vi trc lin kt v cc tiu phn (nguyn t, nhm nguyn t)
c th quay tng i t do quanh trc m nng lung tng tc khng thay i.
trong ho hu c, ta hay gp 2 kiu xen ph to lin kt sau y:

sp - sp

sp - s

64

c im ca lin kt :
+ C s i xng theo trc lin kt.
+ Nng lng lin kt tng i ln (~83 kcal/mol) nn lin kt ny kh
bn vng.
+ Cc nguyn t hay cc nhm nguyn t hai u lin kt c kh nng
quay t do xung quanh trc lin kt m khng lm mt s xen ph (th d H-H,
H3C- CH3), do xut hin vn cu dng hp cht hu c.
- Lin kt
Khi cc obitan xen ph vi nhau v c 2 pha m trc obitan vn song song
vi nhau gi l s xen ph bn ta c obitan phn t , lin kt c to thnh
l lin kt . S xen ph nh vy khng su nn km bn. Hai trc ca 2 obitan
song song, nm trong mt phng .

Tuy nhin cc tiu phn khng th t quay quanh trc lin kt v nu quay
l ph v xen ph, ph v lin kt.
c im ca lin kt :
+ Khng c tnh i xng trc.
+ Cc trc obitan p song song nhau to thnh mt phng gi l mt phng
.
+ Nng lng lin kt tng i nh (~60 kcal/mol) nn km bn hn
lin kt , n d b phn cc ha hn lin kt .
+ Cc nguyn t hay cc nhm nguyn t hai u lin kt khng c kh
nng quay t do nh i vi lin kt v khi quay nh th s vi phm s xen ph
cc i ca hai AO, ph v lin kt; do c kh nng xut hin ng phn hnh
hc cc hp cht c ni i C=C, ni ba CN. . .
3.1.3. c im ca lin kt cng ho tr
- Bn v rt bn (kim cng).
- Cc lin kt cng ho tr c di xc nh. di lin kt ca cacbon vi cc
nguyn t mt phn nhm tng khi s th t tng, vi cc nguyn t ca mt chu
k th gim khi s th t tng, sau na l khi ghp tng th di lin kt gim.
- Hng khng gian ca cc lin kt l xc nh v lin kt cng ho tr c tnh
bo ho.
- Hp cht c lin kt cng ho tr thng to mng tinh th phn t.
- phn cc ca lin kt nh, thng < 1,6D.

65

- Tan t hoc khng tan trong nc, dung dch dn in km.

3.1.4. Cc lin kt n, i, ba, h lin hp
3.1.4.1. Lin kt n
Trong cc phn t metan v etan ch c lin kt n, l cc lin kt
kiu sp - s v sp - sp. Nguyn t cacbon trng thi lai ho sp3. Cc lin kt
trong phn t metan v etan c m t nh sau:

etan

metan

3.1.4.2. Lin kt i
Trong phn t etilen, lin kt i C=C gm mt lin kt kiu sp - sp v
mt lin kt . Hai nguyn t cacbon trng thi lai ho sp 2. Cc obitan xen ph
to nn nm lin kt . Trc ca nm lin kt ny cng nm trn mt mt phng
. Cn li hai obitan p chng s xen ph vi nhau to thnh lin kt . Trc ca
hai obitan ny song song vi nhau, cng nm trong mt mt phng giao nhau
trc lin kt C - C v vung gc vi nhau.

H
H
C

C
H

3.1.4.3. Lin kt ba
Lin kt ba trong phn t axetilen gm c mt lin kt v hai lin kt .
Hai nguyn t cacbon trng thi lai ho sp. Cc obitan lai ho sp xen ph to nn
ba lin kt , c trc nm trn mt ng thng. Cn hai obitan py v p z xen ph
vi nhau to hai lin kt c mt phng b dc vung gc vi nhau v ct nhau
trc lin kt C-C:
66

3.1.4.4. H lin hp
H lin hp l h c nhiu ni i xen k u n vi ni i nh buta-1,3ien hay vng benzen.
Tng t nh etilen, cc nguyn t cacbon trong cc h u trng thi
lai ho sp2 v h cc lin kt l mt h phng. Cc obitan p xen ph vi nhau
tng i mt to ra hai lin kt nh trong buta-1,3-ien hoc xen ph v c hai
pha to obitan phn t cc lin kt vng kn nh trong benzen:

H
H

buta-1,3-dien

benzen

3.1.4.5. Tnh thm, phn thm

67

- Tnh thm
Hp cht thm l nhng hp cht vng cha no m tt c nhng nguyn t
mt vng u tham gia to thnh mt h lin hp thng nht, trong cc electron
ca h to nn mt vng electron kn. Nhng hp cht thm c nhng c tnh
m ngi ta gi l tnh thm.
- Cc iu kin ca tnh thm
+ H lin hp hoc p nm trong hp cht vng kn vi s
electron l 4n+2 (bn trng thi c bn): gi l quy tc thm 4n+2 do Hucken
tm ra t nm 1932. Theo quy tc ny th cc polyen vng vi 4n+2 electron
phi bn vng v c tnh thm.
+ Cc lin kt phi nm trn cng mt mt phng (vng thm phi c cu
trc phng). Vng khng nht thit phi ging benzen m c th l vng
cacboxylic khc benzen, d vng hoc vng v c thun tu.
+ Nng lng ca hp cht thm thp hn nng lng ca hp cht c
cng lin hp mch h.
V d: Hp cht c tnh thm l:

benzen

piridin

naphtalen

Hp cht khng thm l:

N
O
H
H

O
H

- Tnh phn thm

L nhng hp cht c y 2 yu t (1), (2) nhng c nng lng tn ti
hoc l bng hoc l ln hn nng lng hp cht mch h c cng lin hp.
V d:

xiclo butadien

pentalen

68

3.2. Lin kt phi tr

Lin kt cng ha tr phi tr (cn c bit n nh l lin kt cng ha tr
cho nhn) l mt dng c bit ca kt c to thnh, bn ca n khng khc
g so vi lin kt cng ha tr.
Cc lin kt cng ha tr phi hp c to thnh khi mt baz Lewis (cht
cung cp in t) cung cp mt cp in t cho axit Lewis (cht nhn in t) v
hp cht to thnh sau c gi l adduct.
Cc lin kt phi tr c th tm thy trong nhiu cht khc nhau, chng hn
nh trong cc phn t n gin nh monoxit cacbon (CO), trong c mt lin
kt phi tr v hai lin kt cng ha tr thng thng gia nguyn t cacbon v
nguyn t oxi, hay trong ion amoni (NH4+), trong lin kt phi tr c to
thnh gia proton (ion H+) v nguyn t nit.
Cc lin kt phi tr cng c to ra trong cc hp cht thiu in t, chng
hn nh trong clorua berili rn (BeCl2), trong mi nguyn t berili c lin
kt ti bn nguyn t clo, hai vi lin kt cng ha tr thng thng v hai vi lin
kt phi tr, iu ny s to cho n mt cp tm (octet) n nh ca cc electron.
Cc lin kt phi tr cng c th tm thy trong cc phc cht phi tr c s
tham gia ca cc ion kim loi, c bit nu chng l cc ion kim loi chuyn tip.
Trong cc phc cht ny, cc cht trong dung dch hot ng nh cc baz Lewis
v cung cp cc cp electron t do ca chng cho ion kim loi, trong lt n hot
ng nh cc axit Lewis v nhn cc electron. Cc lin kt phi tr to ra cc hp
cht gi l phc cht phi tr, trong khi cht cung cp electron c gi l cc
phi t.
C rt nhiu cht vi cc nguyn t c cc cp electron c c, chng hn
oxi, lu hunh, nit v cc halogen hay cc ion halogenua, m trong dung dch c
th cung cp cc cp electron tr thnh cc phi t. Mt phi t thng thng
l nc (H2O), n s to thnh cc phc cht phi tr vi bt k ion kim loi ngm
nc no. Chng hn Cu 2+, to ra [Cu(H2O)6]2+ trong dung dch nc. Cc phi
t n gin khc l amoniac (NH3), cc ion florua (F-), clorua (Cl-) v xianua
(CN).
Lin kt phi tr l mt loi lin kt cng ho tr m c cp electron lin kt
do mt nguyn t cung cp, nh lin kt N-O hoc S-O trong triankylamin oxit
cng nh trong diankyl sunfoxit:
R

Lin kt phi tr cng c th hnh thnh gia hai phn t nh:

69

H3N: + B(CH3)3

H3N B(CH3)3

3.3. Cc loi lin kt yu

3.3.1. Lin kt hydro
3.3.1.1. Bn cht ca lin kt hydro
Lin kt hydro l lin kt hnh thnh gia hai nguyn t c tnh m in
qua nguyn t hidro. y, nguyn t hydro ng vai tr cu ni. Lin kt hydro
c bn cht tnh in v theo mt s d kin mi, ngi ta thy n c phn do to
phc cho nhn, v d: H-F...H-F.
Lin kt hydro l lin kt yu, ch vo khong 5kcal/mol
Mun c lin kt hydro X-H...Y, X v Y phi l cc nguyn t c m
in ln v kch thc nh, X c lin kt cng ho tr vi H v Y phi c i in
t cha lin kt. Ni cch khc, X-H l axit yu v Y l baz yu, v nu khng
nh vy s to ra lin kt phi tr hoc khng lin kt.
Lin kt hydro c th hnh thnh l lin kt lin phn t (A) v lin kt
hydro ni phn t (B) (Ch n iu kin khng gian: Phn t phi c cu hnh
nh th no cho tng tc ni phn t (to ra lin kt hydro) dn n s hnh
thnh nhng vng nm, su cnh vi hiu ng nng lng cao nht. Chnh v vy,
hu nh ch c ng phn octo mi c lin kt hydro ni phn t. Cc - glycol,
- aminoancol, - xetoancolc lin kt hydro ni phn t nhng tng i
km bn. Nu trong mt cht c lin kt hydro ni phn t yu (v d trong o clo
phenol ) th khi ho tan cht vo dung mi c kh nng nhng e- cao
(axeton, ioxan) th lin kt hydro b t ra v xut hin lin kt hydro mi gia
cht tan v dung mi):
O

HO

...O - H...O - H...O - H...O

R

Vi cc iu kin , X v Y thng l O, N, F.
Quy lut: Lin kt hydro tng t tri qua phi theo chu k v tng t di
ln trn theo nhm.
3.3.1.2. Tnh cht ca cc hp cht c kh nng to nn lin kt hydro
Lin kt hydro nh hng ng k n tnh cht ca hp cht.
- Nhit si v nhit nng chy ca hp cht c lin kt hydro lin
phn t tng nhiu nh so snh nhit si ca ru metylic CH3OH v ru
thiometylic CH3SH l 660C v 6 0C v cc phn t trong cht b rng buc
70

vi nhau thnh nhng phn t ln hn. Nc, ancol, phenol, amoniac, amin bc
mt, amin bc hai, axit cacboxylicl nhng cht chu s chi phi ca quy lut
ny. Cn lu l trong khi lin kt hydro gia cc phn t lm tng nhit si v
nhit nng chy ca cht th lin kt hydro ni phn t li khng gy c nh
hng nh vy. V d cc dn xut hai ln th ca benzen, nu hai nhm th trong
vng khng c kh nng lin kt hydro vi nhau th hai ng phn ct v para ni
chung c nhit si gn nh nhau nhng nu hai nhm th lin kt hydro vi
nhau c th ng phn octo (lin kt hydro ni phn t) lun si nhit
thp hn nhiu so vi ng phn para (c lin kt hydro lin phn t).
- tan ca cc cht c kh nng to lin kt hydro vi dung mi tng ln
nh ancol etylic tan v hc trong nc cn etan tan rt t (4,7%). V vy cc ru,
amin, axit thp cng nh cc cht c phn t lng khng nh nh glucoz,
sacaroz, polyvinylancol, u tan tt trong nc. Tinh bt v protit tuy c phn
t lng rt cao nhng nh c lin kt hydro nn c th to ra nhng dung dch
keo. Cc ancol, amin, axit cacboxylic tan trong nc c th ng vai tr cht cho
hay nhn prton khi to thnh lin kt hydro. Nhng hp cht khc nh anehit,
xeton, ete, este khi y ch c th l cht nhn proton m thi. tan ca cc cht
trong nc cn ph thuc vo kch thc ca gc hydrocacon lin kt vi cc
nhm chc. Gc cng ln th tan cng gim. ng ch l tan ca cc
hp cht thm c hai nhm th v c kh nng lien kt hydro, trong khi cc ng
phn meta v para thng d tan so vi ng phn octo trong cc dung mi m
chng c th to ra lin kt hydro lin phn t nh nc, ru. Cc ng phn
octo vi lin kt hydro ni phn t li d tan tong cc dung mi khng phn cc
nhiu hn.
- Lin kt hydro cn nh hng ti bn cc ng phn (s c mt ca
lin kt hydro ni phn t nht l khi lin kt hydro tham gia vo mt h lin
hp vng (c nng lng lin kt cao hn) c th lm cho mt ng phn ca cht
hu c tr nn bn vng hn) v tnh cht axit, baz ca phn t.
3.3.1.3. ngha ca lin kt hydro
- Dng gii thch tnh cht bt thng v tnh cht vt l v ho hc ca
hp cht.
- L nn tng c bn ca s sng (lin kt peptit).
- C ngha quan trng trong cc cng trnh xy dng.
- Lin kt khng bn nhng quan trng.
3.3.2. Lin kt Vandecvan
3.3.2.1. Khi nim
L lin kt c hnh thnh gia cc phn t vi nhau bng c cc ca
chng. Lin kt ny c tc dng gi cc phn t cng ho tr li vi nhau tp
hp chng trong mt trng thi no ca vt cht: lng, rn, kh.
- Lin kt Vandecvan (V) c bn cht tnh in, lin kt V khng c bn
cht ho hc m c bn cht vt l.
71

- Lin kt V yu hn lin kt hydro (ELK = 2 10kJ/mol). E lin kt nm

trong khong l do tu thuc vo s hnh thnh ca cc nguyn t.
- Bn knh V (rV) l 1/2 khong cch gia hai nhn ca hai nguyn t thuc
hai phn t tham gia lin kt.
- Nh c lin kt V m con ngi gii thch c mt s hin tng nh
ma,...
3.3.2.2. Nng lng ca lin kt Vandecvan
- Bn cht ca lc V
Ngun gc ca lin kt V cha c gii thch hon ton y tuy nhin
theo V th lin kt V c bn cht tnh in bao gm lc ht v lc y.
+ Lc ht: Khi khong cch gia cc phn t t n gi tr cn bng th
to ra lin kt V c ngha l xut hin lc ht. Tuy nhin trong tng trng hp th
lc ht c nhng bn cht khc nhau. Lc ht bao gm:
+ Lc nh hng:
i vi nhng phn t c cc ( 0), gia cc phn t lng cc, c lc
tng tc tnh in Coulomb. Ngoi lc ht, gia cc lng cc cn c cc lc
y tng h. Tuy nhin, v phn t c khuynh hng nh hng sao cho h
thng l thun li nht v mt nng lng ng vi mt trng thi vng bn nht,
ngha l c khuynh hng nh hng ngc chiu nhau nn lc ht gia cc phn
t lng cc s chim u th. Do vy, hiu ng trn c gi l hiu ng nh
hng.
Hiu ng nh hng cng ln khi momen lng cc ca phn t cng ln.
Ngc li, hiu ng nh hng gim khi nhit tng v chuyn ng nhit cn
tr s nh hng tng h ca cc phn t. Ngoi ra lc ht ln nhau gia cc
phn t c cc s gim nhanh khi khong cch gia chng tng.
H thc nng lng:
2 4
Uh = 6
3r kT

Trong :
Uh: Nng lng tng tc ca hai phn t c momen lng cc l .
R: Khong cch gia hai phn t.
T: Nhit tuyt i.
k: Hng s Boltzman
+ Lc cm ng:
Nhng phn t khng c cc cng b phn cc ho di tc dng ca in
trng ca cc phn t c cc hay ca cc ion ln cn, s phn cc ny gi l s
phn cc ho cm ng v tng tc gia cc phn t do hin tng phn cc ho
cm ng trn gi l hiu ng cm ng.

72

Hiu ng cm ng cng mnh nu h s phn cc ho v momen lng

cc ca phn t cng ln. Ngc li, hiu ng cm ng gim nhanh khi khong
cch gia cc phn t tng. Hiu ng nh hng khng ph thuc vo nhit .
Hiu ng cm ng c bai nghin cu, theo ng, nng lng tng tc
cm ng tc l nng lng tng tc gia mt lng cc vnh cu v mt lng
cc cm ng xut hin trong phn t ln cn c tnh theo h thc:
Uc = -

2 2
r6

+ Lc khuch tn
Vi hai hiu ng trn, ngi ta vn cha gii thch c lc ht tng h
gia cc phn t, nguyn t khng c mmen lng cc vnh cu, c bit l gia
cc kh tr.
Tng tc V cn c gii thch bng hiu ng ny trn c s ca c hc
lng t c London xy dng nm 1930.
Theo thuyt ny, v cc ht cu to nn phn t, nguyn t lun trng thi
chuyn ng lin tc nn trong qu trnh chuyn ng ny, s phn b in tch
tr nn bt i xng, do lm xut hin nhng lng cc tc thi v s tng
tc gia cc lng cc ny l nguyn nhn th ba ca tng tc V. Hiu ng ny
gi l hiu ng khuch tn.
Hiu ng khuch tn c gii thch bng s phn cc ng ca phn t
hay nguyn t. Nng lng ny c xc nh mt cch gn ng theo h thc:
Ukt = -

3h 0 2
4r 6

Trong :
0 : Tn s dao ng ng vi nng lng im khng, E0 =

h 0
.
2

Nng lng khuch tn t l nghch vi r6 v khng ph thuc vo nhit .

Hiu ng khuch tn tn ti mi h in t ngha l mi phn t,
nguyn t c cc hay khng c cc.
Tm li: trong trng hp chung i vi nhng phn t c momen lng
cc vnh cu v h s phn cc ho , nng lng tng tc (ht) V c xc
nh theo h thc:
Uh = -

1
r6

2 4
3 2 h 0
2
2

4
3kT

+ Lc y: Xut hin khi khong cch gia cc phn t < khong cch cn
bng r0
Nng lng y tnh theo h thc:
U = b.e-cr
trong b, c l nhng hng s
73

Nh vy nng lng tng tc ton phn gia cc phn t c tnh theo

h thc:
U = Uh + Ud
3.3.2.3. Quy lut
- M phn t cng tng th lc V tng.
- Cu trc phn t cng phng th lc V cng tng.
- Tt c cc lc ht tng th lc V tng.
1
m .
r6
1
ph v lin kt V th phi lm cho khng cch tc dng gia cc phn t > 6 m.
r

- Quy lut khong cch tc dng: Bn knh tc dng ca lc V

3.4. Mt s loi lin kt khng mang bn cht ho hc

3.4.1. Lin kt bc Clatrat
- L lin kt to thnh do s lng chp nhng phn t loi ny vo khong
khng gian ca nhng phn t loi khc m khng to ra lin kt ho hc bnh
thng. Nh vy, trong hp cht bc phi c hai thnh phn chnh:
+ Phn t lm lng cha c gi l phn t ch.
+ Phn t nm trong lng c gi l phn t khch.
- Lc tc dng trong hp cht bc l nhng lc lin kt yu, trong c th
c lc V, tng tc lng cc nh hng, s bao bc n gin, v.v....Mt khc
nhng lc cn ph thuc tng loi thnh phn ca hp cht bc.
V d: Hp cht bc ca ur
+ Ur l phn t ch.
+ Hidrocacbon l phn t khch.
3.4.2. Lin kt Catenan, Rotaxan
Trong ho hu c thng gp nhiu hp cht a vng ngng t hay ri rc,
trong phn t ca nhng hp cht ny, cc vng lin kt vi nhau bng lin kt
ho hc vi s tham gia ca mt s e- ho tr.
Ngi ta tm ra cc hp cht a vng kiu khc gi l catenan, trong
cc vng lun vo nhau nh nhng vng xch:

Nh vy, lin kt gia hai vng y khng phi l lin kt ho hc m c

tnh cch c hc.

74

iu ch catnan gm nhng vng cha t nht l 20 nguyn t cacbon.

Hiu sut iu ch thp.
Rtaxan c cu to theo cch gn tng t catenan: mt vng ln vy
quanh mt mch di ni vi hai nhm i phn t hai u

75

CU HI V BI TP
Bi 1. Lin kt cng ha tr l g? Hy cho bit mi lin quan gia s cp electron
dng chung ca mi nguyn t cc nguyn t C, O, H, Cl vi s electron ha tr
ca chng trong phn t hp cht hu c. Gii thch?
Bi 2. Da vo cu to v tnh cht ca nguyn t, hy gii thch v sao
a, Cacbon ch yu to thnh lin kt cng ha tr ch khng phi lin kt ion?
b, Cacbon c ha tr IV trong cc hp cht hu c?
Bi 3. Lin kt n, lin kt bi l g? Khi etilen cng vi brom th lin kt hay
lin kt b ph v? V sao?
Bi 4. S lai ha l g? C my kiu lai ha? Cho v d v gii thch?
Bi 5. Hy trnh by cc loi lin kt yu v cho bit ngha ca cc loi lin kt
?

76

TI LIU THAM KHO

1. Phan Tng Sn, Trn Quc Sn, ng Nh Ti, C s l thuyt ho hu c,
tp 1,2, NXB i hc v trung hc chuyn nghip H Ni, 1980
2. Trn Quc Sn, ng Vn Liu Gio trnh c s ha hc hu c, Tp 1, 2,
NXB i hc s phm, 2007.
3. Trn Quc Sn, Trn Th Tu, Danh php hp cht hu c, NXB Gio dc,
H Ni, 2007.
4. Thi Don Tnh, C s ho hc hu c, Tp 1, 2, NXB Khoa hc v K thut,
H Ni, 2006.
5. ng Nh Ti, C s l thuyt ha lp th, NXB Gio dc, H Ni, 1998.
6. Ng Th Thun Ho hc hu c phn bi tp (tp 1,2), NXB Khoa hc v k
thut, H Ni, 2006.
7. Hong Trng Ym, Ho hc hu c, NXB Khoa hc & K thut, H Ni,
2002.

77

CHNG 4: HIU NG CU TRC PHN T HU C

4.1. Hiu ng in t
4.1.1. Khi nim
4.1.2. Phn loi
Gm 3 loi:
- Hiu ng cm ng
- Hiu ng lin hp
- Hiu ng siu lin hp
4.1.2.1. Hiu ng cm ng (k hiu l I: Inductive Effect)
a. Khi nim
Hiu ng cm ng l s phn cc lan truyn cc lin kt lin tip theo mch
lin kt do s phn cc ca mt lin kt no (hoc do s ht hoc y
electron ca mt nguyn t hay nhm nguyn t no trong phn t).
V d: Trong n propyl clorua, do m in ca Cl m lin kt C-Cl phn
cc ko theo s phn cc ca cc lin kt C1 C2, C2 C3
H

1 ( )
3
1
2
C
C
H
Cl
C

b. Cch biu din: Dng mi tn ch chiu in t chuyn dch.

c. Phn loi
Ty theo tnh cht ca nhm gy hiu ng, ngi ta phn loi hiu ng cm
ng thnh hiu ng cm ng m (-I) v dng (+I).
- Hiu ng cm ng m gy ra bi nguyn t hay nhm nguyn t ht
electron v pha mnh, nh Cl, Br, NO2 (X ).
- Hiu ng cm ng dng gy ra bi nguyn t hay nhm nguyn t y
electron ra khi n nh CH3, C2H5, O-, (X ).
- Ngi ta cn thy c hiu ng trng (F) l hiu ng cm ng truyn lc
tnh in qua khong khng gian gia cc nguyn t gn nhau khng lin kt vi
nhau.
Qui c: Hiu ng gia cacbon v hidro = 0 (IC-H = 0).
d. c im
Hiu ng cm ng gim nhanh theo chiu di mch truyn.
1 2 3
Hiu ng cm ng khng b cn tr bi yu t khng gian.

78

e. Quy lut
- Cc gc hidrocacbon no c hiu ng +I, hiu ng cng mnh khi bc ca
gc cng tng, cc gc hidrocacbon khng bo c hiu ng I, gc cng khng no
th hiu ng I cng ln.
+I: CH3 - < CH3CH2 - <(CH3)2CH - < (CH3)3C
-I: R2C = CR - <C6H5 - < R C C
- Cc phi kim c hiu ng I, hiu ng cng ln khi nguyn t tng
ng cng bn phi (chu k) v cng pha trn (phn nhm) theo bng h thng
tun hon.
- F > - Cl > - Br > - I
- OR > - SR > -SeR
- F > - OR > - NH2
- Cc nhm mang in dng c hiu ng I, cc nhm mang in m c
hiu ng +I. in tch cng ln hiu ng cng mnh.
+I: - O- < - S- < -Se-I: - O+R2 > - S+ R2 > -Se+R2 ; - N+R3 > - NR2
V d v biu hin cc quy lut trn l tnh cht axit ca cc axit th. Cc
nhm c I cng mnh v cng gn nhm COOH th tnh axit cng mnh.
f. ngha
- Dng gii thch tnh cht bt thng hoc tnh cht ca cc hp cht hu
c nh tnh axit,
- Dng gii thch hng phn ng v c ch xy ra ca phn ng.
4.1.2.2. Hiu ng lin hp (k hiu l C:Ting Anh Conjugation Effect)
a. Khi nim
- H lin hp l cc h cc lin kt i xen k cc lin kt n. Cc electron
p c xem nh lin kt i.
V d:
CH2 = CH CH = CH2 ( )
CH2 =.. CH CH = CH CH = O ( )
CH2 = CH CH = CH OH ( p )
Trong h lin hp, obitan phn t bao trm tt c cc nguyn t c h, ta
gi l obitan gii to.

79

Hiu ng lin hp: Hiu ng lin hp l s phn cc lan truyn cc

electron trong h lin hp khi c s dch chuyn cc electron
hay p no ca h.

V d:
CH 2

CH

CH

CH

CH

Do s dch chuyn electron ca nhm CH=O. Ngi ta phn bit hiu

ng lin hp tnh (Cs) do cu trc ni phn t m lun lun c, nh trng hp
trn v hiu ng lin hp ng (C) ch xut hin khi c tc ng bn ngoi, chng
hn, phn t butaien i xng khi c HBr th b bin dng v xut hin hiu ng
(theo chiu mi tn cong)
CH 2

CH

CH

CH 2

H +Br -

Tuy nhin, v Cs v C cng mt c tnh nn ngi ta ch dng khi nim

chung: Hiu ng lin hp C.
b. Cch biu din: Dng

biu din chiu chuyn dch ca in t.

c. Phn loi v quy lut

- Hiu ng +C (h lin hp y in t ra khi n?): Cc nhm X gy hiu
ng lin hp dng +C ni chung u c cp electron d trong h p- , tham gia
chuyn electron v pha lin kt :
X

Cc nhm ny thng c c -I.

- Quy lut
+ Hiu ng +C ca cc nguyn t cc nguyn t gim khi s th t tng
trong mt chu k hoc mt phn nhm:
NR2 > OR > F
F > Cl > Br > I
+ Nguyn t mang in tch m c hiu ng +C ln hn chnh nguyn t
y: O > OR.
Hiu ng -C (h lin hp ko in t v pha mnh): a s cc nhm cha no
u gy hiu ng lin hp m -C ht in t v pha mnh nh NO2, CN, CHO,
COOH. Cc nhm ny ng thi c c hiu ng -I:
-

80

- Hiu ng -C ca nhm C = Z cng tng nu:

+ Z cng bn phi trong mt chu k.
+ Z mang in tch dng.
+ Z tham gia lin kt bi tng
- C = O > - C = CR2
- C = N+R2 > - C = NR
- NO2 > - C N > - C = O > - COOR > - COO+ Mt s nhm c lin kt bi C = C s c hiu ng +C hay -C l tu thuc
vo nhm lin kt vi chng nh:
C

CH 2
-C

CH 2

Cl

+C

CH

+C

CH

-C

d. c im
- Hiu ng lin hp ch thay i t khi ko di mch lin hp.
- Hiu ng lin hp ch xut hin trn h lin hp phng tc l h obitan
gii to.
- Hiu ng lin hp chu nh hng ca hiu ng khng gian.
e. ngha: Ging hiu ng cm ng.
4.1.2.3. Hiu ng siu lin hp H: Hyperconjugation Effect (ph bin l hiu ng
lin hp )
a. Khi nim
Hiu ng siu lin hp l hiu ng electron do tng tc gia cc electron
ca lin kt C - H hay C - F vi electron ca ni i hoc ba cch nhau mt
lin kt n C - C:
H

CH

CH 2

Ngi ta gii thch rng cc lin kt C - H tp hp li thnh obitan nhm,

nh mt ni ba, ni i gi. Hiu ng siu lin hp yu v pht huy tc dng
trng thi phn ng mnh hn.
b. Phn loi v quy lut

81

C hai loi hiu ng siu lin hp:

- Hiu ng siu lin hp dng (+H) ca cc lin kt C - H y in t v
pha ni i, theo chiu ca hiu ng +I, nhng c quy lut ngc nhau:
+I: - CH3 < CH3CH2 - < (CH3)2CH - < (CH3)3C +H: - CH3 > CH3CH2 - > (CH3)2CH - > (CH3)3C Hiu ng ny do Baker v Nathan pht hin nm 1935 khi nghin cu phn
ng: p-R-C6H4CH2Br + piridin nn gi l hiu ng Baker Nathan.
V d:
CH2Br

CH2Br

CH2Br

CH3

CH2CH3

CH

CH2Br

CH3 CH3 C

CH3

CH3

CH3

- Hiu ng siu lin hp m (-H) ca cc lin kt C - F ht in t ca

lin kt i:
F

CH

CH 2

Ngi ta chng minh c hiu ng -H ca nhm CF3 khc vi hiu ng -I

ca n.
c. ngha
- Gii thch c tnh linh ng ca nguyn t H khi lin kt C-H gn trc
tip vi nguyn t C mang lin kt bi hoc nhn thm:
H
O
H

H
H

82

- Gii thch c tnh bn ca but-2-en hn hn but-1-en do hiu ng siu

lin hp c m rng hn:

CH3

CH

CH

but-1-en

but-2-en

4.2. Hiu ng khng gian S (Ting Anh Steric Effect)

4.2.1. Khi nim
Hiu ng do kch thc ca cc nhm nguyn t gy nn c gi l hiu
ng khng gian (S).
V d: Trong phn t 2.6-imetyl quinon di y c hai nhm C=O song
ch c C=O tham gia phn ng vi NH2OH, cn C=O khng phn ng c v hai
nhm bn cnh gy hiu ng khng gian cn tr NH2OH n gn:
CH3
(2)

(1)
O

CH3

V d: Phenol l mt axit yu, nu a nhm NO2 vo v tr para s lm

tng mnh tnh axit v nhm ny gy hiu ng - C v - I. Tuy nhin, nu cc v
tr ortho i vi nhm NO2 c nhng nhm CH3 th tnh axit ch tng t v hai
nhm CH3 gy hiu khng gian, lm gim s lin hp do gim hiu ng C ca NO2.
4.2.2. Phn loi
Hiu ng S rt a dng, song ph bin hn c l:
- Hiu ng khng gian loi mt (S1)
- Hiu ng khng gian loi hai (S2)
- Ngoi ra cn c hiu ng oct l hiu ng ca nhng nhm th v tr
oct i vi nhau. Khng nn coi hiu ng octo l hiu ng khng gian n thun
m l mt hiu ng hn hp trong thng c yu t khng gian.
4.2.3. Hiu ng khng gian loi mt (S1)

83

CH2

Hiu ng khng gian loi mt (S1) l hiu ng ca nhng nhm th c kch

thc tng i ln chim nhng khong khng gian ng k v do cn tr hay
hn ch khng cho mt nhm chc no ca phn t tng tc vi phn t hay
ion khc, hoc lm thay i hiu s nng lng t do F gia phn t v trng thi
chuyn tip.
V d: Phn t 2,6-imetyl-1,4-quinon c hai nhm cacbonyl nhng ch c
mt nhm trong tham gia phn ng vi NH2OH (hidroxylamin) cn nhm th
hai v b n ng khng gian bi hai nhm metyl nn khng li gn phn t NH2OH
phn ng c.
O
H 3C

CH 3

Cn lu rng trong mt phn ng lng phn t nh hng khng gian c

th do cht phn ng hay do tc nhn hoc do c hai cng gy nn. L tt nhin
trong trng hp sau cng (c hai cng gy nn) nh hng t ti mc cao nht.
Khi xt kh nng phn ng th u tin u tin xt tiu ch in t trc ri
mi xt nh hng ca khng gian
4.2.4. Hiu ng khng gian loi hai (S2)
L hiu ng ca nhng nhm th c kch thc ln vi phm tnh song
song ca trc cc m my electron v n trong h lin hp (gy ra bin i v
mt cu trc ca cc h lin hp). Loi hiu ng ny thng gp cc hp cht
thm.
V d: N imetylanilin d tham gia phn ng ghp i vi mui iazoni
v tr para do hiu ng +C ca nhm N(CH3)2. Trong khi dn xut 2,6-imetyl
ca amin ny li khng tham gia phn ng do hiu ng khng gian lm cho
nhm N(CH3)2 b xoay i, do s xen ph gia cc obitan v n b vi phm v
hiu ng +C gim.

84

H 3C
N

C 6H 5 N 2+

H 3C

H 3C
N

H 3C

H3C

CH3
N

CH3

CH3

Hiu ng khng gian loi hai th hin rt r qua cc tnh cht vt l nh

momen in, quang ph,v.v... cho nn c th dng rng ti cc phng php vt l
kho st loi hiu ng ny.
4.2.5. Hiu ng octo
Ta bit rng cc nhm th v tr octo trong vng benzen thng gy
nhng nh hng rt bt ng (khc nh hng ca nhng nhm cc v tr
khc) n tnh cht vt l cng nh tnh cht ho hc ca phn t .
V d: Khi so snh hng s phn ly Ka ca cc axit C6H4(R)COOH, ta thy
hu nh bt k bn cht ca nhm th l g ,cc axit ng phn octo lun lun c
Ka ln hn cc ng phn khc. Loi nh hng c bit ca cc nhm th v tr
oct nh vy gi l hiu ng oct.
Vi danh t hiu ng octo ta hiu l loi hiu ng hn hp bao gm
nhiu yu t, m nhng y t c khi li c tc dng nghch hng vi nhau.
Cc yu t l :
a. Hiu ng khng gian loi mt: Nhm th X v tr octo cn tr s tn
cng ca tc nhn Y vo nhm chc Z:
X

b. Hiu ng khng gian loi hai: Nhm th X lm mt tnh phng ca h:

X

85

c. Hiu ng cm ng: v tr octo hiu ng cm ng th hin mnh hn

nhiu so vi cc v tr khc v khng nhng nhm gn nhm chc hn,m
cn c th tc dng trc tip nh hiu ng trng:
X

F
Z

d. Tng tc hyro: to thnh lin kt hyro ni phn t:

H
O
HO

O
C

O
O

Trong tng trng hp c th, c th khng phi tt c m ch mt vi yu

t k trn cng xut hin thi.

86

CU HI V BI TP
Bi 1. Hy so snh s ging nhau v khc nhau gia hiu ng cm ng v hiu
ng lin hp? Cho v d?
Bi 2. Hiu ng khng gian l g? C my loi hiu ng khng gian?
Bi 3. So snh tnh axit ca ankan, anken, v ankin. Gii thch. Tnh axit c lin
quan g vi nng lng phn ly lin kt?
Bi 4. Sp xp cc cht sau theo th t tng dn lc baz v gii thch?
CO(NH2)2, CH3CH2CH2NH2, CH2=CH-CH2-NH2, p-CH3C6H4NH2, analin, pnitroanalin
Bi 5. Sp xp cc cht sau y theo trt t tng dn tnh axit v gii thch?
p-O2N C6H4 COOH (A)
m-O2N C6H4 COOH (B)

p-CH3 C6H4

COOH (C)

m-CH3 C6H4

COOH (D)

Bi 6. Sp xp cc cht sau y theo trt t tng dn tnh baz v gii thch?

CH3 NH2 (X) CH2Cl NH2 (Y) CH3 NH CH3 (Z) CH3 CH2 NH2 (T)
Bi 7. Sp xp cc cht sau y theo trt t tng dn kh nng phn ng vi dung
dch brom nhit phng: vinylclorua, propilen, etilen, but-2-en, tetrametyl
etilen?

87

TI LIU THAM KHO

1. Phan Tng Sn, Trn Quc Sn, ng Nh Ti, C s l thuyt ho hu c,
tp 1,2, NXB i hc v trung hc chuyn nghip H Ni, 1980
2. Trn Quc Sn, ng Vn Liu Gio trnh c s ha hc hu c, Tp 1, 2,
NXB i hc s phm, 2007.
3. Chu Phm Ngc Sn, Nguyn Hu Tnh, Bi tp ha hc hu c, NXB Hn
Thuyn, Thnh ph H Ch Minh, 1995.
4. Thi Don Tnh, C s ho hc hu c, Tp 1, 2, NXB Khoa hc v K thut,
H Ni, 2006.
5. ng Nh Ti, C s l thuyt ha lp th, NXB Gio dc, H Ni, 1998.
6. Ng Th Thun Ho hc hu c phn bi tp (tp 1,2), NXB Khoa hc v k
thut, H Ni, 2006.

88

CHNG 5: CC AXIT-BAZ HU C
5.1. Khi nim axit - baz
5.1.1. Thuyt axit, baz
5.1.1.1. Thuyt Arhenius
Axit l nhng hp cht c cha Hydro, khi phn ly trong nc cho ion H+.
HnX nH+ + XnHCl H+ + ClBaz l nhng hp cht c cha ion OH-, khi phn ly trong nc cho ion
OH

M(OH)m Mm+ + mHOCa(OH)2 Ca 2+ + 2HOu im

- Phn loi c thnh cc hp cht axit, baz.
- Gii thch c bn cht ca phn ng trung ho: H+ + HO- H2O
- Gii thch kh nng xc tc: tnh xc tc tng khi [H+] tng.
- Thao tc n gin, d vit.
Nhc im
- Khng gii thch c tnh axit, baz ca mt s hp cht nh NH3,
AlCl3, x phng.
- Khng gii thch c cho nhng hp cht lc ny l axit nhng lc khc
n l baz.
5.1.1.2. Thuyt Lewis
Axit l nhng cht trong c th l ion, nguyn t hay phn t c kh
nng kt hp vi i in t t do ca baz.
Cc axit theo Lewis c:
Proton
H+ + :NH3 NH4+
H+ + CH2=CH2 CH3 - +CH2
-

Cc cation
Li+ + CH3OH CH - O+Li - H
Ag+ + 2NH3 [H3N:Ag:NH3]

- Tnh axit ca cc cation tng khi:

89

+ in tch dng ca cation tng: Fe+2 < Fe+3

+ in tch ht nhn ca cation tng: Li+ < Be+2 < B+3
+ Bn knh ion gim: K+ < Na + <Li+
+ S lp electron ca cation gim.
Cc lin kt bao quanh cation trn khng phi l lin kt cng ho tr m a
s l lin kt ion-ion, ion-lng cc. Cc nhm bao quanh cc cation gi l Ligan.
Cc hp cht c nguyn t trung tm c lp in t ngoi cng
cha y , cn cha qu o trng nh BF3, AlCl3,...cc hp cht
ny c kh nng tc dng vi i in t ca baz to ra lp in
t ngoi cng 8e-:
AlCl3 + Cl- AlCl4- Trng hp ny tnh axit tng khi:
+ in tch ca ht nhn nguyn t trung tm tng (p dng cho cc nguyn
t cng nhm).
+ m in ca cc nguyn t lin kt vi nguyn t trung tm tng.
+ Bn knh nguyn t trung tm gim.
+ S lp in t xung quanh nguyn t trung tm gim.
Cc nguyn t c 6 in t lp ngoi cng v d nh oxy, lu
hunh, cc nguyn t ny c th tng tc vi baz to ra lp
ngoi cng 8e -.
O

NR 3

NR 3

Cc hp cht c ni kp b phn cc
O-

RCH = O

CN -

CN

Cc hp cht m lp in t ngoi cng ca nguyn t trung tm c

th m rng nh nguyn t silic c qu o d cn trng c th m
rng lp in t:

90

2F

Si

F
F

2F -

Si

F
F

Baz l nhng anion hay phn t, k c olefin hay hydrocacbon thm c

kh nng cho i in t khng chia ca mnh.
Trong cc phn ng gia axit v baz ni trn ta thy, axit i vo ch nhiu
in t ca baz nn gi l tc nhn electrophyl. Ngc li, baz i vo ch trng
electron ca axit nn gi l tc nhn nucleophyl.
Tuy vy, thuyt Lewis cn nhc im l khng gii thch c cc axit
loi hydroaxit. Nu vn dng theo khi nim ca Lewis th trong phn ng:
Cl - H + :NH3 Cl:H:NH3
nguyn t hydro phi c ho tr hai, iu mu thun vi l thuyt cu to cht.
5.1.1.3. Thuyt Bronsted
Axit l nhng cht (phn t trung ho, ion) c kh nng cho proton.
V d:
CH3COOH + H2O CH3COO- + H+
HSO4- + H2O SO42- + H3O+
Al(H2O)63+ + H2O [Al(H2O)5OH]+2
Nhng anion CH3COO- , SO42-, ...: Baz lin hp.
Baz l nhng cht ( phn t trung ho, ion) c kh nng nhn proton.
V d:
NH3 + H2O NH4+ + HOCH3O- + H2O CH3OH + HONH2 - NH3+ + H2O H3N+ - N+ H3
Nhng cation NH4+ , H3N+ - N+H3, CH3OH l axit lin hp.
Qua y ta thy nc cng nh nhiu cht khc c chc nhm hydroxyl tu
theo cht tc dng vi n m th hin tnh axit hay baz.
Theo Bronsted, nhng axit rt mnh phi c nhng baz lin hp rt yu v
ngc li, nhng baz rt mnh phi c nhng axit lin hp rt yu.
Thuyt ny khc phc nhc im ca thuyt Arhenius v c nhiu u
im hn l m rng phm vi cht; mt cht l axit hay baz khng nht thit
phi c H+ hay OH- trong phn t; quy v 1 thc o H+.
91

ng dng cc thuyt axit-baz

- Gii thch c ch cc phn ng hu c nh phn ng loi nc, ankyl ho,
cracking, ng phn ho, trng hp ho,...
- D on chiu hng mt s phn ng hu c.
- Gii thch mt s phn ng ca hydrocacbon.
5.1.2. Cch o axit, baz: Dng thang o: Thang nc
- n v o: pH
- Cch o:
+ o bng ton hc: Cch tnh pH.
+ o bng my o pH.
+ o bng cht ch th.
5.2. Cu trc phn t nh hng n tnh axit, baz hu c
5.2.1. Tnh cht axit v cu trc ca hp cht hu c
5.2.1.1. Cc nhm axit hu c ph bin
- Nhm I: C cha cc nguyn t c cp in t khng phn chia lin kt
c dng - YH bao gm nhng ancol R-OH, tiancol R-SH, amin R2NH, halofom
X3CH, v,v...
y nguyn nhn lm cho nguyn t hydro linh ng ch yu l do s
phn cc ca lin kt Y - H. Thng thng s phn cc cng mnh, tnh axit
cng tng, m s phn cc lin kt Y - H li ph thuc vo m in ca Y.
- Nhm II: C dng
C

Gm c cc i din l enol, phenol Ar - OH, tiphenol Ar-S-H, arylamin

Ar2NH v c nhng hydrocacbon nh cc arylamin Ar3CH, v.v...
Trong trng hp ny, nguyn t hydro tr nn axit hn khng phi ch v
s phn cc ca lin kt Y-H v m in hi cao ca nguyn t C trng thi
lai ho sp2 m ch yu cn v c s lin hp lm chuyn dch mt electron v
pha ni i.
S lin hp ny c th xy ra trng thi phn t cha phn ly (lm cho YH d phn ly) hay trng thi anion (lm cho anion tr nn bn vng hn).
V d:

92

O-

V vy khi so snh nhm I vi nhm II, nu Y ging nhau v phn cn li

ca phn t khng khc nhau nhiu v nhm th th tt nhin hp cht thuc nhm
II phi c tnh axit mnh hn. V d phenol so vi ancol, amin thm so vi amin
bo,v.v...
Nhm III: C dng
C

i din rt tiu biu l cc axit cacboxylic RCOOH hoc ArCOOH. Ngoi

ra cn c cc axit tiocacboxylic, cc amit,v.v...
Nguyn nhn xut hin tnh axit y tng t nh cc hp cht nhm II
nhng c tnh axit cn mnh hn nhiu v Z l nguyn t ca nguyn t c m
in ln hn cacbon v lin kt C=Z lun lun phn cc mnh. V d:
R

Kt lun: i vi hp cht thuc c ba nhm, bt k yu t cu trc no

lm tng phn cc ca lin kt Y-H v tnh bn ca baz lin hp (anion) u
lm cho lc axit tng ln.
5.2.1.2. Tnh axit cc loi
Tnh axit ca cc
ancol
- Axit rt yu:
ROH RO- + H+
Mc phn ly ph
thuc vo bn cht
ca gc hydrocacbon

Tnh axit ca phenol Tnh axit ca axit

cacboxylic aliphatic
- Phenol cng nh - Axit cacboxylic
enol (axit nhm II) (thuc nhm II) l
nn tnh axit ca nhng axit hu c
phenol lun lun in hnh, c i din
mnh hn ancol no n gin nht l

93

Tnh axit ca cc
axit c vng thm
- Khi thay th
nguyn t H trong
HCOOH bng gc
phenyl, tnh axit
gim i v gc

R.
- phn ly ca
ancol
no
nh
CH3OH,
C2H5OH,..yu hn
nc. Nguyn nhn
l ancol c nhm
ankyl th hin hiu
ng +I. Chnh hiu
ng ny lm tng
cng
mt

electron nguyn t
oxy trong ROH v
lm gim bn
vng ca anion RO(so vi OH-).
- C2H5OH < C2H5SH
(?)
- Khi thay th
nguyn t H trong
nhm
CH3
ca
metanol bng nhng
nhm nguyn t
khc nhau s lm
thay i tnh axit ca
ancol.
+ Cc nhm ankyl
lm gim tnh axit
(v c hiu ng +I).
+ Halogen, metoxyl
v cc nhm -I khc
s lm tng tnh axit.
- S nhm hydroxyl
trong ancol tng ln
(polyol) th tnh axit
cng tng tuy khng
nhiu.
- Ch : Tnh axit
ca cc enol. Enol
thuc nhm axit II,
trong ngoi s
phn cc cm ng
trong phn t cn c

v nc
- tiphenol (C6H5SH)
c tnh axit mnh hn
thiancol (C2H5SH),
C6H5OH < C6H5SH
(?)
- Cc nhm th khc
nhau trong vng
benzen ca phenol
lm thay i tnh axit
mt cch r rt. Cc
nhm ht electron
lm tng tnh axit cn
cc
nhm
y
electron lm gim
tnh axit.
- Cc nhm th v
tr oct i vi nhm
OH gy nh hng
khng gian khng ln
lm so vi nh hng
nh th i vi NO2
hoc COOH.
V d:
OH

OH

OH
H3 C

H 3C

CH 3
NO2

NO 2
pKa

CH3

NO2
7,21

8,24

7,16

- So snh:
>

NO2

OH

OH

OH

>

OCH 3

OH

>

CH3

NH 2

- Xt v hiu ng
in t th para c
nh hng mnh hn
so vi oct, meta.
Nhng xt v hiu
ng khng gian th
oct c nh hng
mnh hn p-, m- (tuy
nhin nh hng
khng ln).

94

HCOOH. Khi thay

th nguyn t H-C
trong HCOOH bng
cc gc ankyl (th
hin hiu ng +I),
tnh axit yu i r rt.
V d: HCOOH (pKa
= 3,75) > CH3COOH
(pKa = 4,76).
Tuy nhin nu tng
thm chiu di mch
n-ankyl th pKa thay
i rt t (nguyn
nhn c th l nh
hng +I y
khng phi l yu t
duy nht lm thay i
tnh axit ca nhm
COOH m cn nhng
yu t khc nh hiu
ng siu lin hp,
tng tc gia nhm
cacboxyl vi nguyn
t H no trong
mt
s
gc
hydrocacbon,v.v...
- Thay th cc
nguyn t H trong
axit axetic bng cc
nhm metyl r rng
c lm gim tnh axit
v khng nhng hiu
ng +I tng ln m c
hiu ng khng gian
n ng qu trnh
sonvat ho anion
cng tng.
- Thay th H bng
nhng nhm th c
nh hng -I th tnh
axit tng, cng nhiu
nhm th -I, tnh axit
cng tng nhanh.

phenyl mt mt th
hin hiu ng -I,
mt khc cn th
hin hiu ng +C.
- Khi thay th
nguyn t H trong
CH3COOH
bng
gc phenyl th c
axit phenylaxetic c
tnh axit mnh hn
axit axetic v gc
phenyl ch yu ch
th hin hiu ng -I.
V d:
C6H5CH2 - CH2 COOH
<
C6H5CH2COOH.
Ch : C6H5COOH
> C6H5CH2COOH?
(theo l thuyt v
hiu ng l ngc
li:
-C
+C

O
C

-I

+C

-C

CH 2

+C

-I
<

- Khi a cc nhm
th vo gc phenyl
trong phn t cc
axit trn, tnh axit
s bin i tu theo
bn cht v v tr
ca nhm th trong
nhn thm v v
mc nh hng
ca nhm th cn
ph thuc c vo
cu to ca mt
xch trung gian gia
gc phenyl v nhm
cacboxyl.
- nh hng ca
cc nhm th v

s lin hp gia cp
electron
vi
electron
n
ca
nguyn t O lm
gim mt electron
ca nguyn t O.
Chnh v vy m tnh
axit ca enol cao hn
ca ancol no, nht l
khi trong gc R c
nhm cacboxyl lin
hp vi ni i.
V d:
CH 3

C
O

CH

V d:
a, O2N - CH2 COOH > CH3SO2 CH2 - COOH >
CH3O - CH2 - COOH
> HO - CH2 - COOH.
b, Cl3C - COOH > F CH2 - COOH > Cl CH2 - COOH > Br CH2 - COOH.
- Cc nhm th
nhng v tr cng xa
v tr gy nh
hng cng yu do s
tt nhanh hiu ng
khi mch lin kt
ko di.
V d:
F3C - COOH > F3C CH2COOH > F3C CH2 - CH2COOH.
Nhng
axit
cacboxylic cha no
ni chung c tnh axit
mnh hn axit no
tng ng v cc
nhm C=C c hiu
ng -I. V tr ca ni
i
trong
gc
hydrocacbon c khi
cng gy nh hng
ln n tnh axit ca
nhm COOH. Nhm
C=C cng gn
nhm COOH th tnh
axit cng tng, tr
trng hp ni i
v tr , l v tr
thun li cho s lin
hp gia nhm C=C
vi nhm C=O. Hiu
ng ny (+C) gy nh
hng ngc li hiu

CH3

OH

95

tr mta v para:
+ Ankyl: lun lm
gim tnh axit.
+ Cc nhm metoxy
v hydroxy v tr
meta (-I) nn lm
tng
tnh
axit,
nhng v tr para
chng c th pht
huy y nh
hng +C (cng vi
-I) do phn ly
ca axit gim.
+ Cc halogen bt
k v tr no cng
c hiu ng -I mnh
hn +C, nht l
mta nn chng
lun lm tng
phn ly ca axit, khi
y ng phn mta
phn ly mnh hn
ng phn para.
+ Nhm NO2- l
nhm ht e- mnh
c v -C v -I nn
cc axit c nhm
NO2 v tr para
bao gi cng phn
ly mnh hn mta
v tt c u mnh
hn cc axit tng
ung
c
cha
halogen trong nhn
thm.
- Cc nhm th v
tr oct gy nh
hng rt c bit
n tnh axit ca
axit benzoic. Bt k
nhm th thuc loi
no t nhiu cng
u lm tng

ng -I. Do axit
cacboxylic
, cha no khng phi
l axit mnh nht
trong dy cc axit
cha no.
V d:
CH3 - CH=CH - CH2
- COOH > CH2=CH CH2 - CH2 - COOH >
CH3 - CH2 - CH =
CH - COOH.
- Gia hai ng phn
cis - trans ca axit
cacboxylic
, cha no, ng phn
cis thng phn ly
mnh hn. Nguyn
nhn ca hin tng
khc bit ny l do
nhng nhm ankyl v
aryl trong ng phn
cis gn nhm
COOH nn gy
nh hng tng t
nh hng oct.
- Lin kt CC d
v tr , cng lm
tng mnh tnh axit
ca nhm cacboxyl
mt cch t ngt do
nguyn t C trng
thi lai ho sp th
hin hiu ng -I ln
hn cc nguyn t C
khc, mt khc trong
s hai lin kt ca
ni ba ch c mt trc
tip tham gia lin hp
vi -CO-, cn mt
na v c mt phng
thng gc vi mt

96

phn ly ca axit do
hiu ng octo. Khi
ko di qung cch
gia gc phenyl vi
nhm COOH bng
cch a thm cc
nhm trung gian
nh CH2, CH2 CH2 vo th hiu
ng oct khng cn
r na.
- Xt v hiu ng
in t th para c
nh hng mnh
hn so vi octo,
meta. Nhng xt v
hiu ng khng
gian th oct mnh
hn p-, m-. (Nu
ion COO- c kh
nng bn ho bi
hiu ng o- nh lin
kt hidro th lm
tng tnh axit, nu
nhm th o- gy
hiu ng khog
gian loi mt th
lm tng tnh axit?)

phng ca nhm CO- nn khng c

tng tc .
Cc
axit
icacboxylic phn ly
theo hai nc, nc
th nht c nh
hng ca nhm
COOH lm tng tnh
axit, cn nc th
hai c nh hng ca
nhm mang in m
COO- gy tc dng
ngc li. Trong i
a s trng hp cc
nh hng ch
yu l nh hng cm
ng ( I )
V d:
a, HOOC - COOH >
HOOC - CH2 COOH > HOOC CH2 - CH2 - COOH
b, HOOC - CH2 CH2 - COOH <
HOOC - CH=CH COOH.
5.2.2. Tnh cht baz v cu trc ca hp cht hu c
5.2.2.1. Cc loi baz hu c thng dng
- Loi 1: Cc hp cht trc tip phn ly thnh cation v anion OH-. Loi
ny tng i t gp
V d: Triarylankyl cacbinol

C+

OH

97

HO -

- Loi 2: Cc hp cht c kh nng kt hp vi axit nh h thng electron

trong phn t. l nhng anken, ankin, aren,...
V d:
H

HCl

+
C

H
C

C H

HOH

Cl-

HO -

- Loi 3: Cc hp cht c kh nng kt hp vi axit nh cp electron khng

chia ca n. Loi baz hu c ny rt ph bin v bao gm nhiu loi hp cht
hu c nh cc amin, ete, ancol, andehyt, xeton, este, hp cht d
vng,v.v...Nhng hp cht c th kt hp ly proton to ra nhng hp cht
trong s oxy ho ca nguyn t c cp electron khng chia (by g kt hp
proton) tng ln mt n v.
V d:

R 3N

H A
h/c amoni

R3N

HA

NH 4+

H+

NH 3

HA

A-

H
h/c oxoni

Quan trng nht v c cp n nhiu l cc baz c kh nng to

thnh hp cht amoni v oxoni.
Nguyn nhn lm cho cc hp cht thuc nhm ny c tnh baz l s c
mt cp electron cha s dng v kh nng cho cp electron . Cho nn cc yu
t cu trc lm cho kh nng y tng ln u lm cho tnh baz tng ln.
CH3-NH2 > NH3 > C6H5NH2
CH3COO- > Cl-CH2-COONH3 > H2O
Trong trng hp cc baz c cu to kiu RZH th gia lc baz ca phn
t do Z gy ra v lc axit ng vi s phn ly ca H trong ZH c mi lin quan
nghch: Tnh baz cng tng, tnh axit cng gim v ngc li. V mi mt trong

98

hai tnh cht trn li c mi lin quan nghch vi tnh cht ca dng lin hp ca
n:
Tnh baz: C2H5OH > H2O > C6H5OH
Tnh axit: C6H5OH > H2O > C2H5OH
Tnh baz: C2H5O- > HO- > C6H5O-.
pKa cng ln, tnh baz cng mnh, v ngc li.
5.2.2.2. Tnh baz cc loi
Amin
khng Amin thm
vng thm
- Trong dung - Trong phn t
dch nc, cc anilin, gc phenyl
amin tn ti di khng nhng c
dng t do v nh hng -I m
hydrat,
hydrat cn c nh hng
ny phn ly mt -C lm gim mt
phn thnh cc electron
ion:
nguyn t N. V
R3N + HOH vy anilin c tnh
R3N...HOH [ baz yu hn
R3NH]-HOamin bo v amin
- S bin i lc c vng no tng
baz ca amin ng
ph thuc vo (xyclohexylamin)
cu trc phn t v cng yu hn
amin v iu kin c amoniac.
thc hin php o - Khi thay th
lc baz.
nhng nguyn t
- Khi thay th H cn li trong
nguyn t H nhm NH2 bng
trong NH3 bng cc gc phenyl
cc nhm ankyl khc s lm gim
(c hiu ng -I) mnh tnh baz.
th tnh baz s V
d:
tng.
iphenylamin c
H-NH2 < CH3- th to mui vi
NH2 < CH3-NH- axit mnh nhng
CH3.
mui ny b thu
Tuy nhin amin phn hon ton
bc ba < amin trong nc cn
bc hai, c khi triphenylamin
yu hn c amin khng to mui

Hp cht d vng
cha nit
- Cc d vng khng
thm c tnh baz
tng t amin tung
ng.
- i vi cc d vng
thm trong cp
electron cha s dng
ca d nguyn t ni
chung cn t do th
tnh baz ch gim
mt phn.
V d:
N

N
N
N

PYRIDIN
pKa

5,23

N
H

PYRAZOL
2,53

N
H

IMIDAZO L
7,03

TIAZOL
2,53

N
H

PYRROL
-0,27

- Trong trng hp
cp e- n ca d nguyn
t tham gia to thnh
h lin hp thm th
tnh baz ca nguyn
t thc t coi nh
b mt (v d pyrol).
- Trong pyrazol v
imidazol, trung tm
baz chnh l nguyn
t N mang ni i
=N- ch khng phi
l nguyn t N trong
nhm -NH-. Nhng
nguyn t N ny (=N) tuy cn cp e- cha
s dng nhng tnh
baz th hin yu hn
99

Hp cht cha
oxi
- Cc hp cht
cha oxy nh
ancpl,
ete,
andehyt, xeton,
axit cacboxylic,
este, hp cht
nitro,v.v... c
coi l nhng
baz yu v to
ra sn phm t
bn.

bc mt l do s
khc nhau v kh
nng sonvat ho
cc
ion
ankylamni
tng ng: Trong
dung dch nc,
s hydrat ho cc
ion ankylamoni
lm cho cc ion
tr nn bn
vng hn. Tng
tc

cng
mnh, ion cng
bn v cng d
sinh ra, do lc
baz ca amin
tng ng cng
mnh. So vi ion
iankylamoni
R2NH2+ th ion
triankylamoni
R3NH+ b sonvat
ho yu hn
khng nhng v
s nguyn t
hydro t hn m
cn v hiu ng
khng gian loi
mt gy ra bi ba
nhm ankyl.
Tuy nhin nu
tin hnh xc
nh lc baz ca
amin trong nhng
dung mi khng
c kh nng
sonvat ho th
baz mnh hn
c l amin bc ba.
- Khi thay th
nguyn t H
trong nhm ankyl

ngay c vi nhng
axit mnh.
- Khi thay th
nhng nguyn t
H bng cc gc
ankyl (hiu ng
+I) th tnh baz
s tng ln.
- Cc nhm th
trong vng benzen
ca amin thm
gy nh hng
khc nhau n
tnh baz tu theo
bn cht v v tr
cuat nhm th
trong vng. Ni
chung, cc nhm
y e - lm tng
tnh
baz
v
ngc li.
- nh hng ca
nhm th v tr
p- l mnh nht,
cc nhm th v
tr o- i vi
nhm amino th
hin hiu ng on tnh baz ca
amin. Trong a s
trng hp bt k
bn cht nhm
th, tnh baz u
gim (nh hng
electron, lin kt
hydro, nh hng
khng gian).
V
d:
C6H5NHCH3
>
C6H5N(CH3)2
>
C6H5NH2 (do hiu
ng khng gian).

c NH3 v cp e -
trng thi lai to sp2
li lin kt vi
nguyn t Csp2. Ngoi
ra cn c nh hng
ca cc nguyn t
khc nh N, S trong
trng
hp
ca
pyrazol,
imidazol,
tiazol, ...
- nh hng ca
nhm th n tnh
baz ca d vng th
hin kh r, v d
trng
hp
ca
pyridin. S bin i
tnh baz theo cu
trc dy ni chung
cng tun theo cc
quy lut v nh hng
electron (cc v tr
, tng ng vi
cc v tr o- ,p- trong
vng benzen. V tr
tng ng v tr m).

100

ca amin bng
nhm th c hiu
ng -I (OCH3,
CN, CH=CH2,...)
lm cho tnh baz
gim i r rt.
Nhng nhm th
c hiu ng -I
hoc -C mnh
nh trc tip vo
nguyn t nit c
th lm trit tiu
tnh baz. V d:
(CF3)3N,
CH3CONH2.

101

CU HI V BI TP

Bi 1. Hy trnh by cc thuyt v axit-baz. Hy nu u im v nhc im ca

cc thuyt?
Bi 2. Hy trnh by cu trc phn t nh hng n tnh axit, baz hu c?
Bi 3. Hy sp xp tnh axit tng dn: H2O, CH3OH, CH3COOH, CH3NH2,
CH3CH3?
Bi 4.
a) T gi tr pKb, th t gim tnh baz: RNH2< R2NH > R3N>NH3. Gii thch th
t .
b) Th t ny thay i th no trong pha kh.
c) Gii thch tnh baz gim ca amin bc 3 vi th tch nhm th.
Bi 5. So snh tnh baz ca RC N, RCH=NH, RCH2NH2
Bi 6. Gii thch th t thay i tnh baz sau:
a) C6H5NH2 , m-NO2C6H4NH2, p-NO2C6H4NH2, o-NO2C6H4NH2
b) p- CH3OC6H4NH2, o- CH3OC6H4NH2, m- CH3OC6H4NH2, C6H5NH2
c) o-CH3C6H4NH2, m-CH3C6H4NH2, p-CH3C6H4NH2, C6H5NH2
Bi 7. So snh tnh baz ca anilin, iphenylamin, xyclohexylamin.
Bi 8. Trong tng cp hp cht sau, hp cht no c tnh baz cao hn.
a) m-xyanoanilin v p- xyanoanilin
b) N-axetylanilin v N-etylanilin
c) Anilin v benzylamin
d) N-cloanilin v o-cloanilin
Bi 9. So snh v gii thch tnh axit ca dy hp cht sau:
a) o-metylphenol, m-metylphenol, p-metylphenol
b) o-bromphenol, m-bromphenol, p-bromphenol
c) o-metoxyphenol, m-metoxyphenol, p-metoxyphenol
Bi 10.
a) Gii thch ti sao xyclopentadien c Ka = 10-15 ln hn 1,3-xyclohexadien
b) Xc nh cu trc electron trn MO ca anion xyclopentadienyl.
c) Gii thch ti sao cation xyclopentadienyl l gc kp.

102

TI LIU THAM KHO

1. Phan Tng Sn, Trn Quc Sn, ng Nh Ti, C s l thuyt ho hu c,
tp 1,2, NXB i hc v trung hc chuyn nghip H Ni, 1980
2. Trn Quc Sn, ng Vn Liu Gio trnh c s ha hc hu c, Tp 1, 2,
NXB i hc s phm, 2007.
3. Thi Don Tnh, C s ho hc hu c, Tp 1, 2, NXB Khoa hc v K thut,
H Ni, 2006.
4. Thi Don Tnh, C ch v phn ng ha hc hu c (tp 1,2,3), NXB Khoa
hc v k thut, H Ni, 2008.
5. ng Nh Ti, C s l thuyt ha lp th, NXB Gio dc, H Ni, 1998.
6. Ng Th Thun Ho hc hu c phn bi tp (tp 1,2), NXB Khoa hc v k
thut, H Ni, 2006.

103

CHNG 6: PHN NG HU C
6.1. nh ngha c ch phn ng hu c
C ch phn ng l s m t ca tt c cc giai on c th xy ra ca mt
phn ng ho hc.
Ngi ta phn bit hai loi c ch phn ng:
- Loi c ch th nht l loi c ch trong xy ra qu trnh gy d ly cc
lin kt ca phn t tham gia phn ng v hnh thnh lin kt mi nh i in t
ch do mt phn t ng gp (ca tc nhn) phn ng hay ca mt phn t tham
gia phn ng. Cc phn ng xy ra theo c ch ny gi l phn ng d ly hay ion.
S phn ng d ly:
X:
Tc nhn

R :Y
R:X
Phn t tham gia phn ng

- Loi c ch phn ng th hai l loi c ch trong xy ra vic gy lin

kt theo kiu ng ly, lin kt mi c to thnh do phn t tham gia phn ng
v tc nhn phn ng cng gp chung in t. Phn ng xy ra theo c ch ny
gi l phn ng ng ly hay phn ng gc t do.
S phn ng ng ly:

R:Y

R:Y

6.2. Phn loi phn ng hu c

6.2.1. Phn loi theo hng bin i thnh phn cht phn ng.
6.2.1.1. Phn ng th
L phn ng trong mt nguyn t hay nhm nguyn t trong phn t
c thay th bng mt nguyn t hay nhm nguyn t khc.
V d:
R

Cl

Cl

HO

Cl

Cl

HCl

OH

Cl

6.2.1.2. Phn ng tch

L phn ng lm cho hai nguyn t hay nhm nguyn t b tch ra khi
mt phn t m khng c nguyn t hay nhm nguyn t no thay th.
V d:

104

OH

HOH

Br

HBr

6.2.1.3. Phn ng cng

L phn ng trong hai phn t (hoc ion) kt hp vi nhau to thnh
mt phn t (hoc ion) mi.
V d:

HOH

HCN

OH

OH

CN

Trng hp phn ng cng ca nhng phn t ging nhau (thng l nhiu

phn t) c gi l phn ng trng hp.
Ba loi phn ng trn c k hiu bng ch u ca t ting Anh hoc
ting Latinh tng ng, c th l S: th (substitution), E: tch (elimination) v A:
cng (addition).
Trong c ba loi phn ng , u c th xy ra s chuyn v lm chuyn
ch ca mt nguyn t hay nhm nguyn t no trong phn t. i khi ngi
ta coi s chuyn v l mt loi phn ng th t.
6.2.2. Phn loi theo c im ca s bin i lin kt
Cc phn ng ng ly v d ly.
Trong phn ng ho hc cc lin kt ho hc b t ra v hnh thnh theo
hai cch khc nhau:
- Theo cch th nht: Lin kt cng ho tr b t ra theo kiu ng ly,
ngha l MO lin kt b phn ct sao cho mi nguyn t ca lin kt cn mt
AO, lin kt mi hnh thnh trong phn t sn phm l do s xen ph ca hai AO
hai nguyn t mi tham gia lin kt mi :

105

ng ly

Phn ng hai giai on

ng hp

A:C

A:C

Phn ng mt giai on

Nhng phn ng xy ra theo kiu nh trn c gi l phn ng ng ly

hay phn ng gc.
- Theo cch th hai: Lin kt cng ho tr phn cch d ly ngha l b phn
cch khng i xng mt pha no , sao cho MO lin kt s thuc v mt
nguyn t nht nh, khi hnh thnh lin kt mi, MO lin kt c ngun gc t mt
nguyn t nht nh lin kt c em li theo cch phi tr:

A:B
d ly

A:B

Phn ng hai giai on

A:C

phi tr

A:C

Phn ng mt giai on

Nhng phn ng xy ra theo kiu nh vy gi l phn ng d ly.

6.2.3. Phn loi theo s lng tiu phn ca giai on quyt nh tc phn
ng
Theo cch phn loi ny ta phn bit:
- Phn ng n phn t
- Phn ng lng phn t
- Phn ng a phn t
6.2.4. Phn loi theo tin trnh phn ng
- Phn ng Nuclephin (N)
V d:

CH3

CN

HCN

(N)
CH3

H
C
CN

- Phn ng electrophin (E)

106

OH

H
O

O
S

OH

(E)

O
6.3. C ch phn ng hu c
6.3.1. Phn ng th
6.3.1.1. nh ngha
Phn ng th l phn ng trong mt nhm nguyn t (hoc mt nguyn
t) trong phn t c thay th bng mt nhm nguyn t (hoc mt nguyn t)
khc. Thng thng nhm th hai kt hp ngay vo nguyn t cacbon trc kia
lin kt vi nhm th nht, nhng trong mt s trng hp c th sinh ra sn
phm chuyn v, trong nhm th hai li khng nh vo nguyn t cacbon ni
trn.
6.3.1.2. Phn loi
3 loi chnh
- Th nucleophin (SN)
- Th electrophin (SE)
- Th theo c ch gc (SR)
6.3.1.2.1. Phn ng th nucleophin (SN)
a. Khi nim chung
Phn ng th nucleophin SN xy ra bng s tn cng ca tc nhn
nucleophin (Y) vo trung tm thiu electron v s phn ct anionit ca nhm i ra
(X) cng vi cp electron ca mnh (X:):

X:

Tc nhn Y l anion nh C-, H-, O-, S-, N-,hoc l nhng phn t trung
ho nh: HOH, RNH2, PH3
Tc nhn i ra X l nhng nguyn t hay nhm c m in cao i ra
dng anion X- nh Hal, OH, OR, OSO2R, OCOR,hoc nhng nhm cha in
tch dng i ra dng phn t trung ho nh: N+R2, S+R2
Trung tm phn ng l nguyn t cacbon trng thi lai ho sp3, sp 2 hay sp
v nhng nguyn t khc nh O, N, S,
Phn ng in hnh l phn ng SN d xy ra cacbon lai ho sp 3 c mt
e nh nht, ht nhn khng b chn v tc nhn d tip cn.

107

b. Phn loi
- Phn ng SN c s phn ct lin kt C-X trc, tn cng Y- sau: (Phn
ng thuc loi n phn t SN1).

- Phn ng SN c s phn ct nhm i ra v tn cng Y ng thi: (Phn

ng i qua trng thi chuyn tip lng phn t nn l SN2).

- Phn ng xy ra bng hai giai on tch - cng qua hp cht trung gian
cha ni i:

- HX
C

+ HY

- Phn ng c s tn cng ca Y trc v phn ct nhm i ra sau. Phn

ng thng xy ra nhng hp cht c cha nhm CO, CN,
c. Nhn dng phn ng SN
Cht phn ng: Cht phn cc:

R X

+ R: Nguyn t cacbon trng thi lai ho sp 3, sp2 hay sp v nhng nguyn

t khc nh O, N, S, Phn ng in hnh l phn ng SN d xy ra cacbon lai
ho sp3 c mt e nh nht, ht nhn khng b chn v tc nhn d tip cn.

108

+ X: Nhng nguyn t hay nhm c m in cao i ra dng anion Xnh Hal, OH, OR, OSO2R, OCOR,hoc nhng nhm cha in tch dng i ra
dng phn t trung ho nh: N+R2, S+R2
- Tc nhn
+ Anion nh C-, H-, O-, S-, N-
+ Phn t trung ho
Y nh HOH, H-Hal, H-OR, H-NH2,
Y nh Cl : PCl4, Cl : PCl2, Br : PBr2,
d. iu kin phn ng
- Xy ra nhit khng cao.
- Dung mi phn cc.
- Phn ng thng c xc tc (axit, baz tu thuc l xc tc cho cht phn
ng hay tc nhn).
e. Cch vit c ch
C ch SN1
Phn ng xy ra qua hai giai on:
+ Giai on 1:

chm

+ Giai on 2:

nhanh

V d:

CH3
CH3

CH3
OH

HCl

CH3

CH3

C
CH3

+ Giai on 1:

109

Cl

H2O

CH3

CH3
chm

CH3

OH

CH3

CH3

HO

C
CH3

+ Giai on 2:

CH3
CH3

CH3
Cl

nhanh

CH3

CH3

Cl

CH3

Nhn xt
C ch SN1 xy ra qua hai giai on. giai on u, nhm X b tch ra
di dng anion X- to thnh cacbocation, cation ny c solvat ho t nhiu.
Giai on hai thng cacbocation rt km bn nn n phn ng ngay vi bt k
tc nhn nucleophin no xung quanh n. Giai on ny xy ra nhanh, ph thuc
vo tng tc tnh in, l tng tc khng ch in tch, ngha l tng tc ny
c nh gi bng lc Coulomb. Gin phn ng nh sau:
E
C

t hp Ion
Ion ho
C

To phn ng

110

Giai on quyt nh tc l giai on ion ho. Ngi ta chng minh

rng giai on ion ho c tnh cht thun nghch (chiu thun chm hn chiu
nghch rt nhiu).
- Cu trc cacbocation ca cht phn ng
+ Tc phn ng ph thuc vo bn ca cacbocation. Cacbocation
cng bn, tc phn ng cng cao. Nhm th c hiu ng +I, +C v tr i
vi trung tm phn ng lm n nh cacbocation, lm tng tc phn ng:
(CH3)3CBr > (CH3)2CHBr > CH3CH2Br > CH3Br
(C6H5)3CBr > (C6H5)2CHBr > C 6H5CH2Br > CH3Br
Nh vy phn ng SN1 thng xy ra cacbon bc 3 ca cc gc aralkyl v ankyl.
+ Do bn ca cacbocation nn trong cc phn ng th SN1 c s chuyn
v cacbocation t bc thp sang bc cao v sn phm th thu c cng ph thuc
vo s chuyn v ny.
V d:
CH3
CH3

CH

CH3Cl
HCl

CH3

CH3

H OH

C C

CH3
CH3

CH3

H H

2 clo 3 - metylbutan

C CH2

CH3

Cl

2 clo 2 metylbutan (u tin)

Do c s chuyn v cacbocation:
H

H3C

H3C

H
H

CH3

H3C

CH3

CH3

Cation bc 3

Cation bc 2

- Bn cht ca nhm i ra X
Tc phn ng SN1 ph thuc vo bn cht nhm i ra X, nu nhm i ra
X thnh dng X- cng n nh th tc phn ng cng ln. Cc nhm th ht
electron trong nhm i ra lm n nh in tch m anion, lm tng phn ng. S
tng tnh n nh ca nhm i ra c th t c bng xc tc.
V d: Phn ng ca dn xut halogen RX tng khi c xc tc Ag+ c kh nng to
phc vi halogen.

111

Cl

Ag

Cl

Ag

AgCl

- Bn cht tc nhn nucleophin Y

+ Trong phn ng SN1, tc khng ph thuc vo nng v bn cht Y
nhng sn phm hnh thnh li ph thuc vo tng tc ca cacbocation vi Y.
Theo nguyn tc cacbocation c th tng tc vi bt k Y no c trong dung dch
phn ng tuy c s chn lc v cnh tranh.
+ Tng tc ca C+ vi Y l tng tc axit baz, do tng tc ph
thuc vo tnh baz ca Y. Tc ca qu trnh tng tc ny tng khi tng tnh
baz ca Y.
- ng hc ca phn ng
Phn ng SN1 l phn ng bc 1. Phn ng ch ph thuc vo cht phn
ng m khng ph thuc vo tc nhn phn ng.
- nh hng lp th
+ Trong cacbocation, nguyn t trung tm l lai ho sp2, cn cht ban u
l sp3, nu tng th tch ca nhm th nguyn t trung tm, tng lc y lp th
v tng nng lng ca h, trong trng thi u tng ln hn l cacbocation cho
nn trng thi chuyn i gn v phi cacbocation hn. Nh vy, tng th tch
nhm th l mt n nh cht ban u nhiu hn trng thi chuyn, do , tc
phn ng tng.
+ V mt ho hc lp th, hp cht ban u l chiral, ngha l c trung tm
bt i xng, s to thnh hp cht trung gian cacbocation achiral c tinh i
xng. Tnh hnh hc ca cacbocation ny c nng lng cc tiu nu c s phn
b phng cc lin kt i vi nguyn t cacbon lai ho sp 2. Cation ny c mt
phng i xng nn l achiral. Tc tng tc ca cation ny vi nucleophin
khng ph thuc vo phi no ca mt phng xy ra s tn cng ca Y. Nh vy,
hp cht ban u hot ng quang hc th sn phm to thnh ca SN1 l sn phm
raxemic ho.

Y
C

chm

Br

+ Ynhanh

quay cu hnh

hn hp
raxemic

gi nguyn cu hnh

112

+ Tuy vy cng c nhng phn ng cn thu c mt lng sn phm quay

cu hnh so vi cht ban u, c th gii thch bng s chn ca nhm i ra pha
nhm i ra lm gim kh nng tn cng vo pha ca nucleophin.
V d 1: Khi thu phn 1- phenylmetylclorua thu c hai sn phm vi t
l 51 : 49%
H

H
Cl
H3C
C6H5

a, H2O
A
C6H5

B Cl
CH3

HO
b, -H

H
OH

CH3
C6H5

51%

H3 C
C6H5

49%

V d 2: S thy phn 2 bromoctan quang hot trong dung mi khng c

mt baz giai on quyt nh tc , kt qu l octan-2-ol c hnh thnh vi
83% sn phm quay cu hnh.

83%

17

Nguyn nhn l C khng hon ton t do khi b tc nhn nucleophin tn

cng. Nhm i ra chn mt mt ca cacbocation lm cho tc nhn nucleophin
chim gi cacbocation pha i din nhanh hn.
- nh hng ca dung mi
Trong phn ng SN1, trng thi chuyn phn cc hn cht ban u nn khi
tng phn cc ca dung mi, s sonvat ho trng thi chuyn ln hn cht ban
u, nng lng trng thi chuyn gim mnh hn cht ban u, nn tng phn
ly khi tng phn cc dung mi, tc phn ng tng.
- Kh nng cnh tranh
+ SN1 E1: Sn phm ca phn ng SN1 bao gi cng km theo sn phm
E1 v ngc li.
V d:

113

CH3

CH3

Y
SN1

CH3

CH3

-H

CH3

E1

CH2

CH3

+ S chuyn v
Do bn ca cacbocation nn trong cc phn ng th SN1 c s chuyn v
cacbocation t bc thp sang bc cao v sn phm th thu c cng ph thuc
vo s chuyn v ny.
V d:
CH3
CH3

CH3Cl

CH

HCl

CH3

CH3

H OH

CH3

C C

CH3

CH3

H H

C CH2
Cl

2 clo 3 - metylbutan

2 clo 2 metylbutan (u tin)

Do c s chuyn v cacbocation:

H3C

H3C

CH3

CH3

H
H
CH3

H3C

Cation bc 3

Cation bc 2

Thng c hai trng hp chuyn v:

Chuyn v ankyl:
R1
R

R1
CH R

Chuyn v hirua:

114

R
C

R2

R3

CH3

CH
R3

R1

R1
CH CH

CH2 R

C ch SN2
+ C ch: Phn ng xy ra qua mt giai on

CH3

V d:
CH2

Cl

HOH

CH3

Y
CH2

R
OH

X
HCl

CH3

CH3

CH2

Cl

HO

HO
H

Cl

HO

CH2

CH3 Cl

Nhn xt
C ch SN2 xy ra qua mt giai on, l c ch ng b, trc tip khng c
hp cht trung gian m to thnh trng thi chuyn lng phn t xc nh tc
ca phn ng.
Gin nng lng ca phn ng SN2 nh sau:
E

Trng thi chuyn

To phn ng

- Cu trc cht ban u

115

+ Khi tng th tch nhm th trung tm phn ng, tng tc y lp th

trng thi chuyn tng, ln hn cht ban u, do tc phn ng gim.
+ Kh khn lp th tng t dn xut bc 1 n bc 3, do dn xut bc 3
khng tham gia phn ng SN2, tr mt vi trng hp dn xut bc 3 khng c
kh nng to cacbocation v dng Y mnh th dn xut bc 3 ny cng c th xy
ra theo SN2. Nh vy dn xut bc 1 tham gia phn ng SN2 l d nht.
CH3Cl > CH3CH2Cl > CH3CHCH3Cl > CH3C(CH3)2Cl.
+ Cn hot ha nhm OH trc khi cc cht tham gia phn ng.
V d:
+

HI

CH3OH2 + I

S N2

CH3OH

nhanh
-

CH3OH2
+

I- - -CH2- - -OH2

+
I - CH3

I
+ H2O

- nh hng ca nhm X: Tng t nh SN1.

Khi tng th tch ca nhm i ra, trng thi chuyn b mt n nh hn l
cht ban u, do tc phn ng gim. Vai tr quan trng l nhng yu t lm
n nh anion hnh thnh X-. Cc nhm i ra cha nhm th ht electron lm tng
phn ng SN2 v n nh anion hay in tch m hnh thnh trong trng thi
chuyn.
- nh hng ca tc nhn nucleophin
+ Phn ng SN2 ph thuc vo tnh nucleophin ca tc nhn. Tnh
nucleophin cng mnh, tc phn ng cng nhanh.
+ Mi quan h gia cu to v tnh nucleophin:
Tc nhn nucleophin mang in tch m c lc nucleophin ln hn axit lin
hp ca n:
HO- > HOH
NH2- > NH3
Cc tc nhn nucleophin c nguyn t tn cng thuc cng mt chu k: s
bin thin lc nucleophin tng t lc baz.
NH2- > RO- > HO- > R2NH > ArO- > NH3 > F- > H2O
Trong nhm nguyn t, tnh nucleophin tng t trn xung, tri vi tnh
baz:
F- < Cl- < Br- < I- ; HO- < HS-

116

i vi tc nhn nucleophin c nhm th, kh nng phn ng gim khi s

n ng khng gian tng (bt k tnh baz tng hay gim).
HS- CN- I- C6H5NH2 HO- Br- C6H5O- C5H5N Cl- CH3COO- F- H2O
5,1 5,1 5,0 4,5
4,2 3,9 3,5
3,6 3,0 2,7
2,0 0
+ V mt lp th, th tch ca Y tng lm mt n nh trng thi chuyn,
lm gim kh nng phn ng
+ V mt electron, khi chuyn t cht ban u sang trng thi chuyn tip,
nu l Y- th in tch m ca Y trong phc gim, nu Y l phn t trung ho th Y
trong phc xut hin in tch dng.
R X + YRX +Y

[ Y R X ] R Y + X [ Y RX ] RY+ + X-

+ Cc Y c nhm th ht e c tnh baz gim, ng thi cng lm gim kh

nng phn ng, chng hn:
Y
kt

NO31

CH3COO20

C6H5O400

C2H5O1000

( kt : Hng s tc )
Khi a nhm th cho e, tnh baz ca Y tng lm tng kh nng phn ng
song mi tng quan ny khng c tnh cht chung cho mi Y v ch so snh c
khi cc Y cng c in tch m cng mt nguyn t.
+ Trong phn ng SN2, tc nhn Y tn cng vo trung tm phn ng bng
kh nng ua cp e tham gia vo lin kt vi C hay nguyn t khc c nh hng
ti tc phn ng ( khc vi tnh baz l nh hng ti cn bng). Kh nng
gi l tnh nucleophin. Tnh nucleophin tng i thay i t phn ng ny ti
phn ng khc nn khng c thang tuyt i. C nhiu nhn t nh hng ti tnh
nucleophin nhng ch yu gm cc nhn t sau:
Nng lng solvat ho ca Y cao lm gim nng lng trng thi c bn so
vi trng thi chuyn c in tch gii to hn.
Lc lin kt ca Y vi 2p ca C bng lin kt bn hn th trng thi chuyn
bn hn nn tng tc phn ng th.
Th tch Y ln lm gim tc phn ng.
Nguyn t tn cng vo trung tm phn ng ca Y c m in ln gi
cht hn nn cn phi c nng lng ln hn t trng thi chuyn.
phn cc ho ln lm d dng bin dng m my e ngoi nn tng
tc n nh trong trng thi chuyn hn.

117

+ S lin quan gia tnh nucleophin v tnh baz ph thuc vo dung mi.
Trong dung mi aproton th hai tnh ny trng nhau cn trong dung mi prton th
hu nh ngc nhau.
- nh hng lp th
V mt ho hc lp th, phn ng SN2 l quay cu hnh v hp cht ban u
c tnh hot ng quang hc s i qua phc hot ho c trung tm chiral hay bt
i xng m khi thu phn s cho sn phm hot ng quang hc. Cu hnh ca
sn phm ngc vi cu hnh ca cht ban u, ngha l c s quay cu hnh, gi
l quay Valden.

Y
R1
Y

+ R2

(I)

R1

.... C.... X
R2

R1

Y-C

R2 + X
R3

R3

C- X
R1

R3

R2
(II) R3

X
....
C...
.
Y

R1
C-Y + X

R2
R3

V d: Khi tc dng NaI vi (S) 2 clobutan s thu c (R) 2- iotbutan

H
C
H3C

Cl

Na I

CH3COCH3

Na Cl
CH3
C2H5

C2H5

- ng hc phn ng
Phn ng SN2 l phn ng bc hai, song nu tc nhn Y va l dung mi th
c bc nht hay gi bc nht.
- nh hng ca dung mi

118

+ nh hng ca dung mi ti kh nng phn ng th hin hng s in

mi, trong cc dung mi phn cc solvat ho tt nhng trng thi c in tch
nh ch so snh gia cht ban u v trng thi chuyn.
+ nh hng ca dung mi rt phc tp, song cn ch rng vai tr quan
trng ca dung mi l solvat ho in hnh hay solvat ho c bit v solvat ho
khuch tn.
- Kh nng cnh tranh
+ SN1 SN2
V mt ho hc lp th: C ch SN1 thng cho sn phm raxemic ho cn
SN2 c s quay cu hnh do cu trc ca cht trung gian cacbocation v trng thi
chuyn phi tr 5, song thc t tnh ho hc lp th khng thu c nghim ngt
nh vy.
Hai phn ng trn ch l hai gii hn v c ch, s thay i gia hai c ch
ph thuc vo th tch nhm th trong cht ban u, hiu ng e ca nhm th, nht
l nh hng ca tc nhn Y v dung mi. Ni mt cch nghim ngt th khng c
s khc nhau gia 2 c ch v phn ng c th xy ra qua nhng c ch trung
gian ca hai c ch .
V d:
CH3
2 CH3

CH2

OH

SN2
H2SO4

CH2

E2
2 CH2

CH2

CH3

H2O

H2O

CH2

6.3.1.2.2. Phn ng th Electrophin - SE

a. Khi nim chung
Phn ng th electrophin SE xy ra do s tn cng ca tiu phn thiu
electron vo trung tm phn ng giu electron ca cht ban u.
S chung nh sau:

Cht ban u phi c trung tm c mt electron ln nh nhng hp cht

thm aren, hp cht cha no hoc hp cht no c hot ho bng nhng nhm
th cho electron.
Tc nhn electrophin l nhng tc nhn c obitan trng nh cc ion dng
hoc nhng hp cht c obitan cha cht y.
b. Phn loi
- SE1: Hp cht trung gian l cacbanion.

119

- SE2: Hp cht trung gian trng thi chuyn mang in tch dng.
Quan trng v ph bin l phn ng SE ca cc aren v ankan c trung tm
hot ho.
c. Nhn dng phn ng
- Cht phn ng: L nhng cht phi c trung tm c mt electron ln
nh nhng hp cht thm aren, hp cht cha no hoc hp cht no c hot ho
bng nhng nhm th cho electron.
- Tc nhn: L nhng tc nhn c obitan trng nh cc ion dng hoc
nhng hp cht c obitan cha cht y nh:

Hal : Hal

X:Y

Hal

NO2

HO

HO

SO3H

Hal

d. iu kin phn ng
- Phn ng xy ra nhit khng cao.
- Dung mi phn cc.
- Phn ng thng c xc tc ( thng l axit Liwis).
e. Vit c ch
Phn ng th SE vo hp cht no (Cacbon no)
Nhng hp cht c lin kt phn cc d dng chu s tn cng ca tc nhn
electrophin, in hnh l cc hp cht c kim, xy ra theo phn ng th SE. Chng
hn nh mt s phn ng sau:
CH3

Mg

C2H5

Hg

CH2

CH

Br

Br

C2H5
CH2

CH3

Br
HgCl2

Li

2 C2H5
HOH

MgBr2

Br

HgCl

CH2

CH

Phn ng c th xy ra theo c ch SE1 v SE2.

C ch SE1
- Vit c ch

V d:

120

Z
E

CH3

LiOH

CH2

CH

CH2

CH2

CH

CH2

CH2

CH

CH2

Li

HOH

CH2

CH2

Li
H

CH

CH

CH2

CH3

LiOH

Li

CH2

CH

CH3

- Bn cht ca cht phn ng

Phn ng ph thuc vo bn ca cacbanion. Cacbanion bn khi c nhm
th ht electron hoc c gii ta. Cacbanion to thnh c cu hnh phng hay
gn phng hoc hnh thp vi s nghch o cu hnh.

..

R
R'

Cu hnh cacbanion

C :

R''

C
H

H
S nghch o cacbanion

..
C

H
Cacbanion phng

- Bn cht dung mi
T cacbanion phng c th cho sn phm bo ton cu hnh, quay cu hnh
hay raxemic ho ph thuc ch yu vo dung mi.
+ i vi dung mi phn cc ln nh imetylsunfoxit th thu uc sn
phm raxemic ho.
+ i vi dung mi ion ho thp th cho sn phm u tin bo ton cu
hnh.
+ i vi cc dung mi phn cc axit yu nh etylenglycol, metanol th thu
c sn phm quay cu hnh.
- nh hng lp th
Ni chung, cacbanion c cu trc hnh thp to thnh khi d ly R Z, trong
trng hp chung, ho hc lp th ca trung tm phn ng c bo ton. So vi
SN1, giai on th hai y l s tn cng ca E+ v R- c th xy ra ba trng
hp ph thuc vo mi tng quan vi tc nghch o:
+ Phn ng xy ra nhanh hn tc nghch o hnh thp kp cacbanion,
sn phm c bo ton cu hnh.
+ Phn ng chm hn s nghch o, sn phm l quay cu hnh.
+ Phn ng xy ra cng tc vi s nghch o th thu c sn phm
raxemic hon ton hay mt phn.
- Sn phm

121

Trong p/ SE1 dn xut anlyl c th to ra sn phm chuyn v khi c t xc

tc axit- proton hoc axt Lewis hoc baz. S chuyn v ni i nhiu hp cht
cha no xy ra cho nhiu ng phn cha no, ng phn no bn v nhit ng s
chim u th:
V d:
CH3CH2CH
ArCH2CH

CH2 + H
+B

CH2

CH3CH

CH3CH2CHCH3

ArCH

CH

CH2

-BH

+BH
-B

ArCH

CHCH3
CHCH3

C ch SE2
- Vit c ch
C ch xy ra qua mt giai on theo c ch chung:

CH3

V d:
Mg

Br

CH3

Z
Br
Mg

Br

Br

Br

Br

CH3

E
CH3

Mg

Br

R
Br

CH3

Z
MgBr2

BrH

MgBr

- Bn cht ca cht phn ng v tc nhn

+ Ty thuc mc kh khn lp th v mc n nh trng thi chuyn
tip thiu electron.
V d: Kho st phn ng: R4Sn + HaI2
R3SnHal + Rhal
Tc phn ng theo th t sau: CH3 > CH3CH2 > (CH3)2CH > (CH3)3C
Do nh hng ca hiu ng khng gian.
+ Trong cc dung mi t phn cc hn (clobenzen, tetraclocacbon,) trt
t v kh nng phn ng li khc: CH3 < CH3CH2 < (CH3)2CH. C th do c hai
hiu ng cm v khng gian cng tc dng.
+ Trong phn ng SE2, tc nhn electrophin c obitan trng tn cng vo
obitan b chim cao ca cht ban u, ngha l cht ban u bt buc phi c
obitan cht y kt hp vi obitan trng. iu lm cho s tn cng din
thun li hn lin kt C Z, do bo ton cu hnh m khng nghch o cu
hnh nh SN2.
+ Trong trng thi chuyn SE2, nguyn t cacbon trung tm phn ng bo
ton cu hnh t din sp3.
- nh hng lp th

122

+ Tc nhn electrophin c obitan trng tn cng vo obitan b chim cao

ca cht ban u, ngha l cht ban u bt buc phi c obitan cht y kt
hp vi obitan trng. iu lm cho s tn cng din thun li hn lin kt C
Z, do bo ton cu hnh m khng nghch o cu hnh nh SN2.
+ Trong trng thi chuyn SE2, nguyn t cacbon trung tm phn ng bo
ton cu hnh t din sp3.
V d:
C6H5
H

C6H5
B(OC4H2)2

HgCl2

C6H5

CH3
R(-)

HgCl

Br2

CH3
R(+)

Br

CH3
R(+)

Phn ng th electrophin hp cht thm

C ch: Phn ng xy ra qua mt giai on v c hnh thnh mt s
hp cht trung gian.
H
X

X
H+

X
X

Phc

Phc

Phn ng th electrophin hp cht thm xy ra qua 1 giai on v hnh

thnh mt s hp cht trung gian l phc v phc .
Gin nng lng ca SE

Cht u
Sn phm

123

To phn ng

- Phc : Khi tc nhn electrophin tc dng vi nhn benzen trc ht to

c phc nh l mt tiu phn trung gian khng bn. Trong phc ny, h
electron ca nhn thm vn bo ton. Tc to thnh v phn hu phc ny xy
ra rt nhanh. S to thnh phc ny thc t khng nh hng ti tc phn ng
cng nh bn cht ca sn phm to thnh.
- Phc hay ion benzoni l hp cht trung gian mang in tch dng tp
trung trong nhn thm v gii to gia vi nguyn t. S hnh thnh phc ny c
s thay i trng thi lai ho t Csp3 sang Csp2 nn ph hu tnh thm ca nhn
benzen. Do giai on ny l thu nhit. Qua nghin cu thy c tnh tng quan
gia tc th v tnh n nh ca phc hay ni cch khc tnh bn ca phc
ny quyt nh tc ca phn ng SE.
- nh hng ca cu trc cht ban u n kh nng phn ng
V kh nng phn ng, mt electron ni chung trong nhn benzen cng
ln th tc dng ca X+ cng d. Do , cc nhm th c hiu ng +I, +C lm tng
kh nng phn ng, cc nhm th -I, -C lm gim kh nng phn ng.
- S nh hng ca nhm th
Th mt ln:

( Mi tn ch th mt ln vo cc v tr )
Th ln 2:
Nhm th trong nhn benzen gy ra s phn b mt electron cc v tr
cn li ca nhn: ortho, meta v para nn kh nng th ca tc nhn electrophin
tip theo vo cc v tr cng khc nhau nn gi l s nh hng ca nhm th.
Hm lng tng i ca sn phm th ortho, meta, para hay kh nng
nh hng ca nhm th c xc nh bng trng thi n nh ca phc cc
v tr khc nhau. Phc cng n nh, tc th cng ln v sn phm
chim u tin.
+ Cc nhm th c hiu ng +I nh cc gc ankyl R - nh hng th vo
v tr ortho v para.
+ Cc nhm th ch c hiu ng I u lm th ng ho nhn v nh
hng vo v tr meta.

124

+ Nhm th c hiu ng I v C lm b ng ho nhn v nh hng vo

meta.
+ Nhm th c hiu ng +C mnh nhng I yu nh OH, OR, NH2, NHR,
NR2, hot ho nhn v nh hng vo ortho v para.
+ Nhm th c hiu ng I mnh v +C nh F, Cl, Br, l b ng ho
nhn nhng nh hng vo ortho v para. Trong trng hp ny, cc halogen c
hiu ng I mnh hn +C nhiu trng thi tnh.
Khi vng benzen c hai nhm th, s nh hng ca nhm th th ba ph
thuc vo c hai nhm th. C cc trng hp sau:
+ Nu hai nhm th u hot ho nhn, nhm th hot ho mnh nht
khng ch s nh hng:
CH3

CH3

CH3
Cl

Cl2
>>>
Cl
NH2

NH2

NH2

+ Nu mt nhm th hot ho cn mt b ng ho th nhm th hot ho

quyt nh hng th ca tc nhn th ba:
OH

OH
Br
Br2

NO2

NO2

+ Nu c hai nhm th v tr meta vi nhau, hng th th ba khng

tn cng vo v tr gia hai nhm th v hiu ng lp th khng ph thuc vo
nh hng nh hng ca hai nhm th.
Nh vy trong SE c sn phm th 1 ln, 2 ln, nhiu ln.
- T l ng phn ortho para: T l ny ph thuc vo hiu ng lp th v
c hiu ng electron.
+ Khi tng th tch nhm th, t l ng phn ortho cng gim.
+ Khi a nhm th cho electron vo tc nhn cng gim xc sut ortho.

125

+ Trong trng hp nhm th c hiu ng C nh NO2, CN, ng phn

ortho to thnh khng ln. Nhng khi nitro ho th lng ng phn ortho li ln
hn ng phn para.
- Tc nhn eletrophin
+ Tc nhn X+ l axit Lewis, ngha l thiu e, c nh hng ti tc phn
ng cng nh t l ng phn.
+ Nu X+ l axit yu, ngha l s thiu ht electron nguyn t tc nhn
cng nh, s khc nhau v tc ca tc nhn vi benzen v dn xut th cng
ln.
+ Nu X+ l axit mnh th bn thn n c nng lng cao cn thit cho
phn ng, khng hay t i hi s chuyn e t nhm th ti trung tm phn ng.
+ Tc nhn c s la chn cht ban u.
+ Tc nhn cng nh hng ti sn phm th cc v tr khc nhau trong
phn t cht ban u.
+ Tc nhn giu nng lng s to thnh lng ortho v para ln hn khi
c nhm th u tin nh hng meta v lng ln meta khi c nhm th u tin
ortho para.
+ Tc nhn ngho nng lng hn th t l sn phm ph thuc vo bn
cht ca nhm th theo quy tc chung.
+ Electrophin c tnh chn la cao vi cht ban u thng cho t l sn
phm ortho/para khng cao v lng meta nh. Electrophin khng chn la, c
kh nng phn ng cao, c khuynh hng xut hin tnh chn la thp vi cht
ban u cng nh la v tr.
- nh hng ca dung mi v xc tc
+ Dung mi nh hng n tc phn ng cng nh hm lng ng
phn.
+ Khi dng xc tc th dung mi c nh hng ti tc tuy khng nhiu
nhng khng c nh hng ti hm lng cc ng phn. Phn ng SE vo nhn
thng dng xc tc Friedel Crafts c kh nng to phc cho nhn.
6.3.1.2.3. Phn ng th theo c ch gc SR
a. Khi nim chung
Nt c trng ca cc hp cht no, c bit hyrocacbon no, l tham gia
phn ng th theo c ch gc SR, trong nguyn t hyro nh vo cacbon no
c thay th bng halogen hay mt nhm nguyn t khc. Quan trng hn c l
phn ng halogen ho theo c ch gc. Ngoi ra cn c nhng phn ng th khc
cng theo c ch SR nh nitro ho, sunfoclo ho, t oxy ho, v.v.
S cc phn ng theo c ch gc t do SR:

RX

XY

XY: Hal2, SO2Cl2, R3C OCl, CCl3Br,.

126

HY

Phn ng xy ra khi c chiu sng hoc c cht khi mo.

b. Nhn dng phn ng
- Cht phn ng: L cacbon lai ho sp3 ( hidrocacbon no).
- Tc nhn: Phi l gc t do.
c. iu kin phn ng
- Phn ng xy ra nng lng cao (un nng, askt, n chiu).
- Xc tc: Thng dng cc loi peoxit.
- Dung mi: Khng phn cc nh ete, CCl4, CS2, xiclo hexan
d. Vit c ch
- C ch: 3 giai on
V d: Phn ng gia ankan v clo:
+ Giai on khi mo
h

Giai on hnh thnh gc trung gian phn ng X. l giai on khi mo. S

to thanh gc t do bng cht kch thch, nhit hay quang ho hoc bng phn ng
oxi ho kh.
+ Giai on pht trin mch

XH

H
X

(1)
n ln

(2)

Giai on ny c nng lng hot ho nh, mi gc to thnh trong phn

ng kch thch gy ra s chuyn ho nhiu phn t, do tc kch thch c th
nh nhng tc pht trin mch rt ln. Phn ng chui c trng bng chiu di
mch tng ng vi s giai on pht trin mch lp li nhiu ln cho mt giai
on khi mo. Tc giai on ny xc nh tc chung ca phn ng cng
nh tnh chn lc ca phn ng th.
+ Tt mch
R

127

Phn ng tt mch lm mt trung tm gc cn thit cho s pht trin mch,

nn giai on tt mch cng ln th chiu di mch cng nh.
Phn ng tt mch c th thc hin bng tng tc ca hai gc t do gi l
t hp, hoc bng chuyn hidro gia hai gc to thnh hp cht no v cha no,
gi l s chuyn khng cn i. Ni chung tr thnh phn t trung ho cn hai
gc t do.
- nh hng ca cht ban u
+ H lin kt vi gc benzyl c kh nng phn ng cao hn H lin kt vi
gc ankyl.
+ H lin kt vi cacbon c bc cng cao th kh nng phn ng cng mnh.
HCI < H CII < H CIII (ngoi ra cn do: bc ca cacbon cng cao, nng lng
phn li ca lin kt C H cng nh)

< H3C

CH3

<

H3C

<

H3C

CH3

CH3

+ Nu gi ri l kh nng phn ng tng i ca nguyn t H cacbon bc

i, ta c bng s liu sau:
halogen
flo
clo
clo
brom

Nhit (oC)
25
27
100
127

rI

rII

rIII

1
1
1
1

1,2
3,9
4,3
82

1,4
5,1
7,0
1600

+ Khi bc ca cacbon nh nhau, H cng gn nhm th ht electron, kh

nng phn ng SR cng gim.
V d:
CH3 CH2 CH2 CH2 Cl
ri: 1
3,7 2,1 0,8

CH3 CH2 CH2 COOH

1
3,1 0,24

+ V tnh ton: Phn ng SR to ra hn hp sn phm vi s thay th H

cc cacbon khc nhau:

128

rn
i i
100 %
rni i

ai %

ai: % cc ng phn

ri : kh nng phn ng tng i ca H C bc i.

ni: s H cacbon bc i.

Cl CH2 CH2 CH

CH3 (A)

CH3
CH3
CH3

CH3

CH2 CH

Cl2

CH

Cl

CH3

CH2

Cl
C CH3

CH3
CH3

CH3

CH

(B)

(C)

CH3
CH3 CH2 CH CH2 Cl (D)
CH3

1.3
100 % = 13,70%
1.3 3,9.2 5,1.1 1.6
3,9.2
%(B) =
100 %= 35,62%
1.3 3,9.2 5,1.1 1.6

%(A) =

%(C) =

5,1.1
100 % = 23,29%
1.3 3,9.2 5,1.1 1.6

%(D) =

1.6
100 % = 27,39%
1.3 3,9.2 5,1.1 1.6

+ Phn ng th theo c ch gc SR l phn ng to ra mt hn hp sn

phm th nhiu ln: sn phm th 1, 2, 3, ln ngay c khi s mol hirocacbon
nhiu hn halogen.
CH4
CH3Cl

+
+

Cl2
Cl2

129

CH3Cl + HCl
CH2Cl2 + HCl

CH2Cl2
CHCl3

+
+

Cl2
Cl2

CHCl3
CCl4

+
+

HCl
HCl

- nh hng ca tc nhn phn ng

+ Flo thng tc dng rt mnh lit to ra sn phm hu (HF, C). Trong
nhng iu kin tht m du nh pha long tng kh bng CF2Cl2 hoc nit
trong ti hoc thc hin phn ng nhit thp 800C, ngi ta cng ch thu
c dn xut pliflo.
+ Iot rt km hot ng, phn ng it ho thu nhit, thun nghch (phn ng
nghch d hn), cho nn mun phn ng xy ra phi dng HIO3 oxi ho HI sinh
ra.
+ Clo v brom c hot ng va phi. Phn ng clo ho v brom ho
xy ra tng i du dng v m du (nu chiu sng mnh hoc t , clo s tham
gia phn ng hu). C hai iu ng ch :
Kh nng phn ng ca brom km hn clo. Brom tc dng rt chm vi
CH4, kh phn ng vi (CH3)4C v khng phn ng vi C6H5C(CH3)3.
Tnh chn lc ca brom cao hn clo. Khi brom ho hu nh ch to ra dn
xut bc cao.
- nh hng lp th
Giai on quyt nh cu hnh ca sn phm l (2) trong giai on pht
trin mch. V R. c cu trc phng hay gn phng nn X2 tn cng R. t hai pha
vi xc sut gn nh nhau. Nh vy, phn ng SR dn ti s raxemic ho. iu
ny c thc nghim xc nhn.
- nh hng ca dung mi
Phn ng gc t nhy vi tnh phn cc ca dung mi. Tnh chn lc ca
phn ng ln khi dng dung mi cso kh nng to phc vi gc t do, nht l
tnh chn lc tng khi dng dung mi thm.
6.3.2. Phn ng tch
6.3.2.1. nh ngha
Phn ng tch E l qu trnh i ra khi phn t cht ban u ng thi hai
nguyn t hay hai nhm nguyn t.
6.3.2.2. Phn loi
- Phn ng tch halogenua hydro (hyrohalogen ho) cc dn xut
halogen nh tc dng ca baz

RCH2

CH2

Hal

RO

RCH

CH2

- Phn ng tch nc (ehydrat ho ) cc ancol nh tc dng ca axit

130

HHal

RCH2

CH2

OH

- Nhit phn hydroxyt tetraalkylamoni

t0
RCH2
CH2
NR3
HO

RCH

RCH

- Nhit phn cc axetat v xantogenat ankyl

t0
RCH2
RCH
CH2
OCOCH3
0
t
RCH2
RCH
CH2
OCSSR'

CH2

CH2

HOH

H2 O

NR3

CH2

CH3COOH

CH2

COS

R'SH

Cc phn ng tch ni trn c th theo hai loi c ch. Loi th nht

thng xy ra trong dung dch, bao gm cc c ch E2, E1 v E1cb. Loi th hai
thng xut hin khi nhit phn tng kh, bao gm c ch Ei v mt vi c ch
khc na.
6.3.2.3. Nhn dng phn ng
- Cht phn ng: R X
- Tc nhn phn ng: Tch hp cht no th dng tc nhn i lp tnh cht
ca hp cht ( Dng baz tch axit v ngc li).
6.3.2.4. iu kin phn ng
- Nhit cao
- Dung mi phn cc
- Phn ng thng c xc tc.
6.3.2.5. Vit c ch
6.3.2.5.1. C ch E1
a. C ch
Tng t SN1, E1 l phn ng hai giai on, sn phm trung gian l R+.
Nu khng ghi vai tr rt quan trng ca dung mi ta c s :

131

ChmX

Nhanh

Nhanh

V d:

- Br
(CH3)3C

(CH3)3CBr

H2 O

(CH3)2C

CH2

-H3O

b. Nhn xt
- C ch tch n phn t E1 tng t c ch SN1 v giai on chm to ra
cacbocation, nhng giai on sau th khc v hng ca phn ng. Trong phn
ng E1, cacbocation tch prton to ra sn phm cha no. Phn ng xy ra theo
hng nhm X b tch ra cng vi nguyn t -hidro cacbon bc cao nht v
to ra ni i c nhiu nhm th nht (qui tc Zaixep), ngha l to ra cacbocation
bn.
- Cu trc cacbocation ca cht phn ng, tc nhn:
+ Tc phn ng ph thuc vo bn ca cacbocation. Cacbocation
cng bn, tc phn ng cng cao.
Nhm th c hiu ng +I, +C v tr i vi trung tm phn ng lm n
nh cacbocation, lm tng tc phn ng:
(CH3)3CBr > (CH3)2CHBr > CH3CH2Br > CH3Br
(C6H5)3CBr > (C6H5)2CHBr > C 6H5CH2Br > CH3Br
Nh vy phn ng xy ra d dng vi dn xut bc ba hnh thnh
cacbocation bc ba.
+ Phn ng tch E1 thng dng cho cc hp cht ancol trong mi trng
axit mnh tng hp anken qua cacbocation hn l cc dn xut halogen hay
sunfonat cho hn hp sn phm phc tp:
OH

H3PO4

H 2O
85%

132

+ Tc nhn: khng c tnh baz hoc baz rt yu thun li cho E1.

- nh hng ca nhm i ra: Tc phn ng tch ph thuc vo bn
lin kt C X. Lin kt cng km bn, phn ng xy ra cng d. Tc phn ng:
RF

<< R Cl < R Br < R I

- ng hc ca phn ng: Phn ng E1 l phn ng bc 1 v vn tc ca

phn ng ch ph thuc nng ca cht phn ng ch khng ph thuc vo nng
tc nhn nucleophin.
- nh hng lp th
V phng din ho hc lp th, cc phn ng E1 trong dung dch khng
c tnh c th nh phn ng E2, v cacbocation trung gian sinh ra c cu trc
phng, do s tch khng ph thuc vo cu hnh ca phn t ban u. Tuy vy
nu nhm X cha ri khi nguyn t C mang in dng mt khong cch xa
m xy ra s tch proton hoc nu trong phn ng ch to ra nhng cp ion
trung gian, th s tch theo kiu trans s chim u th hn.
V d: Trong thc t, nhng iu kin ca phn ng E1, t hai ng phn
cis v trans ca 1-metyl-2-cloxyclohexan u to ra 1-metylxyclohexen l chnh,
cng vi 3-metylxyclohexen, nhng t ng phn cis ( tch kiu trans) t l 1metylxclohexen cao hn:
H

CH3

H
CH3
CH3
H

1-Metylxyclohexen

CIS- Cl H

CH3
H Cl
TRANS-

CH3
3-Metylxiclohexen

- S chuyn v
Phn ng E1 cn c s chuyn v ca cacbocation nh SN1, biu hin
trong nhng phn ng xc tc axit. Chng hn, phn ng tch ca 3 metyl 2
butanol khng phi cho 2 m 3 sn phm:

133

CH3

CH3

CH3

CH3

CH3

CH3

OH

CH3

3-metyl-2-butanol

CH3

CH3
CH2

2-metyl-2-buten

CH2

3-metyl-1-buten

2-metyl-1-buten

Bi v c qu trnh chuyn v hidrua t cation bc 2 ti bc 3:

CH3
CH3

CH3
C

CH3

CH3

H
H
Cation 3-metyl-2-butyl

H
C

CH3

H
cation 2-metyl-2-butyl

Theo c ch chung sau:

CH3 OH
CH3

CH3 H
CH3

CH3

H
H
3-metyl-2-butanol

OH2

CH3

- H2O
CH3 H
CH3

C
H

134

CH3

CH3

CH3 H

CH3 H

CH3

- Ha
CH3

CH2

Hb

CH3

CH3 H
- Hb

Ha
3-metyl-2-butanol

CH3

CH2

H
CH3 H

Hx

CH2

CH3

- Hy

CH3

CH3

CH3

CH3
- Hx

Hy

CH2

C
CH2CH3

6.3.2.5.2. C ch E2
a. C ch
-

YH

C
C
H
Trng thi chuyn tip

y:
- X c th l F, Cl, Br, I, OSO2R,.
- Y- l mt anion hay phn t trung ho vi cp electron cha s dng (
baz) nh OH-, C2H5O-, C6H5O-, NR3,
V d:
Phn ng tch HBr t bromua nh tc dng ca etylat natri trong etanol:

135

Br

H
C
H3C H

Br

C
H

H3C H

H
C

H3C

BrH

C2H5OH

C2H5O

b. Nhn xt
- C ch phn ng tch nucleophin lng phn t E2 c nhng nt tng t
c ch phn ng SN2 v cng l phn ng mt giai on v i qua phc hot ng
( trng thi chuyn tip).
Khc vi phn ng SN2, trong phn ng E2, phc hot ng sinh ra do
tng tc gia tc nhn Y- v nguyn t - hydro trong phn t cht phn ng,
phn ng ny tch prton cng vi Y- v nhm X, ng thi to sn phm cha
no.
- nh hng ca cht ban u
+ Phn ng E2 l ng b, giai on quyt nh tc xy ra s phn ct
lin kt C H v C Z ng thi.
+ Trong phn ng tch ca cc ankylhalogenua, tnh cacbanion nh, nn
a thm nhm ankyl vo C hay C u lm tng tc phn ng.
+ Kh nng phn ng ca cht u cng ph thuc vo bn cht ca nhm
i ra. Nhm i ra dng anion cng n nh th tc E2 tng, ngha l nhng
nhm th ht electron trong nhm i ra s lm tng tc phn ng.
+ Trong thc nghim vn tc phn ng E2 ca cc halogenua ankyl bc 1
RCH2CH2Br ph thuc vo bn cht ca nhm th R v tr theo th t
CH3 > CH3CH2 > CH3CH2CH2 > H
+ Khi a mt nhm ankyl vo v tr hoc ca halogenua ankyl bc 2
hoc bc 3 ta cng thy vn tc phn ng E2 tng ln.
- nh hng ca tc nhn nucleophin
Phn ng E2 t l vi nng ca baz trong phng trnh tc , mt
khc E2 cng rt nhy vi tnh baz ca tc nhn. Tnh baz ca tc nhn ln, tc
phn ng cng tng. V thy rng trong phn ng E2 cn dng baz mnh hay
dng tc nhn KOH/C2H5OH.
- ng hc ca phn ng
Phn ng E2 l phn ng bc 2 v vn tc phn ng thng ph thuc c
hai thnh phn tham gia phn ng.

136

- nh hng ca dung mi: Dung mi cng phn cc th lm gim tc

phn ng.
- nh hng lp th
+ V mt l thuyt, nhm X c th b tch ra cng nguyn t - hydro
cng pha ( tch kiu cis hay l kiu syn) hoc khc pha vi n ( tch kiu trans
hay l kiu anti).

X
C

X
C

C
X

Hp cht cha no

Hp cht no

TCH KIU CIS

Hp cht cha no

H
Hp cht no

TCH KIU TRANS

- Thc t chng t phn ng E2 xy ra theo kiu trans. Tnh c th lp th

ny c nhiu nguyn nhn:
+ Mt l, nu so snh nng lng ca cc trng thi chuyn tip th trng
thi ng vi s tch kiu trans n nh hn trng thi ng vi s tch kiu cis, v
khng c s y nhau gia cc nhm CHY v CX
+ Hai l, s to thnh cc obitan s thun li hnnu phn ng tch xy
ra theo kiu trans.
Ta c th pht biu mt qui lut chung nh sau: S tch lng phn t E2
ch xy ra d dng khi no mt trung tm tham gia phn ng ( H C C X )
nm trong mt mt phng, ngha l cc nhm b tch v tr trans (hay anti) i
vi nhau.
- Phn ng E2 cc hp cht vng cng chy theo kiu trans.
- Tuy nhin, quy lut tch kiu trans ch p dng c cho cc hnh th (cu
dng) c nhng nhm b tch v tr trans kiu trc. Cc hnh th trans (e,e) c
nhng nhm b tch v tr bin khng tham gia phn ng tch lng phn t, v
bn trung tm H C C X khng nm trong mt mt phng. Cc ng phn cis
(a,e) hoc (e,a) ch phn ng rt chm hoc khng phn ng.
- S cnh tranh E1 v E2
+ E1: u tin tch cacbon bc cao nht v to ra ni i c nhiu nhm
th nht. ( Tch theo qui tc Zaixep).
V d:

137

CH3

CH

CH2

CH3

KOH/C2H5OH

CH2

CH

CH2

CH3

E1

Cl

+ E2: Trong phn ng E2, nu X khng mang in dng v khng c n

ng khng gian ( Cl, Br) th s tch ra cng vi H C bc cao nht ( Quy tc
Zaixep), nu X mang in tch dng v km hot ng hoc rt cng knh (+NR3,
+
SR2) th s tch cacbon bc thp.( Tch theo qui tc hpman). Nh vy, quy
tc Hpman ngc vi quy tc Zaixep v ch yu p dng cho phn ng E2.
V d:

(CH3)2CH

CH

CH3

HO

(CH3)2CHCH

CH2

NMe3
6.3.3. Phn ng cng(A)
6.3.3.1. nh ngha
L phn ng trong 2 phn t (hoc ion) kt hp vi nhau thnh 1 phn
t (hoc ion) mi.
6.3.3.2. Phn loi
6.3.3.2.1. Da vo c im ca lin kt
- Phn ng cng cacbon-cacbon (C=C, CC)
- Phn ng cng cacbon-oxy (C=O)
6.3.3.2.2. Da vo hng bin i thnh phn cht phn ng v phn chia tc nhn
phn ng, ta c cc phn ng
- Phn ng cng electrophin
- Phn ng cng nucleophin
- Phn ng gc
6.3.3.3. Phn ng cng electrophin
6.3.3.3.1. Nhn dng phn ng
- Cht phn ng: L nhng hp cht cha no c cha lin kt bi, ch yu
l anken v ankin.
- Tc nhn: L nhng tiu phn c obitan trng dng cation hay phn t
trung ho.

Y: H, RO, Hal..
Y:X
X: - OH, Hal, - NH2....
138

6.3.3.3.2. iu kin phn ng

- Nhit khng cao
- Dung mi phn cc
- Xc tc: Axit Liwis
6.3.3.3.3. Vit c ch
a. C ch
Y

Y:X

Chm

Nhanh
Y
Y

Nhanh

V d

HOH

OH

b. Nhn xt
- Phn ng cng AE gm nhiu giai on, quyt nh tc chung ca phn
ng l giai on cng tiu phn mang in tch dng to thnh sn phm trung
gian R+. Trc khi to thnh R+ c th to thnh phc gia C = C vi XY. C
ch AE vo ni ba ni chung tng t c ch AE vo ni i.
- Tc : v = k [C=C][X Y] nn ng hc phn ng: phn ng bc 2.
- Gin nng lng nh sau:

E
R+

Cht u
Sn phm

139

To phn ng

- Kh nng phn ng ca cht phn ng

+ Cht phn ng c mt in t ca ni i (ni ba) ln th kh nng
phn ng cng cao.
+ Tc phn ng quyt nh giai on to ra cacbocation, nu R+ cng
bn th phn ng xy ra cng tt. Nh vy nhm th y e lin kt bi lm tng
kh nng phn ng AE, nhm ht e lm gim kh nng phn ng.
Ch :
(CH3)2C=CHCOOH
> trans CH3CH=CHCOOH

>
>

transC6H5CH=CHCOOH >
CH2=CHCOOH

CC< CH2=CH2 < C6H5CC-COOH < C6H5CH=CHCOOH

C v lin kt C=C ln n
S khc nhau v kh nng gia lin kt C
mc ngi ta c th brom ho chn lc ch ring ni i ca anken
V d:

CH2=CH-CH2-CCH + Br2 BrCH2-CHBr-CH2-CCH

Gii thch: Ankin kh tc dng vi tc nhn electrophin hn anken l v cc
e ni 3 c gi cht hn bi 2 nguyn t cacbon lai to sp ( CSP c m in
ln hn Csp2 ) v lin kt CC ngn hn lin kt C=C.
Ankin d tc dng vi tc nhn nucleophin hn.
- nh hng ca tc nhn
Tc nhn cng phn cc th kh nng tham gia phn ng cng tt.
V d:
HCl > HBr > CH3COOH > HOH
- Sn phm phn ng AE
+ Thc nghim cho thy phn ng AE to ra hn hp sn phm, ph hp
vi c ch nhiu giai on. Phn ng AE xy ra theo hng to cacbocation bn
vng hn ( Quy tc Maccpnhicop).
V d:

NaCl
CH2

CH2

Br2

Br

CH2

CH2

Br

Br

CH2

CH2

Cl

Br

CH2

CH2

ONO2

NaNO3

140

CH

H3 C
H3 C

CH

CH2

HOH

CH3

OH

Sn phm chnh

CH2

H3 C

Sn phm ph
- Trng hp khng tun theo qui tc Maccopnhicop:
+ CH2=CH-A : A l nhm ht e mnh (N+R3, CF3, )
V d:

CH3
OH

(CH3)3N+-CH=CH2 + HI (CH3)3N+ -CH2-CH2I

+ Hydrat ho gin tip: (qui tc Hopman) AE (BF3 electrophin)
(Hydrobo ho):
3RCH=CH2 + BF6

(RCH2CH2)3B

(Oxy ho):
RCH2CH2OH + H3BO3

(RCH2CH2)3B + H2O2

- nh hng lp th
+ Cc nguyn t lin kt bi vi nhau khng th quay t do quanh trc ni
gia hai nguyn t c. Nu nh s cng hp xy ra ng thi th phn ng phi
chy theo kiu cis ( kiu syn ) ngha l X v Y cng tn cng t mt pha nht
nh ca ni i:

Y
Y

X
C

Cng kiu cis

Cn nu nh XY cng khng ng thi th phn ng c th chy theo kiu

cis hay kiu trans ( kiu anti ):

141

X
X

Cng trans

C
Y

+ C nhiu d kin chng t s cng hp vo ni i (AE) ch yu xy ra

theo kiu trans, nht l khi to c cacbocation vng:
(Z) anken + XY cp i quang treo
(E) anken + XY cp i quang erytro
(E) anken i xng + Br2 (dung mi phn cc) ng phn meso
Gii thch: do proton dng phc (hoc ion protoni) lm n ng 1
pha ca ni i lm cho anion cn li ch c th tn cng pha cn li.
V d:

H
Br
H

COOH

H
COOH

(I)

COOH

Br Br

dmpc

COOH

COOH
H

axit maleic

Br
COOH

(II)
COOH

Br

COOH Br
H
COOH Br

H
H
Br

(1)

COOH Br

(1)

COOH(2)
(I)

H
Br
COOH
COOH

nhanh
(2)

HOOC
H

Br
Br

COOH H

Br

Br

H
COOH

142

Sn phm l cp i quang treo vi lng bng nhau nn l hn hp tiu

trin.
Tuy nhin cng c rt t trng hp xy ra kiu cis: hidrat ha gin tip cc
anken bng phn ng hidrobo ha, sau oxi ha sn phm triankylbo vi tc
nhn H2O2 c NaOH lm xc tc.
- S chuyn v
V d:
CH3

CH

CH2

CH

CH2

CH2

CH

CH3

HOH

CH3
CH3

CH
CH3

CH3

Thc t thu c t

OH

CH

CH

CH3

OH

CH3

CH

CH3
CH3

CH2

Thc t thu c nhiu

CH2

CH3

OH

Do c s chuyn v:
CH3

CH

CH2

CH

CH2

HOH

CH3
CH3

CH

CH2

CH

CH3

CH3

CH3

CH

CH

CH2

CH3

Chuyn v CH3

Chuyn v H

143

CH3

6.3.3.4. Phn ng cng nucleophin - AN

6.3.3.4.1. Nhn dng phn ng
- Cht phn ng
+

( O, N, ...)

L andehit, xeton, axit, dn xut, amin, nitrin. Cc lin kt C=C cng tham
gia phn ng ny khi phn t c nhm th ht electron mnh.
Tc nhn phn ng
X: H, RO, Hal..

+ -

Z:Y
Y: - OH, Hal, - NH2....

6.3.3.4.2. iu kin phn ng

- Nhit khng cao
- Dung mi phn cc
- Xc tc:
+ Axit: Xc tc cho cht phn ng
+ Baz: Xc tc cho tc nhn
6.3.3.4.3. Vit c ch
a. C ch: Phn ng lng phn t, hai giai on, sn phm trung gian l
mt oxanion.
Y

+ C
X

+ Z:Y

Chm

Y
X

Nhanh

V d:

HCN

C
OH

b. Nhn xt
144

CN

XZ

- nh hng cht phn ng:

+ Nhng hiu ng lm tng phn cc ca cht phn ng lm tng kh
nng phn ng v ngc li.
+ Kh nng phn ng ca nhm C=X s cng cao nu cacbon cng
ln v in tch m trng thi chuyn tip cng c gii to. Nh vy, nhm
th ht e ( CCl3, CF3,) lm tng kh nng phn ng, tri li nhm y e ( Me,
Et,..) lm gim kh nng phn ng.
V d:

HCH

>

CH3

CH

>

CH3

CH3

O
- nh hng ca tc nhn
Tc nhn cng phn cc th kh nng tham gia phn ng cng tt.
- nh hng ca xc tc
+ Xc tc bng baz: Baz lm gim kh nng tham gia phn ng ca cht
phn ng nhng lm tng kh nng phn ng ca tc nhn.
V d:
OR
HO

RO

ROH

OR
ROH

OH

+ Xc tc bng axit: Axit lm gim kh nng phn ng ca tc nhn nhng

lm tng kh nng phn ng ca cht phn ng.
V d:
C

OH

OHR

ROH

OR

-H

OH

OH

+ pH ti u
Kh nng phn ng
Tc nhn

Cht phn ng

pH ti u
145

pH

- nh hng lp th
+ Bnh thng phn ng cng XY vo R1R2C=O khng c tnh c th lp
th v s to ra bin th raxemic R1R2C(OX)Y. Tuy nhin nu nhm C=O ni vi
C* th s u tin to ra mt ng phn quang hc khng i quang no , theo
quy tc Cram: YX cng vo nhm C=O t pha t b n ng khng gian v ng vi
trng thi chuyn tip n nh hn. l hai sn phm ng phn ph thuc kch
thc cc nhm th trong hp cht cacbonyl v tc nhn.
R3

R3 R
R

R2

R3
R

+ ZY

R1
2

R O
1

Kch thc: R < R < R

R2

R1
OZ

V d:
C6H5

C6 H 5

H5C6 CH3

CH3
H

1. C6H5MgBr
2. H2O

C6 H 5

C6H5

CH3

+
H3 C

H3C O

H
OH
83%

H3C

H
OH
17%

- ng hc
Phn ng AN lng phn t, hai giai on. giai on to anion l giai on
chm quyt nh tc phn ng.
6.3.3.5. Phn ng cng gc - AR
6.3.3.5.1. Nhn dng phn ng
- Cht phn ng: Hp cht c lin kt bi C=C
- Tc nhn: XY: Cl2, HBr, HSCH3,.
6.3.3.5.2. iu kin phn ng
- Nhit cao, nh sng
- Dung mi khng phn cc
- Xc tc bng tc nhn to gc t do nh oxi, pexit
- Thc hin phn ng tng kh.

146

6.3.3.5.3. Vit c ch
a. C ch
Ba giai on
Giai on 1: Khi mo: To gc t do hot ng
R

O:O

2RO

RO

H : Br

Br

ROH

- Giai on 2: Pht trin mch

C

Br

Br

C
n ln

Br

HOR

Br

RO

Giai on 3: Tt mch

RO

RO

O:O

b. Nhn xt
- C ch cng AR (Cng hpman) tri vi quy tc cng Maccpnhicp. Nn
sn phm phn ng AR khc vi sn phm phn ng AE, tuy c hai phn ng u
din ra theo hng to sn phm trung gian tng i bn. C ch gc l c ch
dy chuyn.
- nh hng ca cht phn ng
+ Phn ng AR din ra theo hng to thnh gc t do trung gian tng i
bn.
+ Gc t do Y. tn cng vo v tr no thun li v mt e -.
+ Nu Y. c tnh e- nh Cl., Br., CF.,ta xp kh nng phn ng ca anken
theo th t gim vi CF3. nh sau:
Me2C=CHMe > (E)MeCH=CHMe > MeCH=CH2 > CH2=CH2 > CF2=CF2 (1)
+ Nu Y. c tnh nucleophin th trt t v kh nng phn ng s ngc li.
V d khi X. l CH3. th chiu ca (1) ngc li.
V d:
147

Br

CH3CH

CH3CHCH2Br

CH3CHCH2Br

CH2

>

CH3CH2CH2Br

H : Br

CH3CHBrCH2
Br

- nh hng ca tc nhn: Tc nhn ( gc t do X. ) tn cng vo v tr no

thun li v mt e-.
+ Nu X. c tnh e- nh Cl., Br., CF.,ta xp kh nng phn ng ca anken
theo th t gim vi CF3. nh sau:
Me2C = CHMe > (E) MeCH = CHMe > MeCH = CH2 > CH2 = CH2 > CF2 = CF2
+ Nu X c tnh nucleophin (v d CH3) th trt t v kh nng phn ng
ca dy trn s ngc li.
- Lp th ca phn ng: u tin cng theo kiu trans:

X
X

Cng trans

C
Y

148

6.4. Phn ng oxi ha kh

6.4.1. Khi nim chung
Trong phn ng v c, chng hn:
Na
+
Cl Na+
Cht kh
Cht oxi ho
(Cht b oxi ho) (Cht b kh)

Cl-

Qu trnh nhn electron l qu trnh oxi ho, qu trnh cho electron l qua
trnh kh.
Trong a s trng hp, phn ng oxi ho - kh l phn ng cn bng gia
dng oxi ho v kh. Hai dng ny t hp trong mt phng trnh chung gi l
phn ng oxi ho kh. Quan nim trn khng c dng rng ri trong ho hu c
v:
- Lin kt trong hp cht hu c l lin kt cng ho tr, t c kh nng
chuyn thnh ion.
- Kh o c s chuyn dch electron v cng kh gii thch cc gi tr o
c trong phn ng oxi ho - kh.
- Phn ng oxi ho - kh trong ho hc hu c lin quan cht ch vi c
ch ca phn ng, ngha l lin quan ti cc trng thi chuyn tip hoc cc hp
cht trung gian.
Tuy nhin, trong mt s h oxi - ho kh ca hu c, chng hn nh h
quinon, hidroquinon, bng phng php cc ph c th o v xc nh c cc i
tr ca qu trnh chuyn dch thun nghch .Trong ho hu c, ngi ta dng cc
khi nim khc l s oxi ho v bc oxi ho.
- S oxi ho: S oxi ho thng k hiu l n, l s in tch quy c khi gi
thit rng, phn t hu c gm nhng ion n gin kt hp vi nhau hay l in
tch xut hin nguyn t khi c s dch chuyn electron lin kt v pha nguyn
t c m in cao hn.
V d:
H-H
H-O-H
CH4
CO2

H c n =0
H c n = +1, O c n = -2
H c n = +1, C c n = -4
O c n = -2, C c n = +4

Nh vy, cacbon c th c s oxi ho t -4 n +4

-4
CH4

-3
RCH3

-2
-1
0
+1
+2
+3
+4
CH3OH RCH2OH HCHO RCHO HCOOH RCOOH CO2

- Bc oxi ho
149

+ Bc oxi ho ca C l s lin kt ca C nh vi oxi khi thu phn hay l

s nhm hidroxyl lin kt vi C khi thu phn hon ton:

CH3-Li
CH3-Cl
CH2Cl2
CH2O

HOH

CH3-H
CH3-OH
CH2(OH)2
CH2(OH)2

Bc oxi ho ca C l bc 0
Bc oxi ho ca C l bc 1
Bc oxi ho ca C l bc 2
Bc oxi ho ca C l bc 2

+ Bc oxi ho ca nguyn t C tng ng vi s lin kt ca C vi cc

nguyn t khc c m in ln hn H:
C-H
Bc 0
C-Z (Z: Cl, O, S, N) v C=C
Bc 1
CZ2, C=Z, C=C-Z, CC
Bc 2
CZ3, C=C-Z, C=C=Z, CC-Z, CZ Bc 3
CZ4, Z=C=Z, Z=CZ2, Z-CZ
Bc 4
- Phn ng oxi ho l qu trnh lm tng s oxi ho ca cht phn ng v
lm gim s oxi ho ca tc nhn phn ng. Phn ng kh l qu trnh ngc li.
6.4.2. Phn ng oxi ha
6.4.2.1. Khi nim: Qu trnh oxy ho l qu trnh lm tng s oxy ho cht
phn ng v lm gim s oxy ho tc nhn phn ng.
6.4.2.2. Tc nhn: O. (H2O2, KMnO4, KClO3), O2 (khng kh, bnh cha kh O2),
O3 (bnh cha), HIO4
6.4.2.3. Mt s phn ng v c ch
- Oxy ho lin kt ca Hyrocacbon
Ta bit rng nng lng phn ly cc lin kt trong phn t alkan thng
khng khc nhau nhiu, cho nn t c phng php oxy ho lm t mt cch
chn la hoc lin kt C C hoc lin kt C H m khng ng n phn t ni
chung. Tuy vy, nng lng phn ly ca cc lin kt C H bc ba hay cc v tr
alyl v benzyl yu hn cc lin kt khc mt cch r rt, do ta c th ch oxy
ho cc lin kt m phn cn li ca phn t vn c nguyn vn. Th d:
CH2 = CHCH3

O2

CuCl2

Propen
(CH3)2C - H
C 6H5
Cumen

O2

CH2 = CHCHO

Acrolein
(CH3)2C - OOH
C6H5
Hyopcoxylcumyl

150

(CH3)2CO + C6H5OH

C6H5CH3

(CH3CH)2O
CrO3

C6H5CHO

C6H5CH3

KMnO4

C6H5COOH

Phn ng oxy ho cc arylalkan bng Cr(VI) c nghin cu tng i

nhiu. Toluen b oxy ho thnh axit benzoic, iphenylmetan to ra benzophenon
cn triphenylmetan to ra triphenylcacbinol. Tc oxy ho ph thuc nhiu cu
to ca hyrocacbon. Trong trng hp oxy ho, nhm p metyl lm tng tc ,
cn nhm p nitr lm gim tc , hiu ng n c t hp tuyn tnh vi +,
= -1,4. Nu hai nguyn t hyro tham gia phn ng c thay bng teri, tc
phn ng s gim 6,4 ln, iu chng t rng tc phn ng xy ra s phn
cch lin kt C H. Tuy vy c ch ca giai on ny ni ring cng nh ton b
phn ng ni chung cn cha r rng.
Phn ng oxy ho nhm alkyl nhn thm bng pemanganat kali cng
thng to ra axit. Cc dn xut th nhn ca toluen b oxy ho to thnh axit
benzic tng ng. So vi CrIV th Mn VII thng oxy ho mnh hn.
Chng hn 2-5 ibrom-p-xylen b oxy ho c hai nhm metyl bi
penmanganat Kali, nhng ch oxy ho mt nhm myl bi axit crmic.
Bt k cht oxy ho l CrVI hay MnVII, phn ng oxy ho nhm alkyl vi
vng benzen thng xy ra v tr (to ra cc axit benzic tng ng). Tuy vy,
cn lu rng nhm alkyl bc 3 th d t- butyl rt kh b oxy ho v khng cn
nguyn t hyro.
- Oxy ho lin kt ca hyrocacbon
+ zn phn

C = C

O3

O O
C

Zn
AcOH

C = O + O = C

Hp cht c ni i C = C tc dng vi ozon sinh ra ozonit. C th phn

lp c ozonit, nhng ngi ta thng em phn hu n bng cch kh thnh hai
phn t hp cht cacbonyl. Cng c th kh ozonit thnh hai phn t alcol (tc
dng ca LiAlH4) hoc oxy ho thnh xton v cacboxylic (tc dng ca H2O2).
C ch ca giai on to thnh ozonit c th nh sau:

151

O3

C = C

C - C

O (+)

Alken

O (-)

O
C = C
O O

(+)

O3

O =

O
(-)
(III) O

Ozonit

(IV)

Nu qu thc c to ra sn phm trung gian III v Iv nh nu s

trn th III c th ime ho
(+)

(-)

C
O

(-)

(+)

(III)

C
(V)

hoc chuyn ho thnh hyropeoxyt.

Trong mt s trng hp, th d ozon ho (CH3)2C=C(CH3)2, ngi ta
tch c sn phm V, v nu c ozon ho trong metanol c th phn lp c
hyropeoxyt:
(CH3)2C -

OCH3

O - OH

Mt dn chng na v c ch ozon ho trn l s to thnh cc sn phm

cho: theo c ch nu xut pht t mt alken khng i xng RCH = CHR ta
phi c 3 ozonit khc nhau:
O
RCH
O

CHR
O

O
RCH

CHR'
O

152

R'CH
O

CHR'
O

Trong thc t, khi ozon ho nhng hp cht nh pent-2-en, hex-2-en, oleat

metylngi ta phn lp c c ba loi ozonit trn cc dng ng phn cistrans tng ng.
Cc hp cht c ni ba C C v hp cht thm b zn ho kh hn alken.
+ ihyroxy ho:
C = C

OH

OH

Mun cng hai nhm OH vo ni i (ihyroxy ho) c th dng OsO4

hoc KmnO4 trong mi trng kim. l nhng phn ng cng theo kiu cis.
Khi dng cht oxy ho l OsO4 c ch phn ng nh sau:
C ==C

HOH

OH OH

OsO2
(I)

Ngi ta phn lp c este vng trung gian I.

Khi dng KMnO4 trong mi trng kim, ta c c ch:
C

C
+

O
(-) H O
MnO4 2

(-)
MnO4

(MnVII)
(-)

H2MnO4

C
C

OH
OH

(-)

+ MnO4
(MnVII)

(MnVII)
(-)

MnO4

MnO42-

(MnV)

(MnV)

C = C

MnO2
(MnV)

Hin nay, tuy cha phn lp c este vng MnV nhng c chng c
khc v c ch trn, c th l khi dng Mn18O(-)4 ngi ta thu c:
H18 O - C - C - 18OH

153

Ngoi ra, chng minh rng phn ng chy theo kiu cis, ngi ta
ihyroxy ho axit d,l-tactric, ng nh d on theo c ch trn.
Mun trans-ihyroxy ho ni i C=C ngi ta dng H2O2 v axit fomic.
Trong trng hp ny, axit pefomic sinh ra t H2O2 v axit fomic poxy ho ni
i theo kiu cng cis, sau pxit sinh ra s b thu phn theo c ch SN2 vi
s quay cu hnh, kt qu xt ton b th phn ng chy theo kiu trans:

H - C - OH + H2O2

H - C - O - OH + H2O
O

Epoxy ho:
O
C

H
C

C
O +

HO

Thu phn:
OH2
(+)

O
C

OH

O - H

H2 O

-H (+)

C
HO

HO

Do c tnh cng trans ca phn ng, khi cho H2O2 v HCOOH tc dng
vi xyclohexen ta c trans-1,2-xyclohexandiol
HCOOH
H2 O2

+ Oxy ho ct mch:

154

H 2O
(+)
H

OH

OH

- C = C -

- C = O + O = C -

H H
- C = C -

OH
OH
- C = O + O = C -

H
- C = C -

OH
- C = O + O = C -

Ni i C=C c th b oxy ho ct mch theo cc s trn nh tc dng

ca nhiu cht oxy ho khc nhau, ph bin l cc cht oxy ho pemanganat v
bicromat trng mi trng axit.
C ch phn ng cn cha c r rng, cng c th trong phn ng
sinh ra nhng sn phm trung gian l glycol hoc este ca n.
Ni ba CC thng kh b oxy ho hn ni i. Axtylen b oxy ho bng
pemanganat kali to thnh mt hn hp sn phm trong c axit oxalic.
Vng thm cng c th b oxy ho t mch bi cc cht oxy ho mnh.
Khi oxy ho benzen v naphtalen bng V2O5 ta c ln lt anhydrit maleic v
anhydrit phtalic.
- Oxy ho alcol
+ Oxy ho mnalcol thnh hp cht cacbonyl
CHOH

= O

S oxy ho cc alcol bc mt v bc hai bng pemanganat kali xy ra rt

chm trong dung dch trung tnh, nhng thng li rt nhanh trong dung dch baz
v axit mnh.
Kho st phn ng oxy ho (C6H5)2CHOH trong dung dch trung tnh v
baz, ngi ta thy: V = k [alcol][MnO4-][OH-] hiu ng ng v 250C khi oxy
ho (C6H5)2CDOH c gi tr bng 6,6; benzophenon sinh ra khng cha oxy t
pemanganat kali. T cc d kin ngi ta ngh c ch phn ng nh sau:
(-)

(C6H5)2CHOH
(-)

(-)

(C6H5)2CHO
2-

HMnO4

(-)

+ HO

+ MnO4
(-)

+ MnO4

(-)

+ HO

(C6H5)2CHO

chm
nhanh

(C6H5)2C = O
2-

2MnO4

+ H2O
2-

+ HMnO4

+ H2O

Kho st phn ng oxy ho alcol isopropylic bng axit cromic ngi ta thy
tc phn ng trong dung dch axit axetic ln hn trong dung dch axit v c vi
cng gi tr v H0; khi thay th nguyn t -hydro bng teri 25 0C tc gim
6,6 ln, trong khi thay th cc nguyn t - hydro bng teri hu nh khng
lm thay i tc phn ng:
155

(CH 3)2 CH - OH
Tc :

(CH 3)2 CDOH

1,0

(CD 3)2 CHOH

0,16

1,0

T cc d kin ngi ta ngh c ch phn ng nh sau:

(-)

(CH3)2 CHOH + HCrO4 + 2H

(+)

(+)

(CH3)2CHOCrO3H2 + H2O

VL

(Cr )
(+)

CH3

CH3

O - CrO3H2

(+)

C = O + BH

C
CH3

(CrIV)

CH3

(+)

+ HCrO3

:B
(+)

Sau :

3Cr

IV

IV

Cr

III

+ 2Cr

Hoc:
IV

IV

+ 2CrV

3Cr + Cr
V

Cr

+ (CH3)2CHOH

III

-H

(+)

Cr

+ (CH3)2 C = O

+ Oxy ho ct mch 1,2 iol

Cc 1,2 iol c c tnh khc v monoalcol ch chng b oxy ho bi
axit peioic v tetraxetat ch lm t lin kt
- COH - COH - C - OH

HIO4 hoc
Pb(CH3COO)4

C - OH

- C - OH
+
C - OH

Khi oxy ho bng HIO4 phn ng i qua mt este vng trung gian:

156

- C - OH

- C - O

- C - OH

IO3H

+ HIO4

C - OH

C- O

C - OH

+ HIO3

Nhng th nghim dng 18O cho thy rng nguyn t oxy cacbonyl sn
phm cng chnh l nguyn t oxy glycol.
C ch to este vng trung gian ca phn ng trn c xc nhn bng
cc d kin ng hc v quang ph, dn chng c bit l cc glycol vi hai nhm
trans-OH th d trans-9,10-ecaliniol khng phn ng vi axit peioic.
OH
+

HIO4

OH

Khi oxy ho 1,2 -iolbng Pb (CH3COO)4 ngi ta cng c nhiu d kin

cho thy phn ng xy ra theo c ch vng. Th d phn ng c bc mt ni i
vi mi cht phn ng gim i, cis-iol b oxy ho nhanh hn trans-iol tng
ngC ch vng nh sau:
- C - OH

- C - O
+ Pb ( CH3COO)4

C - OH

-2CH3COOH

C- O

Pb(CH3COO)2

Pb(CH3COO)2

- C - OH
+
C - OH

Tuy nhin, c mt s trans-1,2-iol li d phn ng hn dng cis tng

ng. V d trng hp 9,10 ihyrophenantren-9,10 -iol dng trans phn ng
nhanh hn dng cis 9,4 ln, trans 9,10 ecaliniol khng phn ng vi HIO4
nhng li b oxy ho bi Pb(CH3COO)4. Nh vy, c th y phn ng xy ra
theo c ch khng vng.
O

OH

O
+ Pb(CH3 COO)2

Pb(CH3 COO)2
-CH3COOH

OH

-2CH3COOH

O
Pb(CH3COO)2

157

1,2-iol cng c th b oxy ho ct mch bi axit cromic v phn ng cng

chy theo c ch este vng trung gian.
- Oxy ho anehit v xeton
+ Oxy ho bng tc nhn v c:
Cc hp cht cacbonyl, nht l alehyl c th b oxy ho bi cc hp cht
oxy ho khc nhau nh MnVII, CrVI, Cu'', AgI, CeIV
Nghin cu phn ng oxy ho anehit thm bng KMnO4 trong dung dch
trung tnh ngi ta thy rng phn ng c bc mt i vi anehit cng nh i
vi pemanganat, hiu ng ng v teri bng 7, nu dng KMn18O4, 18O s xut
hin trong thnh phn phn t ca axit thm sinh ra, cc nhm th vng thm
ch c nh hng yu n tc phn ng ( = -0,25).
Ta c th m t c ch phn ng oxy ho bng s sau:
O

OH
(-)

ArC

+ MnO4

(+)

+ H

Ar - C OMnO3
H

OH

chm
Ar - C - O - MnO3
H

(+)

(+)

ArCOOH + BH + MnO3

:B

Phn ng oxy ho anehit bng axit cromic c nhiu nt tng t phn ng

oxy ho alcol cng bng tc nhn . C ch phn ng nh sau:

OH

O
(-)

RC - H + HCrO4

(+)

+H

OH
RC - H

O - CrO3H

:OH2

(+)

RC + HCrO3 + H3O
O

Trong trng hp dng C6H5CDO ngi ta thy hiu ng ng v bng 4,3,

iu chng t giai on phn ct lin kt cacbon-hyro quyt nh tc chung
ca phn ng.
Gia hai phn ng oxy ho anehit v oxy ho alcol bng axit crmic c
hai im khc nhau ng k. Mt l, cc nhm th ht electron xc tin s oxy ho
anehit ( = +1,02) nhng li lm gim nh tc oxy ho alcol ( = -1,0). Hai l
thay th dung mi nc bng axit axetic khng lm tng mnh tc oxy ho
anehit nh thy khi oxy ho alcol. Khc vi anehit, xeton tng i kh b
158

oxy ho bi pemangant kali v axit cromic. Tuy vy cc xetn vng d dng b

oxy ho thnh axit icacboxylic.
V d:
O

COOH
COOH

Cr2O3
hay HNO3

Axit aipic

C th cc xeton tc dng di dng enol to ra este v c trung gian,

sau este ny b thu phn:
- C -CO

- C = C -

H2CrO4

(+)

- C - C (+)

OH OCrO3 H2

OH

(+)

-H

Oxy ho tip

thu phn
- C - C O

- C - C -

OH

(-)

OCrO3 H2

ng ch l nhm -metylen ca xeton cng nh anehit c th b oxy

ho thnh cacbonyl th hai nh tc dng ca oxyt selen:
- C - CH2 - + SeO2

AeOH
-H2O

- C - C - + Se +H2O
O

Trong phn ng trn, tc nhn oxy ho trc tip c l l axit selen: axit
ny tc dng vi lin kt ca dng enol theo s :

159

- C - CH2 -

- C = CH -

H2SeO3
- C = CH -H2O

OH

O - SeO2H

- C - C O

- Se - C - CH - H2 O

O - SeOH

+ Oxy ho bng tc nhn hu c:

Nhng phn ng oxy ho anehit bng cht hu c cn c th c coi l
phn ng kh i vi cht hu c . Nhng phn ng ny thng chy theo c
ch chuyn dch ion hyrua, m tiu biu hn c l phn ng Cannizar v phn
ng Tissenc.
Khi c tc dng ca mt baz mnh nh NaOH chng hn cc anehit
thm v anehit bo khng c nguyn t -hyro s tham gia phn ng Cannizaro,
trong mt phn t anehit b oxy ho thnh cacboxylic tng ng, cn phn t
anehit b oxy ho thnh alcol tng ng. Trong phn ng ny, thot tin anion
HO(-) tc dng vo nguyn t cacbon-cacbonyl ca mt phn t anehit:
(-)

OH

O
(-)

(-)

R - C - H + HO

HO

R - C - H

R - C - H

(-)

(-)

Sau anion sinh ra s chuyn ion hyrua sang nhm cacbonyl ca phn t
anehit th hai:

OH

OH

O
(-)

R-C -H +C=O

R-C + H-C-O

H2 O

(-)

R - C + H - C - OH

(-)

hoc:

160

(-)

(-)

O
(-)

R-C -H +C=O

R-C + H-C-O

H2 O

(-)

R - C + H - C - OH

(-)

Phn ng trn bc hai i vi anehyt, phn ng ca RCHO trong D2O kim to ra alcol khng cha teri, iu c s chuyn dch trc tip hyro t
phn t anehyt th nht sang phn t anehyt th hai.
Phn ng Cannizaro c th xy ra gia hai nhm C = O ca mt phn t
(V d: C6H5CO CHO) hoc gia hai nhm C = O ca hai phn t khc hn
nhau (V d: (CH3O)2C6H3CHO v HCHO2.
Tt c cc anehit khng c hoc c -hyro ni chung u tc dng
c vi alkoxyt nhm, khi y mt phn t anehit b oxy ho to ra axit
cacboxylic, cn phn t khc b kh to ra alcol, hai sn phm ny dng este
(Phn ng Tisenco):
RCHO + RCHO

Al(OR')3

RCOOCH2R

Khi dng hn hp hai anehit khc nhau ta c th thu c ti bn este

RCOOCH2R', R'COOCH2R, RCOOCH2R v R'COOCH2R'. Tng t phn ng
Cannizaro, phn ng Tisenco chy theo c ch chuyn dch ion hyrua:
(-)

O
RC
H

O Al(OR')3
Al(OR')2

RC
H

O = CHR

(-)

O Al(OR')3
RC - O - CHR

Al(OR')3

RC - O - CH2R

6.4.3. Phn ng kh
7.3.1. Khi nim: qu trnh kh l qu trnh lm gim s oxy ho cht phn ng
v lm tng s oxy ho tc nhn phn ng.
6.4.3.2. Tc nhn: H0, H2, LiAlH4,
6.4.3.3. Mt s phn ng v c ch
a. Kh lin kt gia cacbon cacbon
- Kh bng hyro trn b mt cht xc tc kim loi
Bt k c nhm th l y electron cc lin kt bi cacbon-cacbon u c
th b hyro ho trn b mt cht xc tc kim loi. Nhng cht xc tc hay dng l
Ni, Pt, Rd, Ru v CuCr2O4. Kh ho v hyro ho l nhng qu trnh thun
nghch i vi nhau. Qa trnh hyro ho pht nhit (28-33kcal/mol), cn qu
161

trnh ehyro ho thu nhit. C ch ca phn ng hyro ho trn b mt cht xc

tc kim loi l mt vn phc tp cn cha c gii quyt trn vn.
Phn ng hyro ho lun lun xy ra theo kiu cis. Vy cc ankin b hyro
ho to thnh cis-anken.
RCH2
RCH2 - C

H2,Pd

C - CH2R

CH2R
C=C

quinlin
H

Cc axit imetylmaleic v imetylfumaric khi b oxy ho to ra nhng ng

phn khc nhau ca axit imetylsucxinic:
CH3

CH3

COOH
H

H2/Ni
CH3

COOH

COOH

CH3

Axit dimtylfumaric

Mz-

CH3

HOOC
COOH

H
H

H2/Ni
CH3

COOH

CH3

COOH

CH3

COOH

COOH

CH3
HOOC

CH3

D, L -

V kh nng phn ng, ankin d b hyro ho hn anken. Nu so

snh kh nng phn ng hyro ho ca cc lin kt bi cacbon-cacbon vi cc lin
kt bi khc ta c th t gn ng nh sau:
RC = O > RNO2 > RC

CR > RC = O > RCH = CHR >RC = O >

H

Cl

> dn xut ca naphtalen > RC = O > O dn xut ca benzen

OR'

162

Vng benzen khi b hyro ho thng khng dng li giai on cng

mt phn t hyro, v anken d b hyro ho hn vng benzen rt nhiu. Th d
mt mol benzen tc dng vi mt mol hyro khng cho xycllexaien hay
xyclohexen m cho 1/3 mol xyclohexan. Trong iu kin nh vy naphtalen b
kh cho ta tetrahyronaphtalen (tetralin). Tuy vy, i vi nhng hp cht thm
nhiu vng ngng t hn nh antraxen, phenantren ta li d dng cho phn ng
dng giai on cng hyro vo hai nguyn t 9, 10 v nhng v tr ny hot ng
hn c:

H2
xt
Benzen

H2
xt

Xyclhexan

Antraxen

9,10- Dihydrantraxen

H2
xt
Napncaten

H2
xt
Tetralin
Phenantren

9,10- Dihydrantraxen

- Kh bng cc tc nhn khc:

Cc ank-1-en d dng b kh bi hyrua nhm to thnh alken:
(+)

RCH = CH2 + AlH3

Benzen

(RCH2CH2)3Al

H 3O

RCH2CH3

iboran cng kh c anken tng t nh vy

(+)

RCH = CH2 + B2H6

(RCH 2CH2)3B

RCH2CH3

Tc cng iboran vo anken s gim khi s nhm alkyl ni i tng ln.

Khi dng iboran kh alkyl ta c cis-anken.
(+)

RCH2C

CC2R

B2H6

RCH2CH = C - B
RCH2

163

H3O

RCH2

CH2R
C=C

Tri li nu dng cht kh l natri trong amoniac lng ta s c transanken:

(+)

RCH2
RCH C = CCH R
2

2Na

(-)

2NH
-2NaNH

C=C
(+)

RCH2

Na

(-)

C=C
H

CH R

Na

H
CH R
2

Dng natri-amoniac kh vng thm ta c sn phm cng 1,4 l

xyclohexaien khng lin hp:
H

(+)

Na

Na

NH3

NH3

Na

Nd

Cc nhm th y electron (th d OCH3) trong vng benzen nh hng

phn ng to ra dn xut 2,5 ihiro, trong khi cc nhm th ht electron (v
d COOH) li nh hng to ra dn xut 1,4-ihyro:
OCH3

OCH3

COOH

COOH

H
H

Naphtalen b hyro ho bi natri-etanol trc tin cho ta 1,4ihyronaphtalen nhng cht ny khng bn, n chuyn ho ngay thnh 1,2ihyronaphtalen (c hai phn ng u to nhit).

Na
C6 HOH
5
Naptalen

1,4-ihyrNaptalen

c. Kh anehit v xtn
- Kh thnh alcol

164

1,2 -ihir
Naptalen

Anehit v xeton ni chung d b kh thnh alcol bc mt v bc hai. Cc

cht kh c th l: natri trong ru, hyro trn niken Rany, hyrua litinhm,
hyrua natribo
+ Kh bng LiAlH4 v NaBH4:
V thc cht cc phn ng ny l phn ng cng nucleophin vo nhm cacbonyl:

R'

R'

R'
(-)

R - C = O

R - C = OAlH3

RR'C = O

R'
(-) H O
2

R - C = O Al

R - C = OH

(-)

H - AlH3

Cc hyrua kim loi nh LiAlH4 thng khng kh lin kt bi cacbon

cacbon v th chng c th kh chn lc nhm C = O ca hp cht cacbonyl cha
no.
V d:
C6H5CH = CH - CH = O

LiAlH 4

C H CH = CH - CH2OH
ete -100C 6 5

Tuy vy iu kin nhit phng phn ng kh trn to ra alcol no

C6H5CH2CH2CH2OH.
Dng NaBH4 lm cht kh c u im l tnh chn la cao v c th thc
hin phn ng trong mi trng nc. NaBH4 khng kh cc nhm C = C,
COOH, COOR9v tnh kh chn la, xem bng XV-3)
b. Kh bng izproopylat nhm:
Mt s alcolat kim loi, c bit l izprpylat nhm c kh nng kh
anehit v xtn thnh alcol tng ng theo mt qu trnh thun nghch.
R

R
C = O + (CH3)2CHOH

(i-C3H7O)3Al

R'

CH - OH + (CH3)2C = O

R'

Qa trnh thun, dng kh hp cht cacbny, c gi l phn ng

Mecvai-Pondoo-Vecly, cn qu trnh nghch, dng oxy ho alcol, c gi l
phn ng Openao.
Bn cht ca cc phn ng trn l qu trnh chuyn dch ion hyrua t
alcolat nhm sang nhm cacbonyl qua mt trng thi chuyn tip vng:

165

CH3

CH3

CH3

CH3

C
O

CH3

H
+

(i - C3H7O)2Al

C
H

O
+

R
(i - C3H7O)2Al

(i - C3H7O)2Al

C
O

R'

CH3

C
O

R'

HHR

R'

Dn chng v s chuyn dch ion hyrua l khi dng izprpylat nhm c

cha - teri RRCDOH.
Khi kh bng izprpylat nhm ngi ta chng ct cho axtn thot ra khi
mi trng phn ng v cn bng v bn phi. Tri li khi mun oxy ho alcol
ngi ta dng d axtn v dng t-butylat nhm lm xc tc, v cht ny khng
cn - hyro c th kh axtn m ch c th chuyn alcol cn oxy ho thnh
alcolat tng ng.
Kh thnh hyrocacbon no
RCR'

RCH2R'

C mt s phng php kh nhm C = O thnh nhm CH2, quan trng nht

l phng php Kizne Vnf v phng php clemmenxen.
Trong phng php clemmenxen ngi ta un nng anehit hoc xtn hn
hp km trong axit clohyric m c. C ch ca phn ng cn cha r rng, ch
bit rng sn phm trung gian khng phi l mt alcol v cht ny khng b kh
thnh hyrocacbon trong iu kin ni trn.
Nu trong phn t anhyt v xtn c nhng nhm th khng bn trong
mi trng axit, th tt nht nn dng phng php Kizne Vnf. Theo phng
php ny hp cht cacbonyl c chuyn thnh hyraz tng ng, ri un
hyrazon vi kim c hoc etylat natri:

C = O + NH2 - NH2
R

-H2O

C = N - NH2

C2H5ONa

CH2 + N2

2000C

C ch ca giai on chuyn ho hyrazon thnh hyrocacbon c th c

m t bng s sau:
166

(-)

C = NNH2

C2H5O

R'

(-)

C - N = NH

C = NNH2
R'

R'
R

(-)

C2H5O

CH2

-N2

CH - N = N

R'

R'

R'

(-)

(-)

CH

Phng php Kizne Vnf c Hong Minh Long ci tin bng cch
un trc tip hp cht cacbonyl vi hyrazin v kim trong etylenglycol di p
sut thng (v th c tn gi phng php Hong Minh Long). Cram li ci tin
thm bng cch dng i-butoxyt kali lm baz v imetylsunfoxyt lm tng dung
mi, do c th thc hin phn ng ngay nhit phng m hiu sut t c
vn cao.
d. Kh axit cacboxylic v cc dn xut ca chng
Axit cacboxylic RCOOH khng b kh bng cc cht kh thng thng,
nhng li d b kh bi LiAlH4, v mt vi cht khc to thnh alcol bc nht:
RCOOH

LiAlH4

RCH2OH

C ch ca phn ng c th nh sau:
(-)

RCOOH + LiAlH4

(+)

H2 + AlH3 + RCOO Li

LiAlH4
H
RCH2OH

1.LiAlH4
(+)

2.H2O

(-)

R - CH = O

Li2O

R - C - OLi
(-)

(+)

(-)

Li

Este d b kh hn axit cacbonxylic, phn ng kh este bng LiAlH4, xy

ra tng t phn ng kh anehit v xeton.

167

R'

R'

R - C = O

R - C - O
H

(-)

H - Al H2

(-)

- RO

R- C = O

(-)

1.LiAlH
2.H2O

R - CH2OH

Ngoi LiAlH4, este cn c th b kh bi mt s cht khc nh hyro trn

cromit ng, natri trong etanol
Phng php kh este thnh alcol bng natri trong etanol c gi l
phng php Buv-Blng. Trc khi tm ra LiAlH4, phng php Buv-Blng
c dng rt ph bin.
Clorua v anhyrit axit cng d b kh bi LiAlH4, thnh alcol bc nht:
LiAlH4

RCOOCOR
RCOCl

LiAlH4

2RCH2OH
RCH2OH

Clorua axit c th b kh bi hyro trn cht xc tc Pd to thnh alcol, qua

cht trung gian l anehit:
RCOCl

H2

xt

RCHO

H2

xt

RCH2OH

ngn cn giai on chuyn anehit thnh alcol ngi ta dng BaSO4

lm cht c i vi Pd (phng php kh Rzenmun):
RCOCl

H2

Pd-BaSO4

RCHO

Mun kh clorua axit thnh anehit ta cn c th dng cc cht kh l liti

hyrua hoc tri-t-butoxy nhm hyrua. Trong trng hp dng cht kh l hn
hp natri trong ete ta s c este ca eniol:
R

R
4RCOCl + 4Na

C = C
RCOO

+ 4NaCl
OCOR

Kh nng phn ng ca mt s nhm chc i vi cc cht kh khc nhau:

Phn ng
Hyro
LiAlH4
B2H6
NaBH4
NaBH4 +
ho
c trong te trong
trong
AlCl3 trong
xc tc
THF
etanol
iglime
RCH = CHR RCH2CH2R
+
+
+
TCHO
RCH2OH
+
+
+
+
+
RCOR
RCHOHR
+
+
+
+
+
RCHO

168

RCOCl

RCH2OH
+
RCOOR
RCH2OH + +

+
+
ROH
+
RCOOH RCH2OH
(-)
RCOO RCH2OH
THF: tetrahyrofuran, iglime: (CH3OCH2CH2)2O

+
+
+

e. Kh cc hp cht cha nit

S kh cc hp cht cha nhm C N, - C = N v CONH2 ni
chung tng t s kh hp cht cacbonyl, sn phm sinh ra thng l amin. Th
d cc xim b kh bng LiAlH4 thnh amin bc nht:
R

R
C = NOH

LiAlH4

CHNH2

R'

R'

Phn ng kh oxim chy chm hn phn ng kh xeton. Amit b kh bi

LiAlH4(NaBH4 khng c tc dng) tng t este. C ch phn ng kh nh
sau:
R - C - NH2
O
RCH2 - NH2

H2O

(-)

(-)

AlH4

RC - NH

(-)

AlH4

(-)

R - CH - NH
(-)

RCH2 - NH

(-)

(-)

AlH4

R - CH = NH

Amit, oxim cng nh nitrin u c th b kh bng hyro nh cht xc tc

kim loi.
Cc hp cht nitro v nhng dn xut th ca chng rt d b kh bng
nhiu tc nhn khc nhau. S kh trong mi trng axit hoc kh bng hyro trn
cht xc tc kim loi thng cho ta hp cht amino.
S kh nhm nitro trong mi trng kim phc tp hn nhiu v c nhng
phn ng ngng t gia cc sn phm kh khc nhau:

169

RNO

Hp cht
nitr

RNO
Hp cht
nitrz

Hp cht
hyrxyamino

RNH2
Amin

RNO
RN - NR

Cht kh, kim

OH OH
-HO
2

RN = NR
O
Hp cht
azxy

RNO
RN - NHR
OH
- H 2O

RN = NR
Hp cht az

RNHNHR
Hp cht
Hyrz

Tuy s kh hp cht nitro phc tp nh vy, nhng nu chn cc cht kh

thch hp ngi ta c th cho phn ng u tin dng li mt giai on nht nh
no .
6.4.4. Cn bng oxi ho kh (Phng php thng bng electron)
6.4.4.1. Cch xc nh s oxi ho ca C trong hp cht hu c
- S oxi ho ca cacbon l dng nu n lin kt vi nguyn t c m
in ln nh O, N, Cl,...
- S oxi ho ca C l m nu n lin kt vi H, l ion nu n lin kt vi
nguyn t kim loi.
- xc nh s oxi ho ca cacbon trong hp cht hu c c hai cch:
+ Da vo cng thc cu to.
+ Da vo s oxi ho trung bnh ca cacbon.
6.4.4.2. Cn bng theo phng php thng bng electron
V d: Cn bng phn ng sau:
RCH2OH + K2Cr2O7 + H2SO4 RCHO + K2SO4 + Cr2(SO4)3 + H2O
3x
R-CH2OH R-CHO + 2H+ +2e
2x
Cr+6 + 3e Cr+3
3RCH2OH + K2Cr2O7 + 4H2SO4 3RCHO + K2SO4 +Cr2(SO4)3 + 7H2O

170

Ch : Phng php rng ri hn l dng phng php cn bng theo cc

nguyn tc sau:
- in tch c cn bng bng H+ trong dung dch axit hay bng OH- trong
dung dch kim.
- Oxi c cn bng bng H2O.
- Hidro c cn bng bng H.
V d 1: Cn bng phn ng sau:
RCH2OH + K2Cr2O7 + H2SO4 RCHO + K2SO4 + Cr2(SO4)3 + H2O
* Phn ng kh:
Cr2O72-
Cn bng in tch Cr2O72- +8H+
Cn bng oxi
Cr2O72- +8H+
Cn bng hidro
Cr2O72- +8H+

2Cr+3
2Cr+3
2Cr+3 + 7H2O
+6H 2Cr+3 + 7H2O

* Phn ng oxi ho
RCH2OH RCHO
Khng cn cn bng O, in tch, ch cn bng H
RCH2OH RCHO + 2H
* Kt hp hai phng trnh trn, loi b thnh phn H bng nhn h s c
H gia hai phn ng:
3x RCH2OH RCHO + 2H
Cr2O72- +8H+ +6H 2Cr+3 + 7H2O
3x RCH2OH + Cr2O72- +8H+ RCHO + 2Cr+3 + 7H2O
Bo ho bng gc axit v mui ta c phng trnh:
3RCH2OH + K2Cr2O7 + 4H2SO4 3RCHO + K2SO4 +Cr2(SO4)3 + 7H2O
V d 2: Cn bng phn ng sau:
C6H5CH3 + MnO4- C6H5COOK + MnO2
* Phn ng kh
Cn bng in tch
Cn bng oxi
Cn bng hidro

C6H5CH3 C6H5COOC6H5CH3 + HO- C6H5COOC6H5CH3 + HO- +H2O C6H5COOC6H5CH3 + HO- +H2O C6H5COO- + 6H

* Phn ng oxi ho MnO4- MnO2

Cn bng in tch MnO4- MnO2 + HOCn bng oxi
MnO4- MnO2 + HO- + H2O
171

Cn bng hidro
* Kt hp hai phng trnh v loi b H:
C6H5CH3 + HO- +H2O C6H5COO- + 6H
3x MnO4- + 3H MnO2 + HO- + H2O
C6H5CH3 + 2KMnO4

C6H5COOK + 2MnO2 + KOH + H2O

6.4.4.3. c im ca phng php oxi ho kh

- Theo c ch gc
- Sn phm: ancol, andehyt, xeton, axit cacboxylic, CO2 tu thuc vo tc
nhn oxi ho.
Nu iu kin phn ng khc nghit (t0 cao, tc nhn phn ng oxi ho
mnh, m c nh HIO4, KMnO4) th c mi ln oxi ho, s oxi ho tng ln mt
bc.
- Phn ng ny thng dng xc nh cu to mch phn t ca cc hp
cht hu c.

172

CU HI V BI TP

Bi 1. Cho bit cc phn ng sau y xy ra theo c ch g? Vit sn phm to

thnh?
a. R MgCl + R" C R'
b. R CH2Cl + KCN
O
nh sng

d. CH3 CH2 CH3 + Cl2

c. CH3 CH2 CH CH3 + H2O

CH3
e. CH3 C

SO3H
f. CH2 CH CH2Br + HBr

I + C2H5OK

CH3
Bi 2. Gii thch ti sao butyl bromua phn ng vi NaI trong axeton nhanh hn
tert-butyl bromua nhng khi phn ng vi AgNO3 trong C2H5OH/H2O th chm
hn. Trnh by c ch phn ng.
Bi 3. a. un nng ancol neopentylic vi axit HBr cho ta hn hp 2 anken vi t
l 85%:15%. Cho bit cu to v gii thch s to thnh ca cc anken ny.
b. ng phn neopentyl bromua c th cho phn ng tch E2 c khng?
Nu un nng ng phn ny trong ancol long th thu c 2 sn phm nh cu
(a). Gii thch? Cho bit ti sao phn ng tng t nh trn m khng cn xc tc
axit.
Bi 4. un nng (S)-1-phenyl-1-brompentan trong CH3COOH to hn hp
raxemic, cn trong CH3COONa/axeton to sn phm nghch chuyn cu hnh. Xc
nh c ch phn ng.
FeBr
Bi 5. ngh c ch ca phn ng sau: C6H6 + Br2
C6H5Br + HBr
Bi 6. Tert-butyl peoxit l cht to ra gc t do xc tin cho phn ng SR. Khi un
nng 2-metyl propan v cacbon tetra clorua c mt tert-butyl peoxit n 130 oC thu
c sn phm gm 2-clo-2-metyl propan v clorofrom. Trnh by c ch phn
ng.
Bi 7. Hp cht n chc A c cng thc n gin nht l C3H6O v c tnh quang
hot. un nng 23,2g A vi mt lng d dd NaOH, sau ngui ri lc hh
thu c vi dimetyl ete. Tch ly phn lp trn ri chng ui ete th thu c
14,8gam cht lng c tnh quang hot. Lp bn di khng c tnh quang hot.
Gi s hiu sut phn ng l 100%.
a) Xc nh cu to ca A v vit ptp
b) Cn c vo kt qu th nghim hy xc nh c ch p.
Bi 8. T-Butyl axetat tc dng vi dd natri metylat trong metanol bin thnh metyl
axetat, phn ng chm 10 ln so vi p tng t chuyn etyl axetat thnh metyl
3

173

axetat trong iu kin th nghm nh nhau. Ngc li t-butyl axetat phn ng

nhanh vi CH3OH trong s c mt ca mt lng nh hiroclorua to ra axit
axetic v metyl t-butyl ete. Tng t etyl axetat li chuyn rt chm thnh etanol
v metyl axetat.
a) Vit c ch p v gii thch tc p
b) C th s dng ng v 18O nh th no kho st tnh ng n ca c ch
c ngh trn.
Bi 9. Xyclopropanon khng c phn ng chung vi cc xeton khc l ch phn ct
mt lin kt cacbon-cacbonyl. Xyclopropanon p vi NaOh trong nc cho natri
propionat. ngh c ch cho phn ng ny. D on sn phm khi 2metylxyclopropanon trong cng p. X l 2-brom-3-pentanon vi NaOH trong
nc thu c axit 2-metylbutanoic. ngh c ch cho p ny.
Bi 10. Vit phn ng v suy ra c ch cho cc chuyn ho sau:
1) C6H5-CO-CHO + HO- C6H5CH(OH)COO2) C6H5-CO-CO-C6H5 +OH- (C6H5)2-C(OH)COO3) C6H5-CO-CO-C6H5 + CH3O- (C6H5)2C(OH)COOCH3
Bi 11. So snh phn ng ca etilen v CF2=CF2 vi C2H5ONa trong etanol
Bi 12. So snh phn ng ca but-1-in v but-2- in vi cc tc nhn sau:
a) H2/Ni
b) dd AgNO3/NH3
c) Na/NH3 lng
d) H2/Pd, BaSO4, quinolin
) n-butylliti,THF
e) 1-B2H6,2-H2O2,NaOH
f) 2 mol HBr
g) HgSO4, H2SO4,H2O
Bi 13. Sp xp cc cht sau y theo th t gim dn kh nng phn ng ca cc
cht sau y vi HNO3 trong H2SO4 m c: C6H5NO2, C6H5CH2NO2,
C6H5CH2CH2NO2
Bi 14. Sp xp theo th t tng dn kh nng phn ng ca cc ancol:
1-phenylpropan-1-ol (A), 1-phenylpropan-2-ol (B), 3-phenylpropan-1-ol (C) vi
thuc th Luca (HCl c + ZnCl2).
Bi 15. Cho tc dng C7H15Br vi kim mnh cho hn hp anken c phn tch
bng sc k kh cho thy gm 3 anken C, D, E c cng cng thc chung l C7H14.
Hydro ho mi anken u cho 2-metyl hexan. Phn ng ca C vi B2H6 trong ete
ri tc dng tip vi H2O2 v OH- cho ancol F. Phn ng tng t ca D v E cho
mt lng bng nhau ca F v ng phn ca n l G. Xc nh cng thc cu to
ca C v G.
Bi 16. Mt hp cht (H) C11H24O p vi PBr3 trong ete 0oC cho (I) C11H23Br.
Cho (I) tc dng vi etoxit kali trong etanol cho mt lng ln (L) v mt lng
nh (K) c cng cng thc C11H22. Cho mi cht p trc ht vi ozon trong
CHCl3 0oC ri x l vi NaBH4 u cho hn hp 3-metyl-1-butanol v 4-metyl1-pentanol. Xc nh (H) v (K)
Bi 17. Hp cht E c cng thc C7H12 phn ng vi HCl -25oC cho F c cng
thc C7H13Cl. Hp cht F phn ng vi Kali tert-butoxit trong tert-butanol cho
174

mt lng nh E v mt lng ln G c cng thc C7H12. Ozon ho G cho xyclohexanon v formadehit. Xc nh cng thc ca E v G.
Bi 18. Xc nh cu to hp cht (A) C10H10 m khi oxi ho ch cho mt axit
CH(CH2COOH)3 (B)
Bi 19. Vit cc phn ng ca furan v thiopen vi iazometan. Ti sao furan cho
hiu sut cao hn.
Bi 20. Chn tc nhn kh RCOOH RCH2OH bng cc tc nhn sau:
a) NaBH4 b) LiAlH4 c) Na/C2H5OH d) H2/xc tc e) BH3/THF ri vi H3O+
Bi 21. Cho bit sn phm oxiho bng peiodat cc hp cht sau
a) CH3COCHO
b) C6H5CHOHCHO
c) CH3CH2CHOHCOCH3
Bi 22. Hp cht A C7H16O vi natri icromat trong dung dch H2SO4 cho B
C7H14O. Khi un nng B vi NaOD 25oC phn tch sau 4 gi th sn phm c 2
deuteri. Hp cht B khng b oxi ho bng Ag2O. Xc nh A v B?
Bi 23. a) Vit c ch kh Wolff Kishner ca anehyt RCHO.
b) Cho bit sn phm kh Wolff Kishner ca cc cht sau:
(1) C6H5COCH2CH3 (2) CH3CH=CHCH2CHO (3) p-CH3OC6H4COCH3
(4) 4,4-dimetylxyclohexanon.

175

TI LIU THAM KHO

1. Phan Tng Sn, Trn Quc Sn, ng Nh Ti, C s l thuyt ho hu c,
tp 1,2, NXB i hc v trung hc chuyn nghip H Ni, 1980
2. Trn Quc Sn, ng Vn Liu Gio trnh c s ha hc hu c, Tp 1, 2,
NXB i hc s phm, 2007.
3. Chu Phm Ngc Sn, Nguyn Hu Tnh, Bi tp ha hc hu c, NXB Hn
Thuyn, Thnh ph H Ch Minh, 1995.
4. Trn Quc Sn, Trn Th Tu, Danh php hp cht hu c, NXB Gio dc,
H Ni, 2007.
5. Thi Don Tnh, C s ho hc hu c, Tp 1, 2, NXB Khoa hc v K thut,
H Ni, 2006.
6. Thi Don Tnh, C ch v phn ng ha hc hu c (tp 1,2,3), NXB Khoa
hc v k thut, H Ni, 2008.
7. ng Nh Ti, C s l thuyt ha lp th, NXB Gio dc, H Ni, 1998.
8. Ng Th Thun Ho hc hu c phn bi tp (tp 1,2), NXB Khoa hc v k
thut, H Ni, 2006.
9. Hong Trng Ym, Ho hc hu c, NXB Khoa hc & K thut, H Ni,
2002.
10. John D. Roberts, Marjorie C. Caserio, Ha hc hu c hin i, tp 1,2,3,
NXB Khoa hc v K thut, H Ni, 1984.
11. Francis A Carey, Organic Chemistry, Mc-Graw Hill Companies, 2001.
12. R. Morrison and R. Boyd, Organic Chemistry, Prentice-Hall International
(UK) Limited, London, 2001.

176

MC LC
Trang
Li ni u ......................................................................................................... 1
Chng 1. M u ............................................................................................. 2
1.1. i tng ca ho hc hu c ...................................................................
1.2. S lc lch s pht trin ca ho hc hu c ..........................................
1.3. Nhng quan im v cu to ca hp cht hu c...................................
1.3.1. Thuyt gc .........................................................................................
1.3.2. Thuyt kiu........................................................................................
1.3.3. Thuyt Butlerop ................................................................................
1.4. Cch biu din cng thc cu to hp cht hu c ..................................
1.4.1. Cng thc Lewis ...............................................................................
1.4.2. Cng thc Kekul .............................................................................
1.5. Danh php hp cht hu c .......................................................................
1.5.1. Danh php thng thng ..................................................................
1.5.2. Danh php hp l .............................................................................
1.5.3. Danh php thng mi .....................................................................
1.5.4. Danh php IUPAC ............................................................................
1.6. Phn loi cc hp cht hu c ...................................................................
Cu hi v bi tp ........................................................................................

2
2
3
3
3
5
5
5
6
7
7
7
8
8
10
11

Chng 2. Cu trc khng gian phn t hp cht hu c ......................... 12

2.1. Chit tch v tinh ch hp cht hu c .....................................................
2.1.1. Tinh ch cht rn...............................................................................
2.1.2. Tinh ch cht lng ............................................................................
2.1.3. Phng php sc k ..........................................................................
2.2. Cng thc phn t hp cht hu c ..........................................................
2.2.1. Phn tch nguyn t ..........................................................................
2.2.2. Thit lp cng thc tng qut ca hp cht ....................................
2.2.3. Xc nh khi lng phn t ca mt cht .....................................
2.2.4. Thit lp cng thc nguyn ca mt hp cht ................................
2.3. Cu trc phn t hp cht hu c..............................................................
2.3.1. ng phn .........................................................................................
2.3.2. ng ng .........................................................................................
2.3.3. ng cp............................................................................................
177

12
12
13
16
17
18
20
21
22
23
23
50
50

2.3.4. Cu hnh ............................................................................................ 51

Cu hi v bi tp ........................................................................................ 54
Chng 3. Lin kt trong ha hc hu c ..................................................... 57
3.1. Lin kt cng ho tr ..................................................................................
3.1.1. Theo thuyt c in ..........................................................................
3.1.2. Quan nim hin i ...........................................................................
3.1.3. c im ca lin kt cng ho tr ..................................................
3.1.4. Cc lin kt n, i, ba, h lin hp ..............................................
3.2. Lin kt phi tr ..........................................................................................
3.3. Cc loi lin kt yu ...................................................................................
3.3.1. Lin kt hydro ...................................................................................
3.3.2. Lin kt Vandecvan ..........................................................................
3.4. Mt s loi lin kt khng mang bn cht ho hc ..................................
3.4.1. Lin kt bc Clatrat ..........................................................................
3.4.2. Lin kt Catenan, Rotaxan ...............................................................
Cu hi v bi tp ..............................................................................

57
57
57
64
64
67
68
68
70
73
73
73
74

Chng 4. Hiu ng cu trc phn t hp cht hu c .............................. 75

4.1. Hiu ng in t .........................................................................................
4.1.1. Khi nim ..........................................................................................
4.1.2. Phn loi ............................................................................................
4.2. Hiu ng khng gian S ...............................................................................
4.2.1. Khi nim ..........................................................................................
4.2.2. Phn loi ............................................................................................
4.2.3. Hiu ng khng gian loi mt..........................................................
4.2.4. Hiu ng khng gian loi hai ...........................................................
4.2.5. Hiu ng octo ....................................................................................
Cu hi v bi tp..............................................................................

75
75
75
80
80
80
80
81
82
84

Chng 5. Cc axit baz hu c .................................................................. 85

5.1. Khi nim axit - baz .................................................................................
5.1.1. Thuyt axit, baz ..............................................................................
5.1.2. Cch o axit, baz ............................................................................
5.2. Cu trc phn t nh hng n tnh axit, baz hu c ..........................
5.2.1. Tnh cht axit v cu trc ca hp cht hu c ..............................
5.2.2. Tnh cht baz v cu trc ca hp cht hu c.............................
Cu hi v bi tp .............................................................................

85
85
88
88
88
93
98

Chng 6. Phn ng hu c ........................................................................... 99

178

6.1. nh ngha c ch phn ng hu c.......................................................... 99

6.2. Phn loi phn ng hu c......................................................................... 99
6.2.1. Phn loi theo hng bin i thnh phn cht phn ng ............. 99
6.2.2. Phn loi theo c im ca s bin i lin kt ............................ 100
6.2.3. Phn loi theo s lng tiu phn ca giai on quyt nh tc phn
ng ....................................................................................................................... 101
6.2.4. Phn loi theo tin trnh phn ng ................................................... 101
6.3. C ch phn ng hu c ............................................................................ 102
6.3.1. Phn ng th ...................................................................................... 102
6.3.2. Phn ng tch .................................................................................... 125
6.3.3. Phn ng cng................................................................................... 133
6.4. Phn ng oxi ha kh ................................................................................. 144
6.4.1. Khi nim chung .............................................................................. 144
6.4.2. Phn ng oxi ha ............................................................................. 145
6.4.3. Phn ng kh ................................................................................... 156
6.4.4. Cn bng oxi ho kh ...................................................................... 165
Cu hi v bi tp............................................................................. 168
Ti liu tham kho ................................................................................................ 171
Mc lc ................................................................................................................. 172

179