HO HC HU C

Organic Chemistry
CHNG 4
HIU NG TRONG HA HU C

GII THIU CHNG

GII THIU
PHN LAI HIU NG
HIU NG CM NG
HIU NG LIN HP
HIU NG SIU LIN
HP HIU NG KHNG GIAN
NH HNG CA CC HIU NG
HIU NG CM NG (INDUCTION)
Hiu ng cm ng l s tc dng tng h ca cc nguyn t, nhm nguyn t
trong hp cht hydrocarbon no hoc khng no, khng lin hp gy ra.
HIU NG CM NG (INDUCTION)
c im ca hiu ng cm ng:
-Do s chnh lch m in ca cc nguyn t, nhm nguyn t lm chuyn dch
cc in t lin kt xchma.

-Hiu ng tt dn theo mch lin kt xchma ( qua 4-5 lin kt xchma).

-Hiu ng cm ng dng ( + I) l hiu ng cho in t v
hiu ng cm ng m (-I) l hiu ng ht in t.
-Hiu ng cm ng tnh c hnh thnh do s chuyn dch in t trong mch
phn t trng thi tnh, c lp. Hiu ng cm ng ng xut hin khi phn t
trng thi chu tc ng bn ngai (ang tham gia phn ng, dung mi, tc cht)
HIU NG CM NG (INDUCTION)

xc nh tr s v du ca hiu ng cm ng tnh dng hai phng php:

-So snh hng s phn ly ca acid
-So snh gi tr moment lng cc
HIU NG CM NG (INDUCTION)
So snh hng s phn ly ca acid
HIU NG CM NG (INDUCTION)
So snh moment lng cc
HIU NG CM NG (INDUCTION)
Mt s lu :

-Yu t khng gian t nh hng n hiu ng cm ng

- Hiu ng -I ca Csp > Csp2> Csp3
HIU NG CM NG (INDUCTION)
V d hiu ng tt dn theo mch
HIU NG LIN HP (CONJUGATION)
Hiu ng lin hp hay cng hng ch th hin nhng phn t c h thng lin
kt pi v xch ma lin hp.
H lin hp pi-pi v n-pi ( h lin hp m rng)
HIU NG LIN HP (CONJUGATION)
Hiu ng lin hp hay cng hng ch th hin nhng phn t c h thng lin
kt pi v xch ma lin hp.
H lin hp pi-pi v n-pi ( h lin hp m rng)

Duai tac d\lng cua nh61n hut electron, h electron n linh d{>ng se
ch11yen djch

ve phia nhon1 hut electron.

S\t

djch din

chuyen

ieu hin s\f

chuyen

djch da111 111ay din

tru. e n6i tan1 hai nguyen tit:

t>ous -

tli n nay duQc ky hiu bang n1ui ten

cong,

t\t n xen phunhau ngoai

o+

<S + (j1

CH2 =

CH - CH

CH - C

H
c
C-H
O' ,o
HIU NG LIN HP (CONJUGATION)
Conjugated unsaturated systems have a p orbital on a carbon adjacent to a
double bond
-

The p orbital can come from another double or triple bond

The p orbital may be the empty p orbital of a carbocation or a p orbital with

a single electron in it (a radical)

-

Conjugation affords special stability to the

molecule

+
1,3-Butadiene

Electron Delocalization

- Bond Lengths
C-C : 1.54
C=C : 1.34

bond between C2 and C3 made from sp2-sp2 overlap

- Overlap between the C2-C3 p orbitals

Allyl Cation

The energy of the allyl cation actual lower than the energy calculated for any
the contributing resonance structures

- Allyl cation stabilized by resonance effects

Allyl Radical
The Stability of the Allyl Radical
-

Both molecular orbital theory and resonance theory can explain the stability

of allyl radicals
-

Molecular Orbital Description of the Allyl Radical

the p orbital on the sp2 carbon overlaps with the p

orbitals of the alkene

The new p orbital is conjugated with the double bond p orbitals
Delocalization of charge and electron density leads to
increased stability
Allyl Radical

Resonance Description of the Allyl Radical

The true structure of the allyl radical as suggested by resonance theory is as

follows
Resonance

Benzene
H
H

HC C

H
Writing Resonance Structures

When writing resonance structures the connectivity cannot be altered (only

lone pair electrons and electrons in double and triple multiple
be

moved).

bond

can

A structure with the lowest magnitudes of formal charges is preferred

(greater contribution

to

the

hybrid).

A structure with a negative charge on the most

electronegative atom is preferred.
Writing Resonance Structures

Resonance Structures

CH3NCO

+1
H

-1

H
0
H

H
-1
H

C
H
H

0
C

+1

O
HIU NG LIN HP (CONJUGATION)
Hiu ng lin hp hay cng hng l s tc dng tng h gia cc nguyn t hay
nhm nguyn t trong h lin hp lm chuyn dch cc in t lin kt pi gy ra s
phn cc phn t .
c im ca hiu ng lin hp:
+ S dch chuyn in t pi ( k hiu l mi tn cong)
+ Lan truyn sut mch lin hp.
+ Hiu ng lin hp dng ( + C) cho in t. Hiu ng lin hp m (-C) ht in
t.
= Hiu ng lin hp ph thuc vo yu t lp th: h s gim
tnh lin hp khi mt hay gim cu to phng
HIU NG LIN HP (CONJUGATION)

 xc nh du v ln tng i ca hiu ng lin hp ca nguyn t hay

nhm nguyn t da vo moment lng cc ca dy cc hp cht thng v thm
c cha cng mt nguyn t hay nhm nguyn t
HIU NG LIN HP (CONJUGATION)
Trong chu k v phn nhm chnh theo chiu tng ca in tch ht nhn, hiu ng
lin hp dng (+C) gim. Cc nhm nguyn t c cp in t khng lin kt s
gy hiu ng lin hp dng.

iu ung lien hQp am (-C) cac nguyen tii', nh6m nguyen t o cho hiu

ung liAn hQp am th\tCJng la nh\lng nh6m c6 lin kt pi.

/"'"'\, ro
HO"'-@-

C '7 0 - H

N02, COOR, CHO, CONH, C = N, COR, - S03H. Trong d6

C = 0 > C = NR > C = CR2
/
N02 > CN > CHO > COOH

'

Cac nh6m nay cha hiu ung lin hQp a va

1iu ung ciim ung am ( J)

cung chieu vdi nhau, truang hQp nay hiu dng Uf1C tAng C\tC1ng.

Cung nhu hiu ung cam ung, hiu ung lien hQp mnh la nh\lng nh6m
c6 dQ an1 din ldn ... nh6m

nao c6 d(> am din mnh hdn se chi ph6i chieu

ctia hiu ung.

CH30 - CH = CH2
+ C . -C
CH3 = CH - C = N
+C

-C

!:\r'
NH2
-C

+C

HIU NG SIU LIN HP (HYPERCONJUGATION)

HIU NG SIU LIN HP (HYPERCONJUGATION)
HIU NG SIU LIN HP (HYPERCONJUGATION)
HIU NG KHNG GIAN

HIU NG KHNG GIAN

Svante Arrenhius
3rdNobel Prize Chemistry Greatest American Chemist
not Awarded Nobel Prize
According to the the-0ry proposed. by Svante Arrhenh , a S\.ved ish chen1ist and
\\1inne1.
of the 1903 Nobe] Pdze h1chen1istry, an acid jonjze . in aqueous solution to Ub
erate protons (H+ , hydrogen ions), \\ herea bases ionize to liberate hydroxjde ions
(HO-).A nJore general the-0ry of acids and bases wa . . devised independentJy by
Johannes BHinsted (Denntark) and Thoinas IVl. Lowry (England) in 1923. In the

Br@nsted-L-0\\1ry appoach, an add ls a proton donor, and a ba e is a proton

acceptor.
s/+ H rA -- +

Btl!se Acid Conjugate

add
Conjugate base

In aqueous oluOon, an acid transfers a proton to wate.r. Water acts as a Bn nsted

base.

\Vater

{base)
Acid

Coujugate acid of water

Conjugate
base

The systematic mune for tJ1e conjugate acid of water (H30+) is oxonium ion.Its
com mon name i h)1droniun1 ion.
The strength of an add is measured by its acid cli ociation con tant or ionization
constant K3 o
K

= [H30+][A-]

[HA]

Acid Dissociation Constants Ka and pKa Values for Some Brninsted Acids*
Dissociation
Acid Formula1

Conjugate
constant, KapKa base

Hydrogen iodide HI

=1010

=- 10 1-

Hydrogen bromideHBr = 109 =-9

Br-

Hydrogen chlorideHCI =107 =-7

c1-

5
Sulfuric acid
+

HOS020H 1.6 x 10

-4.8 HOS020Hydronium ion

H-OH2

3.5 x 10-4
0

3.5

55

-1.7 H20 Hydrogen fluoride HF

F-

II
Acetic acid CH3COH
+
Ammonium ion

H-NH3

1.8 x 10-5
5.6 x 10-10
II
4.7

CH3co-

9.2

NH3

Water HOH 1.8 x 10- 16:1:

15.7 HO-

Methanol

CH30H

=10-16

Ethanol

CH3CH20H=10-16

=16 CH30=< 16 CH.3CH20-

lsopropyl alcohol (CH3)iCHOH

=10-17

alcohol

= 18 (CH 3hCO- Ammonia

(CH3hCOH =10- 18

=10-36
Dimethylam ine

-17

(CH3hCHO- tert-Buty l
H2NH

=36 H2 N(CH3)iNH =10-36

=36 (CH3hN-

*Add strength decreases from top to bottom of the table. Strength of conjugate
base i ncreases from top to bottom of the table.
tnie most addic proton -the one that is lost on ion izati on-is h ighlighted.

*The "true " K,. for water is 1 x rn-14 Divi d ing this value by 55.5 (the nu mber
of m oles of water i n 1 L of
water) gives a
K,. of
1.8 x
10- 16
and puts water on the same concentration basis as the other substances in
the table. A paper in the May 1990 issue of the Journal of Chemical Educa tion (p.
386) out I i nes the
just ification for this approach . For a dissenting view, see the March 1992 issue of
the Journal of Chemical
Education (p. 255).

.....,.......

= Br--1..H + o
"H
+ H-Q :

+/
:sr :

"H

&+

}{2{)---tl---:B.r Transition state

Reaction coord inate

.,

NH HNG CA HIU NG TNH CHT ACID- BASE

NH HNG CA HIU NG TNH CHT ACID- BASE
NH HNG CA HIU NG TNH CHT ACID- BASE

NH HNG CA HIU NG TNH CHT ACID- BASE

NH HNG CA HIU NG TNH CHT ACID- BASE

CH3 CH3 CH3 CH3

N02
HNO?,
Ace:ti...::
:iii

:iohydride N02
'Jol11.11e11e

ni-NitJ?oto111.11em.e

HN

N0:2

>

NO'.).

NQi
(Tdfi

ororniethylbenzene

'1-N ttrn tF:ifl uoro

rue1nyt)benzene
(6%)
n:i-Nitro utfih.mro fifiletltilyl be1J1z.ene
(9 l
p-N.iitro tr.iifiuo-ro.
lil!tet111yt)Ilemzellle
J

C CH3b
p- 1u1-BlrityJ.toJme-me
C CH:d3
4-Urt-Blliltyl-...:..-mJi1r0to 11.1ene SS%

B:r

N02
p-N.i trroto.]11J1e11e
N02
2-Brom.o-4-niWoto1.11eirae .86-9oqi; )

Effects of Slrllcfllro on Equilibrium:AJdehydes and ketoues react with water iu

11
rnpid equilibrium:

0
II
RCR'

Aldehyde

Water or ketone

fil3t
...----OH
I
RCR1
I
OH
Ge:m na!I diol
(hydrrue)

[hydrate]

hydr - [carbonyl compmmd][water]

!Equ i libriu m Const ants (Khydr) for Hydration of 'Some Aldehydes and Ketones

Carbon yl
c-0mpound Hydrat:e
Percent c,onversion
to hydratet

0
II
HCH
0
I
CH 3CH
0
II

41

99 96

50
(CH 3hCCH
0
II
CH 3CCH3

2.5 x 10-5
19

0.14

[hyd rate]

U n its of K a re M _ ,

lr1'dr [ca rbonyl compound][water] ITJ'dr o

trot:al conc.ent ration ( hyd rate plus carbonyl compoun::I) assumed to be 1 M.
Water concentration is 55.5 M.

Jncreasiug free radical stabilhy

H

./

./

./

./

H-C R-C R-C R-C

'H

'H

'R

'R

Methyl

Primary

Secondary Tertiary

rndJcal

rndkal

ra.dkal

ra.dkru (least stable)

(most stable)
We assess the relative stability o:f alky1 radicals by measuring tile enthalpy change
H0 ) for the llomol.ytic deavage of a C-H band in an alkane:

The more stable the radical, the lower the energy requil'ed to generate it by C-H
bond homolysis.

Hal f-fillcd

Hal f-fiJlcd
sp3 orbital
)

(a)

(b)

CM N S THEO DI CA CC BN