2/14/14

1
!"#$%&'
sp hybrldlzauon (red) wlll form a slgma bond,
Lwo unhybrldlzed p orblLals (grey and whlLe)
wlll form Lwo pl bonds
!
!
#
!
!
#
8ond lengLhs and bond angles of dlerenL 2C hydrocarbon sysLems:
eLhane
eLhene
(eLhylene)
eLhyne
(aceLylene)
alkane ane
alkene
alkyne
eoe
yoe
tetmlool lotetool
)*+,&*-&' +. !"#$%&'
1-hexyne (1-hexene) (hexane)
bp/C 72 63.4 68.7
mp/C -124 -139.8 -93.3
denslLy(g/
mL)
0.719 0.673 0.660
waLer
solublllLy
negllglble negllglble negllglble
nonpolar, soluble ln mosL organlc solvenLs
bolllng polnLs are slmllar Lo alkane of same slze
less dense Lhan waLer
up Lo four carbons, gas aL room LemperaLure
!/0102$ +. 3&*40%5" !"#$%&'
hybrldlzau
on of C
sp
3
sp
2
sp
geomeLry LeLrahedral planar llnear
s
characLer
23 33 30
pka 62 43 26
relauve acldlLy of Lermlnal alkynes
(over oLher hydrocarbons) can be
explalned by Lhe hlgher s characLer
of Lhe C. 1hls means Lhe C has a
greaLer elecLronegauvlLy and
Lherefore can carry Lhe negauve
charge beuer (Lhan sp
3
and sp
2

carbons).
A sttooq bose llke NoNn
2
(pko of Nn
J
=
J8) coo Jeptotooote o tetmlool olkyoe.
AlkoxlJes (
-
Ok, pko of kOn = 16-18)
ooJ byJtoxlJes (
-
On, pko of wotet = 14)
ote oot sttooq eoooqb. (kecoll pko,
oclJ-bose epolllbtlom)
6$1*+7&%5-+% +. !"#$%&'
Llke alkenes, alkynes undergo slmllar reacuons (malnly due Lo Lhelr unsaLuraLed
naLure, le Lhe Lrlple bond)
under normal hydrogenauon condluons (le P
2
, d, L or nl caLalysL) lL's hard Lo sLop Lhe
reacuon aL Lhe alkene sLage so lL ls reduced furLher Lo Lhe alkane
1o sLop aL Lhe alkene, Lhe caLalysL can be polsoned" Lo reduce lLs acuvlLy: use Llndlar's
caLalysL:
cls
cls
80%1"5*9' /525"$'2
2/14/14
2
:0''+";0%7 <&25" =&1>/-+% +.
!"#$%&'
MeLal dlssolved ln llquld ammonla ls e
-
source
8educuon vla free-radlcal lnluaLed-mechanlsm
roducL ls ttoos (complemenLs Llndlar reducuon)
8educuon sLops aL Lhe alkene
ttoos
!110-+% +. 6? 2+ !"#$%&'
8ecall Px addluon Lo alkenes:
WlLh alkynes:
C$ (2)
2 vlnyl C$
sLablllLy : 2 vlnyl C$ = 1 C$,
1 vlnyl C$, hardly forms aL all
P8r
qem-dlbromoalkane
(2 8r on Lhe same C)
wltb excess, n8t, qemJlboloolkooes
ote ptoJoceJ
teocuoo ls osefol ooly
wltb tetmlool ot
symmettlcol olkyoes
oJJluoo follows
Motkovolkov tole
1 vlnyl C$
!110-+% +. 6? 2+ !"#$%&' @02A
)&*+B01&
8ecall peroxlde eecL ln Px addluon Lo alkenes:
oou-Motkovolkov
1 vlnyl l8 2 vlnyl l8
WlLh alkynes:
+
mlxLure of and 2 alkenes
allyllc l8
CD
*&5**5%7&4&%2E
2
!110-+% +. F65"+7&%'G ?
H
3+ !"#$%&'
Addluon reacuons of alkynes are slmllar Lo Lhose of alkenes
lnLermedlaLe alkene reacLs furLher wlLh excess reagenL
8eglospeclclLy follows Markovnlkov rule (lrrelevanL wlLh
excess reagenL)
x = 8r, Cl or l
ttoos
2/14/14
3
!110-+% +. I52&* 2+ !"#$%&'
8ecall hydrauon of alkenes:
teqlo-ooJ steteocbemlsttles
JepeoJ oo tbe cooJluoos
WlLh Lermlnal alkynes:
=

eool
(alkene and alcohol)
keto
(keLone)
!"#$%"&$'
#)*#$+",-.+/
osoolly tbe ketooe
fotm ls mote stoble
ooJ tbetefote tbe
fovoteJ sttoctote
follows
Motkovolkov
oJJluoo
,*+1>/2
35>2+4&*0J5-+%: equlllbrlum beLween Lwo lsomers (LauLomers)
LhaL lnvolves rearrangemenL of a proLon and pl bond
under hydroborauon condluons:
!110-+% +. I52&* 2+ !"#$%&'
oou-Motkovolkov, syo oJJluoo
=

olJebyJe
eool
0'#1$*21 -#3. )& )'4"154"6
-#3. .7'' 8$&.-4","4
#)*#$+",-.+ ,*+1>/2
WlLh lnLernal alkynes:
K. = L =9 M
'54& ,*+1>/2'E
DB015-;& N"&5;57& +. !"#$%&'
@02A DJ+%&
8ecall alkene reacuon:
keLones and/or aldehydes
WlLh Lermlnal alkyne:
WlLh lnLernal alkyne:
cotboolc oclJ
lo tetms of teocuvlty, olkeoes ote mote teocuve tboo olkyoes towotJ ozooolysls
DB015-+% +. !"#$%&' @02A )+25''0>4
)&*45%75%52& FO<%D
P
G
o Jlketooe
CD3QR %&>2*5" /+%10-+%
kMnC
4

kCP, heaL
P
3
C
+

+
+
CD3QR S5'0/M @5*4
/+%10-+%
uepeoJloq oo tbe cooJluoo, petmooqooote
oxlJouoo coo moke Jlketooes ot
cotboxyllc oclJs
- 2P
2
C