Chapter 13

compds to Iorm chains : open-chain compds

compds to Iorm ring : cyclic compds alicyclic compds
nomenclature
Cl
OH OH
chemistry is similar
to open-chain compds
Mo

Al

, high P
H

, Ni
, high P
X
X
M MX
X
Cl
Cl
MX
X
Zn
NaI
intramolecular rxn cI) intermolecular rxn
cycloaddition
cycloalkane : halogenation by Iree radical mechanism
cycloalkene :
O
O
I
HI
Br
Br Br

, Ni
, high P

Ni, H

Cl

, FeCl

conc. H

SO

CH

H
CH

CH

H
CH

Cl
CH

CH

Cl
CH

H
CH

CH

OH
X
Y
X
Y
general trend
Ior addition rxn
alkene
cyclopropane cyclobutane
Baeyer : strain theory deviation Irom 109.5

cyclopropane : 109.5 60 49.5

cyclobutane : 109.5 90 19.5

heats oI combustion relative stabilities CH

group oI open-chain alkane

157.4 kcal
puckered rings are Ilat?
compare with
Baeyer theory
Table 13.2
cylopropane : planar
cyclobutane
large rings are stable Is it easy to synthesize them?
No
Why? the larger ring
the longer chain
the less likely the
two ends oI the chain
approach each other
intramolecular rxn
intermolecular rxn
high
dilution
the greater overlap oI atomic orbital the stronger bond C : 109.5

Ior the strongest

bond
Ior cyclopropane
60

less
overlap
weaker
bond
higher
reactivity
cyclopentane
: puckered in spite oI increased angle strain
(Fig 13.3)

quantum mechanics :
H
H
sp

s
sp

sp
high p character
locate largely
outside the ring
more
reactive
more exposed
chemistry oI
cyclic compd
conIormational
analysis
angle strain, tortional strain, van der Waals strain
dipole-dipole interaction (steric strain)
cyclohexane
perIectly staggered. Iree oI angle strain
tortional strain
the most stable
conIormer
energy minimum
chair Iorm
twist boat
minimize Ilagpole-Ilagpole interactions
relieve tortional strain
energy minimum
conIormer
halI chair
at the highest energy barrier Eig 13.7
cyclopentane puckered at the cost oI angle strain due to tortional strain
cyclobutane puckered at the cost oI angle strain due to tortional strain
boat Iorm
Ilagpole H
not conIormer
but transition
state between
two conIormers
eclipsed, tortional strain, van der Waals (sum oI
radius 2.5 ) strain between Ilagpole H's (1.83 ) A
energy maximum
( Irom sp

p ? )
A
H
H
H
H
H
H
H
H
H
H
H
H
axial
equatorial
2.3 is Iavorable distance A
2.3A
2.3A
H
H
CH

H
CH

H
H
less
interaction
1.8 kcal
more interaction
1,3-diaxial interaction
CH

: 1.8 kcal
gauche n-butane
interaction
H
CH

H
2
1 : 0.9 kcal

diIIerent orientation in space
stereoisomer
not conIormational isomer
but conIigurational isomer
no interconversion
by rotation
diastereomer not mirror image
I : cis
II : trans
not superimposable
enantiomer
meso
trans -1,2-dimethylcyclohexane
cis-1,2-dimethylcyclohexane
CH

CH

CH

CH

diequatorial diaxial
eq-ax ax-eq
H

C CH

CH

CH

I II
OH
OH
HO
OH
HO
OH
HO
OH
HO
OH

trans is more stable than cis : the same distance between methyl groups.
the diIIerence is 1,3-diaxial interactions.
~ 1.8 kcal/mole is more stable.
t-Butyl group locks the molecule in a single conIormation.
CH

CH

C
H

C
H

C
CH

CH
H

C
not superimposable
not interconvertible
enantiomer
not superimposible
interconvertible
Elimination
X
H
H
X
B
anti-elimination syn-elimination
electronically periplanar eliminations are the most Iavorable.
anti-elimation is more Iavorable due to conIormational eIIects
Cl
CH

i-Pr
CH

i-Pr
CH

i-Pr
Cl
CH

i-Pr
CH

i-Pr
cyclohexane : syn-elimination diIIicult
cyclopentane : syn-elimination easy
due to
anti-elimination
25
75
B

CH

NN
uv
CH

diazomethane
CH

CO
uv
CH

methylene, carbene
H C
H
H C
H
singlet
triplet
lose
energy
(diradical)
CH

in
CH

in
(l)
h
stereospeciIic
CH

singlet
C
CH

C
stereospeciIic electrophilic
addition
(l)
h

CH

in
(g) or cis/trans
CH

C C
CH

non-stereospeciIic Iree-radical
addition
triplet
cycloaddition
cI) CH

C H C CH

H (insertion)
CH

CH CHCH

CHCl

tBuOK
H

CC
C
CCH

Cl Cl
H H
CHCl

tBuO CCl

tBuOH

CCl

CCl

Cl

1,1-elimination
CH

CHCHCH

CHC
CCl

CHCH

believed to be singlet stereospeciIic addition (syn)

CCl

ketene
(g)

CH

Zn (Cu) ICH

ZnI (not Iree carbene but carbenoid)

C C
ICH

ZnI
C
CH

C
Zn I I
(stereospeciIic)
cyclic ethers
O
O
O O
1,4-dioxane Iuran tetrahydroIuran (THE)
18-crown-6 :
18 atoms in the ring
6 oxygen atoms
O O
O O
O O
interior : hydrophilic
exterior : lipophilic
hole : 2.7 diameter A
K : 2.66 diameter
Iit to 18-crown-6
potassium salt can
be delivered into
organic layer
loose ion pair
anion is very reactive
18-crown-6 : host
K : guest
15-crown-5
12-crown-4
Na
Li
antibiotics
A

epoxide :
C
O
C
( oxirane )

CH

CH

Ag
ethylene oxide
O
BrCH

CH

-OH OH
CH

CH

Br
O

C
O
CH

Br


O
Ph C O O H
O
O PhCOOH
epoxide is reactive due to angle strain.
C C
Me
H
Et
Me
C
O
C Me
Et
H Me
C
O
H
C
Me Et
H Me
C C
H Me
Me
Et
HO OH
MnO

or OsO

H
ROH
H
C C
Me Me
H Et
HO OH
C C
H ROH
Me
Me
HO Et
CH

O (cat) H

C
O
CH

CH

OCH

CH

O
CH

OH
CH

OCH

CH

OH
H

C
O
CH

RMgX RCH

CH

OMgX
H

O
RCH

CH

OH
(require strong Nu under
alkaline conditions)
CH

(not Ior other epoxides)

C
O
CH

CH

C
OCH

C
O
CH

CH

C
ROH
H
C
O
H
CH

CH

C C
O
H
CH

CH

C
C
O
CH

C
CH

ONa, CH

OH
charge dispersal
crowding is less
important.
more bond-breaking
less bond-making
HOR
H

C
+
+
+
+
H

C C CH

OCH

CH

OH
bond-making bond-breaking
steric eIIect is important.
S

2


H

C C CH

OH
OR
CH

not S

1
S

2-like
oleIin Br

O
IN

or BrN

+
O

KMnO

NaIO

Zn, H

O
CHO
CHO
COOH
COOH