Documente Academic
Documente Profesional
Documente Cultură
I. Conformations of Alkanes
A. Ethane: torsional strain
H
C
C
H
H
H
staggered
conformation
rotate 60
H C C H
H
H
in between:
skewed
eclipsed
conformation
H
H
H
H
H
H
H
H
Chem3D
H
H
H
H
Stereoisomers:
Isomers with the
same connectivity,
but different 3-D
orientation of their
atoms in space.
2
I. Conformations of Alkanes
A. Ethane: torsional strain
H
H
H
H
H
H
H
H
H
H
H
H
lower energy
higher energy
DG ~ 3 kcal/mol
K ~ 0.01
torsional strain
Ea ~ 3 kcal/mol
DG
0
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
I. Conformations of Alkanes
B. Butane: steric repulsions
CH3
CH3
I
anti
(180)
CH3
H3C
CH3
CH3CH2CH2CH3
CH33
CH3
CH3
CH3
H3C
CH3
II
III
gauche
(60)
IV
V
gauche
(60)
VI
Chem3D
I. Conformations of Alkanes
B. Butane: steric repulsions
CH3
CH3
H3C
CH3
CH33
CH3
CH3
CH3
H3C
CH3
I
CH3
II
III
IV
VI
4
DG
~6
2
3.6
0.8
0.8
3.6
0
I
II
III
IV
VI
per CH2
small
normal
medium
Total
ring strain
166.6 kcal
31.5 kcal
162.7
26.4
157.3
7.0
156.1
157.0
6.3
157.3
9.6
156.2
1.2
minimal strain
transannular
steric strain
7
H H
H
H
H
H
plus ,
H
H
H
H
all Hs eclipsed =
torsional strain
H
Chem3D
8
H
H
Chem3D
H
H
H
H
H
H
planar, 90
but all eclipsed
H
H
puckered, 88
slightly more angle strain,
but less eclipsing strain
envelope
relieves eclipsing
planar, 108
but all eclipsed
9
H
H
H
H
H
H
H
flagpole interaction
H
H
H
H
H
H
H
H
chair conformation
- all staggered
- no eclipsing
- no steric strain
no ring strain
(99.99% at room temp.)
DG ~ 7 kcal
Chem3D
boat conformation
- eclipsing ~ 4 kcal
- steric strain ~ 3 kcal
ring strain ~ 7 kcal
skewed boat ~ 1.5 kcal
more stable than boat
(0.01% at room temp.)
10
H
H
H
H
H
H
H
H
H
H
H
H
H
H
axial positions
equatorial positions
3. chair-chair interconversion
H
H
H
H
H
H
H
H
H
H
H
H
Ea ~ 10 kcal
H
H
H
H
H
H
11
12
Ray
C. Substituted cyclohexanes
CH3
1,3-diaxial
repulsions
CH3
H
H
CH3
H
equatorial
(95%)
no steric strain
(anti)
Chem3D
DG ~ 1.8 kcal
(or 0.9 kcal
per CH3-H
repulsion)
axial
(5%)
steric repulsions
(gauche)
13
(99.99%)
DG ~ 5.5 kcal
(0.01%)
14
CH3
CH3
CH3
trans-
cis-1,4-dimethylcyclohexane
stereoisomers
*configurational
conformational
(cannot convert from
(can be converted from
one to another without
to another by rotation
breaking bonds)
about a bond)
*geometric isomers
15
CH3
CH3
CH3
CH3
H
CH3
DG ~ 3.6 kcal
CH3
H
CH3
diequatorial
no repulsions
diaxial
4 1,3-diaxial repulsions
= 4 x 0.9 = 3.6 kcal
16
CH3
H3C
CH3
CH3
H
CH3
equatorial-axial
2 x 0.9 = 1.8 kcal
CH3
CH3
DG = 0 kcal
axial-equatorial
2 x 0.9 = 1.8 kcal
17
CH3
H
CH3
CH3
H
1 gauche interaction
= 0.9 kcal
DG ~ 2.7 kcal
H
CH3
4 1,3-diaxial repulsions
= 4 x 0.9 = 3.6 kcal
18
CH3
CH3
CH3
H3C
no repulsions
DG ~ 5.4 kcal
CH3
19
tBu
CH3
DG ~ 3.7 kcal
CH3
1.8 kcal
5.5 kcal
20
CH3
CH3
CH3
CH3
Check Answer
21
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH(CH3)2
borneol OH
decalin
bicyclic
Bicycloalkanes:
Cy
C
Cx
Cz
adamantane
prismane
tricyclic
tetracyclic
bicyclo[x.y.z]alkane (x y z)
numbering starts at a bridgehead,
proceeds around the largest bridge first,
then around successively smaller
bridges
23
bicyclo[4.0]decane
bicyclo[2.2.1.]heptane
bicyclo[4.1.0]heptane
bicyclo[3.2.1]octane
24
ethylene oxide
oxirane
oxacyclopropane
H
N
pyrrolidine
azacyclopentane
oxetane
oxacyclobutane
O
tetrahydrofuran
oxacyclopentane
N
piperidine
azacyclohexane
O
tetrahydropyran
oxacyclohexane
furan
pyran
25