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3
Hf298 (kcal/mol)
-20.04
-49.90
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
- = (CH3)2
n-octane cyclohexane
H3C-(CH2)6-CH3 (CH2)6
-49.90 kcal/mol -29.58 kcal/mol -20.32 kcal/mol
H H
C - 3 (CH3)
CH3 C
H 3C CH3
isobutane
(CH3)3CH 3 * (-10.02 kcal/mol) -2.01 kcal/mol
-32.07 kcal/mol -30.06 kcal/mol ~ -2 kcal/mol group increment
CH3
C - 4 (CH3) C
CH3
H 3C CH3
neopentane
(CH3)4C 4 * (-10.02 kcal/mol) -0.06 kcal/mol
-40.14 kcal/mol -40.08 kcal/mol ~ 0 kcal/mol group increment
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
H H
H CH3 H CH3
or
H 3C H H CH3 2 "skew"
interactions
CH3 CH3
"skew"
interaction
2 skews 1 skew
- = 1 skew
H 3C CH3
CH3 Which of these compounds is more strained?
H 3C
Why?
CH3 What are their respective heats of formation?
H 3C
H 3C CH3
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
H
H 3C CH3 H 3C CH3 2 skew interactions
CH3
H 3C H CH2CH2CH3 -53.67 kcal/mol
CH3
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
H H AlBr3 H H
H2, cat. low temp.
H H H H
mixture of isomers expt Hf -58.13
10 x -5 = -50
Thermal
4 x -2 = -8 rearrangement
of
Benson = -58 kcal/mol
-12 kcal/mol anthracene
to
AlBr3
driving force
higher temp. tetramethyl-‐
CH3
adamantane
AlBr3 AlBr3
even higher temp.
even higher temp.
Benson
helps
to
4 x -10 = -40
3 x -10 = -30
1 x -10 = -10
understand
7 x -5 = -35
6 x -5 = -30
4x0=0
1 x -2 = -2
8 x -5 = -40
5 x -2 = -10 reac2ons
also.
3x0=0
Benson = -70 kcal/mol Benson = -60 kcal/mol
2 skew = +2
Benson = -65 kcal/mol
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
H H H H Favorable
arrangements
exist
H H H 3C CH3 for
all
subs2tuent
H
H H
H H
H H
H
groups
except
t-‐
R= CH3 R=C2H5
butyl,
which
has
a
H-H bumping H-H bumping much
larger
cis/trans
H H H H
isomer
difference
of
10
kcal/mol
(versus
1
H 3C CH3 H 3C CH3 kcal/mol
for
others)
H 3C CH3 H 3C
CH3H3C
CH3
H H
Bulky
subs2tuents
R=i-C3H7 R=t-C4H9
H-H bumping CH3-CH3 bumping aren’t
always
less
favorable!
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
R = Me ~ Et ~ iPr << tBu R = Me ~ Et << iPr << tBu R = Me << Et << iPr << tBu
-2.04
kcal/mol
-30.03 -32.07 Branching
is
known
to
kcal/mol kcal/mol stabilize
alkanes
(calimetric
-1.65
studies
by
Rossini
in
the
kcal/mol 1930s).
-35.08 -36.73
kcal/mol kcal/mol
What
is
the
physical
origin
of
-5.06 the
stabiliza2on?
kcal/mol
-35.08 -40.14
kcal/mol kcal/mol
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
-2.04
-30.03
kcal/mol At
least
in
part,
this
is
due
to
-32.07
kcal/mol kcal/mol stabilizing
van
der
Waals
interac2ons
between
C
and
H
-1.65
-35.08
kcal/mol atoms
on
1,3-‐disposed
carbon
-36.73
kcal/mol kcal/mol atoms.
-5.06
-35.08
kcal/mol
-40.14
Computa2onally,
very
sensi2ve
to
kcal/mol kcal/mol electron
correla2on.
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
1 protobranch
2 protobranches
But how do we determine the
3 protobranches quantitative value of a protobranching
interaction?
4 protobranches
5 protobranches
* John Pople was the co-recipient of the 1998 Nobel Prize in Chemistry
Changes
in
the
number
of
branches
are
par2cularly
difficult
to
describe
computa2onally.
Systema2c
devia2ons
are
apparent.
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
0 reference standard
CH
C
"Standards" for the assessment of strain should be
selected based on "strain-free" structural features. acetyleneic
27.1
27.3
-bond angles olefinic
8.55
10.19
-torsional angles
-non-bonded interactions
aroma=c
3.29
5.49
alipha=c
-‐2.40
-‐0.10
Illustration: (CH)6
(hypothetical,
Olefins: Hf = 51.3 kcal/mol
resonance free)
(hypothetical,
Aliphatics: Hf = -14.4 kcal/mol
strain free)
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
CH3
H 3C CH3
H 3C CH3
CH3
C12H18 C12H18
Hf -14.6 kcal/mol -36.0 kcal/mol At the extreme, the
aromatic graphite is
CH3
0.5 kcal/mol more stable
than the aliphatic diamond!
H 3C
C14H20 C14H20
Hf -22.4 kcal/mol -48.8 kcal/mol
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
Unsaturation Strain
C6H12
+4.6 kcal/mol
C10H18
-44.0 kcal/mol
-5.8 kcal/mol
Baeyer Strain
60 90
109.49 109.49
109.49 109.49
- 60 - 90
49.49 angle deviation 19.49
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
Based
on
Baeyer’s
assump=on
that
all
rings
are
planar.
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
Strain in Cyclobutane
1.55Å
H H
H
H
H -1.3 kcal/mol H
H
"puckers" H H
H H
H H
H
H
1,3 - transannular CC interactions destabilize cyclobutane
(sum of van der Waals radii ~3.2Å)
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
Cyclopropane Cyclobutane
3 - CH2 groups 4 - CH2 groups
3 * (-5.0) = -15.0 kcal/mol 4 * (-5.0) = -20.0 kcal/mol
expected heat of formation expected heat of formation
Actual heat of formation = 12.7 kcal/mol Actual heat of formation = 6.8 kcal/mol Benson
group
12.7 - (-15.0) = 27.7 kcal/mol 6.8 - (-20.0) = 26.8 kcal/mol increments
can
Ring strain of cyclopropane
be
used
to
derive
Ring strain of cyclobutane
strain
energies
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
Homodesmotic Equations*
The
same
values
can
+ 3 C2H6 3 27.7 kcal/mol
reproduced
directly
12.7 3(-20.0) 3(-25.0)
using
chemical
equa=ons
coupled
with
+ 4 C2H6 4 26.8 kcal/mol
experimental
(or
6.8 4(-20.0) 4(-25.0)
computa=onally
determined)
heats
of
+ 5 C2H6 5 6.7 kcal/mol forma=on.
-18.3 5(-20.0) 5(-25.0)
But
are
these
equa=ons
+ 6 C2H6 6 0.6 kcal/mol appropriate?
-29.4 6(-20.0) 6(-25.0)
What
about
the
* a reaction which has: (a) equal numbers of each type of carbon-carbon bond
[C(sp3)-C(sp3), etc.] in reactants and products and (b) equal numbers of each
type of carbon atom (sp3, sp2, sp) with one, two, or three H atoms attached
reference
compounds?
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
2 cross-ring
geminal C-C + 4 C2H6 4 4 protobranches
interactions
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
2 protobranches 4 protobranches
2 protobranches 0 protobranches
2 protobranches 2 protobranches
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
5 protobranches 5 protobranches
6 protobranches 6 protobranches
Antibonding
Partial occupation of
antibonding orbital
H
C C CH2 sigma pi
H
H
Bonding
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
Homodesmo=c
+ C2H6 + 4.9 kcal/mol
assessments
(equa=ons
1
and
2)
are
imbalanced.
1 "yne" hyperconjugation 1 protobranch
Equa=ons
3
and
4
are
+ CH4 + 5.5 kcal/mol more
appropriate!
1 "ene" hyperconjugation
+ CH4 + 7.7 kcal/mol
1 "yne" hyperconjugation
Chapter
3
3.
Strain/Stabiliza=on
of
Organic
Molecules
"textbook" description
of diene conjugation
???
+ 2 3.7 kcal/mol
+ 2 0.0 kcal/mol
1. Using
what
you
have
learned
about
alkane
stabili2es,
rank
the
following
alkanes
in
order
of
lowest
(most
nega2ve)
to
highest
heat
of
forma2on.
2. Write
appropriate
equa2ons
to
es2mate
the
cage
strain
of
tetrahedrane
and
H
adamantane.
H H C
C
CH
C 2 2
H 2C
HC CH
C C
H C H2
HC CH H
H 2C C
H2
tetrahedrane adamantane
Hint:
Start
with
isobutane
to
balance
“CH”
groups
and
propane
to
balance
“CH2”
groups