Chapter3 StructuralEffects PDF

CHEM 35
ORGANIC CHEMISTRY I
III. Structural Effects
Reference: Principles of Organic Chemistry. Lim-Sylianco. 8th Edition
Chem 35 Ch3. Structural Effects 01

3.1 Polycentric Pi Molecular Orbital
• formation of p MOs involving more than two nuclei

• can be noncyclic or cyclic
d-
O
O
R C R C p e- delocalized
O H O H
d+
carboxyl group of organic acids

1,3-butadiene: has 4 p electrons in two p MOs extending over all
the four C nuclei
C CH2 C CH2
H2 C C H2 C C
PMO with one nodal plane PMO with two nodal planes
benzene: has 6 p electrons in three p MOs extending over all 6 C nuclei
one nodal plane two nodal planes two nodal planes

3.2. Pi Electron Delocalization (Resonance)
• popularly known as resonance in the Valence Bond Theory
• associated with systems in which the atoms are sp2 hybridized
• consequences:
1. bond shortening/ strengthening
C-Cl bond is shortened

/strengthened.
2. bond lengthening/weakening
C-O bond is lengthened/

weakened.

3. charge distribution: substituted benzenes
Effect of an electron-donating group (EDG):
Increased electron charge on benzene
 The lone pairs of oxygen (or N and the halides) can delocalize to the benzene
ring or a p system. Even if the lone pair is on an sp3 lobe, a certain degree of
overlapping can occur between the electron cloud of the lone pair and the
sp2 C of the ring due to considerable p character (75%) of the lone pair.

Effect of an electron-withdrawing group (EWG):
decreased electronic charge on benzene
 The direction of p electron movement is away from the ring because of the
partial positivity of the carbonyl C which is attached to the ring. This results
to depletion of electrons from the ortho and para positions.

 The presence of the cyano group on the ring leads to the p electron
delocalization away from the ring. This is due to the orbital electronegativity
of the sp C of CN: greater S character (1/2) than that of benzene (1/3)
making it more EN.

• Different groups on the benzene ring can enhance/reduce the non-
uniform p electron density as a result of delocalization.
• Even without substituents, there is still p electron delocalization

or resonance in benzene as a consequence of the presence of p
polycentric MOs .
 However, the delocalization in the system results in uniform

p electron density on each C: no + or – signs indicated in the
resonance structures.

• Alternant Hydrocarbons: planar unsubstituted rings of HC having
uniform p electron density on all carbons
• Non-alternant Hydrocarbons: those that do not possess p electron
density
 To qualitatively predict whether a planar ring HC is alternant or not: star the

alternate carbons and if no starred carbons/ unstarred carbons are right
next to each other, then the ring is an alternant hydrocarbon.
* * * * * *
* * CH2
* * * * *
* *
*
benzene naphthalene azulene fulvene
(alternant) (alternant) (non-alternant) (non-alternant)

 With alternant HCs, this uniform p electron density is characteristic
of the ground state of the system, i.e., when it is not reacting.
 For benzene, usually an electron deficient species is drawn towards
it because of its p electron cloud above and below the plane of
the ring.
 During reactions, there will be polarization of the p electrons
towards the C that is oriented close to the attacking species. Such
C will have higher electron density than the others as a result of
polarization by the reacting species.
E+ (positive reacting species)

 In alternant HC, wave mechanical theory predicts that auto-
polarization of p electrons at some positions differ.
  
  
1 2 3
(  C: the C right next to the C common to both rings)
 for naphthalene, an E+ will easily form a bond at the  position: has

high autopolarizability at this position (resonance contributing
structures possess a double bond between the  and  positions).

4. Stabilization in some Cyclic systems
• often called conjugate stability or aromaticity
• This thermodynamic stability is exhibited by planar and
conjugated ring systems.
• Aromaticity can be qualitatively detected via the 4n + 2 Rule:
4n + 2 = no. of p electrons If n= 0, 1, 2, 3… : system is aromatic

Examples:
a. Benzene (6 p e-s, 6 MOs)
MOT antibonding
4n + 2 = 6
n=1 bonding
 aromatic

b. Cylcobutadiene (4 p e-s, 4 MOs)
MOT antibonding
4n + 2 = 4
n = 1/2
bonding
 not aromatic
c. Naphthalene (10 p e-s) d. Cyclopentadienyl anion (6 p e-s)
4n + 2 = 10 .. 4n + 2 = 6
n=2 n=1
 aromatic  aromatic
e. Tropylium cation (6 p e-s) f. Cyclopropenyl cation (2 p e-s)

4n + 2 = 6 4n + 2 = 2
n=1 n=0
 aromatic
 aromatic

3.3 Sigma Electron Delocalization (Hyperconjugation)
• The s electrons delocalized usually comes from a C-H bond of

the sp3-s type with a neighboring atom with p orbitals (sp2).
• The s electron release is possible because of the appreciable

p character (75%) of sp3 electrons: allows weak overlap of
sp3 orbitals with a neighboring p orbital.
• Consequently, delocalization of s electrons takes place towards

the sp2 hybridized atoms.
• However, this delocalization does not take place more readily

than p electron delocalization: s electrons are more strongly
attracted to the nuclei than p electrons.

H
Propene
H
H H
H C C CH2 H C C CH2
H H
 Electron delocalization of the three C-H s bonds will give three contributing
structures:
H+
H H
.. .. ..
H C C CH2 +
H C C CH2 H C C CH2
H H H+
1 2 3
 This explains the increase in electron density on the first C of propene.

2-Butene
H H  Hyperconjugation of the 2 CH3s will
H3C C C CH3 give 6 contributing structures.
 Hyperconjugation is responsible for the stability (less reactivity) of 2-butene

towards hydrogenation over propene. 2-Butene has more contributing
structures than propene.

• Alkyl groups attached to benzene can hyperconjugate resulting to
the enrichment of p electron density of ortho and para positions.
toluene CH3
 has 6 contributing structures due to hyperconjugation

 Comparing methylbenzene, ethylbenzene and isopropylbenzene in
terms of number of contributing structures formed:
CH3- > CH3CH2- > CH(CH3)2-
6 > 4 > 2
 The slight acidity of the -Hs of aldehydes and ketones can also be
attributed to hyperconjugation.
H H O H
O
H C C H C C H
H
H H H
H+ O H+ O H
H C C H C C C H
H H H H
acetaldehyde acetone

• Both s and p electron delocalization can be invoked in the
stabilization of some reactive species.
(a) Carbocation or Carbonium ion or Carbenium ion
R
R C
R
(c) Carbanion
(b) Free radical R
R R C
R C R
R

 Carbocations and free radicals are stabilized by hyperconjugation. If
attached to a benzene ring, e--donating groups (EDG) can greatly
add to the stability.
CH2 CH2 CH2 CH2
CH3 CH3 H CH3 CH2 H

H3C C H3C C H2C C H3C C
CH3 CH2 CH3 CH3
H

 A carbocation will be destabilized by the presence of e--withdrawing
groups (EWG).
CH2 CH2 destabilized by adjacent

positive charges
C C
N N

 A carbanion will be stabilized by EWGs and destabilized by EDGs.
CH2 CH2
Stabilization brought by the delocalization

of negative charge.
N O N O
O O
CH2 CH2
Destabilization brought by the adjacent

negative charges.
H C H H C H
H H

3.4 Inductive Effect
• does not involve delocalization of s or p electrons
• results in distortion of electron cloud because of the presence
of strong electronegative groups or atoms, electron-repelling
groups, or groups that have highly polarizable outermost
electrons
(1) Electron-attracting by inductive effect

 those which contain atoms with excess positive charges
R N R S R NH3 NO2
R R

 those which have electronegative atoms
NH2 OH OCH3 Cl Br F
 those with groups exhibiting orbital elecronegativity

N
C N C CH N N
N
 those with outermost electrons which are easily polarizable -I

 When any of these groups is bonded to a tetrahedral C (sp3), the
result is distortion of the electron cloud away from the C: the C
will acquire a partial positive charge
H H
d+
H C Cl H C Cl
H H

 The transmission of inductive effect is attenuated(minimized) as
the distance from the group to the sp3 C is increased.
d+ d++ d+ d++ d+++

CH3—CH2—Cl CH3—CH2—CH2– Cl
(2) Electron-repelling by inductive effect
 usually exhibited by alkyl groups and those that possess excess

negative charges
CH3
CH3 CH2CH3 CH etc.
CH3
COO S O

 When a negative group is bonded to an sp3 C, the electron cloud will
be distorted towards the C increasing the electron density around it.
 For alkyl groups, the bigger the group, the greater is the number of
sp3 electrons polarized, the greater will be the electron-repelling effect.
CH3
H3 C
H3 C C > CH > H2CH3C > H3 C
H3 C
CH3
 This order is the reverse of that due to C-H hyperconjugative electron

release.

3.5 Steric Effects
• structural effects as a result of the presence of bulky groups
• consequences:
(1) p electron delocalization
HC3 C3 H
N
N CH3
vs H3 C CH3
I II
 no hindrance to the  due to the presence of a bulky

delocalization of the CH3 group at the ortho position,
N lone pair towards the amine is rendered out-of-plane
the ring inhibiting lone-pair delocalization

(2) Out-of-plane to in-plane p electron delocalization in the presence
of large atoms in the meta position .
CH3 Br CH3
NO2 vs NO2
CH3 Br CH3
Congestion is relieved by  With the large Br atoms at the

compressing the NO2 group 3 and 5 positions, the CH3 groups
making it out-of-plane. are rendered out-of-plane to
relieve congestion making the
NO2 group remain planar with
the ring (in-plane).

(3) Bulky groups in the ortho positions (2 or 2’) of biphenyl causes
twisting of the 1-1’ bond.
CH3 CH3
vs
CH3 CH3
(4) Some groups that are flexible enough, although present in the ortho
positions, may not cause steric inhibition of p electron delocalization.
H O CH3
 the methyl group of methoxy bends

away from the ortho position to avoid
congestion.
H3 C O H

 But if other bulky groups are present in the meta positions, there will
be loss of flexibility of –OCH3. As a consequence, the 1-1’ bond of
biphenyl will twist (out-of-plane) to relieve congestion.
CH3
OCH3
H3CO
CH3  Buttressing effect: the effect of a
distal bulky group in pushing one
forward to cause congestion.

(5) Steric acceleration of bond cleavage (weakening of some bonds) to
relieve congestion
O O H 2-tert-butyl-benzoic acid
C
 H is compressed out (steric acceleration of
CH3
O-H bond cleavage) due to the bulky
C CH3 t-butyl at the ortho position.
CH3  As a consequence, the acidity is increased.
CH3 H3 C CH3
H3 C C X C
X
CH3 CH3
t-butylhalide  Congestion is relieved.

 congested

(6) Presence of bulky groups may inhibit bond formation.
H H3 C CH3 H CH3
H N + B H N B CH3
H CH3 H CH3
CH2CH3 H3 C CH3
No bond formation
H3CH2C N + B due to steric
CH3 hindrance
CH2CH3
3.6 Hydrogen bonding

Reading Assignment
Van der Waals Forces

3.7 Experimental Observations and Structural Effects
A. Dipole Moments, m
• the product of the magnitude of the charge and the distance
that separates them
• a physical property derived from experimental studies
• examples (all are arranged in order of increasing dipole moment):
(1) Ethyl chloride and vinyl chloride
H H2
H2C C Cl < H3C C Cl
 Because of p electron delocalization present in vinyl chloride, the

negative charge (electron density) in chlorine is reduced.
 The Cl atom on ethyl chloride has enriched electron density because
of its being electron-attracting by inductive effect.
CH3 NO2 NO2
H3C CH3
(2)
< < <
H3C CH3
 Benzene, being aromatic, has uniform p electron density distribution,

hence m = 0. H+
CH3 CH2
 Charges are induced in toluene because of
hyperconjugation. This, however is weak
compared to p electron delocalization.
 Nitrobenzene has a larger m than H3C CH3

2,3,5,6-tetramethylnitrobenzene because
in the latter, p electron delocalization is NO2
inhibited due to steric effects.
H3C CH3

(3) Methanal and propanal
O H
O
C < H3C C C
H H H
H
 Because of hyperconjugation in propanal, its carbonyl O has a denser

electron density than that of methanal.
H2 H2 H2
(4) H3C Br < H3C C Br < H3C C C Br
 The bigger the alkyl group, the greater will be its electron-repelling
inductive effect, the greater its m.

B. Boiling Point/ Volatility
• Boiling point is inversely proportional to volatility.
• B.pt. of a substance depends on the strength of the IMFA

(intermolecular forces of attraction): the stronger the IMFA
interaction between molecules, the higher is the B.pt. of
the substance (the less volatile).
H-bonding Decreasing strength for

Dipole-dipole molecules of comparable
London dispersion/Van der Waals MW.

• Examples (arranged in order of increasing boiling point):
(1) Alkanes CH3CH2CH3 < CH3CH2CH2CH3 < CH3CH2CH2CH2CH3
 For straight-chain alkanes, increasing the number of C’s increases

the boiling point.
 London dispersion/VdW strength depends on the surface area of
the electron surface and the ability of the molecule to approach
more closely.
(2) Branched alkanes
CH3
CH3
H3 C C CH3 < < H3 C CH2CH2CH2CH3
H3 C CH2CH CH3
CH3
 Branching (of comparable MW) lowers the B.pt. because the surface
area of the electron cloud is decreased (weaker VdW).

 Aside from the decrease in e- cloud surface area, branching also inhibits
a close approach among the molecules.
vs
(3) Different hybridizations

H
H3C C CH2 < CH3CH2CH3 < H3C C CH
 sp2 hybrid C has diffused p electron cloud (p orbitals) making approach

between molecules more difficult (lower B.pt.).
 sp hybrid C has orbital electronegativity and that its electron cloud is

tightly held making approach between molecules better (higher B.pt.).

(4) Aromatics
O O O O
CH3 OH NH2 N N
OH
< < < < <
OH
VdW dipole-dipole H-bonding
 Toluene has dipole-dipole IMFA because of the ability of the CH3 to

hyperconjugate.
 Between nitrophenol vs phenol and aniline, nitrophenols have higher B.pt.

because of greater dipole-dipole interaction (greater m, charge separation).

 Aniline has higher B.pt. than phenol since it has less counteracting inductive
effect compared with phenol (O is more EN than N).
OH
Electron Inductive  -OH gives greater e- attracting

delocalization effect effect than –NH2
(5) Other classes of organic compounds (of comparable MW)
Ethers < Ketones < Aldehydes < Carboxylic acids
VdW only though polar, cannot H-bond can have 2 H-bonds

C. Melting Points: have similar concepts involved as in B.pt.
D. Solubility in Water
• Low MW aliphatic alcohols, acids and amines are very soluble
in water. These compounds can form H-bond with water.
• Only polar molecules will dissolve in the polar solvent, like
water.
• As the number of C chain increases, solubility in water
decreases since the nonpolar tail increases making the
molecule more nonpolar.
pentanol < butanol < propanol

• Branching of the molecule will increase its solubility in water.
This is due to the decrease of the surface area of the hydrophobic
portion (weaker VdW).
CH3
CH3CH2CHOH
CH3CH2CH2CH2OH < < H3C C OH
CH3
CH3
• Intramolecular H-bonds reduce the chance of intermolecular

H-bonding.
H OH
O
O
N
O
<
N
O O

• For ethers (ROR’), ketones (RCOR’), aldehydes (RCOH) and esters
(RCOOR’):
 There is no reciprocal H-bonding (i.e. the oxygens in these

groups are not covalently bonded with H).
 The absence of reciprocal H-bonding prevent large

solubilities of these compounds, except for lower aldehydes
and ketones.

E. Acidity
• a measure on the ease by which a compound gives up H+ or
accepts an electron pair
O O
R C R C + H+
O H O
• A good acid must

 possess certain structural effect to give up H+ easily
(in the case of carboxylic acids, a more positive
carbonyl C)
 or have a stable anion counterpart

• Examples (all are arranged in order of increasing acidity)
(1) Difference in length of alkyl groups (or size)
CH3 O
O
H3C C C < CH3CH2CH2COOH < CH3C
OH OH
CH3
 The bigger the alkyl group, the greater will be its e- -repelling by
inductive effect towards the carboxylate group (-COO-) making it
less stable (less acidic).

(2) Presence of electron-attracting groups
CH3CH2COOH < CH2CH2COOH < CH3CHCOOH

Cl Cl
 Chloro substituent makes the compound more acidic because it

draws the electrons to itself by inductive effect, thereby decreasing
the electron density of the carboxylate group.
 2-Chloropropanoic acid is more acidic than 3-chloro because the

inductive effect of chlorine will be felt greatly if it is closer to the
carboxylate group.

(3) Benzoic acids with ortho substituents
 Benzoic acid is very sensitive to steric effect if it has bulky groups in the
ortho position: Steric effect accelerates the H-bond cleavage, enhancing
acidity.
COOH COOH CH3 COOH COOH COOH
C CH3 CH3 Cl NO2
< CH3 < < <
Substituent Effect
-C(CH3)3 steric and e--repelling inductive
enhances negative
charge -CH3 e--repelling inductive and hyperconjugation
-Cl e--donating by resonance but e--attracting
by inductive
decreases negative -NO2 e--withdrawing by both resonance and
charge inductive

(4) Intramolecular H-bonding has an acid-strengthening effect due to
stabilization of the carboxylate ion.
O O O O
C C
H H H
O O O
<

(5) Substituents on the para position depends only on their abilities to
decrease the electron density of the ring.
COOH COOH COOH
< <
OCH3 C
N
 -OCH3 increases the electron density of the ring making the

carboxylate group more unstable, hence less acidic.
 -CN depletes the electron density of the ring making the –COO-
more acidic.

(6) Other classes of organic compounds
Amines (RNH2) < H2O < alcohols (ROH) < phenol
 Phenol is more acidic than aliphatic alcohol because of resonance that
stabilizes the phenoxide anion:
O O O O
 Phenols are not sensitive to steric effect because –OH is not as big a
group as –COOH. However, when large alkyl groups are ortho to the
-OH group, acidity is reduced.

F. Basicity
• a measure on the degree of the availability of lone pair
• Any group that will donate electrons will increase basicity

and groups which withdraw electrons will decrease basicity.
NH3 < H3C N CH3 < H3C NH2 < H3C N H

CH3 CH3
 CH3 substituents increase electron density on N by e- - repelling
inductive effect
 Trimethylamine has low basicity (although there are 3 CH3’s) since

steric hindrance prevents solvents from approaching the lone pair on N.

 Aliphatic amines are more basic than aniline due to delocalization
of the lone pair towards the ring making it less available.
 Presence of alkyl groups on N is base-weakening in aromatic amines

due to pushing effect hastening delocalization of the lone pair
towards the ring.
CH3
HN NH2
<

• Among the anilines, p-methoxyaniline is most basic because of
the e-- donating effect of the -OCH3 substituent (more available
lone pair for N).
NH2 NH2 NH2 NH2 NH2

CH3
< < < <
CH3
N CH3 OCH3
O O
 Presence of an e--withdrawing group (e.g. NO2) decreases the basicity

because it enhances delocalization of the lone pair of N towards the ring.
 Meta position has a weak base-strengthening effect due to induction effect.
However, ortho position is base-weakening due to steric hindrance.

 Steric hindrance that can lead to rotation of N out-of-plane
can strengthen basicity since the lone pair of N is now available

because it can no longer delocalize towards the ring.
H3C CH3 H3C CH3

N N
CH3
<

• Alcohols, esters, ethers and the sulfur analogs also have available
lone pairs but not as available as that in N, hence they are regarded
as weak bases.
 These compounds can share the lone pairs to an H+ (acid) forming
oxonium ions:
H
H+
R O R R O R
H
+
H
R O H R O H
O + OH
H
R C OR R C OR
 When these lone pairs favor delocalization,

their availability will be reduced thus O CH3
reducing basicity.

Chapter3 StructuralEffects PDF

Încărcat de

Informații document

Titlu original

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

Chapter3 StructuralEffects PDF

Încărcat de

Drepturi de autor:

Formate disponibile

CHEM 35

III. Structural Effects

Reference: Principles of Organic Chemistry. Lim-Sylianco. 8th Edition

Chem 35 Ch3. Structural Effects 01

• formation of p MOs involving more than two nuclei

carboxyl group of organic acids

Chem 35 Ch3. Structural Effects 02

benzene: has 6 p electrons in three p MOs extending over all 6 C nuclei

one nodal plane two nodal planes two nodal planes

Chem 35 Ch3. Structural Effects 03

C-Cl bond is shortened

C-O bond is lengthened/

Chem 35 Ch3. Structural Effects 04

Increased electron charge on benzene

Chem 35 Ch3. Structural Effects 05

decreased electronic charge on benzene

Chem 35 Ch3. Structural Effects 06

Chem 35 Ch3. Structural Effects 07

• Even without substituents, there is still p electron delocalization

 However, the delocalization in the system results in uniform

Chem 35 Ch3. Structural Effects 08

 To qualitatively predict whether a planar ring HC is alternant or not: star the

Chem 35 Ch3. Structural Effects 09

E+ (positive reacting species)

Chem 35 Ch3. Structural Effects 10

(  C: the C right next to the C common to both rings)

 for naphthalene, an E+ will easily form a bond at the  position: has

Chem 35 Ch3. Structural Effects 11

4n + 2 = no. of p electrons If n= 0, 1, 2, 3… : system is aromatic

Chem 35 Ch3. Structural Effects 12

c. Naphthalene (10 p e-s) d. Cyclopentadienyl anion (6 p e-s)

e. Tropylium cation (6 p e-s) f. Cyclopropenyl cation (2 p e-s)

Chem 35 Ch3. Structural Effects 13

• The s electrons delocalized usually comes from a C-H bond of

• The s electron release is possible because of the appreciable

• Consequently, delocalization of s electrons takes place towards

• However, this delocalization does not take place more readily

Chem 35 Ch3. Structural Effects 14

 This explains the increase in electron density on the first C of propene.

Chem 35 Ch3. Structural Effects 15

 Hyperconjugation is responsible for the stability (less reactivity) of 2-butene

Chem 35 Ch3. Structural Effects 16

 has 6 contributing structures due to hyperconjugation

Chem 35 Ch3. Structural Effects 17

Chem 35 Ch3. Structural Effects 18

Chem 35 Ch3. Structural Effects 19

CH2 CH2 CH2 CH2

CH3 CH3 H CH3 CH2 H

Chem 35 Ch3. Structural Effects 20

CH2 CH2 destabilized by adjacent

Chem 35 Ch3. Structural Effects 21

Stabilization brought by the delocalization

Destabilization brought by the adjacent

Chem 35 Ch3. Structural Effects 22

(1) Electron-attracting by inductive effect

Chem 35 Ch3. Structural Effects 23

 those with groups exhibiting orbital elecronegativity

 those with outermost electrons which are easily polarizable -I

Chem 35 Ch3. Structural Effects 24

d+ d++ d+ d++ d+++

(2) Electron-repelling by inductive effect

 usually exhibited by alkyl groups and those that possess excess

Chem 35 Ch3. Structural Effects 25