Todd's Chapter 8 Review Sheet

10. Resonance Stabilization Effect

1. Hydrogen Halide
H

20

H 3C

H Br

10

Br

Z = EN atom with a lone pair (ie: Br, OR, OH, SH)

X = Br, Cl, I, F

C H3

H 3C

Both (Anti, Syn)

H3C

Br

CH3 H

H
C

H 3C

Written by Todd Rothman (C)opyright 2014, Do Not Reproduce without written permission from Todd Rothman

H 2O

1. H 2O

H3C

2. -H

OH

H 3C

H
C

H 2 SO 4

H 3C

Cold

HSO 4

H3C

HO 3 SO

If no H 2O then this is product

H 3C

Both (Syn, Anti)

b.

Nu

C H3

Nu

CH3

C H3

C H3 C H 3

Z = EN atom without a lone pair (ie: C=O , NO2, Z+)

Both (Anti, Syn)

CH3 H

11. Inductive Destabilization Effect

H 2O or ROH
H

CH3

2. Acid Catalyzed Hydration

a.

H 3C

+
H 3C

CH3

Nu

H 3C

CH3

Nu

CH3

12. Oxidative Cleavage rules

if H 2O then same as above.

A. Alkenes

3. Halogenation
H

H
C

KMnO4 /warm

Br

H 3C

Br

Cl
H 3C

Cl

CH 2 Cl 2

H 3C

Br

Cl

X = Br, Cl, I, F

O 3 with Zn or (CH 3)2S

1H

COOH

Just add C=O

2H

CO2

Just add C=O

No H

C=O

Just add C=O

Anti Only

4. Halohydrin (competition)
+

H
C

Br

H 3C

H 2O

Br

Br
H3C

1. H 2O

5. Oxymercuration

Anti Only

Hg Oac

H
C

Hg(Oac)

H 3C

H 2O

H3C

1. H 2O

H2 O or ROH

2. -H

H 3C

2. -H

H3C

Br

OH

B. Alkynes
X = Br, Cl, I, F

HgOac

NaBH 4

O3 with Zn or (CH 3)2S

No H = COOH

Stereochemistry

Anti, Syn

H 3C

or

1H = CO2

Anti Only
H 2O or ROH

KMnO4 /warm

OH H

OH

- If you create a chiral center then 50:50 (R & S)

H

Enantiomers

6. Hydroboration
a.

H
C

H 3C

b.

H
C

H 3C

BH 3

BH2

H2O 2
H

OH

CH3 H

BD 3

THF

Cl
HCl

CH3 H

BH2

R
CH 3 COOT

Syn Only

OH-

CH3 H

CH3 H

BH 3

CH 3COOH

BD 3

CH 3COOD

H
C

H2

H 3C

H
H

BT 3

CH 3COOT

H
C

O
C

H
C

CH3
C

H 3C

RO

20

30

Cl

20
H

A B

Cis -> Syn -> Meso

Syn Only

Syn Addition

Trans -> Anti -> Meso

CH3 H

or

Cl

B
A

CH 2 I2 / Zn(Cu)

Allyl > 3o > 2o > 1o > me

Weakest bond forms the

most stable radical
CH3

Anti Addition

B
A

Syn Only

Alkynes

5
4

+
1

HBr

H2

1
3 2 +

H 3C

H 3C

H 2O

OH

H 2O

6
3

H2

1
2

H 3C

+ 6 5

1
OH

6
5 1
4 3 2

CH3

CH3
C

NH3

H 3C

Br

H 3C

Br 2

Br
H

NaNH 2
C

Br
C

Br

C H3

C
Br

Br
C

H 3C

H 3C

HBr

Br

H 3C

CH3

OH

H
C

Na or Li
C

CH3

Lindlar (P2)

H 3C

Br
Br

CH3 H

5
4

H
C

H3C
+

H 3C

Ni, Pd, Pt

Enantiomers

Best when you can make a 5 or 6 member ring

H 2O

OH

Enantiomers

X = Br or Cl

H 3C

20

alternative: KMnO 4 /cold

H

Br

Intramolecular Reactions

Syn Only

C
H

CH 2 N 2

CH3

CHBr 3

Cation & Radical Stability

H 3C

CH3

OH

Cl

If Meso Potential

CH2

Br

b.

OH
3

H2O

CH 2 N 2

9. Carbenes

H 3C

NaHSO

H
H

NaHSO3 or H2 O2

Cl

CH 2 CH 3

H 3 C CH 2

Os

OsO 4

H 3C

H+ , H2SO4 , H3O+, HX,

H3PO4 , NH4Cl

H 3C

a.

H 2 or D 2 or T

Syn Only

CH3 H

H 3C

Stereochemistry for 2 chiral centers

Common Acids

Ni, Pd, Pt

8. Hydroxylation
H

Diastereomers

7. Hydrogenation
H

Cl

- If you did not create chiral center then it remains the same configuration.
For every BH 3 you
make 3 alcohols

Syn Only

OH-

THF

Cl

HCl

Br 2

C
CH3

Todd's Chapter 9 Review Sheet

Chapter 9 (NMR)
Radio frequency =

- Magnetism = B o

- H1 and C13 have local magnetic fields (LMF) around their nucleus (general rule is atoms with odd atomic number, odd mass
number or both will contain a LMF)

Energy

spin

Bo= 0 T

7T

- By adding an Applied Magnetic Field (AMF) we align the nuclei parrallel ( ) or antiparrallel () to the AMF

spin

- Effective Magnetic Field (EFM) = AMF - LMF

Magnetic field strength

- Depending on the Effective MF, we will resonate to with higher or lower radio frequency

Written by Todd Rothman (C)opyright 2014, Do Not Reproduce without written permission from Todd Rothman

HNMR - 0 - 12

- The greater the EMF (Bo) the greater the energy (rf) required to resonate to spin state

CNMR - 0 - 220

down field
(deshielded)

- Atoms with greater electron density around their nuclei have stronger LMF thereby decreasing the EMF

up field
(shielded)

CH3

Delta Scale (PPM)

12

(TMS) tetramethylsilane =

0 - TMS

H3C

Si C H 3
CH3

HNMR (Characteristics)

a. If the alkene holds a more electronegative atom that does not have a pi bond,
we consider the group inductively effecting the alkene.

Trends to remember

1) signals - (chemical shifts)

O

- only different H's show chemical shifts

a
a

H3C

10 - 9

sp2

> sp

8.5 - 6
>

example 1:
C H

6-4

b
C H

= 4 chemical shifts

methine

H3C

OCH 3

CH2

CH3

methylene

methyl

b. If the alkene holds an atom that has a pi bond, then we must consider the
group resonance effects the alkene.

C H3

a
Ha is most shielded and Hd is least shielded
(closer to the EWG the less shielded)

sp3

Br

c
a

H
H

12 -10

= 2 chemical shifts

O
OH

5) Resonance compared to Inductive influences on chemical shift

- Closer to the EN group, further downfield

- benzene with EN group attached shows separation of the signal

example 1:

2) Integration

a
CH3

d H

Area under the chemical shift tells us the ratio of of H's. This number is provided to you.

CH3

Has resonance

+
3) Multiplicity of a signal

C H

(doublet, triplet, quartet, pentet, sextet, septet, multiplet)

a. only different neighbor H's split

pulls on the
d-bond

(The H's must be 3 or less bonds away to be coupled)

6) Chart Analysis Tips

example 1:

CH3-CH3

example 2:

these H's do not split.

Alkane formula

Hb is split by Ha & Ha is split by Hb

b
a

1. IHD (X = add 1 O = ignore N= Subtract 1)

- Given Formula

# of missing H's / 2 = IHD

b. (n+1) where n = total # of neighbor H's if neighbor H's are different than target.
b

2. Integration (helps us figure out # of H's for each shift)

H

Target

n=6+1=7

C
a

3H = CH3 or 6H = 2 CH3 or 9H = 3CH3

CH 3 a

H 3C

2H = CH2 or 4H = 2 CH2 or 6H = 3CH2

Neighbor H's

3. Count the number of shifts on the chart and compare w/ # of C's

c. The distance between splits is called the Coupling Constant (J). All H's that are
coupled share the same J value (reciprocity of coupling constant)

if # of H-NMR shifts is half or less than # of carbons you know there is

symmetry in your molecule (or a benzene)
4. Look for "key trends to remember" from the chart above

example:

If the J for J ab = 6 Hz then we know the J ba = 6 Hz

5. IR ( 3300 = alcohol or alkyne, 1600 - 1800 C=O or alkene)

6. left side is closest to EN group Right side is furthest away from EN group

d. if coupling constants are different for neighbor H's than we use the formula (n+1)(n+1) to

7. OH and NH groups do not split or get split (have strong H-bonding)

determine multiplicity
H b H
C
C
H3 C
a

Br

8. (splits -1) tells us how many neighbor H's there are for a chemical shift
Hb splitting pattern = (Ha +1)(Hc +1) = (3+1)(1+1) = 8

9. J of ~15Hz = trans alkene

H C

Assuming J is different for J ba and Jbc

Br

You can assume J is different when the neighbors are very

different from each other. The J values are usually
different when H's are attached to sp 2 carbons.

7) C-NMR

e. The intensity of the split can be determined by pascals triangle. (ex. quartet is 1:3:3:1)
4) Splitting diagrams
We do not know when J's are the same or different. They must give you J
values to know for sure. General trend is alkene H's have different J values.
H

H3 C
a

H3 C
b

example where
n+1 = quintet

CH3 a
H

CH3

Jc

- There is no integration, no splitting, no peak intensities because C-NMR works with

C13. C13 is the least abundant in nature (1% chance) so the chances of neighbors being
C13 is no likely. This is why we dont see any common characterisitcs that we see with
H-NMR.

- Generally speaking, the C-NMR identifiers have a similar trend to H-NMR. For example
methyl is furthest to the right, then methylene, then methine.

Jca = Jcd

- C-NMR provides for us the unique number of carbons in a molecule. We determine

unique carbons the same way we determine unique hydrogens.

- C-NMR chart runs from 0 ppm to 220 ppm (H-NMR is only 0-12) They both use TMS as
the reading for 0 ppm Since C-NMR chart is spread out so much more, you don't see
H-NMR readings on a C-NMR chart. H-NMR would be a small clump for the entire
spectrum in a C-NMR chart.

J of ~10 Hz = cis alkene

10. Use C-NMR shifts to determine the number of unique carbons

example where J ba = 3J bc

Jb

(n+1)(n+1)
Quartet of doublets

Jca

Jba

Jcd

Jbc

Todd's Chapter 10 Review Sheet

2) Bond dissociation Energies & Diagrams

1) General Mechanism
H = 440

293

193

CH4 + Br 2

366

CH3Br + HBr

Br2 ---> 2Br.

Written by Todd Rothman (C)opyright 2014, Do Not Reproduce without written permission from Todd Rothman

+H = endothermic

193

.CH

74

+ Br2 ---> CH3 Br + Br.

Br2

1600

82

Cl2

(CH4 + Br2)

1) If Bonds Break --> Eact > 0

3) If Bonds only Form --> Eact = 0

2) If Bonds only Break --> Eact =H

4) If Bonds Break & Form --> Eact > H

4) Thermodynamics (Stability of Products)

(1 X 1600)/1609

H 3C

CH 3

10 H's = 9
# of H's * Selectivity = reactivity factor for the H type (RF)

when comparing 2 products (find the difference in

energy between the 2 (Ga - Gb)

Br2

CH 3

NOTE: I is even more selective and F is even more reactive

strongest bond

Energy of Activation (Eact ) rules

Br

Radical Stability

(- value)

Br

>

Allyl > 3o > 2o > 1o > me > vinyl

weakest bond

3) Determine the Major Product

Selectivity rate

Br

most selective

-100

> Cl >

most reactive

P2

-193

- (products)

Broken = energy required (+ value)

Termination (T)
2Br. ---> Br2

(reactants)

Formed = energy released

P1

Propagation(P1 & P2)

CH4 + Br. ---> .CH3 + HBr

H =

-H = exothermic

Initiation (I)

Rate Step = P1

H = (Bonds broken) - (Formed)

= 633 - 659 = -26

Cl2

(9 X 1)/1609

when the Gdifference = -5.7 then K eq = 101 = 10

the greater Keq the more the major product will form (10 1
= 10 , 10 2 = 100, etc.)

Cl
Cl

if G difference is smaller at the TS compared to the G

of the products then the % of each product will be closer
and not reflect the estimated based on K eq

30 H's = 1
(9 X 1) / 14

(1 X 5) / 14

(RF / sum of all RF) * 100 = percentage of product

5) Stereochemistry

6) Alkene Addition (HBr only)

Cl

Note: this is only 1 of the many

products that can form.

ROOR ---> 2RO.

Ini 2

RO. + HBr ---> ROH + Br.

Cl

P1

Br . +

--->

Br

RR & RS (Diastereomers)

Cl2

Ini 1

R & S (enantiomers)

Cl2
Cl

Br

peroxide

- If you did not create Chiral Center then it remains the same configuration.

Cl

HBr

- If you Form Chiral Center then 50:50 (R & S).

P2

Note: this is only 1 of the many

products that can form.

Br

HBr

--->

Br

R&S

7) Other Reactions:

OH

a)

Br

O2

b)

AIBN

Bu3 SnH

AIBN or H2 O 2

Bu3 SnBr

AIBN
H3 C

Ini 1

H3 C

H3 C

CN

N2

H3 C

Ini 2

HO

Ini 2

HO

Bu3Sn.

OH

OH

P2

Configuration
a) R & S

b) RR & SS

Bu3 SnH

Properties
c) RS & SR

a) RR & RS

H2O

Bu3SnBr

Bu3Sn.

ie.

Br

Yes
unless a racemic mixture is
formed (50:50)

- can be separated (fractions)

Br

RS

or

SR

Optical

-cannot be separated (fractions)

- different properties

b) SS & RS

2 or more chiral centers & plane of symmetry

Meso

- same properties
- can be resolved
Diastereomers

Bu3Sn.

Enantiomers

HO

Br

P1

P2

Bu3 SnH

CH3

CH3

NC

NC

P1

HO

CH3

CH3

H3 C

Ini 1

NC

CH3

NC

- different properties compared to its

diastereomer
- can be separated (fractions)

YES

NO

Br