O

H2CrO4
R

OH

or Na2Cr2O7 /H2SO4
or CrO3/H2SO4

1o ROH

OH

Carboxylic Acids

OH

H2CrO4
R'

or Na2Cr2O7 /H2SO4
or CrO3/H2SO4

2o ROH

R
R'
Ketones

PCC or PDC
R

OH

CH2Cl2

1 ROH

Aldehydes

OH

O
PCC or PDC

R'

CH2Cl2

2 ROH

R
R'
Ketones

Nao or Ko
R

OH
ROH (solvent)

2R

O Na

NaH
OH

2R
ether; THF or alkanes

O Na + H2

(reaction is irreversible)

OH

HX
R''

R'

R'

3o ROH

3 Halides

OH

HX (conc)
R

R''

R (H)

Heat

R (H)
H

1o & 2o Halides

1o & 2o ROH

OH

Cl
SOCl2

R (H)

Pyridine or N(Et)3

R (H)

1o & 2o ROH

1o & 2o Chloride

OH

R (H)
H3O+

R
CH2

R (H)
R (H)

R
CH

-H2O

Alkene
(Zaitsev's rule)

ROH
OH

OR'

1) Nao
R

R (H)
R (H)
ROH

R (H)

2) R'X
o

R
o

1 or 2

R (H)
R (H)
Ether

OH + H

H2SO4
OR'

R
C

CH2 + H

H2SO4
OR'

OR'

Heat

OR'
C

Heat

CH2H

2 H2C

CH2

O2
2 H2C

Ag

R
C

CH2

CH2

RCO3H
C

CH2Cl2

CH2

R
R

OH

NaOH
C

CH2

C
R

O
C
R
R

CH2

CH2

OH

H3O+

C
R
R

CH2
OH

O
C

CH2

OH

Na+CNH2O

(H)R

CH2
CN

(H)R

O
C

CH2

2) H2O

(H)R

OH

1) Na+ C CH

(H)R

O
C

CH2
CH

OH
NH3

CH2

(H)R

CH2
NH2

(H)R

Second Semester
Chap 15:
Mg
R

Mg

ether or THF

MgBr

Mg
ether or THF

OH

O
1) R"
R

(H)R

CH2

2) H3O+

Mg

X
R

(H)R

CH2
R"

OH
1) R"

Mg

C
R

2) H3O+

R(H)

R(H)
R"

R'

R2CuLi

R'

ether or THF

R
+

R2CuLi

ether or THF

Cl3CH + K+ -OtBu

Cl2C
used immediately

R
Cl2C

H
Cl

+
R

Cl
Stereospecific Rxn

O
H2CrO4 (aq)

C
R

aldehyde

or Na2Cr2O7 /H2SO4
or CrO3/H2SO4

C
R

Carboxylic Acid

O
2

O
O2

C
R

OH

aldehyde

C
R

OH

Carboxylic Acid

OH
1) LiAlH4

H(R)

2) H2O

H
H(R)

Carbonyl

Alcohol
O

OH
NaBH4

C
R

H(R)

MeOH; H2O

C
R

Carbonyl

H
H(R)

Alcohol
O

OH
H2

C
R

H(R)

RT, 2 atm

H
H(R)

Carbonyl

Alcohol

O
H2C

2 H2

H2
C

C
C
H

Ni

H(R)

H
C

H
H
H(R)

Carbonyl

Alcohol

C
R

C
H(R)

Zn(Hg), HCl

Carbonyl

H
H(R)

Hydrocarbon
O
C
R

N2H4; KOH
heat;
H(R)

Carbonyl

HO

C
OH

H
H(R)

Hydrocarbon

Nucleophilic Acyl Substitution

O
R'OH

C
R

OH

(cat)

OR'

Carboxylic Acid

Ester

O
HOH

C
R

+ HCl

Cl

Acid Chloride

OH

Carboxylic Acid

+ HOH

H2O

H+ (cat)

C
OH

Carboxylic Acid

Acid Anhydride

H2O
O

H+ (cat)
O

C
R

OR'
C

Ester

NaOH

Carboxylic Acid

O
Na
C
R

OH

H3O

R'OH

H2O
O

H+ (cat)
O

C
R

NH2
C

Amide

NaOH

OH

NH4

Carboxylic Acid

O
H3O+

Na
C
R

H2O
O

H+ (cat)
O

C
R

NH2
C

Amide

NaOH

NH4

OH

Carboxylic Acid

O
+

Na

H3O

C
R

O
R'OH

C
R

Cl

Acid Chloride

+ HCl

C
OR'
Ester

R'OH
R

O
Acid Anhydride

C
R

C
OR'

Ester

HO

Carboxylic Acid

O
R''OH

OR'
Ester

R'OH

OR''
Ester

Alcohol

O
Cl

2 R'NH2

C
R

Cl

Acid Chloride

R'NH3

NHR'

Ammonium
Hydrochloride Salt

Amide

O
2 R'NH2

R'NH3

Acid Anhydride

NHR'

O
2 R'NH2

C
R

OR''

Ester

NHR'

R"OH
Alcohol

Amide

Na
C
R

+
Cl

Acid Chloride

C
O

C
R

Sodium
Carboxylate Salt

Ammonium
Carboxylate Salt

Amide

C
O

Acid Anhydride

OH
1) 2 eq R'MgBr

C
R

OR'

R'

2) H3O+

Ester

R'

3o Alcohol

OH
1) 2 eq R'Li

C
R

OR'

R'

2) H3O+

Ester

+ HOR'

R'

3o Alcohol

O
1) (R')2CuLi

C
R

+ HOR'

Cl

2) H3O+

Acid Chloride

R'

Ketones

OH
1) LAH

C
R

OR'

2) H3O+

C
R

Ester

H
H

1o Alcohol

O
1) DiBAlH

C
R

OR'

2) H3O+

Ester
2AlH2

C
R

Aldehydes

O
H2
C

1) LAH
C
R

2) H3O+

NH2

NH2
-N(H)R2

-N(H)R2
Amide

Amines

H2
C

1) LAH
R

2) H3O+

NH2

Nitrile
Amines

O
C
R

H3O+

H(R')

OH

H3O+

+
HC
O

C
R

OH-

H(R')

H(R')

Na+-OR

C
OR

C
H3C

OR

ROH

OH

-hydroxycarbonyl

H3C

H(R')

-unsaturated carbonyl

C
C
H2
-ketoester

+ ROH
OR

1) Na+-OR / ROH

C
H2

C
R

OR

2)

R"

O
C
HC

OR

R"

-ketoester

O
N

N
H

Br
H

Br

HCl( aq)

R
-substituted ketone

Enamines

Iminium Salt

Chemistry of Acidic Methylene compounds (Acetoacetic & Malonic Ester Synthesis):

O

1) Na+-OR / ROH

C
H2

OR

C
R

2)

R"

O
C
HC

R"

-ketoester

1) NaOH( aq)

2) H3O+( aq)
3) heat

HC
R"

OR

OR

C
R

CH2
O
R"
This is irreversible and leds to
ketone products

Conjugate Addition (1,4 addition or Michael Addition):

1

Nu

Nu

3
2

Nu

OH

The Robinson Ring Anulation:

Stage 1:
Michael Addition

H2CH
O

Stage 2:
Intramolecular
Aldol Condensation

Chapter 22
X
X2
FeX3

Arenes

Halogenated arenes

NO2
HNO3
H2SO4

Arenes

Nitro arenes
SO3H
SO3
H2SO4

Arenes

Arene Sulfonic Acids

R
R

Cl

AlCl3
Arenes

Alkylbenzenes
O

O
C
R

Cl
AlCl3

Arenes

Acylbenzenes

OH
H2
C
R

Phenol

O
Cl

R
C
H2

NaOH(aq);
CH2Cl2;
Bu4N+BrArylethers

CHR

C
OH

H2CrO4
or
KMnO4
Benzoic Acids

Arene

X
CHR2

R2C

X2
heat or h

Arene

Benzyl Halides
Br
CHR2

R2C

NBS
peroxides

Arene

Benzyl Bromides

H2
C

H2
O

Pt or Pd

HO

the
desired
product

CH3

the side product