R

Alcohols - Preparation
R

H2O
or
R'OH

NaBH4

Hg(OAc)2

R
H OH

or
R
H

H2O2

BH3

Markovnicov
(see CHEM212)

R
R
H OR'

Anti-Markovnicov

H
R
HO H

OH
R

RX + Mg

RMgX
O

H2O
acid or base

Grignard reaction
X = halogen (F, Cl, Br, I)

OH
OR'

+ HOR'

R
R

R-OH + HX
O

Li
RX + or
Na
O

RLi
or
RNa

OH
R

reduction
HO

(see aldehydes and ketones section)

oxidation

Alcohols - Reactions

HX
ROH

PX3

RX

SOCl2

ROH + M

RO- +M

acid-base reaction
M = Li, Na, K, or appropriate base
see pKa list and other acid-base reactions

HF or TBAF
R'OH + R3SiCl

R'OSiR3

R'OH

Protection/
Deprotection

Ethers - Preparation

RO- +Na

+ R'X

Williamson synthesis
X = halogens =F, Br, Cl or I

RO-R'

+ CF3CO3H

epoxide formation

NaOH
Cl2

OH
Cl

Ethers - Reactions
Epoxides are the only ethers that react

OH

ROH, H+

OR

RO- +Na

OH
OR

trans-1,2-diols
acidic: attack at more substituted C
basic: attack at least substituted C

Aldehydes and Ketones - Reactions Part 1

OH
R'
R

Mg

+ Br-R'

+ R'-SH

Acetal Formation
(protection)
Hemiacetals are NOT stable

OR'
R
OR'
R

anhydrous H+

R'-OH

Grignard (see alcohol section)

anhydrous H+

SR'
SR'
R

Thioacetal Formation

RaNi
H2

H
R

H
R

O
R

+ H2N-NH2

O
R

NH2

NaOH

R
R

+ H2N-R'

Wolff-Kishner reaction

R'
N

imine

primary amines
R' = alkyl, aryl, -OH, -NH2, -NHCONH2

R'
O
R

+
R

R'
HN

R'

secondary amines

R'
R

enamine

Cont'd Aldehydes and Ketones - Reactions Part 2

R"
C
R'''

R'''

Br

base

C PR3

R"

R'

R'''

strong base if R' = alkyl

weak base if R' is conjugated to C=P

Br2, P
R'

Wittig

Z product
E product

R'

or
Br2, H+

alpha-halogenation
(at C-2)

Br

Br2, P

OH

alpha-halogenation
(at C-2)

OH
Br

+
R

R'
O

O
R

R"

PR3

R'''

R'

OH

NaOH

-H2O
R'''

R'

R'''

R' R"

R"

Aldol

R"

aldehydes or ketones

+
R

OR'

OR'

NaOR'

R"

Claisen Condensation
OR'

R"

esters
Nuc O

Nucleophile

R'

aldehydes, ketones or esters

R'

Michael addition
Nucleophile = carbanion,
RSH, RNH2, ROH, etc.

Carboxylic Acids - Preparation

Oxidations

RCH2OH

O
R

KMnO4
OH-

RCO2H

KMnO4
or
CrO3
or
Ag2O, -OH

O
R

OH

KMnO4

R
R'

OHO3

R
O

HO

H2O2

OH
O
R'

Different from ozonolysis

O3
R'

PPh3

or Zn

Substitutions (add more carbons)

R-Mg-X + CO2

R-X + NaCN

H+

H+ or OHR-CN

Grignard

RCO2H

RCO2H

H
R'

Carboxylic Acids - Reactions

R'CO2

O
O

R'

R'OH
SOCl2 or

RCO2H

PCl3 or PCl5

O
R

OR'
O

NH3

Cl

NH2
O

R'NH2
R

H2O

R'2NH
R

H2O

OH

O
R

-O

NH3

OR'

+
+

NR'2

RCO2R'

RCO2H + R'NH2 + DCC

RCONHR'

OR'

R-CH2-CO2H

X2, P

-O

+ DCU
+ DCU

Ester hydrolysis

OH

H2O

-O
O

RCO2H + R'OH + DCC

NaOH

R
O

NHR'

-O

R'2NH

R
O

NH2

-O

R'NH2

R
O

O
O

NR'2

R'OH

NHR'

alpha-halogenation

R-CH-CO2H
X

O
R

heat
OH

acid or base

+ CO2

Decarboxylation of beta-keto
carboxylic acids

Amines - Preparation
H2, Pt

R-NO2
Ar-NO2
R C N

R-NH2

1) Fe, HCl, heat

2) HOH2, RaNi

Ar-NH2

R-CH2-NH2

or LiAlH4

Reductions

O
R

NH2

RX +

H2, RaNi

R-CH2-NH2

or LiAlH4

NaN3

H2N-OH

RN3

OH

LiAlH4

NaBH3CN

R-NH2

NH2

NHR

Nucleophilic
Substitution

or H2, Ni
oxime
O

R-NH2

imine

R-NH-R'

NaBH3CN

Reductive
Amination

or H2, Ni

+ R'

NaCNBH3
or H2, Ni

immonium salt

R
N R'

Amines - Reactions

R-NH2

O
R

+ Cl

R'

N
H

RCO2H

+ R'NH2 + DCC

N
H

R'

Ar-NH2 + HONO

+ HONO

R'

Ar-N2+

HO

R'

+ DCU

H2O, H+
KI
HBr, CuBr
HCl, CuCl
HBF4, heat
H3PO2
NaCN or CuCN

Ar-OH
Ar-I
Ar-Br
Ar-Cl
Ar-F
Ar-H
Ar-CN

N=O

Ar N

Amide Formation

RCONHR'

diazonium salt

1o amine arom

R-NH2

R'

R'
O

Ar N

Reaction with acids

R-NH3+ + A-

R-NH2 + HA

N-nitrosamine

2o amine arom

R N

+ HONO

R N

N=O
R

N-nitrosamine

2o amine aliphatic

R
R

+ HONO

O N

R
R

3o amine arom

1o and 3o amines aliphatic + HONO

complex mixtures (useless)