CHEM 353

BRIEF REVIEW
OF

ORGANIC REACTIONS
METHODS OF SYNTHESIS FOR THE MAJOR
FUNCTIONAL GROUPS OF ORGANIC CHEM
THIS SET OF SLIDES IS STILL
UNDER CONSTRUCTION.

PLEASE BE PATIENT
 O

R C Cl

ACID
HALIDES
 SYNTHESIS OF ACID CHLORIDES

thionyl chloride
O O
SOCl2
R C OH R C Cl + SO2 + HCl

Thionyl chloride is a liquid.

You can do the reaction without a solvent
or sometimes benzene is used.

All of the other acid derivatives can be made

from the acid chloride.
 R OH

ALCOHOLS
 SYNTHESIS OF ALCOHOLS
H2 Ni
catalytic
C O C O
hydrogenation 2 atm 40o
H H
ketone or
aldehyde
low reactivity
1. NaBH4 water and
sodium alcohol solvents
C O C O
borohydride are OK
2. H3O+ H H
reduces only aldehydes or ketones

lithium 1. LiAlH4
ether solvent
aluminum C O C O required
hydride 2. H3O+ H H
CAUTION: reduces aldehydes and ketones and
many other polar functional groups
 SYNTHESIS OF ALCOHOLS - 2

R R H gives low yields,

hydration of H2O
oxymercuration
an alkene is a better method
H2SO4
OH
Markovnikov rule

oxymer-
R R HgOAc
curation Hg(OAc)2
H2O
OH

1. NaBH4
2. H3O+
R H

OH Markovnikov
 SYNTHESIS OF ALCOHOLS - 3
solvolysis H2O
R X R OH
of halides
tertiary, allylic
or benzylic

Grignard
Reaction
R' H3 O + R'
R MgX + C O R C OH
R'' R''
ether Mg
R X

alkyllithium compounds
Alkyllithium Li react just like the Grignard
R X R Li
Compounds
ether or pentane or benzene solvent
 SYNTHESIS OF ALCOHOLS - 4
hydroboration- R H ether R H
oxidation 3 B2H6 H H
H H H B

H 2 O2 NaOH

R H R H
+
H3O
3 H H H H
H OH H O
B
anti-Markovnikoff

Grignard + O
1. RMgX / ether
epoxide R CH2 CH2 OH
H H
H H 2. H3O+
S N2 terminal alcohols
Grignard + oxetane
 O

R C H

ALDEHYDES
 SYNTHESIS OF ALDEHYDES

Sarrett Reagent
CrO3 O
R CH2 O H R C
pyridine H
primary
alcohol

Jones Reagent does not

stop at the aldehyde and
gives a carboxylic acid.

Other oxidizing agents usually continue to the acid RCOOH.

Mild Cleavage of alkenes
 R R''
C C
R' R'''

ALKENES
 SYNTHESIS OF ALKENES
E2 heat
elimination R H NaOMe R
stereospecific
R
MeOH anti
X R
X = Cl, Br, I Saytzev Rule
strong bases such as NaOH, NaOR required

dehydration
R H R watch for
H2SO4 rearrangements
R
heat not
acid-assisted OH R stereospecific
E1 elimination Saytzev Rule
strong acids such as H2SO4 and H3PO4 required
 SYNTHESIS OF ALKENES - 2
catalytic
hydrogenation H2 Lindlar R R
R C C R cis
H H
Lindlar = Pd / BaSO4 / quinoline
syn addition

R R
H2 Pd won’t
REMEMBER R C C R stop
H H
2X H H

dissolving metal
reduction Na/NH3 H R
R C C R trans
R H
anti addition
 SYNTHESIS OF ALKENES - 3
Wittig
reaction
R2 R1
benzene + _
R1 C X + (C6H5)3P : (C6H5)3P C R2 X
heat H
H Triphenylphosphine - ..
halide : O-CH
.. 3

ether strong base

O
R1
R1 R3
R3
C
R4
+ - ..
(C6H5)3P C
R2 R4 R2
ylide
reaction assembles Wittig reagent
the two halves
 R C C R'

ALKYNES
 SYNTHESIS OF ACETYLENES
Acetylene from
limestone

C aCO 3 C aO + C O2
calcium carbonate calcium oxide

CaO + 2 C CaC2 + CO
calcium carbide

CaC 2 + 2 H 2 O Ca(OH)2 +
lime

H C C H
acetylene
 SYNTHESIS OF ACETYLENES - 2
alkylation of
acetylene

elimination of dihalides
 O

R C NH2

AMIDES
acid chloride or anhydride with ammonia
 R NH2

AMINES
 O O
R C C R
O

ANHYDRIDES
 SYNTHESIS OF ANHYDRIDES

acid chloride O NaOH O

and sodium - +
R C OH R C O Na
salt
sodium salt
Section 19.25
O O
SOCl2
R C OH R C Cl
acid chloride
O O
R C O C R
anhydride + NaCl
 SYNTHESIS OF ANHYDRIDES - 2

dehydration of
O P2O5 O O
carboxylic acids
R C OH R C O C R
heat

works for small

symmetric anhydrides
only
acids + sulfuric acid
 O
R C
OH

CARBOXYLIC
ACIDS
 SYNTHESIS OF CARBOXYLIC ACIDS
Jones Reagent
CrO3 O
cannot
R CH2 O H R C isolate
H2SO4 H
primary acetone oxidation continues
alcohol O
Sarrett Reagent will stop R C
at the aldehyde. OH
carboxylic acid
oxidation of
an aldehyde O O
[Ox]
R C R C
H OH

Many oxidizing agents will oxidize aldehydes

including: CrO3, K2Cr2O7, KMnO4, H2O2,
Ag(NH4)OH (Tollen’s).
SYNTHESIS OF CARBOXYLIC ACIDS - 2
Grignard or 1) CO2
R-Li + CO2 R-MgX R-COOH
2) H3O+

1) CO2
R-Li R-COOH
2) H3O+
cleaving double
and triple bonds
(oxidation) R R R R
KMnO4 KMnO4
C O C O
H H H HO

Alkenes must have cannot oxidation

…..
hydrogen on the isolate continues
double bond.
SYNTHESIS OF CARBOXYLIC ACIDS - 3
hydrolysis NaCN H2 O 
of a nitrile R-X R-CN R-COOH
acetone H2SO4

NaOH
 H2O
H3O+
R-COO Na
- +
hydrolysis of
acid derivatives
O O O R
or H2O
C C C C O
R Cl R O R HO

O or O R
H2O
C C C O
R NH2 R O R' H2SO4 HO
or
NaOH
SYNTHESIS OF CARBOXYLIC ACIDS - 4
oxidation of a
side chain on
an aromatic
ring O
C
KMnO4 OH

or

CrO3/H2SO4
 O

EPOXIDES
 SYNTHESIS OF EPOXIDES
peracid R R R O R
RCO3H

H H H H
cis cis
stereospecific

R OH R R O R
via NaHCO3
bromohydrin H H H H
Br cis
anti
Br2 H2O
addition
R R stereospecific
overall
cis
H H
 O

R C OR'

ESTERS
Fischer synthesis

acid chloide or anhydride + alcohol

 HO OH

GLYCOLS
DIOLS
 R X

HALIDES
 SYNTHESIS OF HALIDES

* #
thionyl chloride
pyridine
inversion of configuration SN2

thionyl chloride * * + +
ether
retention of configuration S Ni

phosphorous
halides

1o, 2o alcohols inversion of configuration

S N2
 SYNTHESIS OF HALIDES - 2
watch for rearrangements !

concentrated
acids the halide
is often
racemized

1o, 2o alcohols proceed by SN2

(acid assisted)
3o, allylic, benzylic alcohols by SN1
 SYNTHESIS OF HALIDES - 3

R R H
HCl
addition of HX
to alkenes Cl
also HBr, HI Markovnikov rule

free radical R Cl2 R

halogenation R R + HCl
h
H Cl
usually not a rate = 3o H > 2o H > 1o H
good laboratory chain reaction
synthetic method
 O

R C R'

KETONES
oxidation of
alcohols

cleavage of
alkenes
hydrolysis of imines

don’t forget nitrile + Grignard

don’t forget organocadmium + ester

 R C N

NITRILES
 NaCN is soluble in acetone,
SN2 displacement or DMSO could be used
with cyanide
acetone
R CH2 Cl + NaCN R CH2 C N

Primary or
secondary
halides

cyanohydrins
RINGS
CYCLOHEXENES

Diels-Alder

CYCLOPROPANES

Diazomethane

-Eliminations

Simmons-Smith