Organic Reactions Summary

Alkanes
1. 2. 3. Combustion: Cracking: Halogenation: alkane + O2 CO2 + H2O alkane alkane + alkene halogen + alkane uv haloalkane light
heat, no O2

Alkenes
1. Oxidation reactions a) Combustion: b) moderate oxidation: 2. a) b) c) d) alkene + O2 CO2 + H2O alkene + cold dilute KMnO4 diol + 2 MnO2 + 2 KOH H2 alkane X2 dihaloalkane H2O alcohol HX haloalkane
Pt

Electrophilic Addition reactions Hydrogenation: alkene Halogenation: alkene Hydration: alkene with HX: alkene

+ + + +

Note: For the final two addition reactions, use Markovnikov's Rule add the hydrogen to the carbon with the most hydrogens. If they have the same number of hydrogen atoms, you will have two possible products. 3. Addition Polymerization alkene
,P

polymer (long chain alkane)

Alkynes
1. 2. 3. Combustion: Acid Addition reactions: exception: alkyne + O2 CO2 + H2O R-C CH R-C C - + H + see alkenes use Markovnikov where applicable
R C C R + H 2O

OH C CH R

O C

CH2 R

Haloalkanes
1. 2. 3. 4. Nucleophilic Substitution (SN2)(1 RX, non-polar solvent, strong Nu) Nucleophilic Substitution (SN1)(3 RX, polar solvent, weak Nu) Elimination (E2)(3 RX, strong Nu) Unimolecular Elimination (E1) (3 RX, polar solvent, weak Nu) RX RX RX RX + + + + NuNuNuNu R-Nu + XR-Nu + Xalkene + NuH + Xalkene + NuH + X-

Aromatics
1. a) Electrophilic Substitution FeX3 or AlX3 Halogenation: Benzene + X2 halobenzene + HX Note: Alkyl side chains will readily undergo free radical halogenation without any addition to the ring. H+ Benzene + HNO3 nitrobenzene + H2O FeX3 or AlX3
CH HC CH
CH HC CH CH C CH C R

b) Nitration

CH C CH
O

c)

Friedel-Crafts Alkylation

Benzene + RX =O

+ HCl

d) Friedel-Crafts Acylation

FeX3 or AlX3 Benzene + RCX

+ HCl

ortho, para directors meta directors

activating (more reactive) - R (least) , - OR, - OH, - NR2 (greatest) none aromatic + H2Pt cycloalkane
, P,

deactivating (less reactive) -X -NO2, -CO2CH3

2. Hydrogenation

Alcohols
1. Oxidation a) combustion: b) mild oxidation 1 ROH (K2Cr2O7) c) moderate oxidation 1 ROH (KMnO4) d) 2 ROH (KMnO4) 2. Acid Base a) dehydration b) condensation / elimination
Common Tests for Alcohols and Aldehydes

alcohol aldehyde alcohol carboxylic acid alcohol ketone

+

alcohol H alkene + H2O 2 alcohols (or 1 in excess) ether + H2O alcohol + carboxylic acid
H2SO4

Lucas Reagent : HCl (aq) + ZnCl2 becomes almost immediately cloudy with 3 ROH, approx 5 minutes for 2 ROH, much longer for 1 ROH Fehling's Solution: basic solution of Cu2+ (blue) aldehyde - changes to solid Cu2O (greenish initially, eventually forming thick red ppt) Tollen's Reagent: Ag+ in aqueous NH3 aldehyde causes Ag to ppt as metal (silver mirror on container walls)

ester + H2O

c) halogenation 3. Condensation Polymer

HX + alcohol haloalkane + H2O diol + dicarboxylic acid polyester + H2O ether + HX haloalkane + H2O ether + O2 peroxide

Ethers
1. Halogenation 2. Peroxide

Aldehydes and Ketones

1. Hydrogenation aldehydes + H2 1 ROH ketones + H2 2 ROH aldehyde + KMnO4 carboxylic acid
O R C R OH

2. 3.

Oxidation Nucleophilic Addition

H R C C R N

OH R C C HO R O
O O N
+ -

4.

Nucleophilic Addition-Elimination
O R O C R H N
+

C N H C CH

CH C CH N
+

R C N N H C R

CH C N
+

N H

CH

CH

Carboxylic Acids
1. Acid 2. Elimination 3. Reduction carboxylic acid carboxlyate anion + H+ alcohol + carboxylic acid
H2SO4

ester + H2O

will not reduce with H2 and Pt

Esters
1. Hydrolysis

ester + H2O carboxylic acid + alcohol ester + OH- carboxylate anion + alcohol

H2SO4

Grignard Reagents
RX + Mg RMgX (X does not include F) 1. 2. 3. 4. RMgX + H2O RH + Mg(OH)X (acid base reaction) RMgX + CO2 RCOOMgX RCOOH RMgX + RCHO 2 ROH
R1 C R2 O R1 R1 O Mg X R2 C R3 O H

R3

Mg X

R2

C R3

RMgX + R2CO 3 ROH