Alkane reactions:

O2 (excess)
CO2 + H2O

O2 (limited)
C CO + H2O

O2 (very limited)
C + H2O

Cl2; hv Cl2; hv Cl2; hv Cl2; hv

CH4 CH3Cl CH2Cl2 CHCl3 CCl4
Alkene reactions:
H X
HX
Ether X = Cl, Br, I C C Markovnikov

X
X2
CH2Cl2 C C
X = Cl, Br X
anti

H OH
H+; H2O
C C
Markovnikov
H OH
1. Hg(OAc), H2O
2. NaBH4 C C

OH H
1. BH3, THF
C C 2. H2O2; OH-
C C Anti Markovnikov

H H
H2
PtO2/Pd C C

syn

OH OH
KMnO4
NaOH, H2O C C

syn

OH OH
1. OsO4
2. NaHSO3
C C

syn
O
O
RCOOH C C

1. O3 C O + O C
2.Zn; H+
 H KMnO4
C C C O + CO2
H3O+ HO
H H
H KMnO4
C C C O + CO2
H3O+
H
H OH
KMnO4 C O + O C
C C H3O+

KMnO4 C O + O C
C C

H X H X
HX
C C C C + C C C C Markovnikov
Ether X = Cl, Br, I
H H H H
1,2 Addition 1,4 Addition
C C C C
X X X X
H H X2
CH2Cl2 C C C C + C C C C
X = Cl, Br H H H H
1,2 Addition 1,4 Addition
Alkyne reactions:
1HX
H X
X = Cl, Br, I
C C Markovnikov

X
1X2 C C
X = Cl, Br
anti X

H O
H2O; H2SO4
HgSO4 C C Markovnikov
H

H H
2H2
C C C C
Pd/C
H H

H H
H2 C C
Lindlar catalyst syn
H
Li/Na C C
NH3
anti H

O O
O3/KMnO4
C OH + C OH
NaNH2 RCH2X
C C Na C C CH2R
C CH
Terminal alkyne O
O3/KMnO4
C OH + CO2
Benzene reactions:
X
X2
FeX3
X = Cl, Br

NO2
HNO3
H2SO4

SO3H
SO3
H2SO4

CH2R
RCH2Cl Friedel Craft alkylation
AlCl3

O
O CR
RCCl Friedel Craft acylation
AlCl3

O
R COH
KMnO4
H2O

NO2 NH2
+
1. Fe, H3O
2. OH-
Alkyl halide reactions:
KOH (Alc)
CH CH2 Zaitsev
Mg
Dry ether CH2CH2 MgX
1. NH3
2. NaOH CH2CH2 NH2
R1
1. R1NH2
CH2CH2 NH
2. NaOH

1
R1
1. (R )2NH
CH2CH2 N R1
2. NaOH

1
R1
(R )3 N
CH2CH2 X CH2CH2 N R1 X
X = Cl, Br, I
R1
OH- CH2CH2 OH
SH-
CH2CH2 SH
CN-
CH2CH2 CN
N3-
CH2CH2 N3
+
H

H2O
CH2CH3
CH2CH2 MgX
Grignard ROH
O
1. CO2
2. H 2O CH2CH2 C OH
Alcohol reactions:
PBr3
CH2 Br
O
PCC CH
CH2 OH CH2Cl2
1o alcohol
O
Na2Cr2O7/CrO3
C OH
H3O+
Cl
SOCl2
OH CH
CH O
o PCC, CH2Cl2
2 alcohol C
or
Na2Cr2O7/CrO3
H3O+
OH X
HX
C Ether C
X = Cl, Br
3o alcohol

R OH Na R1X (1o)
or R O Na R O R1
All alcohols NaH, THF
Ether reactions:
C O CH2 C OH + CH2X
H H
1o & 2o alkyl groups

C O CH2 C X + CH2OH

3o alkyl group
Epoxide reactions:
OH
C C
R
OH
HX
O C C Anti
Ether
C C X
H3O+
OH
C C
OH-
OH
Thiol reactions:
Na RX
C S Na C S R
C SH
X2
X = Br; I C S S C

Disulphide reaction:
Zn, H+
C S S C 2 C SH
Aldehyde/ketone reactions:
HNO3 (hot)

KMnO4
O O
AgNO3/Ag2O
CH2 CH CH2 C OH
Ammonia
Only aldehydes
O2; Light

CrO3
H2SO4(aq)
OH
1. RMgX
2. H 3O+
CH2 C
R

OH
1. NaBH4, ethanol
or LiAlH4, ether CH2 C
2. H3O+ H
OR
2ROH
CH2 C
H+ catalyst
OR
OH
H2O; H3O+/OH-
CH2 C
OH
O OH
HCN
CH2 C CH2 C
Aldehyde or Ketone CN

NR
NH2R
CH2 C

RNR
(R)2NH
C C
H
NH2NH2
KOH CH2 CH2 Wolff-Kishner

NH2
NH3
H2/Ni CH2 C
H
Carboxylic acid reactions:
O
Na/NaOH
CO Na

O
SOCl2
O CHCl3 CCl
COH O
ROH
H2SO4 catalyst COR Fischer esterification

OH
1. LiAlH4, ether
2. H3O
+ CH2

O O
NH3
COH CO NH4
Carboxylic acid chloride (halide) reactions:
O
H2O
COH

OH
1. LiAlH4, ether
CH2
2. H3O+
OH
1. 2RMgX
2. H 3O+
C R
R
O
O O O
RCO Na
CCl COC R
Ether
O
ROH
Pyridine COR

O
RNH2
CNHR

O
NaN3
Ethanol
CN3
Acid anhydride reactions:
O O
H2O
COH + COH

OH O
1. LiAlH4, ether
CH2 + COH
O O 2. H3O+
COC O O
ROH
Pyridine COR + CO

O O
RNH2
CNHR + CO
Ester reactions:
O
H2O
H3O+/NaOH COH + ROH

OH
1. 2R1MgX
C R1 + ROH
2. H 3O+
O R1
COR
O
NH3
Ether CNH2 + ROH

OH
1. LiAlH4, ether
CH2 + ROH
2. H3O+

Amide reactions:
O H
LiAlH4, ether
H2O COH + RNH
O H
H2O
CNHR CH2NHR
H+/OH- 
Br2; NaOH
H2O NH2 + CO 2

Nitrile reactions:
O
H2O
H+/OH- COH + NH3

O
1. RMgX
C N 2. H 2O C R
1. LiAlH4, ether
2. H 2O CH2NH2
 NAME REACTIONS
Markovnikov addition:
To alkenes

C H HX X H
C C Ether
C C C H
H H X = Cl; Br; I H H

C H H+; H2O OH H
C C or C C C H
H H 1. Hg(OAc) ; H O/THF H H
2 2
2. NaBH4

To alkynes
C H X H
1HX 1HX
C C C H Ether C C C C C H
H Ether
X = Cl; Br X X = Cl; Br X H

2HX
Ether
X = Cl; Br

O H
H2O; H2SO4
C C C H HgSO C C C H
4
H

Anti-Markovnikov addition
C H 1. BH3; THF H OH
C C - C C C H
H H 2. H2O2; OH H H

Zaitsev elimination
X H H H
KOH (Alc)
C C C C C C + C C C
H H H H H H H
Major Minor

Friedel-Craft alkylation
CH2
CH2X
AlCl3
Friedel-Craft acylation
O
O
C
C Cl
AlCl3

Grignard reagent
Mg
C X Dry ether C MgX

Williamson ether synthesis

Na o
C OH or C O-Na+ RX (1 ) C OR
NaH; THF

Wolf-Kishner reduction
O H
NH2NH2
C C
KOH
H

Fischer esterification
O O
ROH
C OH H2SO4 C OR

Hofmann rearrangement
O
X2; NaOH
C C N C N
H2O
X2 = Br2; I2

Curtius rearrangement
O H
H2O
C C N3 C N H


Hofmann elimination
+
AgO2; H2O
C CH2 CH2 N(R)3 X- 
C CH CH2
 REACTIONS OF THE FAMILIES
Use this to revise your reactions. Can you write the reaction using structural formulas from
the description given?
ALKANES
Preparations
1. From alkenes by catalytic hydrogenation
2. From alkynes by catalytic hydrogenation
3. From alkyl halides by protonolysis of Grignard reagents
4. From aldehydes and ketones by Wolff-Kishner reduction
Reactions
1. Combustion
2. Halogenation
ALKENES
Preparations
1. From alkyl halides by treatment with strong base
2. From alcohols by dehydration
3. From alkynes by catalytic hydrogenation with Lindlar catalyst
4. From alkynes by reduction with lithium in liquid ammonia
5. From amines by methylation and Hoffmann elimination
Reactions
1. Electrophylic addition of HX to yield an alkyl halide
2. Electrophylic addition of halogen to yield a dihalide
3. Oxymercuration/demercuration to yield an alcohol
4. Hydroboration/oxidation to yield an alcohol
5. Hydrogenation to yield an alkane
6. Hydroxylation to yield a 1,2-diol with KMnO4 and a base
7. Hydroxylation to yield a 1,2-diol with OsO4 and then NaHSO3
8. Oxidative cleavage to yield carbonyl compounds
9. Reaction with a peroxyacid to yield an epoxide
CONJUGATED DIENES
Reaction
1. 1,2- and 1,4-addition to an alkene to yield two products
ALKYNES
Preparations
1. From dihalides by base-induced double dehydrohalogenation
2. From terminal alkynes by alkylation of acetylide anions
Reactions
1. Electrophilic addition of HX to yield a vinylic halide
2. Electrophilic addition of halogen to yield a dihalide
 3. Addition of water to yield a ketone
4. Alkylation of an alkyne anion
5. Reduction to yield an alkane
6. Reduction to yield a cis-alkene
7. Reduction to yield a trans-alkene
8. Cleavage of alkynes
BENZENE
Reactions
1. Halogenation
2. Nitration
3. Sulphonation
4. Friedel-Craft alkylation
5. Friedel-Craft acylation
6. Oxidation of alkyl benzenes
7. Reduction of nitrobenzene
ALKYL HALIDES (HALOALKANES)
Preparations
1. From alkenes by electrophilic addition of HX
2. From alkenes by addition of a halogen
3. From alkynes by addition of HX
4. From 1° and 2° alcohols by reaction with SOCl2, or PBr3
5. From 3° alcohols by reaction with HX
6. From ethers by cleavage with HX
7. From benzene through substitution with X2
Reactions
1. Reaction with magnesium to form a Grignard reagent
2. Reduction to form an alkane
3. Nucleophilic substitution
4. Dehydrohalogenation to yield an alkene
ALCOHOLS
Preparations
1. From alkenes by oxymercuration/demercuration
2. From alkenes by hydroboration/oxidation
3. From alkenes by hydroxylation with OsO4 or KMnO4
4. From alkyl halides with hydroxide ion
5. From ethers by acid induced cleavage
6. From epoxides by acid-catalysed ring opening
7. From epoxides by base-catalysed ring opening
8. From aldehydes and ketones by reduction with NaBH4 or LiAlH4
9. From aldehydes and ketones by addition of Grignard reagents
10. From carboxylic acids by reduction with LiAlH4
 11. From esters by reduction with LiAlH4
12. 3° alcohol from acid chlorides by reaction with Grignard reagents
13. 3° alcohol from esters by reaction with Grignard reagents
Reactions
1. Oxidation of 1° alcohol to yield an aldehyde or an acid
2. Oxidation of 2° alcohol to yield a ketone
3. Reaction with a carboxylic acid to yield an ester (Fischer esterification)
4. Reaction with an acid chloride to yield an ester
5. Dehydration to yield an alkene
6. Reaction of anion of alcohol with 1° alkyl halide to yield an ether
7. Reaction of 3° alcohol with HX to yield an alkyl halide
8. Reaction of 1° or 2° alcohol with SOCl2 or PBr3 to yield an alkyl halide
ETHERS
Preparation
1. From 1° alkyl halides by substitution with alkoxide ions
Reactions
1. Acid-catalysed ring opening with HX to yield a halohydrin
ETHERS AND EPOXIDES
Preparation
1. From alkene reaction with a peroxyacid
Reactions
1. Ring opening with an aqueous acid to yield a 1,2-diol
2. Reaction with a Grignard to yield a 1° alcohol 2-C longer
THIOLS
Preparation
1. From 1° alkyl halides by substitution with hydrosulphide anion
2. From disulphide reduction with zinc metal and acetic acid
Reactions
1. Reaction of thiolate ions with an alkyl halide to yield a sulphide
2. Oxidation with Br2 or I2 to yield a disulphide
SULPHIDES
Preparation
1. From thiols by SN2 reaction of thiolate ions with 1° alkyl halides
DISULPHIDES
Preparation
1. From thiols by oxidation with Br2 or I2
Reactions
1. Reduction with zinc metal and acetic acid to yield a thiol
ALDEHYDES
Preparations
1. From disubstituted alkenes by ozonolysis
2. From 1° alcohols by oxidation
Reactions
1. Oxidation to yield a carboxylic acid
2. Reduction to yield an alcohol
3. Reaction with a Grignard to yield a 2° alcohol
4. Grignard reaction of formaldehyde to yield a 1° alcohol
5. Reaction with HCN to yield a cyanohydrin
6. Wolff-Kishner reduction with basic hydrazine to yield an alkane
7. Reaction with an alcohol to yield an acetal
8. Reaction with a 1° amine to yield an imine
9. Reaction with a 2° amine to yield an enamine
KETONES
Preparations
1. From alkenes by ozonolysis
2. From alkynes by mercuric-ion-catalysed hydration
3. From benzene by Lewis-acid-catalysed reaction with acid chloride (Friedel-Craft
acylation)
4. From 2° alcohols by oxidation
5. From a Grignard reagent and a nitrile
Reactions
1. Reduction to yield a 2° alcohol
2. Reaction with a Grignard reagent to yield a 3° alcohol
3. Wolff-Kishner reduction with basic hydrazine to yield an alkane
4. Reaction with HCN to yield a cyanohydrin
5. Reaction with an alcohol to yield an acetal
6. Reaction with a 1° amine to yield an imine
7. Reaction with a 2° amine to yield an enamine
CARBOXYLIC ACIDS
Preparations
1. From mono and 1,2-disubstituted alkenes by oxidation with KMnO4
2. From alkyl benzene oxidation with KMnO4
3. From aldehydes by oxidation
4. From RX be making a Grignard reagent and then reaction with CO2 and then an acid
5. From nitriles by acid or base hydrolysis
6. From acid chlorides by hydrolysis
7. From acid anhydrides by hydrolysis
8. From esters by hydrolysis
9. From amides by hydrolysis
 Reactions
1. Reduction to yield a 1° alcohol
2. Conversion into an acid chloride
3. Conversion into an acid anhydride
4. Conversion into an ester through Fisher esterification
5. Conversion into an ester by reacting with alkyl halide
ACID CHLORIDES
Preparations
1. From carboxylic acids by reaction with SOCl2
Reactions
1. Hydrolysis to yield a carboxylic acid
2. Conversion to an anhydride
3. Alcoholysis to yield an ester
4. Aminolysis to yield an amide
5. Reaction with benzene to yield a ketone
6. Reduction to a 1° alcohol
7. Grignard reaction to yield a 3° alcohol
8. Reaction with NaN3 to yield an acyl azide
ACID ANHYDRIDES
Preparation
1. From acid chlorides by reaction with carboxylate salts
Reactions
1. Hydrolysis to yield a carboxylic acid
2. Alcoholysis to yield an ester
3. Aminolysis to yield an amide
4. Reduction to yield a 1° alcohol
ESTERS
Preparations
1. From carboxylic acid salts by reaction with 1° RX
2. From carboxylic acids reaction with an alcohol (Fisher esterification)
3. From acid chlorides by reaction with an alcohol
4. From acid anhydrides by reaction with an alcohol
Reactions
1. Hydrolysis to yield a carboxylic acid and an alcohol
2. Aminolysis to yield an amide
3. Reduction to yield a 1° alcohol
4. Grignard reaction to yield a 3° alcohol
AMIDES
Preparation
1. From acid chlorides by treatment with an amine or NH3
 Reactions
1. Hydrolysis to yield a carboxylic acid
2. Reduction with LiAlH4 to yield an amine
3. Transformation into amines by Hoffman rearrangement
NITRILES
Preparation
1. From 1° alkyl halides by SN2 reaction with cyanide ion
Reactions
1. Hydrolysis to yield a carboxylic acid
2. Reduction to yield an amine
3. Grignard reaction to yield a ketone
AMINES
Preparations
1. From amides by reduction with LiAlH4
2. From nitriles by reduction with LiAlH4
3. From 1° alkyl halides by reaction with ammonia
4. Reduction of nitrobenzene
5. From acid chlorides by Curtius rearrangement of acyl azides
6. From 1° amides by Hoffman rearrangement
7. From an alkyl halide by reaction with azide and then reduction
8. From ketones and aldehydes by reductive amination
Reactions
1. Alkylation of 1° or 2° amine to yield 2° and 3° amines
2. Reaction with an acid chloride to yield an amide
3. Hoffman elimination to yield an alkene