Preparation of Alkanes

1. Soda-Lime Process
CaO
R-COONa Na0H Na2CO3 R-H

CaO
CH3CH2COONa Na0H Na2CO3 CH3CH3
Alkane
Ethane
2. Wurtz Synthesis
Dry

2 R-Cl 2 Na ether
2 NaCl R- R
Alkane
R-Cl Na Dry
ether
R-Cl Na 2 NaCl R- R

Dry
ether
2 CH3CH2-Cl 2 Na 2 NaCl CH3CH2-CH2CH3
Butane
 Dry
ether
2 CH3CH2-Cl 2 Na 2 NaCl CH3CH2-CH2CH3
Butane

CH3CH2-Cl Na Dry
ether
CH3CH2-Cl Na 2 NaCl CH3CH2- CH2CH3

Dry
ether
2 CH3CH2-Cl
CH2CH3 2 Na 2 NaCl CH3CH2-CH2CH3
 3. Grignard Reaction
Dry

R-X Mg
ether
R-Mg-X H-OH Mg(OH)X R-H

Dry

CH3CH2-Cl Mg
ether
CH3CH2-MgCl H-OH Mg(OH)Cl

CH3CH23-H
Preparation of Alkanes
• 1. Soda-lime process
• 2. Wǘrtz Synthesis
• 3. Grignard Reaction
Preparation of Alkene
1. Dehydration of Alcohol (Intramolecular Dehydration)

H H H2SO4, heat
H C C H H2O CH2=CH2
H OH

H2SO4, heat
CH3CH2CH2OH H2O CH3CH = CH2
 H2SO4, heat
CH3CHCH3 CH3CH=CH2 CH
H2O2=CHCH3
OH
H2SO4, heat
2 CH3CHCH2CH3 CH2=CHCH2CH3
OH Minor Product
CH3CH=CHCH3
Major Product

2 H2O
 2-Ethyl-3-methyl-1-butene

OH CH2=C CH2CH3
H2SO4, heat
3 CH3C CH2CH3 CHCH3
CHCH3 CH3 CH3 C=CHCH3
CH3 CHCH3
CH3
3,4-dimethyl-2-pentene

CH3 C CH2CH3
Major Product C CH3 3 H2O
CH3 2,3-dimethyl-2-pentene
2. Dehydrohalogenation of alkyl halide

H H KOH,
ethanol

H C C H HCl CH2=CH2
H Cl
KOH,
ethanol
CH3CH2CH2Cl HCl CH3CH = CH2
 KOH,
ethanol
CH3CHCH3 CH3CH=CH2 CHHCl
2=CHCH3
Cl
KOH,
ethanol
2 CH3CHCH2CH3 CH2=CHCH2CH3
Cl Minor Product
CH3CH=CHCH3
Major Product

2 HCl
 2-Ethyl-3methyl-1-butene

Cl KOH,
CH2=C CH2CH3
3 CH3C CH2CH3 ethanol
CHCH3
CHCH3 CH3 CH3 C=CHCH3
CH3 CHCH3
CH3
3,4-dimethyl-2-pentene

CH3 C CH2CH3
C CH3 3 HCl
CH3 2,3-dimethyl-2-pentene
3. Dehalogenation of Alkyl dihalide

H H
H C C H Mg MgCl2 CH2=CH2
Cl Cl

CH3CHCH2Cl Mg MgCl2 CH3CH = CH2

Cl
CH3CH ̶ CHCH3 Mg MgCl2 CH3CH=CHCH3
Cl Cl
Preparation of Alkene
• 1. Dehydration of Alcohol
• 2. Dehydrohalogenation of alkyl halide
• 3. Dehalogenation of Alkyl Dihalide
Preparation of Alkyne
1. Lab. Prep. of Acetylene

CaC2 H2O Ca(OH)2 HC CH

2. Dehydrohalogenation of alkyl dihalide
K-OH
H H ethanol
H C C H 2 K-OH 2KCl 2H2O CH CH
Cl Cl
K-OH
ethanol
CH3CHCH2Cl 2 K-OH 2KCl 2H2O CH3C CH
Cl
3. Dehalogenation of alkyl tetrahalide

Cl Cl
H C C H 2 Mg 2MgCl2 CH CH
Cl Cl

Cl Cl
CH3C C H 2 Mg 2MgCl2 CH3C CH
Cl Cl
Preparation of Alkynes
• 1. Lab preparation of acetylene
• 2. Dehydrohalogenation of Alkyl Dihalide
• 3. Dehalogenation of Alkyl Tetrahalide
Properties of Alkanes, Alkenes, and Alkynes
1. Combustion
Akane O2 CO2 H2O
Akene O2 CO2 H2O

Akyne O2 CO2 H2O

 2. Baeyers Test for Unsaturation
Alkane KMnO4 No rxn
H2O
Alkene KMnO4 Diol KOH MnO2
Brown
ppt.
H2O
CH2=CH2 KMnO4 CH2 ̶ CH2 KOH MnO2
OH OH Brown
ppt.
 H2O
Alkyne KMnO4 Carboxylic
Acid KOH MnO2
Brown
ppt.
H2O
CH CH KMnO4 2 CO2 KOH MnO2
CO2 CO2

H2O
CH3C CH KMnO4 CO2 CH3COOH KOH MnO2

COOH CO2
CH3C C ̶ CH3 KMnO4 2CH3COOH KOH MnO2

COOH COOH

CH3C C ̶ CH2CH3 KMnO4 CH3COOH CH3CH2COOH

COOH COOH
KOH MnO2
3. Substitution Reaction (Alkane only)
•A. Halogenation
•B. Sulfonation
•C. Nitration
Halogenation
H H
UV
H C H Cl ̶ Cl H C Cl HCl
H H
UV
CH4 Cl2 CH3Cl HCl
UV
CH4 2Cl2 CH2Cl2 2 HCl
UV
CH4 3Cl2 CHCl3 3 HCl
UV
CH4 4Cl2 CCl4 4 HCl
UV
CH3CH3 Cl2 CH3CH2Cl HCl
B. Sulfonation H2SO4
H H
H C H HOSO3H H C SO3H H2O
H H

CH4 H2SO4 CH3SO3H H2O

methanesulfonic acid

CH3CH3 H2SO4 CH3CH2SO3H H2O

Ethanesulfonic acid
 Nitration HNO3
H H
H C H HONO2 H C NO2 H2O
H H

CH4 HNO3 CH3NO2 H2O

Nitromethane

CH3CH3 HNO3 CH3CH2NO2 H2O

Nitroethane
4. Addition Rxn (Alkenes and Alkynes)
•A. Hydrogenation
•B. Halogenation
•C. Hydrohalogenation
A. Hydrogenation
Pt,Pd,
Ni
CH2=CH2 H2 CH3CH3
Pt,Pd,
Ni
CH3CH=CH2 H2 CH3CH2CH3
Pt,Pd,
Ni
CH CH 2H2 CH3CH3
Pt,Pd,
Ni
CH3C C ̶ CH3 2H2 CH3CH2CH2CH3
Poisoned
Pd
CH3C C ̶ CH3 H2 CH3CH=CHCH3
A. Halogenation
CH2=CH2 Cl2 CH2 ̶ CH2 CH2ClCH2Cl
Cl Cl

CH3CH=CH2 Cl2 CH3CH ̶ CH2 Vicinal Dihalide

Cl Cl
CH3CH=CHCH3 Cl2 CH3CH ̶ CHCH3
Cl Cl
 Cl Cl
CH CH 2Cl2 CH ̶ CH
Cl Cl

Cl Cl
CH3C C ̶ CH3 2Cl2 CH3C ̶ CCH3
Cl Cl
 C. Hydrohalogenation
CH2=CH2 H ̶ Cl CH3 ̶ CH2Cl CH2ClCH3

Markovnikov’s rule
CH3CH=CH2 H ̶ Cl CH3CH ̶ CH3
Cl
CH3CH=CHCH3 H ̶ Cl CH3CH2 ̶ CHCH3
Cl
 Cl
CH CH 2H ̶ Cl CH3 ̶ CH Geminal Dihalide

Cl

Cl
CH3C C ̶ H 2H ̶ Cl CH3C ̶ CH3
Cl
 5. Hydration of Alkene
CH2=CH2 H ̶ OH CH3 ̶ CH2OH CH2(OH)CH3

CH3CH=CH2 H ̶ OH CH3CH ̶ CH3

OH
CH3CH=CHCH3 H ̶ OH CH3CH2 ̶ CHCH3
OH
 END
for the Preparation and
Properties of Alkanes, Alkenes,
and Alkynes