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synthesis
Industrial
large amounts (tons)
(grams)
Laboratory
small amounts
lowest cost
non-profit
pure substances
dedicated apparatus
flexible apparatus
Alkanes synthesis:
1. Reduction of an alkyl halide
a) hydrolysis of a Grignard reagent
b) with an active metal and an acid
2. wurtz synthesis
(coupling of 2 alkyl halides in the presence of sodium
or zinc)
3. Corey-House synthesis
(coupling of an alkyl halide with lithium dialkylcopper)
4. Reduction of aldehydes and ketones
5. decarboxylation of carboxylic acid
(Grignard reagent)
SA
WA
WB
Exemple
CH3CH2CH2-Br + Mg CH3CH2CH2-MgBr
n-propyl bromide
n-butane
CH3
CH3
CH3CCH3 + Zn/H+ CH3CHCH3 + ZnBr2
Br
tert-butyl bromide
isobutane
2. Wurtz reaction
R-X + R-X + 2Na RR + 2NaX
This reaction can give mixture of compounds: RR, RR, RR
Good result for symmetric alcanes with high molecular weight
Same result with Grignard ( no mixture):
RX + Mg RMgX;
2. Corey-House synthesis
R-X + Li R-Li + CuI R2CuLi
CH3
CH3
CH3
CH3CH-Br + Li CH3CH-Li + CuI (CH3CH)2-CuLi
isopropyl bromide
CH3
CH3
(CH3CH)2-CuLi + CH3CH2CH2-Br CH3CH-CH2CH2CH3
2-methylpentane
(isohexane)
CH3COCH2CH3
4.
Zn/ H3O+
CH3CH2CH2CH3 + H2O
NaOH
CH3CH2COOH
CH3CH2COONa
Heating
NaOH
CH3CH3 + Na2CO3
Reactivity of Alkanes
Alkanes have only strong, nonpolar
bonds
No reaction with nucleophiles or
electrophiles
Not much reactivity - paraffins (little
affinity)
Reactions of alkanes:
alkane + H2SO4 no reaction (NR)
alkane + NaOH NR
alkane + Na NR
alkane + KMnO4 NR
alkane + H2,Ni NR
alkane + Br2 NR
alkane + H2O NR
(Alkanes are typically non-reactive. They dont react with
acids, bases, active metals, oxidizing agents, reducing agents,
halogens, etc.)
Alkane reactions:
1. Combustion (oxidation)
2. Pyrolysis (cracking)
3. Halogenation
1. Combustion
CnH2n+2 + ((3n+1)/2) O2, flame n CO2 + (n+1) H2O + heat
3. Halogenation
R-H + X2, heat or hv R-X + HX
HX + R
3) R + XX RX + X
2), 3), 2), 3)
terminating steps:
4) 2 X XX
5) R + X RX
6) 2 R RR
+ HCl
Cl
2) abstraction of 1o hydrogen:
Cl + CH3CH2CH3 CH3CH2CH2 + HCl
or abstraction of 2o hydrogen:
Cl + CH3CH2CH3 CH3CHCH3
+ HCl
CH3 + H
CH3CH2H CH3CH2 + H
H = 104 Kcal/mole
H = 98 Kcal/mole
1o free radical
CH3CH2CH3 CH3CH2CH2 + H H = 98 Kcal/mole
1o free radical
CH3CHCH3 + H
2o free radical
CH3
CH3
CH3CHCH3 CH3CCH3 + H
o
3 free radical
H = 95 Kcal/mole
H = 92 Kcal/mole
ReactivitySelectivity Principle
The very reactive chlorine atom will have
lower selectivity and attack pretty much any
hydrogen available on an alkane
The less reactive bromine atom will be more
selective and tends to react preferentially with
the easy targets, i.e. tertiary hydrogens
ethyl chloride
isopropyl chloride
55%
gives a mixture of both the possible
alkyl halides!
n-butyl chloride
+
CH3CH2CHCH3
Cl
sec-butyl chloride
CH3
CH3
CH3CHCH3 + Cl2, hv CH3CHCH2-Cl
isobutane
28%
64%
isobutyl chloride
+
CH3
CH3CCH3
Cl
tert-butyl chloride
36%
72%
ethyl bromide
isopropyl bromide
97%
n-butyl bromide
+
CH3CH2CHCH3
Br
sec-butyl bromide
CH3
CH3
CH3CHCH3 + Br2, hv CH3CHCH2-Br
isobutane
2%
<1%
isobutyl bromide
+
CH3
CH3CCH3
Br
tert-butyl bromide
99%
98%
CH2=CH-CH2-CH3
Cl2 hv
CH2=CH-CHCl-CH3
Ar-CH2-CH3
Cl2 hv
ArCHClCH3
stabilized by the presence of
aromatic(resonance)