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(chapter 31)
Preparation
Industrial - cracking
Laboratory
1. Elimination
a. Dehydrohalogenation of haloalkanes
RX => alkene
b. Dehydration of alkanols
ROH => alkene
4. Hydrogenation of alkynes
Physical properties
Alkene m.p. oC b.p. oC density
CH2=CH2 -169.4 -102.4 0.610
CH2=CHCH3 -185.0 -47.7 0.610
CH2=CHCH2CH3 -185.0 -6.5 0.643
Cis-CH3CH=CHCH3 -139.0 3.7 0.621
Trans-CH3CH=CHCH3 -106.0 2.9 0.604
CH2CH=C(CH3)2 -140.7 -6.6 0.627
CH2=CH(CH2)2CH3 -138.0 30.1 0.643
Chemical properties
δ+ δ-
C=C + E-N C C
δ+ δ-
E N
δ+ δ-
E-N = H-Cl, H-Br, H-I, H-OSO3H ,
H-OH (H3O+), Cl-Cl, Br-Br,
Br-OH, Cl-OH
Electrophilic Additions of Alkenes
Two
steps:
δ+ δ-
C=C + H-X C C + X-
δ+ δ- +
H
C C + X- C C
+
H H X
Orientation of Addition reactions
CH3-CH-CH3 CH3-CH2-CH2
+ +
(more stable) (less stable)
X- X-
CH3CHXCH3 CH3CH2CH2X
(major product) (minor product)
H
CH3-CH2-CH2
+
CH3-CH-CH3
+
CH3CH2CH2X
CH3CH=CH2 + H-X
CH3CHXCH3
Reaction coordinate
Electrophilic Additions of Alkenes
C=C + c. H2SO4 C C
H OSO3H
(Alkyl Hydrogensulphate)
H2O
Uses:
C C Produce alkanol
H OH Separate alkenes from alkanes
(Alkanol)
Catalytic Hydrogenation
Pt/Pd/Ni
CH3CH=CHCH3 + H2 CH3CH2CH2CH3
heat, pressure
Heterolytic catalyst
Exothermic
Stereochemistry:
The two H atoms are added from the same
side of the π-bond of the alkene molecule.
(syn or cis-addition)
Hardening of oils - Margarine
CH2-OOC(CH2)14CH3
CH-OO(CH2)7CH=CH(CH2)7CH3 + 3 H2
CH2-OO(CH2)6(CH2CH=CH)3CH2CH3
vegetable oil
Powdered
Ni catalyst,
420K and 5 atm. pressure
CH2-OOC(CH2)14CH3
CH-OO(CH2)7CH=CH(CH2)7CH3
CH2-OO(CH2)16CH3
margarine
Link
1. O3
CH2=CH2 2 HCH=O
2. Zn,H2O
Step 1: Oxidation
Step 2: Hydrolysis by adding water, zinc is used
to prevent H2O2 from oxidizing the aldehydes.
Ozonolysis
1. O3
e.g. X CH3CHO + CH3COCH3
2. Zn,H2O
X: CH3CH=C(CH3)2
Ozonolysis
• OHC-(CH2)4-CHO (C6H10)
• CH3CHO, OHC-CH2-CHO (C10H16)
O2,200-400oC
n CH2=CH2 → (-CH2CH2-)n Poly(ethene)
1500 atm
n = 700 – 800
Molar mass 20000 - 25000
Polymerization
Free radical mechanism:
Chain Initiation
RO-OR → 2RO· (organic peroxide)
RO· + CH2=CH2 → RO-CH2-CH2·
Chain Propagation
RO-CH2-CH2· + CH2=CH2 →
RO-CH2CH2-CH2-CH2·
Chain Termination
2 RO-(CH2CH2)m-CH2-CH2· →
RO-(CH2CH2)m-CH2-CH2-CH2-CH2-(CH2CH2)m-OR
Low Density poly(ethene) LDPE
Consists of mainly
irregularly packed, branched
chain polymers.
Consists of regularly
packed, linear
polymers with extensive
crystalline region. Uses: Rigid articles
such as refrigerator ice trays,
buckets, crates.
Poly(propene)
Ziegler-Natta Catalyst
nCH3-CH=CH2 → (-CH-CH2-)n poly(propene)
CH3
peroxides
nC6H5-CH=CH2 → (-CH-CH2-)n
reflux in kerosene C6H5
CH3 CH3
• ?(Alkene) + ?(reagent) => CH3-C-CH2-C-CH3
H OH
Ans. CH2ClCH2CH3