2.

Acrylonitrile Manufacture
NH3, O2
CH2 CH CH3 CH2 CH C N
propylene acrylonitrile

CH2 CH CH3
Cl2, H2O
Cl
CH2 CH CH3
1. Manufacturing
Chemicals containing three carbon fragment
OH
NaOH
Methods with a double bond have common root name
or Ca(OH)2

CH2 CH CH3 t-BuOOH CH2 CH CH3 + t-BuOH Acryl acrid

or
or O
Ph CH OOH O -H2O
Ph CH OH Ph CH CH2
CH3 propylene oxide acrylonitrile CH2 CH C N acrolein CH2 CH C H
CH3 styrene
O O
CH3 O
O2 acrylic acid CH2 CH C OH acrylamide CH2 CH C NH2
CH2 CH CH3 CH CH3 OH + CH3 C CH3
H+ H+
cumene phenol acetone

H+, -H2O Former acrylonitrile processes

CH3
CH CH + HCN CH2 CH CN
HO C OH
CH3 ∆
CH2 CH2 + HCN HO CH2 CH2 CN CH2 CH CN + H2O
bisphenol A

CO, H2
O CH3 O O
CH2 CH CH3 CH3 CH2 CH2 C H + CH3 CH C H Problem???
n-butyraldehyde isobutyraldehyde

3. Acrylonitrile Manufacture 4. Uses of Acrylonitrile

Older methods are not used today Single largest use of acrylonitrile is manufacture
Since 1970, manufacture has been based on of adiponitrile – a C6 compound
propylene chemistry One-third made by electrohydrodimerization of
Ammoxidation of propylene acrylonitrile
400 – 450 oC, 0.5 – 2 atm
2H+ H2
Fluidized bed using Bi2O3.nMoO3 catalyst 2CH2 CH C N N C (CH2)4 C N H 2N (CH2)6 NH2
2e-
Yield about 70 %
acrylonitrile adiponitrile HMDA
acrylonitrile
2CH2 CH CH3 + 2NH3 + 3O2 2CH2 CH C N + 6H2O Adiponitrile is further hydrogenated to
hexamethylenediamine (HMDA)
Mechanism is probably free-radical based Where is HMDA used?
Allylic free radicals are readily formed because … What catalyst could be used for the hydrogenation?
Two-thirds made by hydrocyanation of
butadiene – discussed later

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 5. Adiponitrile Manufacture 6. Propylene Oxide Manufacture
Electrohydrodimerization A second manufacturing method
Peroxidation of propylene – Halcon Process
Head-to-head dimerization
Reaction:
Two phase system using phase transfer catalyst
CH3 CH3 CH3
2e- 2CH2 CH C N
2CH2 CH C N 4CH3 CH CH3 + 3O2 2CH3 C CH3 + 2CH3 C CH3
2H+ O OH OH
N C CH CH2 CH2 CH C N
BHP
t-butylhydroperoxide
HN C CH CH2 CH2 CH C NH
Mechanism:
N C CH2 CH2 CH2 CH2 C N
(1) (CH3)3CH + X (CH3)3C + HX
Reduction of acrylonitrile to radical anion
(2) (CH3)3C + O2 (CH3)3COO
Coupling of radical anions simultaneous with
protonation to form C6 chain (3) (CH3)3COO + (CH3)3CH (CH3)3COOH + (CH3)3C
Hydrogen transfer to form nitrile product then (2), (3), (2), (3), etc.

7. Propylene Oxide Manufacture 8. Propylene Oxide Manufacture

What if you don’t want to make t-butanol?
Mechanism:
CH3 CH3
CH2 CH CH3 + CH3 C CH3 CH2 CH CH3 + CH3 C CH3
OH
OOH
O OH O O CH CH2
CH2 CH3 CH CH3 CH CH3
δ− δ+ H
CH3 [O] CH2 CH CH3 -H2O
CH2 CH CH3 + CH3 C CH3 ∆
Used in MTBE manufacture O OH MBA
How is this used to make +
MTBE? O
CH2 CH CH3

Co-product can be varied to meet market

demands
What if you don’t want any co-products?

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 9. Epichlorohydrin Manufacture 10. Uses of Propylene Oxide
Epoxidation using allyl chloride instead of Recall where propylene glycol was used?
propylene leads to epichlorohydrin CH3 CH3 CH3 CH3
Cl2 Cl2 HO CH CH2 OH + n CH2 CH HO CH CH2 O (CH2 CH O)n H
CH3 CH CH2 Cl CH2 CH CH2 Cl CH2 CH CH2 Cl
500oC H2O O poly(propylene glycol)
allyl chloride OH
+ propylene glycol propylene oxide CH3
n = 7-35
Write a reasonable mechanism Cl CH2 CH CH2 OH N C O

(free-radical) for the formation of Cl TDI

Ca(OH)2
allyl chloride
or NaOH N C O

Cl CH2 CH CH2 CH3 O CH3 CH3

O NH C O CH CH2 O (CH2 CH O)n

Write a reasonable mechanism for
epichlorohydrin
the formation of epichlorohydrin
from allyl chloride C NH
Where was O
this used? x
a polyurethane

11. Cumene Manufacture 12. Acetone Manufacture

Write the mechanism for the formation of Cumene-based route to acetone
cumene from benzene and propylene Initial formation of cumene hydroperoxide
Know the mechanism!!

Acid catalyzed rearrangement of cumene

hydroperoxide via phenyl group migration
CH3 CH3
∆ H2SO4
CH CH3 + O2 C O OH OH
CH3
phenol
cumene cumene hydroperoxide
O

Overall yield = 90 – 92% + CH3 C CH3

acetone

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 13. Acetone Manufacture
Ph Ph

14. (1) CH3 C O OH + H+

CH3
CH3 C O OH2
CH3
cumene hydroperoxide
Cumene route Mechanism: a protonated hydroperoxide

rearrangement Ph Ph
Side products include involving
(2) CH3 C O OH2 CH3 C O + H2O

simultaneous
CH3 CH3
O CH3 CH3 migration to
C CH3 C OH C CH2 electron- (3) CH3
Ph
C O CH3 C O Ph
CH3 C O Ph
deficient CH3 CH3
CH3 CH3
oxygen resonance stabilized

acetophenone 2-phenylpropan-2-ol α-methylstyrene Key is the OH2 OH

inherent (4) CH3 C O Ph + H2O CH3 C O Ph -H+ CH3 C O Ph

Acetone distilled first (bp = 56 oC) weakness of the CH3 CH3 CH3

O-O bond under a hemiketal

α-methylstyrene separated by vacuum distillation and acidic OH OH

hydrogenated back to cumene – recycled conditions (5) CH3 C O Ph + H+ CH3 C O Ph
H
CH3 CH3
Phenol (bp = 181oC) separated from acetophenone
(bp = 202 oC) by further distillation OH OH
-H+
O
HO Ph + CH3 C CH3 C CH3 C CH3

phenol CH3 CH3 acetone

resonance stabilized

15. Bisphenol A Manufacture 16. n-Butyraldehyde Manufacture

Bisphenol A manufactured from phenol and Formed from propylene and syn-gas using oxo-
acetone (50 oC, 8 – 12 hours) process
CH3 CH3
2HO + O C
HCl
HO C OH + H2O Oxo process = hydroformylation
CH3
CH3
Effectively adding a formyl group (CH2O) to
bisphenol A
propylene
Mechanistic steps O CH3 O
1. Protonation of carbonyl CH3 CH CH2 + CO + H2 CH3 CH2 CH2 C H + CH3 CH C H
2. Electrophilic attack on aromatic ring n-butyraldehyde isobutyraldehyde
3. Rearomatization by proton loss
4. Protonation, loss of water Transition metal catalyzed process
5. Electrophilic attack Active form of catalyst is hydridotetracarbonylcobalt
6. Rearomatization by proton loss
H2 CO CO
Some o,p isomer is formed, mainly p,p 2Co + 8CO Co2(CO)8 2 Co H
CO CO

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 17. n-Butyraldehyde Manufacture 18. Hexamethylenediamine (HMDA)
CO CO OC CH2 OC CH2 Anti-Markovnikov addition places the substituent
OC
Co H + CH2=CHR
OC
Co CHR
OC
Co CHR (nitrile group) at the least substituted site
OC
CO OC H OC H Places nitrile groups on the ends
Converts C4 compound to a C6
O CHHR Hydrogenation over Fe catalyst generates
OC
C CH2
OC CH2
CHHR CO OC CH2 HMDA
OC OC OC
Co Co Co CHHR CH2 CH2 CH2
H2C 2 HCN N C C N
OC OC CO CH CH CH2 CH2
OC
Ni
adiponitrile
+ H2 butadiene
for R = Me H2
butyraldehyde Fe catalyst
O CHHR CH3
OC CO CO O CHHR CH2 CH2
C O CH2 NH2 CH2 CH2 NH2
CH2 OC
OC C CH2 CH2
Co Co H + CH2 C CH2
H H H
OC H OC hexamethylenediamine
CO

19. MTBE Manufacture 20. Other C4 Derivatives

MTBE manufactured solely as fuel additive Butylated hydroxytoluene (BHT)
Use has skyrocketed since Clean Air Act mandated Important antioxidant for stabilizing polymers and
oxygenate levels other products
Manufacture of MTBE
Year Billion lb OH CH3 OH CH3
CH3 CH3
1983 0.8 CH3 C C
H+
1984 1.47 + 2CH2 C CH3 CH3 CH3
1990 6
1995 12 CH3 CH3

Formed by acid catalyzed addition of methanol BHT

to isobutylene What’s the mechanism for alkylating hydroxytoluene?

CH3 CH3 CH3 CH3
H+ CH3OH -H+
CH3 C CH2 CH3 C CH3 CH3 C CH3 CH3 C CH3
or ion
O CH3 O
exchange
catalyst
Forms hindered oxygen-based free-radicals that
H CH3
scavenge alkyl free-radicals but are unreactive
MTBE
toward organic functional groups