terpene-based manufacturing for sustainable chemical feedstocks terpene-based manufacturing for...
Post on 16-Dec-2015
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Terpene-based Manufacturing for Sustainable Chemical Feedstocks
An Abundant Resource
A Renewable Hydrocarbon Platform
A Multi-disciplinary Project
Chemistry at the centre
O
OO
O
O
n
PET
Chemistry at the centre
O
OO
O
O
n
PET
Exemplary demonstrationA sustainable synthesis of 'green' paracetamol from limonene
OH
dil. H2SO4
NaNO3
OH
NO2
OH
NO2
+
Step 1 Petrochemical feedstockLow yield, poor selectivityUnreacted phenol in effluent
25 % 36 %
OH
HN
O
Classical petrochemical based synthesis:
OH
NO2
OH
NH2
NaBH4 Explosive nitro-compoundsBatch processStoichiometric reagents/waste
74%
Step 2
OH
NH2
O
O O
OH
O
OH
HN
Peterochemical based reagentsAcetic acid waste
O
99%
Step 3
• 30 million packs sold in UK every year• 180,000 t/yr global production• All 8 carbons from parent skeleton of limonene• Scalable, catalytic flow-synthesis (Kg scale)
O
ozonolysis
O
O
OHi. supported H+
catalysed dehydration
ii. Metal catalysed
aromatisation
OH
HN
O
OH
OH
O
Metal catalysed epoxidation
H2O2 or O2 as oxidant
Supported base-catalysedring opening
2 x CH2O
Ion catalysed Beckmann rearrangement
H2O NH2OH
Limonene to ParacetamolProposed synthetic route:
O
ozonolysis
O
O
OHi. supported H+
catalysed dehydration
ii. Metal catalysed
aromatisation
OH
HN
O
OH
OH
O
Supported base-catalysedring opening
2 x CH2O
Ion catalysed Beckmann rearrangement
H2O NH2OH
1 mol% PW4O24[MTCA]3
1 eq 30% H2O2 (pH 7)RT, 1 h
94%
Limonene to ParacetamolCurrent progress:
Limonene to ParacetamolCurrent progress:
O
1 mol% PW4O24[MTCA]3
1 eq 30% H2O2 (pH 7)RT, 1 h
94%
O
ozonolysis
O
O
OHi. supported H+
catalysed dehydration
ii. Metal catalysed aromatisation
OH
HN
O
OH
OH
O
2 x CH2O
Ion catalysed Beckmann rearrangement
H2O NH2OH
1 mol% PW4O24[MTCA]3
1 eq 30% H2O2 (pH 7)RT, 1 h
94% yield
10 mol% Al(OtBu)3
solvent free, 140 oC, 1 h 86% yield, 75% selectivity
Limonene to ParacetamolCurrent progress:
O
O
O
OHi. supported H+
catalysed dehydration
ii. Metal catalysed aromatisation
OH
HN
O
OH
OH
O
Ion catalysed Beckmann rearrangement
H2O NH2OH
1 mol% PW4O24[MTCA]3
1 eq 30% H2O2 (pH 7)RT, 1 h
94% yield
10 mol% Al(OtBu)3
solvent free, 140 oC, 1 h 86% yield, 75% selectivity
i. O3, MeOH, 0 oC
ii.SNaO
O O
ONa
Limonene to ParacetamolCurrent progress:
O
O
O
OHi. supported H+
catalysed dehydration
ii. Metal catalysed aromatisation
OH
HN
O
OH
OH
O
1 mol% PW4O24[MTCA]3
1 eq 30% H2O2 (pH 7)RT, 1 h
94% yield
10 mol% Al(OtBu)3
solvent free, 140 oC, 1 h 86% yield, 75% selectivity
i. O3, MeOH, 0 oC
ii.
solvent free, ZnO, 140 oC96% yield
NH2.OH.HCl
currently ongoing
SNaO
O O
ONa
still to do
Limonene to ParacetamolCurrent progress:
Acknowledgments
ChemistryMatthew DavidsonSteven BullWilliam CunninghamMatthew JonesChris FrostJanet ScottDuncan Wass (University of Bristol)
Chemical EngineeringMassi VezzoliPawel PlucinskiDarrel PattersonDavide MattiaLaura TorrenteUlrich Hintermair
BiologyDavid LeakMatthew Styles
Systems analysis and Pathways to Manufacture(University of Cambridge, Institute for Manufacturing)Alexei LapkinJag SraiWouter Bam
Environment, Sustainability and Energy Division
Funding
Limonene to Paracetamol
O
OH
Et2O, 35 oC, 3 h
RNH
R1. nBuLi
Et2O, 0 oC
RNLi
ROH
AmineR = EtR = iPrR = TMP
+
Yield 919095
Desired809094
Undesired20106
NH
TMP
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