2-甲基THF

MeTHF is a furan derivative made from renewable resources with considerable advantages over THF.
MeTHF is a rapidly emerging global solvent market and Penn is spearheading the commercialization of this solvent.
%பைடு நூலகம்Sol. In THF
15% 10% 15% 25%
P. Rittmeyer et al., Chemetall DE 19808570
Improved Process: chemical properties
Less impurities under acidic conditions:
– less solvent degradation @ acidic aqueous work-up – better stability to Lewis acids
2-METHYLTETRAHYDROFURAN
2-Methyltetrahydrofuran: Simply Better than Tetrahydrofuran
Dr. Bogdan Comanita , Penn Specialty Chemicals, Inc.
Introduction
Penn Specialty Chemicals Inc. has been a leader in furan chemistry for more than 60 years,
MeTHF is not only an innovative product but at the same time it is an innovation enabler for the fine chemicals and pharmaceutical industry.
I hope that our presentation will convince you that this is in fact the case.
% Energy savings for dry MeTHF vs. THF recovery
Weighted Total
BTU’s/lb of material reclaimed
Energy Savings from
Recovery/ Drying
50% MeTHF THF
966 3,16
69%
– Increased solvent volumes – Hard to recycle solvent mixtures (separation difficult) – Persistent emulsions and rag layers
– Add saline solution for phase separation
B. Comanita; D. Aycock, Industrie Pharma Magazine, No.17, 2005, 54-56 D. Aycock, OPRD, submitted for publication
MeTHF: Higher Yield in Grignard Formation
# Reagent
Solvent
1 benzyl chloride
THF
MeTHF
2 benzyl bromide
THF
MeTHF
3 o-methylbenzyl chloride THF
Organomagnesium MeTHF Yield
Yield
Improvement
85%
14%
99% 83%
99.6 parts dry MeTHF
•Easy product drying and precipitation •Solvent re-use: “one pot” reactions-no product isolation •Solvent recycling: drying through simple distillation
MeTHF Improves Processes
• Advantages from chemical properties
– Increased reaction yields – Increased solubility of organogrignards – Less impurities due to higher solvent stability
– Doesn’t work for polar compounds – Poor product recovery-second extraction needed – End-up with mixtures of solvents
Improved Process: physical properties
Less impurities under basic conditions:
– more stable to n-BuLi than THF – less by-products for some organogrignard reactions
Improved process: acid degradation
O
n-BuLi
O
H
Li
H2C CH2
+
Li O H2C H
The reaction of n-butyllithium with MeTHF is considerably slower
Compound
THF MeTHF
Half life at 35°C minutes
10
70
R. Bates, J. Org. Chem. (1972) 37(4), p560.
Improved Process: chemical properties
• Advantages from chemical properties
– Increased reaction yields – Less impurities due to better solvent stability
15%
98%
78%
19%
MeTHF 4 o-chlorobenzyl chloride THF
97% 20%
66%
5 allyl chloride
MeTHF THF MeTHF
86% 73% 89%
16%
•Dimerization of benzyl and allyl substrates is suppressed
Purchasing
2-MeTHF: The Value Proposition
R&D/Manufacturing
Reduced costs
Improved process
Comparable/better safety
Greener process
Safety
Environmental
Agenda
P. Rittmeyer et al., Chemetall DE 19808570
MeTHF: Increased Solubility of Various Grignard Reagents
Reagents
MeMgBr EtMgBr PhMgBr EtMgCl
% Sol. In MeTHF
35% 40% 45% 30%
• Advantages from physical properties
Improved Process: chemical properties
• MeTHF is a versatile solvent
1. Grignard 2. Lithiation 3. Hydride based reduction 4. Organopalladium 5. Organozinc 6. Biphasic reactions
• MeTHF is the solution to THF’s shortcomings:
1. MeTHF is not miscible with water 2. Clean phase separation with no emulsions & rag layers 3. Reduced number of extraction steps 4. Easy to dry (forms azeotrope like toluene) 5. Easy to recycle and reuse
1. MeTHF improves processes 2. MeTHF; safety aspects 3. MeTHF makes greener process 4. MeTHF cuts costs 5. Conclusions; MeTHF simply better than THF 6. Q&A session
140
160
Hours
Conditions: 50:50 THF/MeTHF: 2 N HCl at 60 C
D. Aycock, OPRD submitted for publication
Improved Process: strong base stability
THF reacts with n-butyllithium
10.6% water in azeotrope
60°C decanter
0.4 parts MeTHF 5.2 parts water (recycled to next batch)
100 parts MeTHF 5.2 parts water (at start of batch distillation)