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A New Ether Process Solvent: Cyclopentyl methyl ether (CPME)
for Green Chemistry and Process Innovation
OMe
Industrial Green Chemistry World, 7 December 2013, MumbaiShunji Sakamoto
Glycol-ethersDMSO
DMF
Boilin
g P
oin
t
MTBE
IPETHF
Polarity(Dielectric Constant)
100℃
180℃
HighLow
CPME
AcOEt
Toluene
Dioxane
Et2O
MeTHF
Positioning of CPME Among Other Solvents
CPME THF MeTHF Et2O Dioxane MTBE
Density (20°C) [g/cm3] 0.86 0.89 0.85 0.71 1.03 0.74
Vapor specific gravity (air = 1) 3.45 2.49 2.97 2.56 3.3 3.03
Boiling point [°C] 106 65 80 34.6 101 55
Melting point [°C] <-140 -108.5 -136 -116.3 11.8 -108.7
Viscosity (20°C) [cP] 0.55 0.55 0.6 (25˚C) 0.2448 1.31 0.35
Surface tension (20°C) [mN/m] 25.17 26.4 Unknown 17.3 33.74 19.8
Vaporization energy (bp) [Kcal/kg] 69.2 98.1 89.7 86.08 98.6 81.7
Specific heat (20°C) [Kcal/kg∙K] 0.4346 0.469 Unknown 0.5385 0.41 0.51
Refractive index (20°C) 1.4189 1.407 1.406 1.353 1.422 1.369
Solubility parameter [(cal/cm3)1/2] 8.4 9.5 8.52 7.4 Unknown Unknown
Dielectric constant (25°C) 4.76 7.58 7 4.197 2.227 2.6
Dipole moment [D] 1.27 (calcd.) 1.7 Unknown 1.12 0.45 1.4
Azeotropic temperature with water [°C] 83 (a) 64 71 (b) 34.2 87.8 52.9 (c)
Solubility of solvent in water (23°C) [g/100g] 1.1 Infinite 14 6.5 Infinite 4.8
Solubility of water in solvent (23°C) [g/100g] 0.3 Infinite 4.4 1.2 Infinite 1.5
Flash point [°C] -1 -14.5 -11 -45 12 -28
Auto Ignition Temperature [°C] 180 205 270 180~190 180 224
LogPow 1.59 0.47 Unknown 0.89 -0.42 0.94
Explosion range [vol%] Lower limit 1.1 1.84 1.5 1.85 2 1.6
Upper limit 9.9 11.8 8.9 48 22 8.4
Comparison with other Ethers
1. Green ChemistryHigh Recovery Rate > 90% --- High HydrophobicityReduces amount of wastes and CO2
Diverse uses as reaction, extraction and crystallization solvents --- Solvent unification, Reduction of solvent amount
Low peroxide formationManufactured by atom economical processMakes Azeotrope with water : 16% water at 83℃
2. Process InnovationDiverse uses as reaction, extraction and crystallization solvents
--- Reduction of solvent exchangeProcess simplification and shortening One-pot synthesis and telescoping Stable under acidic and basic conditions
Summary of CPME Benefits
The Contribution of CPME to Green Chemistry
Reduction of wastes and CO2 Emissions with CPME
ZEON’s Manufacturing Process of CPME
+ MeOH
Molecular Weight 68.12 + 32.04 = 100.16
100% Atom Economical Reaction
No atom waste
One-step continuous system --- energy saving
OMe
Acid Cat.
Peroxide Formation in CPME versus other ethers
The 12 Principles of Green Chemistry
1. PreventionSignificant reduction of water and solvent waste
2. Atom EconomyWe manufacture CPME by the atom economical reaction.
3. Less Hazardous Chemical Syntheses4. Designing Safer Chemicals5. Safer Solvents and Auxiliaries
CPME makes slight peroxides. We manufacture CPME with minimum auxiliaries.
6. Design for Energy EfficiencyCPME can save energy by simplification and shortening of production processes.
7. Use of Renewable Feedstocks8. Reduce Derivatives
We manufacture CPME in the one-step continuous system without derivatizations.
9. CatalysisWe manufacture CPME in the catalytic process in the presence of the solid acid.
10. Design for Degradation11. Real-time analysis for Pollution Prevention
The flow reaction process is continuously monitored.
12. Inherently Safer Chemistry for Accident PreventionCPME has lower formation of peroxides in comparison with common ethers.
CPME meets 8 principles
The Contribution of CPME to Process Innovation
Fixed cost reduction with CPME
CPME shortens and simplifies the process--- saves process time, facilities and labor
--- fixed cost reduction
Variable Cost Reduction with CPME(with solvent recovery)
(Waste solvent, Waste water)C Waste Disposal Cost ($0.5/kg)
CPME THF
$8 x 10 x 0.1 = $8//kg - product $4 x 10 x 0.4 = $16/kg - product
CPME: $0.5 x 10 x 0.1 = $0.5
water: $0.5 x 3 = $1.5
THF: $0.5 x 10 x 0.4 = $2.0
AcOEt: $0.5 x 10 x 0.1 = $0.5
water: $0.5 x (40+20+20) = $40
AcOEt ($1.2/kg)
$1.2 x 10 x 0.1 = $1.2
$59.7/kg-product
2 weight times of water, aqNaCl to Solvent
4 weight times of water
to Solvent
recovery rate = 90% recovery rate = 60%
Total Variable Cost (A+B+C)
A Reaction Solvent Cost
Solvent/Product = 10/1(by weight)
B Extraction Solvent Cost
MeTHF
recovery rate = 70%
$6 x 10 x 0.3 = $18/kg - product
MeTHF: $0.5 x 10 x 0.3 = $1.5
AcOEt: $0.5 x 10 x 0.1 = $0.5
water: $0.5 x 6 = $3
$24.2/kg-product
AcOEt ($1.2/kg)
$1.2 x 10 x 0.1 = $1.2
equal weight of water to
product
equal weight of water, aqNaCl to product
4 weight times of water to
product
Extraction solvent:
unnecessary!
($8/kg) ($6/kg) ($4/kg)
CPME MeTHF THF
* The prices used here are only to demonstrate their cost reduction with CPME. The actual prices would
vary according to conditions such as quality, quantity, location, time, etc.
$10.0/kg-product
Stability of CPME to Acid and Base
Example of Green Chemistry & Process Innovation PINNER REACTION (1)
Requirements for Solvent
stability to acid solubility of raw materialsinsolubility of product
R OCH3
NH4M-HCl solution, CH3OH
solvent, 0oC, 1 h, then 0-5 oC, 48 h
solution solvent Yield (%)
CPME CPME 89b)
a) U.S.Pat.No.: US 6806380 B2b) Work-up of CPME process is only filtration and washing.
R CN
R
CH3
H3CO
1,4-Dioxane Et2O 86a)
CPME CPME 90b)
CPME CPME 91b)
HCl
Solvent Unification
1. Reaction: CPME
2. Cooling
3. Filtration
4. Drying
Product
TelescopingSteps: 9 to 4Solvents: 2 to 1
Greener ProcessWithout:Dangerous Solvents
Example of Green Chemistry & Process Innovation PINNER REACTION (2)
CPME Process4 steps without dangerous solvents
Original Process9 steps with dangerous solvents
Waste
1. Reaction: Et2O - Dioxane
2. Cooling:
3. Warmed at 40℃
4. N2 Bubbling
5. Removal of
solvent in vacuo
6. Precipitated by cooling
7. Addition of Et2O
8. Filtration
9. Drying
Product
Et2O
Dioxane
HCl
Et2O
Comparison of Properties of CPME & MeTHF versus THF
excellent good poor
CPME MeTHF THF
Solubility in water g/100g-water 1.1 14 Infinite
Recovery rate from water % 90 70 60
Waste rate (1 - recovery rate) % 10 30 40
Explosive Peroxide formation slower faster faster
Stability to acid more stable less stable unstable
Boiling Point °C 106 80 65
Flash Point °C -1 -11 -14.5
Vaporization Energy (at bp) kcal/kg 69.2 89.7 98.1
Acid and Base solutions in CPME
2. Process Innovation Process simplification - Fixed cost reduction Solvent unification - Variable cost reduction Facilitate one-pot synthesis and Telescoping Better stability under acidic and basic conditions
Conclusion
1. Green Chemistry – Cradle to Greave Manufactured by Atom economical process Solvent unification and reduction of solvent used Reduction of wastes and CO2
Saving energy Lower Peroxide formation
CPME contributes to:
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Specifications
Toxicity Data
ICH Guideline for Residual Solvents (Zeon)
CPME has not yet classified in ICH guideline for residual solvents (Q3C). However, it is assumed to be in Class 2 according to Zeon's own calculation.
1) Formula
PDE = (NOEL x Weight Adjustment)/(F1+F2+F3+F4+F5)
Concentration Limit (PPM) = 1000 x PDE / dose
*PDE: Permitted Daily Exposure
2) Calculation
PDE = (15x50) / (5 x 10 x 10 x 1 x 1)=1.5mg/day
Concentration Limit = 1000 x 1.5/10 = 150ppm
3) Conclusion
According to the above, Zeon assume CPME would be classified in Class 2.
ICH Guideline for Residual Solvents (Merck)
Antonucci, V et al.: Org. Process Res. Dev., Article ASAP, 10.1021/op100303c, March 18, 2011
PDE (mg/day)
CPME 7.4
MeTHF 6.2
THF 7.2*
Toluene 8.9*
*ICH Guideline
Grignard Reaction
Variable Cost Reduction with CPME(without solvent recovery)
(Waste solvent, Waste water)C Waste Disposal Cost ($0.5/kg)
CPME THF
$8 x 10 = $80//kg - product $4 x 10 = $40/kg - product
CPME: $0.5 x 10 = $5
water: $0.5 x 3 = $1.5
THF: $0.5 x 10 = $5
AcOEt: $0.5 x 40 = $20
water: $0.5 x (40+20+20) = $40
AcOEt ($1.2/kg)
$1.2 x 40 = $48
$153.0/kg-product
2 weight times of water, aqNaCl to Solvent
4 weight times of water
to Solvent
Total Variable Cost (A+B+C)
A Reaction Solvent Cost
Solvent/Product = 10/1(by weight)
B Extraction Solvent Cost
MeTHF
$6 x 10 = $60/kg - product
MeTHF: $0.5 x 10 = $5
AcOEt: $0.5 x 40 = $20
water: $0.5 x 6 = $3
$136.0/kg-product
AcOEt ($1.2/kg)
$1.2 x 40 = $48
equal weight of water to
product
equal weight of water, aqNaCl to product
4 weight times of water to
product
Extraction solvent:
unnecessary!
($8/kg) ($6/kg) ($4/kg)
CPME MeTHF THF
* The prices used here are only to demonstrate their cost reduction with CPME. The actual prices would
vary according to conditions such as quality, quantity, location, time, etc.
$86.5/kg-product
Comparison of Formation of Peroxides in MeTHF versus THF
Aycock, D. Org. Process Res. Dev., 2007, 11 (1), pp 156–159
Cumulative Energy Demand (CED)
Dr. Alireza BanimostafaETH Zurich Institute for Chemical and Bioengineering
CED Production: 95-100 (Mj/kg)
CED Incineration: 70-75 (Mj/kg)
CED Distillation: 25 (Mj/kg)
His paper will be published in AIChE journal in a few months as:"Retrofit design of a pharmaceutical batch process considering “green chemistry and engineering” principles"
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OAc
COOH OCOOMe
H2N COOH
O O O
NH2
O
OMeF F
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