EPOXIDATION OF ALLYL ETHERS

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Mircea Manea

Mirce

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CYCLIC ETHERS

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CYCLIC ETHERS IN NATURE

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� Vernonia oil

3

� Oxylipins are know in nature.

� Some plants such as Vernonia galamentis and Euphoria lagascae produce about 60% vernolic acid in the seed oil.

CYCLIC ETHERS IN NATURE

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� Paclitaxel

O

O

O

OH

NH OO

O

4

� extract from the rare Pacific

yew tree Taxus brevifolia.

OOO

O

HO

OH

O

EPOXY APPLICATIONS

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EPOXY RESINS

� DeTrey Frères produced in 1936, a low melting

bisphenol A-based epoxy resin that gave a

thermoset composition with phthalic anhydride.

� 1946 the first epoxy adhesive was shown at the

Swiss Industries Fair

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Swiss Industries Fair

� First commercial high solids epoxy systems in

1950s (Pittsburgh Coke & Chemical).The coating

exhibited an increased water resistance, thermal

plasticity, durability and corrosion resistance.

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EPOXY MARKET SITUATION 2006

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THE WORKING HORSES

� Cross-linked with amines /

poly(amido-amines) and

anhydrides

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� Cross-linked with polyacids

THE WORKING HORSES IN POWDER

COATINGS

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N

N

N

O

O

O

O

O

O

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(TGIC)1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione

O OO

OH

O

O

O

REACTIVE SOLVENTS (MONOFUNCTIONAL)

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REACTIVE SOLVENTS (POLYFUNCTIONAL)

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PURPOSE

� Manufacturing of glycidyl ethers avoiding the use

of epichlorhydrine

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OPTIONS

� Chemical oxidation via Prileshajev

� Chemo-enzymatic oxidation

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CHEMICAL OXIDATION VIA

PRILESHAJEV

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CHEMO-ENZYMATIC OXIDATION

� Lipase, H2O2, Carboxylic acid

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THE NATURE OF THE ALLYL ETHER

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� TMPME � TMPDE

� TMPTE

Water soluble Organic solvent soluble

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HO O

O

O O

O

CHEMO-ENZYMATIC EPOXIDATION OF

TMPME

� Novozym 435

� Carboxylic acid

� Solvent

� TMPME

Internal standard: hexadecane

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� Internal standard: hexadecane

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STABILITY OF THE GLYCIDYL ETHER

� In situ generated peracid

� Reaction temperature

50ºC

� Allyl group completely

consumed

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20

30

Concentration (mM)

� No glycidyl group detected

at the end

� Acid catalyzed hydrolysis

of the glycidyl group

18

0

10

20

0 12 24 36

Time (h)

Concentration (mM)

20mM/50ºC

DEGRADATION PROFILE OF THE

GLYCIDYL ETHER IN DIFFERENT

SOLUTIONS

� (◊◊◊◊) water,

� (o) mono sodium

phosphate

solution, pH 4,

� (x) phosphate

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100

120

140

160

Norm

alised G

C-area

� (x) phosphate

buffer, pH 7,

� (∆∆∆∆) tri-sodium

phosphate

solution, pH 14,

� (□) acetone

19

0

20

40

60

80

100

0 12 24 36 48

Time (h)

Norm

alised G

C-area

RESIDUAL CONCENTRATION OF PEROXY ACID

AND FORMATION OF THE GLYCIDYL ETHER

DURING EPOXIDATION OF TMPME

� (◊) spontaneous degradation (in the absence of TMPME) of preformed palmitic peracid at 50 ºC

� (□) conversion of the palmitic

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60

70

� (□) conversion of the palmiticperacid during epoxidation of TMPME

� (x) palmitic peracid consumed during epoxidation (excluding spontaneous degradation)

� (∆) concentration of the epoxide product formed during reaction

� Solvent= toluene

200

10

20

30

40

50

60

0 6 12 18 24 30 36

Time (h)

Concentration (mmol/L)

FORMATION OF PEROXY PALMITIC ACID

CATALYSED BY NOVOZYM® 435 IN TOLUENE

� (◊)25ºC

� (□) 50 ºC

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20

25

30Conversion to peracid (%)

21

0

5

10

15

20

0 1 2 3 4 5 6

Time (h)

Conversion to peracid (%)

1

2

3

4

5

6

Form

ation rate (mM/m

in)

INITIAL RATE OF PERACID FORMATION VS

CARBOXYLIC ACID CONCENTRATION AT 30ºC/50ºC

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0.000.050.100.150.200.250.300.350.400.450.500.550.600.65

Peracid concentration (M)

0.00 0.25 0.50 0.75 1.00 1.250

Concentration (M)

Form

ation rate (mM/m

in)

+ Caprylic acid

∆ Lauric acid

30 % H2O2 (19.6 mmol)

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0 1 2 3 4 5 6 70.000.05

Concentration of acid (M)

Peracid concentration (M)

30ºC 50ºC

0.75

1.00

1.25

C Peracid (M)

PERACID FORMATION FROM CAPRYLIC ACID

AT VARYING H2O2 CONCENTRATIONS

� (x) 50%

� (□) 40%

� (∆) 30%

� (o) 20%

(+)10%

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0 1 2 3 4 5 60.00

0.25

0.50

Time (h)

C Peracid (M)

90 % caprylic acid in toluene, 25 °C

� (+)10%

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PERACID FORMATION FROM

DIFFERENT CARBOXYLIC ACIDS

� (+)

Caprylic

acid, C8,

mp 16.3 °C

� (∆) Lauric

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0.100

0.125

Peracid concentration (M)

� (∆) Lauric

acid, C12,

mp 45 °C

� (X)

Palmitic

acid, C16,

63 °C24

0 25 50 75 100 125 150 1750.000

0.025

0.050

0.075

Time (min)

Peracid concentration (M)

0.6 mmol carboxylic acid + 9.8 mmol H2O2

0.3

0.4

0.5

0.6

C Epoxide (M)

Ex situ peracid generation

Yield: 75 %

EPOXIDATION OF TMPME

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0 2 4 6 8 10 120.0

0.1

0.2

0.3

Time (h)

C Epoxide (M)

In situ peracid generation

(5.7 M caprylic acid, 18 mmol H2O2, 50 °C) 25

PROCESS

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Hydrogen peroxide

(Solvent)

Carboxylic acid

Enzyme

(Solvent)

Carboxylic acid

Hydrogen peroxide

Enzyme

Allyl ether

(Solvent)

Peracid

CHEMO-ENZYMATIC EPOXIDATION OF

TMPME

� Two stage process

� Reaction temperature

50ºC

� Allyl group consumed

� Glycidyl group

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20

30

Concentration (mM)

� Glycidyl group

generated

correspondingly

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0

10

0 12 24 36

Time (h)

Concentration (mM)

0.3

0.4

0.5

0.6

Concentration of epoxide (M)

Yield: 75 %

EPOXIDATION OF TMPTE

� (5.7 M

caprylic

acid, 18

mmol

H2O2, 50

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0 2 4 6 8 10 120.0

0.1

0.2

0.3

Time (h)

Concentration of epoxide (M)

H2O2, 50

°C)

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EPOXIDATION OF DIFFERENT ALLYL

ETHERS

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Starting material Concentration Yield*

100 mg/ml 80 %OOH

OH

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100 mg/ml 80 %

100 mg/ml 100 %

100 mg/ml 60 %O

O

O

O

O

O

m

n

p

m+n+p=7

O

O

O

O

3

* By titration (approximate values)

CONCLUSIONS

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� Shorter acid does good

� Many allyl ether may be converted

� Aromatic

� Good

� Aliphatic

� Bad

Carboxylic acids Solvents

• 1 step reaction– Low yields

– Low concentrations

– Water degrades

Process

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may be converted

� Different solvents may be used

� Higher peracidconcentration does good

� Bad

� No solvent

� Very good

– Water degrades epoxide

• 2 steps reaction– Water excluded

– Low concentrations

– Good yields

INTERESTING SPINOFF

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INTERESTING SPINOFF

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ACKNOWLEDGMENTS

University of Lund

Alkindo Mitraraya

Perstorp

� Rajni-Hatti-Kaul

� Pär Tufvesson

� Dietlind Adlercreutz

� Sugianto Effendi

� Keith Ogemark

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THANK YOU FOR YOUR

ATTENTION

mircea.manea@telia.com

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