8/9/2019 Preparation of Alkyl Carbonates

1/3

U n i t e d S t a t e s P a t e n t 0

1

3 , 2 2 7 , 7 4 0

PREPARATION OF

ALKYL

CARBONATES

D o n a l d

M. F e n t o n , A n a h e i m ,

C a l i f . ,

a s s i g n o r t o U n i o n

0 1 1

Company o f C a l i f o r n i a ,

L o s A n g e l e s , C a l i f . , a

c o r

p o r a t i o n o f C a l i f o r n i a

No D r a w i n g . F i l e d F e b . 2 5 ,

1 9 6 3 ,

S e r . No. 2 6 0 , 8 4 4

1 3

C l a i m s .

C l . 260463

This i n v e n t i o n r e l a t e s t o a

method

f o r t h e prepara

t i o n

o f d i a l k y l

c a r b o n a t e s

which

a r e U s e f u l f o r

a

v a r i e t y

o f p u r p o s e s

i n c l u d i n g s o l v e n t s , a n d p o l y a l k y l c a r b o n a t e s )

u s e f u l

a s

p l a s t i c i z e r s , o i l s , e t c .

I h a v e f o u n d t h a t s u c h d i a l k y l

c a r b o n a t e s

a n d

p o l y c a r

b o n a t e s c a n

be

r e a d i l y p r e p a r e d b y t h e r e a c t i o n o f

an a l

k a n o l o r p o l y o l and carbon

monoxide

i n t h e p r e s e n c e o f

a

s o l u t i o n o f

mercuric

s a l t s

i n

an o r g a n i c s o l v e n t . T h e

c r u d e

r e a c t i o n

p r o d u c t s c o m p r i s e

t h e a l k y l

c a r b o n a t e

o r

p o l y a l k y l c a r b o n a t e ) ,

m e r c u r y a n d

t h e

a c i d

c o r r e s p o n d

i n g t o t h e a n i o n , o f t h e m e r c u r i c s a l t

e m p l o y e d .

The d i

a l k y l c a r b o n a t e o r

p o l y a l k y l

c a r b o n a t e )

i s

r e a d i l y r e

c o v e r e d

from

t h e

c r u d e

r e a c t i o n p r o d u c t

and

t h e r e m a i n

i n g

m a t e r i a l s s u b j e c t e d

t o known

o x i d i z i n g c o n d i ti o n s

t o

o x i d i z e t h e

mercury t o t h e m e r c u r i c s a l t

f o r r e c y c l i n g

t o

t h e r e a c t o r .

The

r e a c t i o n

i s

o p e r a t e d a t r e l a t i v e l y

m i l d

c o n d i t i o n s ,

e . g . ,

t e m p e r a t u r e s

between

a b o u t 3 0

and

a b o u t 3 0 0 C .

and

p r e s s u r e s

from a t m o s p h e r i c t o a b o u t 500 atmos

p h e r e s .

While

t h e

p r e s e n c e o f

s l i g h t

amounts

o f

w a t e r

c a n

be

t o l e r a t e d ,

t h e

y i e l d s a r e d e c r e a s e d i n

i t s

p r e s e n c e

a n d , t h e r e f o r e ,

t h e r e a c t i o n

i s

p r e f e r a b l y

c o n d u c t e d u n d e r

a n h y d r o u s

c o n d i t i o n s .

The r e a c t a n t a l c o h o l c a n

b e

any d e s i r e d p r i m a r y

a l

c o h o l c o r r e s p o n d i n g

t o

t h e

p a r t i c u l a r a l k y l

c a r b o n a t e

t o

b e

s y n t h e s i z e d .

G e n e r a l l y , a l i c y c l i c

a n d

a l i p h a t i c p r i m a r y

monohydroxy a l c o h o l s h a v i n g from 1 t o a b o u t

25

c a r

bons c a n b e employed t o p r e p a r e t h e d i a l k y l c a r b o n a t e s ,

e . g . ,

m e t h a n o l , e t h a n o l , p r o p a n o l ,

b u t a n o l ,

i s o b u t a n o l ,

a m y l a l c o h o l , i s o a m y l a l c o h o l , h e x a n o l , i s o h e x a n o l , c y c l o

h e x a n o l ,

h e p t a n o l , i s o h e p t a n o l , c y c l o h e p t a n o l , 3 - m e t h y l

h e x a n o l - l ,

l a u r y l a l c o h o l , 3 , 4 - d i e t h y l h e p t a n o l - l , 4 - e t h y 1

c y c l o h e x a n o l , e t c . P r e f e r a b l y , low

m o l e c u l a r

w e i g h t a l

c o h o l s

having 1 t o

about

6 carbons a r e u s e d .

The

d i a l k y l

c a r b o n a t e p r e p a r e d c o r r e s p o n d s

t o

t h e

a l

k y l g r o u p o f

t h e p a r t i c u l a r a l c o h o l e m p l o y e d , t h u s t h e u s e

o f

methanol

r e s u l t s i n t h e p r o d u c t i o n o f d i m e t h y l c a r

b o n a t e , e t h a n o l

t o

d i e t h y l c a r b o n a t e , p r o p a n o l t o d i p r o p y l

c a r b o n a t e ,

b u t a n o l

t o d i b u t y l c a r b o n a t e ,

c y c l o h e x a n o l

t o

d i c y c l o h e x y l c a r b o n a t e ,

e t c .

Mixtures o f

two

or

more

a l c o h o l s

y i e l d

c o r r e s p o n d i n g

c a r b o n a t e s , e . g . , m e t h a n o l

and

e t h a n o l

when employed a s t h e r e a c t a n t s y i e l d

a mix

t u r e

o f d i m e t h y l c a r b o n a t e ,

d i e t h y l

c a r b o n a t e ,

a n d meth

y l e t h y l c a r b o n a t e , e t c .

The

p o l y a l k y l c a r b o n a t e ) p r o d u c t s

a r e p r e p a r e d b y s u b

j e c t i n g

a g l y c o l o r

a l i p h a t i c

p o l y o l

t o

t h e h e r e i n d e s c r i b e d

r e a c t i o n c o n d i t i o n s .

G l y c o l s

y i e l d g e n e r a l l y

l i n e a r

p o l y

mers whereas t h e v a r i o u s p o l y o l s y i e l d , o f

c o u r s e ,

c r o s s

l i n k e d p o l y m e r s

h a v i n g a d i v e r s i t y o f p r o p e r t i e s .

T o

i l l u s t r a t e , any

o f t h e

f o l l o w i n g g l y c o l s can

be

u s e d a s

r e a c t a n t s : e t h y l e n e

g l y c o l ,

t r i m e t h y l e n e

g l y c o l ,

1 , 2 - p r o

p y l e n e

g l y c o l ,

1 , 2 - b u t y l e n e

g l y c o l ,

1 , 3 - b u t y l e n e

g l y c o l ,

t e t r a m e t h y l e n e g l y c o l , p e n t a m e t h y l e n e g l y c o l , 1 , 2 - p e n t y l

e n e

g l y c o l ,

1 , 3 - p e n t y l e n e

g l y c o l ,

h e x a m e t h y l e n e

g l y c o l ,

1 , 2 - h e x y l e n e

g l y c o l ,

1 , 3 - h e x y l e n e

g l y c o l ,

1 , 4 - h e x y l e n e g l y

c o l , d i p r o p y l e n e g l y c o l , c a r b i t o l ,

g l y c e r o l

m e t h y l e t h e r ,

g l y c e r o l e t h y l

e t h e r ,

d i e t h y l e n e

g l y c o l ,

e t c .

The p o l y a l k y l e n e

o x i d e )

p o l y m e r s c a n a l s o b e em

ployed

a s a

c o n v e n i e n t

s o u r c e o f g l y c o l s .

P a r t i c u l a r l y

u s e f u l a r e p o l y o x y e t h y l e n e , p o l y o x y p r o p y l e n e , a s w e l l a s

b l o c k p o l y m e r s

o f

e t h y l e n e

o x i d e

a n d p r o p y l e n e o x i d e .

These d i o l s a r e c o m m e r c i a l l y a v a i l a b l e i n a v a r i e t y o f

f o r m s a n d d e g r e e s

o f

p o l y m e r i z a t i o n . Examples o f com

1 5

25

35

40

45

50

60

65

3 , 2 2 7 , 7 4 0

Patented

J a n . 4 ,

1966

6

2

m e r c i a l l y

a v a i l a b l e

d i o l s a r e t h e

v a r i o u s P l u r o n i c s

man u

f a c t u r e d b y W y a n d o t t e C h e m i c a l s .

Various

p o l y o l s

can

a l s o be us ed a l o n e o r

i n admix

t u r e

w i t h

any o f t h e a f o r e m e n t i o n e d a l k a n o l s

and g l y c o l s

t o i m p a r t c r o s s - l i n k i n g t o t h e p o l y m e r . E x a m p l e s o f s u i t

a b l e p o l y o l s

a r e t h e

v a r i o u s

t r i o l s

s u c h

a s : g l y c e r o l ,

p e n t a

g l y c e r o l , e r y t h r i t o l ,

p e n t a e r y t h r i t o l , a d o n i t o l , a r a b i t o l ,

h e x a n h e x o l ,

e t c .

A l k y l e n e o x i d e s , e . g . ,

p r o p y l e n e

a n d

e t h y l e n e o x i d e ,

can be condensed on any

o f t h e a f o r e

m e n t i o n e d

p o l y o l s t o p r o v i d e

h i g h m o l e c u l a r w e i g h t r e

a c t a n t s . Examples o f s u c h

a r e

t h e p o l y o x y e t h y l e n e g l y c

e r o l e t h e r , p o l y o x y p r o p y l e n e g l y c e r o l e t h e r ,

e t c .

An

o t h e r

s u i t a b l e

h i g h

m o l e c u l a r

w e i g h t

p o l y o l i s c o m m e r c i a l

l y a v a i l a b l e i n t h e

T e t r o n i c s e r i e s o f

Wyandotte

Chemi

c a l s .

T h e s e t e t r a o l s

c o m p r i s e b l o c k s o f p o l y m e r s o f

p r o p y l e n e

and

e t h y l e n e o x i d e s and a r e p r e p a r e d by

con

d e n s i n g

p r o p y l e n e o x i d e on

an

a l k y l e n e

d i a m i n e and

t h e r e a f t e r

c o n d e n s i n g

e t h y l e n e o x i d e

on

t h e

i n t e r m e d i a t e

p r o d u c t .

P r o d u c ts h a v i n g m o l ec u l a r

W e i g h t s f r o m a b o u t

1 0 0 0

t o 10,000 or

m o re are a v a i l a b l e i n

t h i s

s e r i e s .

P r e f e r a b l y , t h e

p o l y o l s

a r e

u s e d i n c o m b i n a t i o n w i t h

g l y c o l s

and/ r

monohydroxyl r e a c t a n t s t o

l i m i t t h e d e g r e e

o f c r o s s - l i n k i n g a n d

t h e r e b y p e r m i t

f a c i l e

r e c o v e r y o f t h e

p r o d u c t i n a c c o r d a n c e

w i t h

c o n v e n t i o n a l p r a c t i c e i n t h e

a l k y d p o l y m e r a r t .

The r e a c t i o n

medi um

can

be

any

o r g a n i c

s o l v e n t which

i s l i q u i d a t t h e r e a c t i o n c o n d i t i o n s

and which i s i n e r t

t o

t h e r e a c t a n t s , i . e . i n e r t

t o

c a r b o n a t e s , c a r b o n m o n o x i d e ,

mercury

s a l t s a n d / o r

a l c o h o l .

The

p a r t i c u l a r

a l c o h o l

employed a s a r e a c t a n t can be

used

i n

e x c e s s

and

thus

c o m p r i s e t h e

r e a c t i o n

s o l v e n t .

T h i s

i s

t h e p r e f e r r e d

em

b o d i m e n t s i n c e

i t s i m p l i ? e s

t h e p r o d u c t r e c o v e r y s t e p s . I f

d e s i r e d ,

h o w e v e r ,

o t h er o r g a n i c s o l v e n t s

c a n b e

e m p l o y e d

i n c l u d i n g

v a r i o u s

e t h e r s

s u c h a s : m e t h y l e t h y l e t h e r , d i

e t h y l

e t h e r , d i i s o p r o p y l e t h e r , d i c h l o r o e t h y l

e t h e r ,

e t h y l

e n e g l y c o l d i i s o a m y l e t h e r , e t h y l b e n z y l e t h e r , d i e t h y l e n e

g l y c o l d i e t h y l e t h e r , t r i e t h y l e n e

g l y c o l d i e t h y l

e t h e r , t e t r a

e t h y l e n e g l y c o l

d i r n e t h y l e t h e r ,

e t c .

V a r i o u s e s t e r s

can

a l s o be employed a s t h e

s o l v e n t ,

e . g . , m e t h y l

f o r m a t e ,

e t h y l

f o r m a t e ,

m e t h y l a c e t a t e , e t h y l

a c e t a t e , n - p r o p y l

f o r m a t e ,

i s o p r o p y l a c e t a t e , e t h y l p r o p i o

n a t e , n - b u t y l f o r - m a t e , s e c - b u t y l a c e t a t e , i s o b - u t y l a c e t a t e ,

e t h y l

n - b u t y l a t e ,

n - b u t y l a c e t a t e ,

i s o a m y l a c e t a t e , n - a m y l

a c e t a t e , g l y c o l d i f o r m a t e , f u r f u r o l a c e t a t e ,

i s o a m y l

n

b u t y r a t e , e t h y l a c e t y l a c e t a t e ,

d i e t h y l

o x a l a t e , g l y c o l

d i

a c e t a t e , i s o a m y l

i s o v a l e r a t e ,

m e t h y l b e n z o a t e , e t h y l b e n

z o a t e , m e t h y l

s a l i c y l a t e ,

n - p r o p y l b e n z o a t e , n - b u t y l

o x a l a t e ,

e t c .

T h e s a t u r a t e d

hydrocarbons can

o f

c o u r s e

be used

a s

a s u i t a b l e i n e r t s o l v e n t , e . g . , p e n t a n e , h e x a n e , h e p t a n e ,

o c t a n e ,

d e c a n e ,

d o d e c a n e ,

b e n z e n e ,

t o l u e n e , x y l e n e ,

k e r o s e n e ,

e t c .

T he

m e r c u r i c

s a l t s

which can

b e

employed

a r e

t h o s e

s o l u b l e i n t h e r e a c t i o n medium.

I n c l u d e d

i n s u c h s a l t s

. a r e t h e m e r c u r i c h a l i d e s and t h e

c a r b o x y l a t e s

o f t h e

l o w e r m o l e c u l a r w e i g h t c a r b o x y l i c a c i d s , e . g . , m e r c u r i c

c h l o r i d e , m e r c u r i c b r o m i d e , m e r c u r i c

? u o r i d e ,

m e r c u r i c

a c e t a t e , m e r c u r i c f o r m a t e , m e r c u r i c p r o p i o n a t e ,

m e r c u r i c

b u t y r a t e ,

m e r c u r i c

p e n t o n a t e , e t c . Of t h e s e ,

m e r c u r i c

a c e t a t e i s p r e f e r r e d .

The

r e a c t i o n i s

b e l i e v e d

t o p r o c e e d

t h r o u g h

two s t e p s ,

a n d

s e x e m p l i ? e d b y t h e

f o l l o w i n g :

0

w h e r e i n :

X

e p r e s e n t s

t h e

p a r t i c u l a r

a n i o n

o f t h e

m e r c u r i c

s a l t ,

e . g . ,

t h e a f o r e m e n t i o n e d

h a l i d e

o r

c a r b o x y l g r o u p s .

8/9/2019 Preparation of Alkyl Carbonates

2/3

maintained a t

220 C .

f o r

an

a d d i t i o n a l two h o u r s .

3 , 2 2 7 , 7 4 0

3

As

p r e v i o u s l y

m e n t i o n e d ,

t h e p r e f e r r e d

e m b o d i m e n t

c o m p r i s e s t h e u s e o f m e r c u r i c a c e t a t e w i t h t h e

r e s u l t a n t

p r o d u c t i o n o f

a c e t i c a c i d i n t h e

c r u d e r e a c t i o n p r o d u c t .

The

r e a c t i o n

can

b e

performed

i n a

s i n g l e

s t e p

by

i n t r o d u c i n g

t h e r e a c t a n t s ,

i . e .

c a r b o n m o n o x i d e ,

t h e a l c o

hol

and

mercuric s a l t i n t o a r e a c t i o n

zone

a t

t h e d e s i r e d

t e m p e r a t u r e , a b o u t 1 5 0 t o a b o u t 3 5 0

C .

and

d e s i r e d

p r e s s u r e s from a b o u t 1 0 t o a b o u t 1 0 0 0 p . s . i . g . P r e f e r a b l y

t e m p e r a t u r e s from a b o u t 2 0 0 t o about 2 5 0 C . and p r o s

s u r e s

from 50 t o about 500 p . s . i . g . a r e

u s e d .

Because

mercuric s a l t s

a r e

r e a c t i v e

with

a l c o h o l s

a t

e l e v a t e d t e m p e r a t u r e s , i t i s p r e f e r r e d t o p e r f o r m t h e r e

a c t i o n

i n s e p a r a t e

s t e p s .

I n t h e

? r s t s t e p ,

t h e

s o l u t i o n

i s

t r e a t e d

t o

s a t u r a t i o n w i t h carbon monoxide and t h e

a l c o h o l i c o r o r g a n i c s o l u t i o n o f t h e r e s u l t a n t

m e r c u r i c

c a r b o n a t e i s t h e r e a f t e r h e a t e d

t o

t h e n e c e s s a r y r e a c t i v e

t e m p e r a t u r e

t o

form t h e d i a l k y l

c a r b o n a t e o r

p o l y a l k y l

c a r b o n a t e ) . I n t h i s manner

t h e

c o m p e t i n g r e a c t i o n be

tween

t h e

a l c o h o l and

t h e

mercuric s a l t i s

a v o i d e d and

t h e

d e s i r e d c a r b o n a t e f o r m a t i o n i s f a v o r e d .

I n g e n e r a l , t e m p e r a t u r e s b e t w e e n a b o u t 0 a n d a b o u t

1 0 0 C .

can

be

u s e d i n t h e ? r s t s t e p t o

absorb

carbon

m o n o x i d e ; p r e f e r a b l y

t e m p e r a t u r e s from a b o u t 2 5 t o

a b o u t

7 5

C .

a r e u s e d . High p r e s s u r e s a r e p r e f e r r e d

t o

f a v o r a b s o r p t i o n o f c a r b o n

m o n o x i d e ,

g e n e r a l l y p r e s

s u r e s

from

about 1 0 t o about 1000 p . s . i . g . can be u s e d ,

p r e f e r a b l y b e t w e e n a b o u t 1 0 0 and a b o u t 500 p . s . i . g . a r e

u s e d .

The l e n g t h o f t h e p r i m a r y c a r b o n

m o n o x i d e a b s o r p t i o n

s t e p d e p e n d s

on t h e

d e g r e e

o f

c o n t a c t i n g a c h i e v e d b e

tween t h e l i q u i d and

g a s .

The n e c e s s a r y l e n g t h o f

t i m e

i s r e a d i l y d e t e r m i n a b l e by o b s e r v i n g when c a r b o n

mon

o x i d e i s no l o n g e r a b s o r b e d a s

r e ? e c t e d

b y , e . - g . a c h i e v i n g

a s t e a d y r e a c t i o n p r e s s u r e o r

any

o t h e r i n d i c a t i o n t h a t

a

p o r t i o n

o f

t h e

g a s p h a s e i s no l o n g e r b e i n g a b s o r b e d .

T h e r e a f t e r , t h e r e a c t a n t s

a r e h e a t e d t o

t h e n e c e s s a r y

t e m p e r a t u r e

t o

y i e l d

t h e

c a r b o n a t e p r o d u c t . G e n e r a l l y ,

t e m p e r a t u r e s between

about

1 5 0 and about

350 can

be

u s e d ; between a b o u t

1 7 5 and 2 2 5 C .

a r e p r e f e r r e d .

The c r u d e r e a c t i o n

p r o d u c t

i s r e a d i l y

d e c a n t e d t o

s e p a

r a t e t h e o r g a n i c p r o d u c t s

from

t h e

m e r c u r y ,

t h e former

a r e d i s t i l l e d

t o

r e c o v e r

t h e

c a r b o x y l i c a c i d and

t h e d e s i r e d

y i e l d o f a l k y l c a r b o n a t e

from t h e

s o l v e n t

e m p l o y e d . The

s o l v e n t

and a c i d , e . g . ,

a c e t i c , can

b e combined w i t h

t h e

mercury and t h e

m i x t u r e s u b j e c t e d t o o x i d i z i n g c o n d i

t i o n s t o o x i d i z e t h e mercury t o i t s s o l u b l e s a l t

f o r

r e

c y c l i n g t o t h e r e a c t i o n . V a r i o u s

known

o x i d i z i n g con

d i t i o n s c a n

b e

employed i n

t h i s

s t e p , e . g . , n i t r i c a c i d ,

c h r o m i c a c i d , p a r m a n g a n a t e s , o z o n e , c a n b e

employed

t o

g e t h e r w i t h

oxygen u n d e r

t e m p e r a t u r e s

between a b o u t

0

C .

and

a b o u t

250

C .

t o

r e o x i d i z e

t h e mercury

f o r

r e c y c l i n g .

T he f o l l o w i n g

examples w i l l

s e r v e

t o i l l u s t r a t e

a

mode

o f p r a c t i c i n g

my

n v e n t i o n :

E x a m p l e 1

D i b u t y l c a r b o n a t e was p r e p a r e d b y t h e r e a c t i o n o f

1 0 0 m i l l i l i t e r s o f n - b u t a n o l and 3 1

grams

o f

m e r c u r i c

a c e t a t e in

a 300 m i l l i l i t e r

bomb,

which

was

p r e s s u r i z e d

t o

400

p . s . i . g .

w i t h

carbon monoxide. T he m i x t u r e was

t h e n h e a t e d t o 5 0 C . i n

a

r o c k i n g a p p a r a t u s . A f t e r

two

h o u r s a t 5 0 C . ,

t h e

p r e s s u r e

d r o p p e d t o 300 p . s . i . g .

The

mixture

was

t h e n heated

t o

1 1 0

C .

and h e l d a t t h i s

t e m p e r a t u r e

f o r

two

h o u r s

a n d , ? n a l l y ,

h e a t e d

t o and

On

c o o l i n g , t h e p r e s s u r e r e t u r n e d t o 300 p . s . i . g .

The

b o m b

was

opened

and

t h e

p r o d u c t

c o n t a i n e d

t h e r e i n

found

t o

c o m - p r i s e t w o l i q u i d l a y e r s ,

t h e l o w e r

c o m p r i s i n g

1 9

grams o f

m e r c u r y . The

u p p e r y e l l o w

l a y e r

was

d e c a n t e d

and d i s t i l l e d

t o

r e c o v e r

2 m i l l i l i t e r s o f b u t y l

a c e t a t e ,

b o i l i n g p o i n t

1 2 0 ~ 1 3 0 C . , 0 . 6 g r a m s w a t e r

and 1 2

grams d - i b u t y l c a r b o n a t e , h a v i n g

a

d e n s i t y o f 1 . 4 1 0 8 and

a

b o i l i n g

p o i n t

74~75 C .

a t

4

mm.

r e s s u r e . An i n

f r a r e d s p e c t r u m

i n d i c a t e d

t h e s a m p l e

t o b e v e r y p u r e

d i

b u t y l c a r b o n a t e which

was

o b t a i n e d

i n

a 67 y i e l d .

10

15

20

25

30

35

40

45

50

55

60

65

7 0

7 5

;

Example 2

Dimethyl c a r b o n a t e was

p r e p a r e d

i n

t h e same

a p p a r a

t u s

by

t h e r e a c t i o n o f 1 0 0 m i l l i l i t e r s m e t h a n o l , 3 2 grams

mercuric

a c e t a t e and 21 m i l l i l i t e r s t o l u e n e

a s

a

s o l v e n t .

The b o m b

was

p r e s s u r e d t o 400 p . s . i . g . w i t h carbon

m o n o x i d e ,

h e a t e d ,

w i t h

r o c k i n g ,

t o

5 0 C .

f o r

o n e

h o u r ,

t h e n 1 0 0 C . f o r

one

hour

and

? n a l l y , 200 C . f o r two

h o u r s .

A f t e r

c o o l i n g , t h e

p r e s s u r e

r e t u r n e d t o 3 0 0 p . s . i . g .

T he bomb

was

opened

and

c o n t a i n e d 20

grams

o f mer

cury and a

y e l l o w - g r e e n

l i q u i d which

was added

t o 1 0 0

m i l l i l i t e r s w a t e r . T he o r g a n i c p h a s e Was d i s t i l l e d

and

a

h i g h y i e l d o f d i m e t h y l c a r b o n a t e was r e c o v e r e d t h e r e

f r o m .

E x a m p l e 3

T he

20 grams mercury from Example

2

was

added t o

150

m i l l i l i t e r s

a c e t i c a c i d c o n t a i n i n g

2 m i l l i l i t e r s

concen

t r a t e d

n i t r i c

a c i d . Air was

i n t r o d u c e d

i n t o t h e

mixture

and

a w h i t e s o l i d immediately

was

formed. T he mix

t u r e was

heated

and a t 8 0 C . 1

hour

l a t e r ) t h e maxi

mum mount

o f

w h i t e s o l i d

had

formed and

t h e

m e t a l l i c

mercury

had

d i s a p p e a r e d .

F u r t h e r

h e a t i n g

t o

1 0 5

C .

d i s s o l v e d t h e

white s o l i d and

a

c l e a r

s o l u t i o n was l e f t .

Upon c o o l i n g , a w h i t e p r e c i p i t a t e formed which was

? l t e r e d

t o

o b t a i n

27 grams mercuric a c e t a t e w h i c h can be

u s e d

i n

r e p e a t e d r e a c t i o n s f o r t h e f o r m a t i o n o f d i a l k y l

c a r b o n a t e s .

Example 4

A

o l y h e x a m e t h y l e n e c a r b o n a t e )

was

p r e p a r e d

by

c o n

d e n s i n g 1 2

grams

o f

h e x a m e t h y l e n e

g l y c o l

i n

1 0 0

m i l l i

l i t e r s

o f

e t h y l

e t h e r s o l v e n t

c o n t a i n i n g 3 1

grams

o f

mercuric a c e t a t e . T he

s o l v e n t ,

mercuric s a l t

and

r e

a c t a n t

were charged

t o

a

300

m i l l i l i t e r bomb

and

p r e s

s u r e d t o 400 p . s . i . g . w i t h

c a r b o n

monoxide. The

b o m b

wa s rocked

and

heated

and

maintained a t 60 C .

f o r

two

h o u r s , then heated

t o

and

held

a t

220

C . f o r

two

more

h o u r s . Upon c o o l i n g t o

room

t e m p e r a t u r e t h e

b o m b

p r e s s u r e

was

observed

t o

be

3 5 0

p . s . i . g .

T he bomb

was

opened and

t h e

c o n t e n t s

d e c a n t e d t o

s e p a r a t e

t h e o r g a n i c

l a y e r from 1 5

grams

o f

mercury

i n t h e bomb. The

s o l v e n t and e x c e s s

hexamethylene

g l y c o l

were removed

from t h e polymer by

vacuum d i s t i l l a t i o n .

The l i q u i d

r e s i d u e

was a v i s c o u s yellow l i q u i d

having

an i n f r a r e d

a n a l y s i s o f

c a r b o n a t e and h y d r o x y l

g r o u p s

and

a

molec

u l a r

w e i g h t

o f

3 9 1 .

The p r e c e d i n g e x a m p l e s a r e i n t e n d e d

s o l e l y

t o i l l u s

t r a t e my nvention

and a r e

not t o be construed

a s unduly

l i m i t i n g t h e r e o f . My

n v e n t i o n

i s i n t e n d e d t o b e d e ? n e d

by

t h e method s t e p s and t h e i r

e q u i v a l e n t s s e t f o r t h

i n

t h e f o l l o w i n g

c l a i m s .

I c l a i m :

1 .

T h e

s y n t h e s i s

of

a

carbonate from

an

a l c o h o l s e

l e c t e d

from

t h e

c l a s s

c o n s i s t i n g o f a l i c y c l i c a n d a l i p h a t i c

p r i m a r y

a l c o h o l s h a v i n g

1

t o a b o u t

25

c a r b o n s and a l i

p h a t i c p o l y o l s h a v i n g m o l e c u l a r

w e i g h t s f r o m

6 2 t o a b o u t

1 0 , 0 0 0

which

c o m p r i s e s c o n t a c t i n g s a i d

a l c o h o l

w i t h

c a r ~

bon

monoxide

i n t h e

p r e s e n c e o f a mercuric

s a l t s e l e c t e d

from t h e c l a s s c o n s i s t i n g

o f

m e r c u r i c h a l i d e s

and

c a r

b o x y l a t e s o f

l o w e r m o l e c u l a r

w e i g h t c a r b o x y l i c

a c i d s

a t a

t e m p e r a t u r e between a b o u t 1 5 0 and a b o u t 3 5 0

C .

and

a

p r e s s u r e

from a b o u t 1 0 t o 1 0 , 0 0 0

p . s . i . g .

2 .

T he

r e a c t i o n o f

c l a i m 1

f o r t h e p r e p a r a t i o n

o f

a

d i a l k y l c a r b o n a t e

w h e r e i n

a monohydroxy a l c o h o l

i s

u s e d

a s

s a i d a l c o h o l .

3 . The

r e a c t i o n

o f c l a i m 1 f o r t h e p r e p a r a t i o n o f a

p o l y a l k y l c a r b o n a t e ) w h e r e i n a n a l i p h a t i c p o l y o l

c o n t a i n

i n g

p r i m a r y

h y d r o x y l s

i s u s e d

a s

s a i d a l c o h o l .

4 .

The r e a c t i o n o f c l a i m 1 c o m p r i s i n g

t h e

u s e

o f a

m e r c u r i c

c a r b o x y l a t e

o f a l o w e r m o l e c u l a r w e i g h t

f a t t y

a c i d a s

s a i d mercuric s a l t .

5 . T he r e a c t i o n

o f c l a i m

4 c o m p r i s i n g

t h e

u s e

o f

mer

c u r i c a c e t a t e a s s a i d mercuric s a l t .

6 . The manufacture o f

a

d i a l k y l

c a r b o n a t e

which

c o m

p r i s e s

a b s o r b i n g

c a r b o n monoxide i n

a

s o l u t i o n

c o n t a i n i n g

8/9/2019 Preparation of Alkyl Carbonates

3/3

3 , 2 2 7 , 7 4 0

5

a m e r c u r i c c a r b o x y l a t e

o f

l o w e r m o l e c u l a r w e i g h t c a r

b o x y l i c

a c i d s and

a s a t u r a t e d p r i m a r y

a l c o h o l s e l e c t e d

f r o m t h e c l a s s c o n s i s t i n g

o f

a l i c y c l i c

a n d a l i p h a t i c

p r i m a r y

a l c o h o l s h a v i n g 1

t o

about 25 c a r b o n s a t a t e m p e r a t u r e

between a b o u t 0

and

a b o u t 1 0 0 C .

and

a

p r e s s u r e

be

tween

a b o u t

1 0

and

a b o u t

1 0 0 0 p . s . i . g .

u n t i l s a i d

s o l u t i o n

s u b s t a n t i a l l y c e a s e s

t o

a b s o r b s a i d carbon monoxide and

t h e r e a f t e r h e a t i n g s a i d

s o l u t i o n t o a t e m p e r a t u r e b e t w e e n

a b o u t 1 5 0 and

a b o u t

3 5 0 C . t o form s a i d d i a l k y l c a r

b o n a t e .

7 .

The m a n u f a c t u r e

o f d i a l k y l c a r b o n a t e s a c c o r d i n g

t o c l a i m

6

wherein

s a i d

a l c o h o l

i s a s a t u r a t e d primary

a l c o h o l

h a v i n g 1 t o a b o u t

5

carbon

a t o m s .

8 . The m a n u f a c t u r e o f

c l a i m 6

w h e r e i n s a i d a l c o h o l

h a s

from

1 t o a b o u t

6

c a r b o n s .

9 . The m a n u f a c t u r e o f c l a i m 6 c o m p r i s i n g a b s o r b i n g

s a i d c a r b o n m o n o x i d e u n d e r s u b s t a n t i a l l y a n h y d r o u s

c o n d i t i o n s .

1 0 .

The

m a n u f a c t u r e o f

a

p o l y a l k y l c a r b o n a t e )

which

c o m p r i s e s a b s o r b i n g c a r b o n monoxide i n a s o l u t i o n

con

t a i n i n g

a

mercuric

c a r b o x y l a t e

o f

a

lower molecular

W e i g h t f a t t y a c i d

a n d a n

a l i p h a t i c s a t u r a t e d p r i m a r y

p o l y o l h a v i n g a m o l e c u l a r w e i g h t

from

6 2

t o

a b o u t

1 0 , 0 0 0 a t

a

t e m p e r a t u r e

between

a b o u t 0 and

a b o u t

1 0

1 5

20

6

1 0 0 C .

and

a

p r e s s u r e

between a b o u t

1 0 and about

1000

p . s . i . g .

u n t i l s a i d

s o l u t i o n s u b s t a n t i a l l y c e a s e s

t o a b s o r b

s a i d

c a r b o n

monoxide a n d

t h e r e a f t e r h e a t i n g

s a i d s o l u

t i o n

t o

a

t e m p e r a t u r e

between

about 1 5 0

and about

3 5 0 C .

t o form s a i d

p o l y a l k y l c a r b o n a t e ) .

1 1 .

The

m a n u f a c t u r e

o f

c l a i m 1 0 c o m p r i s i n g

u s i n g

mercuric a c e t a t e a s s a i d

mercuric s a l t .

1 2 . The

m a n u f a c t u r e

o f

c l a i m 1 0

c o m p r i s i n g t h e u s e

o f a d i p r i m a r y g l y c o l

a s

t h e p o l y o l .

1 3 .

The m a n u f a c t u r e o f c l a i m 1 0 c o m p r i s i n g a b s o r b

i n g s a i d

c a r b o n

m o n o x i d e u n d e r

s u b s t a n t i a l l y a n h y d r o u s

c o n d i t i o n s .

R e f e r e n c e s C i t e d by t h e Examiner

UNITED STATES PATENTS

2 / 1 9 5 6

Reppe e t a l . ______ __ 260488

OTHER REFERENCES

Wagner

e t

a l . :

S y n t h e t i c

O r g a n i c C h e m i s t r y ,

1 9 5 3

E d i t i o n .

2 , 7 3 4 , 9 1 3

MURRAY

ILLMAN,

P r i m a r y E x a m i n e r .

LEON .

B ERCO VI TZ,

E x a m i n e r .