Synthesis of vinyl carbonates for use in producing vinyl...

Details Synthesis of vinyl carbonates for use in producing vinyl... Synthesis of vinyl carbonates for use in producing vinyl...

2000-06-28

2001-09-04

Oswecki, Jane C. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carbonate esters

C558S277000

Reexamination Certificate

active

06284911

ABSTRACT:

FIELD AND BACKGROUND OF THE INVENTION
The invention generally relates to methods of forming vinyl carbonates, particularly those used in forming vinyl carbamates.
Vinyl chloroformate is a monomer used in various applications such as, for example, the making of contact lenses. Currently, it is believed that this compound is only available via a multi-step synthesis involving the use of phosgene and organomercury intermediates. These intermediates are undesirable in that they present heightened environmental concerns. Therefore, it would be desirable to provide a synthetic method which does not necessitate the use of phosgene and organomercury intermediates.
SUMMARY OF THE INVENTION
The present invention addresses the above shortcomings and provides methods for making vinyl carbonates and carbamates which do not necessitate the use of phosgene and organomercury intermediates.
In one aspect, the invention provides a method for making a vinyl carbonate represented by the formula (I):
CH
2
═CHOC(O)X
1
R
1
  (I)
wherein X
1
is oxygen or sulfur and R
1
is a substituted or an unsubstituted aliphatic alkyl, aryl, aryl alkyl, olefinic, vinyl, or cycloaliphatic group.
Preferably, the compound represented by formula (I) is a vinylphenyl carbonate in which instance R
1
is a substituted or an unsubstituted aryl group. The method comprises:
(a) reacting a compound represented by formula (II):
X
2
C(O)X
1
R
1
  (II)
wherein X
2
is a halogen other than fluorine, with a compound represented by formula (III):
M
1
—F  (III)
wherein M
1
is selected from a Group IA metal, in the presence of a first phase transfer catalyst and a first organic solvent, to form a compound represented by formula (IV):
FC(O)X
1
R
1
  (IV)
 and;
(b) reacting a compound represented by formula (IV) with a compound represented by formula (V):
CH
2
═CHOSi(R
2
)
3
  (V)
wherein R
2
is a substituted or an unsubstituted aliphatic alkyl, aryl, aryl alkyl olefinic, vinyl, or cycloaliphatic group, or any combination thereof, in the presence of a metal salt represented by the formula M
2
—F wherein M
2
is a Group IA metal, a second phase transfer catalyst, and a second organic solvent or solvent combination, to form the compound represented by formula (I).
In a preferred embodiment, the above method further comprises the step of reacting the compound represented by formula (I) with a compound represented by formula (VI):
NHR
3
R
4
  (VI)
wherein R
3
and R
4
may be the same or different and are selected from a substituted or unsubstituted aliphatic alkyl, aryl, aryl alkyl, olefinic, cycloaliphatic, hydrogen or combinations thereof, to form a compound represented by formula (VII):
R
3
R
4
NC(O)OCH═CH
2
  (VIl).
In another preferred embodiment, the above method further comprises the step of reacting a compound represented by the formula (I) with a compound represented by the formula (VIII):
HO—R
5
  (VIII)
wherein R
5
is selected from an unsubstituted or substituted aliphatic alkyl, aryl, aryl alkyl, olefinic, or cycloaliphatic group, to form a compound represented by the formula (IX):
R
5
—O—C(O)OCH═CH
2
  (IX)
In another embodiment, the invention provides a method of forming a carbonate of the formula:
R′—O—C(O)—O—R′  (XVI)
wherein R′ is substituted or unsubstituted alkyl, aryl, aryl alkyl, vinyl, olefinic, or cycloaliphatic group. The method comprises:
reacting a carbonate of the formula (XVII):
R′—O—C(O)—O—R″  (XVII)
wherein R′ and R″ are different and are selected from substituted or unsubstituted alkyl, aryl, aryl alkyl, vinyl, olefinic, cycloaliphatic or any non-equivalent combination thereof (i.e., R′ does not equal R″), in the presence of: (1) a metal fluoride and a phase transfer catalyst or (2) a quaternary ammonium fluoride species to form the compound of formula (XVI) and a compound of the formula R″—O—C(O)OR″.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The invention will now be described with respect to embodiments described herein. It should be appreciated however that these embodiments are for the purposes of illustrating the invention, and are not to be construed as limiting the scope of the invention as defined by the claims.
The foregoing described substituents that can be used in the methods of the invention.
Preferred embodiments of R
1
include, without limitation, Ø-, p-NO
2
Ø-, p-ClØ-, and CH
2
═CH—. Functional groups and isomers thereof of these embodiments can also be employed.
X
1
may be oxygen or sulfur.
X
2
is a halogen, preferably one of the halogens chlorine, bromine, or iodine (i.e., other than fluorine).
M
1
and M
2
are independently selected from one of the Group IA metals, such as, for example, lithium, sodium, potassium, and the like.
R
2
may be selected from unsubstituted or substituted aliphatic alkyl, aryl, aryl alkyl, olefinic, vinyl, cycloaliphatic, or any combination thereof.
R
5
may be selected from unsubstituted or substituted aliphatic alkyl, aryl, aryl alkyl, olefinic, or cycloaliphatic.
R
2
is preferably (CH
2
)
q
CH
3
wherein q ranges from 0 to 6, and is most preferably CH
3
or an aryl group which is most preferably phenyl.
R
5
is preferably CH
2
═C((CH
2
)
p
CH
3
)CO
2
(CH
2
)
s
wherein p ranges from 0 to 6 and is most preferably 0 and s ranges from 1 to 6, and is most preferably 2.
R
3
and R
4
may be independently selected from unsubstituted or substituted aliphatic alkyl, aryl, aryl alkyl, olefinic, cycloaliphatic, or hydrogen, or any combination thereof. In one preferred embodiment, R
3
is hydrogen and R
4
is a group represented by the formula:
 (CH
2
)
n
Si(OSi((CH
2
)
m
CH
3
)
3
)
3
wherein n ranges from 0 to 6 (preferably is 3) and m ranges from 0 to 6 (preferably is 0).
The first and second phase transfer catalysts may be independently selected from those that are known to one skilled in the art, particularly those employed in disproportionation reactions. For the purposes of the invention, the term “phase transfer catalyst” is construed to mean any chemical that can assist in the transfer of a reactive species from one phase (e.g., a solid or liquid phase) to another phase in order to facilitate a chemical reaction in this phase.
Exemplary phase transfer catalysts include, without limitation, crown ethers (e.g., 15-crown-5 or 1,4,7,10,13-pentaoxacyclopentadecane, 18-crown-6 or 1,4,7,10,13,16-hexaoxacyclooctadecane, organoammonium salts, and phosphonium salts.
Various organic solvents, such as those employed for the first and second organic solvents (which can be independently selected) can include those which are known to those skilled in the art. Exemplary organic solvents include, for example, polar, aprotic solvents such as, without limitation, dimethyl formamide (“DMF”), acetonitrile, dimethyl sulfoxide (“DMSO”), and the like. Non-polar organic solvents can also be used such as, without limitation, hexane(s), heptane, toluene, cyclohexane, and the like, along with ether-like solvents such as, but not limited to, diethyl ether, tetrahydrofuran (“THF”), methyl-t-butyl ether (MTBE), the glymes, and the like. Combinations of any of these solvents may be used.
Bases which can be used in the synthesis scheme may include those which are known to one skilled in the art. For example, organic bases may be employed such as, without limitation, 1,8-diazabicyclo[5.4.0.]undec-7-ene (DBU), triethylamine, N-methylimidazole and the like. Combinations of the above can also be used.
An example of a synthetic scheme for producing vinyl carbonates and vinyl carbamates in accordance with the invention is as follows:
Various techniques may be employed for purifying the carbonate and/or carbamate products formed by methods of the invention. Examples of purification techniques include, but are not limited to, wiped film evaporation (WFE), column chromatography (including flash and other pressure types as well as simulated moving bed techniques)

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