Synthesis of vinyl carbonates for use in producing vinyl carbamates

A method for making a vinylphenyl carbonate represented by the formula (I):

• CH2═CHOC(O)X1R1 (I)
• wherein X1 is oxygen or sulfur and R1 is a substituted or an unsubstituted aryl, said method comprising:
• (a) reacting a compound represented by the formula (II):
• X2C(O)X1R1 (II)
• wherein X2 is a halogen other than fluorine, with a compound represented by the formula (III):
• M1—F (III)
• wherein M1 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 the formula (IV):
• FC(O)X1R1 (IV)
• ;
• and
• (b) reacting a compound represented by the formula (IV) with a compound represented by the formula (V):
• CH2═CHOSi(R2)3 (V)
• wherein R2 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 M2—F wherein M2 is a Group IA metal, a second phase transfer catalyst, and a second organic solvent, to form the compound represented by formula (I).

A method of forming a carbonate of the formula:

• R1R2C═CR3OC(O)OR3C═CR1R2 (X)
• wherein R1, R2, and R3 are independently selected from hydrogen, substituted or unsubstituted alkyl, aryl, aryl alkyl, vinyl, olefinic, cycloaliphatic or any combination thereof, said method comprising:
• reacting a carbonate of the formula (XI):
• R1R2C═CR3OC(O)OR4 (XI)
• wherein R1, R2, and R3 are defined above, and R4 is selected from substituted or unsubstituted alkyl, aryl, aryl alkyl, vinyl, olefinic, cycloaliphatic or any combination thereof, 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 (X).

A method of forming a carbonate of the formula:

• R′—O—C(O)13 O—R′ (XVI)
• wherein R′ is substituted or unsubstituted alkyl, aryl, aryl alkyl, vinyl, olefinic, cycloaliphatic or any combination thereof, said method comprising:
• reacting a carbonate of the formula (XVII):
• R′—O—C(O)13 O—R″ (XVII)
• wherein R′ and R″ are different and are selected from substituted or unsubstituted alkyl, aryl, aryl alkyl, vinyl, olefinic,or cycloaliphatic 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).