Synthesis of vinyl carbonates for use in producing vinyl carbamates

Abstract

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 comprises: (a) reacting a compound represented by the 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 the 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 the formula (IV): FC(O)X 1 R 1   (IV) ;and (b) reacting a compound represented by the formula (IV) with a compound represented by the 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, to form the compound represented by formula (I).

That which is claimed:  
     
         1 . 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, said method comprising: 
 (a) reacting a compound represented by the 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 the 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 the formula (IV):  
 FC(O)X 1 R 1   (IV)  
 ;and  
 (b) reacting a compound represented by the formula (IV) with a compound represented by the 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, to form the compound represented by formula (I).  
 
     
     
         2 . The method according to  claim 1 , wherein R 1  is selected from the group consisting of Ø—, p-NO 2 Ø—, p-ClØ—, and CH 2 ═CH—.  
     
     
         3 . The method according to  claim 1 , wherein the compound represented by formula (II) is ClCO 2 Ø—.  
     
     
         4 . The method according to  claim 1 , wherein the first and second phase transfer catalysts may be the same or different and are selected from the group consisting of a crown ether, an organoammonium salt, a phosphonium salt, and mixtures thereof.  
     
     
         5 . The method according to  claim 1 , wherein the first phase transfer catalyst is 15-crown-5 and the second phase transfer catalyst is 18-crown-6.  
     
     
         6 . The method according to  claim 1 , wherein the first and second organic solvents may be the same or different and may be selected from the group consisting of a polar aprotic solvent, a non-polar organic solvent, and mixtures thereof.  
     
     
         7 . The method according to  claim 6 , wherein the polar aprotic solvent is selected from the group consisting of dimethyl formamide, acetonitrile, dimethyl sulfoxide, and mixtures thereof.  
     
     
         8 . The method according to  claim 6 , wherein the non-polar organic solvent is selected from the group consisting of hexane, heptane, toluene, cyclohexane, diethyl ether, tetrahydrofuran (THF), methyl t-butyl ether (MTBE), glycol ethers, and mixtures thereof.  
     
     
         9 . The method according to  claim 1 , wherein X 2  is chlorine.  
     
     
         10 . The method according to  claim 1 , wherein M 1  is sodium.  
     
     
         11 . The method according to  claim 1 , wherein M 2  is potassium.  
     
     
         12 . The method according to  claim 1 , wherein R 2  is ((CH 2 ) q CH 3 ) wherein q ranges from 0 to 6.  
     
     
         13 . The method according to  claim 1 , further comprising the step of reacting the compound represented by formula (I) with a compound represented by the 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 the formula (VII):  
       R 3 R 4 NC(O)OCH═CH 2   (VII).  
     
     
         14 . The method according to  claim 13 , wherein said step of reacting the compound represented by the formula (I) with a compound represented by the formula (VI) is carried out in the presence of a non-polar organic solvent.  
     
     
         15 . The method according to  claim 14 , wherein the non-polar organic solvent is tetrahydrofuran.  
     
     
         16 . The method according to  claim 13 , wherein 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 10 and m ranges from 0 to 10.  
     
     
         17 . The method according to  claim 16 , wherein a compound of the formula (VII) is present in a mixture with a compound of the formula (XVIII):  
       ØOC(O)NHR 1   (XVIII)  
       wherein R 1  is an substituted or unsubstituted alkyl, aryl, aryl alkyl, cycloaliphatic or olefinic group, and wherein the aromatic substituent may be substituted or unsubstituted, said method further comprising the step of: 
 reacting the compound of formula (XVIII) with a compound of formula (XIX):  
 HNR 2 R 3   (XIX)  
 wherein R 2  and R 3  are individually selected from hydrogen, a substituted or unsubstituted alkyl, aryl, aryl alkyl, cycloaliphatic or olefinic group, or any combination thereof, wherein the amine of formula (XIX) selectively reacts with the compound of formula (XVIII) relative to the compound of formula (VII).  
 
     
     
         18 . The method according to  claim 17 , wherein the amine is an alkyl amine.  
     
     
         19 . The method according to  claim 1 , further comprising the step of reacting a compound represented by the formula (I) with a compound represented by the formula (VIII):  
       HO—R 5   (VII)  
       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)  
     
     
         20 . The method according to  claim 19 , wherein R 5  is represented by the formula:  
       CH 2 ═C((CH 2 ) p CH 3 )CO 2 (CH 2 ) s    wherein p ranges from 0 to 6 and s ranges from 1 to 6.    
     
     
         21 . A method for making a vinylphenyl 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 aryl, said method comprising: 
 (a) reacting a compound represented by the 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 the 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 the formula (IV):  
 FC(O)X 1 R 1   (IV)  
 ;and  
 (b) reacting a compound represented by the formula (IV) with a compound represented by the 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, to form the compound represented by formula (I).  
 
     
     
         22 . The method according to  claim 21 , wherein R 1  is selected from the group consisting of Ø—, p—NO 2 Ø—, p—ClØ—, and CH 2 ═CH—.  
     
     
         23 . The method according to  claim 21 , wherein the compound represented by formula (II) is ClCO 2 Ø—.  
     
     
         24 . The method according to  claim 21 , wherein the first and second phase transfer catalysts may be the same or different and are selected from the group consisting of a crown ether, an organoammonium salt, a phosphonium salt, and mixtures thereof.  
     
     
         25 . The method according to  claim 21 , wherein the first phase transfer catalyst is 15-crown-5 and the second phase transfer catalyst is 18-crown-6.  
     
     
         26 . The method according to  claim 21 , wherein the first and second organic solvents may be the same or different and may be selected from the group consisting of a polar aprotic solvent, a non-polar organic solvent, and mixtures thereof.  
     
     
         27 . The method according to  claim 26 , wherein the polar aprotic solvent is selected from the group consisting of dimethyl formamide, acetonitrile, dimethyl sulfoxide, and mixtures thereof.  
     
     
         28 . The method according to  claim 26 , wherein the non-polar organic solvent is selected from the group consisting of hexane, heptane, toluene, cyclohexane, diethyl ether, tetrahydrofuran (THF), methyl t-butyl ether (MTBE), glycol ethers, and mixtures thereof.  
     
     
         29 . The method according to  claim 21 , wherein X 2  is chlorine.  
     
     
         30 . The method according to  claim 21 , wherein M 1  is sodium.  
     
     
         31 . The method according to  claim 21 , wherein M 2  is potassium  
     
     
         32 . The method according to  claim 21 , wherein R 2  is ((CH 2 ) q CH 3 ) wherein q ranges from 0 to 6.  
     
     
         33 . The method according to  claim 21 , further comprising the step of reacting the compound represented by formula (I) with a compound represented by the 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 the formula (VII):    R 3 R 4 NC(O)OCH═CH 2   (VII).    
     
     
         34 . The method according to  claim 33 , wherein said step of reacting the compound represented by the formula (I) with a compound represented by the formula (VI) is carried out in the presence of a non-polar organic solvent.  
     
     
         35 . The method according to  claim 34 , wherein the non-polar organic solvent is tetrahydrofuran.  
     
     
         36 . The method according to  claim 33 , wherein 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 10 and m ranges from 0 to 10.    
     
     
         37 . The method according to  claim 36 , wherein a compound of the formula (VII) is present in a mixture with a compound of the formula (XVIII):  
       ØOC(O)NHR 1   (XVIII)  wherein R 1  is an substituted or unsubstituted alkyl, aryl, aryl alkyl, cycloaliphatic or olefinic group, and wherein the aromatic substituent may be substituted or unsubstituted, said method further comprising the step of:    reacting the compound of formula (XVIII) with a compound of formula (XIX):    HNR 2 R 3   (XIX)    wherein R 2  and R 3  are individually selected from hydrogen, a substituted or unsubstituted alkyl, aryl, aryl alkyl, cycloaliphatic or olefinic group, or a combination thereof, wherein the amine of formula (XIX) selectively reacts with the compound of formula (XVIII) relative to the compound of formula (VII).    
     
     
         38 . The method according to  claim 37 , wherein the amine is an alkyl amine.  
     
     
         39 . The method according to  claim 37 , wherein the amine is hexamethylenediamine.  
     
     
         40 . The method according to  claim 21 , further comprising 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)  
     
     
         41 . The method according to  claim 40 , wherein R 5  is represented by the formula:  
       CH 2 ═CH((CH 2 ) p CH 3 )CO 2 (CH 2 ) s    
       wherein p ranges from 0 to 6 and s ranges from 1 to 6.  
     
     
         42 . A method of forming a carbonate of the formula:  
       R 1 R 2 C═CR 3 C(O)OR 3 C═CR 1 R 2   (X)  
       wherein R 1 , R 2 , and R 3  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):  
 R 1 R 2 C═CR 3 OC(O)OR 4   (XI)  
 wherein R 1 , R 2 , and R 3  are defined above, and R 4  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).  
 
     
     
         43 . The method according to  claim 42 , wherein R 1 , R 2 , and R 3  are each hydrogen.  
     
     
         44 . The method according to  claim 42 , wherein the metal fluoride is potassium fluoride.  
     
     
         45 . The method according to  claim 42 , wherein the phase transfer catalyst is a crown ether.  
     
     
         46 . The method according to  claim 42 , wherein the crown ether is 18-crown-6.  
     
     
         47 . The method according to  claim 42 , further comprising the step of reacting the compound of formula (XI) with a compound of formula (XIV):  
       HO(CH 2 ) n Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) m OH  (XIV)  
       wherein n and m range from 1 to 10 and m ranges from 1 to 10 to form a compound of formula (XV):  
       CH 2 ═CHOC(O)O(CH 2 ) n Si(CH 3 ) 2 OSi(CH 3 ) 2 (CH 2 ) m OC(O)OCH═CH 2   (XV)  
     
     
         48 . The method according to  claim 47 , wherein n is 4, m is 4, and R 1 , R 2 , and R 3  are each hydrogen.  
     
     
         49 . 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, cycloaliphatic or any combination thereof, said method comprising: 
 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, 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).