Method for making carbonates and esters
View Patent ↗A method for forming a monomeric carbonate includes the step of combining a monofunctional alcohol or a difunctional diol with an ester-substituted diaryl carbonate to form a reaction mixture. Similarly, a method for forming a monomeric ester includes the step of combining a monofunctional carboxylic acid or ester with an ester-substituted diaryl carbonate to form a reaction mixture. These methods further include the step of allowing the reaction mixtures to react to form a monomeric carbonate or a monomeric ester, respectively.
1. A method for forming a monomeric carbonate comprising combining a monofunctional alcohol or a difunctional diol with an ester-substituted diaryl carbonate to form a reaction mixture, and allowing the reaction mixture to react to form a monomeric carbonate.
2. The method of claim 1 , wherein the monomeric carbonate has the formula:
R 1 O—C(O)—OR 2
wherein R 1 and R 2 are each independently selected from the group consisting of optionally-substituted linear or branched alkyl, alkene, cycloalkyl, cycloalkenyl, aryl, heteroatom-containing aryl, and aralkyl groups, said method comprising combining monofunctional alcohols HOR 1 and HOR 2 with an ester-substituted diaryl carbonate to form the reaction mixture.
3. The method of claim 1 , wherein the monomeric carbonate has the formula:
wherein R 1 is selected from the group consisting of optionally-substituted linear or branched alkyl, alkene, cycloalkyl, cycloalkenyl, aryl, heteroatom-containing aryl, and aralkyl groups, said method comprising combining HOR 1 with bismethylsalicylcarbonate to form the reaction mixture.
4. The method of claim 1 , wherein the monomeric carbonate has the formula:
wherein:
R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of hydrogen, optionally-substituted linear or branched alkyl, alkene, cycloalkyl, cycloalkenyl, aryl, heteroatom-containing aryl, and aralkyl groups, or R 3 or R 4 in combination with R 5 or R 6 forms a ring structure,
X is 0 or 1 and wherein when X is 0, combinations of R 3 or R 4 and R 5 or R 6 may be absent to form a double bond, and when X is 1, R 7 and R 8 are each independently selected from the group consisting of hydrogen, optionally-substituted linear or branched alkyl, alkene, cycloalkyl, cycloalkenyl, aryl, heteroatom-containing aryl, and aralkyl groups, or combinations of R 7 or R 8 with R 3 , R 4 , R 5 , or R 6 may also be absent to form a double bond,
the method comprising combining an ester-substituted diaryl carbonate with a diol compound of structure HOR 3 R 4 C—(CR 7 R 8 ) X —CR 5 R 6 OH to form the reaction mixture.
5. The method of claim 1 , wherein the ester-substituted diaryl carbonate is bismethyl salicyl carbonate.
6. The method of claim 1 , wherein the reaction is performed at a temperature of less than 180° C.
7. The method of claim 6 , wherein the reaction is performed at a temperature of less than 140° C.
8. The method of claim 1 , wherein the reaction is performed for a period of 24 hours or less.
9. The method of claim 8 , wherein the reaction is performed for a period of one hour or less.
10. The method of claim 1 , wherein the reaction is performed in the presence of a catalyst, wherein the catalyst is present in an amount of 1×10 −6 to 10 mole catalyst per mole of ester-substituted carbonate.
11. The method of claim 1 , wherein the reaction is performed in the absence of catalyst.
12. A composition comprising a monomeric carbonate and a detectable amount of residual ester-substituted diaryl carbonate or the corresponding ester-substituted phenolic byproduct, wherein the monomeric carbonate is a linear carbonate and has the formula:
R 1 O—C(O)—OR 2
wherein R 1 and R 2 are each independently selected from the group consisting of optionally-substituted linear or branched alkyl, alkene, cycloalkyl, cycloalkenyl, aryl, heteroatom-containing aryl, and aralkyl groups, or wherein the monomeric compound is a cyclic carbonate and has the formula:
wherein:
R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of hydrogen, optionally-substituted linear or branched alkyl, alkene, cycloalkyl, cycloalkenyl, aryl, heteroatom-containing aryl, and aralkyl groups, or R 3 or R 4 in combination with R 5 or R 6 forms a ring structure,
X is 0 or 1 and wherein when X is 0, combinations of R 3 or R 4 and R 5 or R 6 may be absent to form a double bond, and when X is 1, R 7 and R 8 are each independently selected from the group consisting of hydrogen, optionally-substituted linear or branched alkyl, alkene, cycloalkyl, cycloalkenyl, aryl, heteroatom-containing aryl, and aralkyl groups, or combinations of R 7 or R 8 with R 3 , R 4 , R 5 , or R 6 may also be absent to form a double bond.
13. The composition of claim 12 , wherein the ester-substituted diaryl carbonate is bismethyl salicyl carbonate and the corresponding ester-substituted phenolic byproduct is methyl salicylate.
14. A method of forming a monomeric activated ester compound of the formula:
wherein R is an alkyl group, phenyl group, or a benzyl group, and R 9 is selected from the group consisting of optionally-substituted linear or branched alkyl, alkene, cycloalkyl, cycloalkenyl, aryl, heteroatom-containing aryl, and aralkyl groups, said method comprising reacting an ester-substituted diaryl carbonate with a compound of the formula:
wherein R 9 is described above and R 10 is selected from the group consisting of hydrogen, and optionally-substituted linear or branched alkyl, alkene, cycloalkyl, cycloalkenyl, aryl, heteroatom-containing aryl, and aralkyl groups, thereby forming the compound.
15. The method of claim 14 , wherein R is a methyl group and the ester-substituted diaryl carbonate is bismethyl salicyl carbonate.
16. The method of claim 14 , wherein the reaction is performed at a temperature of less than 180° C.
17. The method of claim 16 , wherein the reaction is performed at a temperature of less than 140° C.
18. The method of claim 14 , wherein the reaction is performed for a period of 24 hours or less.
19. The method of claim 14 , wherein the reaction is performed for a period of one hour or less.
20. The method of claim 14 , wherein the reaction is performed in the presence of a catalyst, wherein the catalyst is present in an amount of 1×10 −6 to 10 mole catalyst per mole of ester-substituted carbonate.
21. The method of claim 14 , wherein the reaction is performed in the absence of catalyst.
22. The method of claim 14 , wherein R 10 is hydrogen.
23. A method of forming a monomeric ester compound of the formula:
wherein R 9 and R 11 are the same or different and each are independently selected from the group consisting of optionally-substituted linear or branched alkyl, alkene, cycloalkyl, cycloalkenyl, aryl, heteroatom-containing aryl, and aralkyl groups, said method comprising reacting the activated ester compound prepared in claim 14 with an alcohol of structure:
R 11 —OH
thereby forming the monomeric ester compound.
24. A composition comprising a monomeric ester compound and a detectable amount of residual ester-substituted diaryl carbonate or the corresponding ester-substituted phenolic byproduct, wherein the monomeric ester compound has the formula:
wherein R 9 and R 11 are the same or different and each are independently selected from the group consisting of optionally-substituted linear or branched alkyl, alkene, cycloalkyl, cycloalkenyl, aryl, heteroatom-containing aryl, and aralkyl groups.
25. The composition of claim 24 , wherein the ester-substituted diaryl carbonate is bismethyl salicyl carbonate and the corresponding ester-substituted phenolic byproduct is methyl salicylate.
26. A method of forming a cyclic monomeric ester compound comprising reacting an ester-substituted diaryl carbonate with a compound comprising an alcohol group and either an ester group or a carboxylic acid group, thereby forming the cyclic monomeric ester compound.