Production of sulfonyl azide anhydride

1. A process comprising:

(i) thio-acetoxylating an alkenyl carboxylic acid anhydride to form a thioacetate anhydride intermediate;

(ii) oxychlorinating the thioacetate anhydride intermediate to form a sulfonyl chloride anhydride intermediate; and

(iii) azidizing the sulfonyl chloride anhydride intermediate to form an aliphatic sulfonyl azide anhydride having a Structure (4):

wherein R 1 , R 2 , and R 3 may be the same or different; and

R 1 , R 2 , and R 3 each is independently selected from a substituted C 1 -C 40 hydrocarbonyl group, an unsubstituted C 1 -C 40 hydrocarbonyl group, Si(R C ) 3 , OR C , R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, a halogen atom, and a hydrogen atom, wherein R C is a C 1 -C 30 hydrocarbonyl group;

with the proviso that at least one of R 1 , R 2 , and R 3 is selected from a substituted C 1 -C 40 hydrocarbonyl group or an unsubstituted C 1 -C 40 hydrocarbonyl group, and the aliphatic sulfonyl azide anhydride excludes an aromatic sulfonyl azide anhydride.

2. The process of claim 1 wherein the thio-acetoxylating comprises reacting the alkenyl carboxylic acid anhydride with a thioacetic acid in the presence of a radical initiator to form the thioacetate anhydride intermediate.

3. The process of claim 1 wherein the thio-acetoxylating comprises reacting the alkenyl carboxylic acid anhydride with a thioacetic acid in the presence of an azo-containing radical initiator at a temperature from 50° C. to 90° C. to form the thioacetate anhydride intermediate.

4. The process of claim 1 wherein the oxychlorinating comprises reacting the thioacetate anhydride intermediate with a chlorine source to form the sulfonyl chloride anhydride intermediate.

5. The process of claim 1 wherein the oxychlorinating comprises reacting the thioacetate anhydride intermediate with N-chlorosuccinimide in the presence of a hydrochloric acid aqueous solution at a temperature from 0.1° C. to 22° C. to form the sulfonyl chloride anhydride intermediate.

6. The process of claim 1 wherein the oxychlorinating comprises reacting the thioacetate anhydride intermediate with chlorine gas in the presence of water at a temperature from 0.1° C. to 22° C. to form the sulfonyl chloride anhydride intermediate.

7. The process of claim 1 wherein the azidizing comprises reacting the sulfonyl chloride anhydride intermediate with sodium azide in the presence of acetone to form the aliphatic sulfonyl azide anhydride.

8. The process of claim 1 wherein the azidizing comprises reacting the sulfonyl chloride anhydride intermediate with sodium azide in the presence of acetone at a temperature from 20° C. to 25° C. to form the aliphatic sulfonyl azide anhydride.

9. The process of claim 1 comprising:

(i) thio-acetoxylating endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride to form 5-(thioacetoxy)endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride;

(ii) oxychlorinating the 5-(thioacetoxy)endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride to form 5-(chlorosulfonyl)endo-cis-bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride; and

(iii) azidizing the 5-(chlorosulfonyl)endo-cis-bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride to form 5-(azidosulfonyl)endo-cis-bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride.

10. The process of claim 1 comprising:

(i) thio-acetoxylating 2-methyl-2-propen-1-yl succinic anhydride to form S-(3-(2,5-dioxotetrahydrofuran-3-yl)-2-methylpropyl) ethanethioate;

(ii) oxychlorinating the S-(3-(2,5-dioxotetrahydrofuran-3-yl)-2-methylpropyl) ethanethioate to form 3-(2,5-dioxotetrahydrofuran-3-yl)-2-methylpropane-1-sulfonyl chloride; and

(iii) azidizing the 3-(2,5-dioxotetrahydrofuran-3-yl)-2-methylpropane-1-sulfonyl chloride to form 3-(2,5-dioxotetrahydrofuran-3-yl)-2-methylpropane-1-sulfonyl azide.

11. A composition comprising an aliphatic sulfonyl azide anhydride having a Structure (4):

wherein R 1 , R 2 , and R 3 may be the same or different; and

R 1 , R 2 , and R 3 each is independently selected from a substituted C 1 -C 40 hydrocarbonyl group, an unsubstituted C 1 -C 40 hydrocarbonyl group, Si(R C ) 3 , OR C , R C C(O)O—, R C OC(O)—, R C C(O)N(R)—, (R C ) 2 NC(O)—, a halogen atom, and a hydrogen atom, wherein R C is a C 1 -C 3 hydrocarbonyl group;

with the proviso that at least one of R 1 , R 2 , and R 3 is selected from a substituted C 1 -C 40 hydrocarbonyl group or an unsubstituted C 1 -C 40 hydrocarbonyl group, and the aliphatic sulfonyl azide anhydride excludes an aromatic sulfonyl azide anhydride.

12. The composition of claim 11 , wherein

R 2 is hydrogen; and

the R 1 and R 3 groups form an unsubstituted C 3 -C 8 hydrocarbonyl group ring structure.

13. The composition of claim 11 , wherein aliphatic sulfonyl azide anhydride is 5-(azidosulfonyl)endo-cis-bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride having a Structure (4a):

14. The composition of claim 11 , wherein R 1 and R 2 each is hydrogen; and R 3 is an unsubstituted C 1 -C 12 hydrocarbonyl group.

15. The composition of claim 14 , wherein the aliphatic sulfonyl azide anhydride is 3-(2,5-dioxotetrahydrofuran-3-yl)-2-methylpropane-1-sulfonyl azide having a Structure (4b):