Vinylchloroformate-free synthesis of vinyl and allyl(thio) carbamates
View Patent ↗The invention generally relates to methods of forming vinyl(thio)carbamates and more particularly to a vinylchloroformate-free method of synthesizing (N-vinyloxycarbonyl)-3-aminopropyltris(trimethylsiloxysilane).
1. A method for making a compound represented by the following formula (I):
(CH 2 ═CH(CH 2 ) b YC(O)N) x R 1 (I)
wherein x is 0 or 1, b is 0 or 1, Y is O or S and R 1 is a mono- or di-functional organic siloxy containing radical, the method comprising:
reacting a compound represented by formula (II):
CH 2 ═CH(CH 2 ) b OSi(CH 3 ) 3 (II)
wherein b is 0 or 1,
with a compound represented by formula (III):
(Y═C═N—(CH 2 ) m ) x —R1 (III):
wherein x is 0 or 1, Y is O or S, m is 0 to 20 and R 1 is a mono- or di-functional organic siloxy containing radical to provide the compound of formula (I).
2. The method of claim 1 wherein the compound of formula (I) is selected from the group consisting of vinylcarbamates, vinylthiocarbamates, allylcarbamates and allylthiocarbamates.
3. The method of claim 1 wherein the reaction takes place in the presence of a catalyst.
4. The method of claim 3 wherein the catalyst is selected from the group consisting of copper, copper (I) iodide, cadmium, silver (II) acetate, rubidium acetate, tetrakis(triphenylphosphine)palladium (0), 1,10-phenanthroline platinum diacetate, bis(benzonitrile)palladium (II)chloride, tetrakis(triphenylphosphine)palladium(0), tetrakis(triphenylphosphine)platinum (0), platinum oxide, palladium (II) trifluoroacetate, platinum (0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene, 2-imidazolidone, palladium (II) acetate and platinum acetylacetonate.
5. The method of claim 1 wherein the reaction takes place in the presence of a solvent.
6. The method of claim 5 wherein the solvent is an organic solvent.
7. The method of claim 6 wherein the organic solvent is a polar aprotic solvent.
8. The method of claim 7 wherein the polar aprotic solvent is selected from the group consisting of dimethyl formamide, acetonitrile, dimethyl sulfoxide, dimethylacetamide and mixtures thereof.
9. The method of claim 6 wherein the solvent is a non polar solvent.
10. The method of claim 9 wherein the non polar solvent comprises at least one member selected from the group consisting of hexane(s), heptane, toluene, cyclohexane, diethyl ether, tetrahydrofuran, methyl-t-butyl ether, glyme, and mixtures thereof.
11. The method of claim 1 wherein R 1 is a mono-functional organic siloxy-containing radical having the formula:
12. The method of claim 1 wherein R 1 is a di-functional organic siloxy-containing radical having the formula:
wherein R 2 is alkyl, alkyl ether or halo alkyl and n is 1-150.
13. A method of synthesizing vinyl carbamates comprising:
providing a mixture of isocyanopropyl tris(trimethylsiloxy), trimethyl(vinyloxy)silane, water and catalyst;
dissolving the mixture in an organic solvent to yield a reaction mixture; and
subjecting the reaction mixture to reaction conditions suitable to yield a vinylcarbamate product.
14. The method of claim 13 further comprising the step of filtering the reaction mixture containing the vinylcarbamate product to remove the catalyst and provide a solution of the vinylcarbamate product in solvent.
15. The method of claim 14 further comprising the steps of
washing the solution of vinylcarbamate product with a dilute acid solution;
separating the solution of vinylcarbamate product from the dilute acid solution; and
drying the solution of vinylcarbamate product to yield a substantially pure vinylcarbamate product.
16. A method of making an allylcarbamate, the method comprising:
reacting N-hexylisocyanate with a compound selected from the group consisting of trimethyl(vinyloxy)silane, allyloxytrimethylsilane, 2-(trimethylsiloxy)ethyl methacrylate, 2-(trimethylsiloxy)-1,3-cyclohexadiene and trimethyl-N-propoxysilane to yield an allylcarbamate compound.
17. A method of making an allyl thio carbamate, the method comprising:
reacting N-hexylisothiocyanate with a compound selected from the group consisting of trimethyl(vinyloxy)silane, allyloxytrimethylsilane, 2-(trimethylsiloxy)ethyl methacrylate, 2-(trimethylsiloxy)-1,3-cyclohexadiene and trimethyl-N-propoxysilane to yield an allylthiocarbamate compound.
18. The method of claim 1 wherein the compound represented by formula (I) is a trisiloxysilane vinylcarbamate wherein Y is O and R 1 is selected from the group consisting of organic siloxy-containing radicals comprising substituted or unsubstituted trisiloxysilane functional groups.
19. The method of claim 1 wherein the compound represented by formula (I) is a siloxysilane vinylcarbamate wherein Y is O and R 1 is selected from the group consisting of substituted trisiloxysilane groups, unsubstituted trisiloxysilane groups and vinylcarbamate capped polysiloxane groups.
20. The method of claim 1 wherein the compound represented by formula (I) is a vinyltrisiloxysilane thio carbamate wherein Y is S and R 1 is selected from the group consisting of organic siloxy-containing radicals comprising substituted or unsubstituted trisiloxysilane functional groups.
21. The method of claim 1 wherein the compound represented by formula (I) is a vinyltrisiloxysilane thiocarbamate in wherein Y is S and R 1 is selected from the group consisting of substituted trisiloxysilane groups, unsubstituted trisiloxysilane groups and vinylcarbamate capped polysiloxane groups.
22. The method of claim 1 wherein the compound made is (N-vinyloxycarbonyl)-3-aminopropyltris(trimethylsiloxysilane).
23. The method of claim 1 wherein the compound made is a vinylcarbonate capped polydimethylsiloxane.
24. A method of synthesizing vinyl carbamates comprising:
providing a mixture of isocyanopropyl tris(trimethylsiloxy), trimethyl(vinyloxy)silane, water and palladium (II) acetate catalyst;
combining the mixture with dimethylacetamide to yield a reaction mixture; and
subjecting the reaction mixture to reaction conditions suitable to yield a vinylcarbamate product.