Process for preparing unsaturated imidoalkoxysilanes
View Patent ↗A process is provided for preparing unsaturated imidoalkoxysilane which comprises imidating substantially water-free Diels-Alder protected unsaturated N-substituted cyclic imide with aminosilane to provide Diels-Alder protected unsaturated imidoalkoxysilane without the use of chemical desiccants. The Diels-Alder protected unsaturated imidoalkoxysilane produced is then deprotected to provide unsaturated imidoalkoxysilane and the Diels-Alder protecting diene is regenerated to the process. A Diels-Alder intermediate is also provided.
1. A process for preparing unsaturated cyclic imidoalkoxysilane, which comprises:
i) transimidating substantially water-free Diels-Alder protected unsaturated aromatic N-substituted cyclic imide with at least one aminoalkoxysilane to provide at least one Diels-Alder protected unsaturated cyclic imidoalkoxysilane.
2. The process of claim 1 further comprising:
ii) deprotecting the protected cyclic imidoalkoxysilane to provide an αβ-unsaturated cyclic imidoalkoxysilane.
3. The process of claim 1 wherein the Diels-Alder protected unsaturated aromatic N-substituted cyclic imide is obtained by a process which comprises imidating a cyclic unsaturated anhydride with at least one primary aromatic amine to provide at least one unsaturated aromatic N-substituted cyclic imide and protecting the double bond of the unsaturated N-substituted cyclic imide with at least one diene under Diels-Alder reaction conditions to provide at least one Diels-Alder protected unsaturated aromatic N-substituted cyclic imide.
4. The process of claim 1 wherein the Diels-Alder protected unsaturated aromatic N-substituted cyclic imide is obtained by a process which comprises protecting the double bond of unsaturated cyclic anhydride with at least one diene under Diels-Alder reaction conditions to provide at least one Diels-Alder protected unsaturated cyclic anhydride and imidating the Diels-Alder protected anhydride with at least one primary aromatic amine, to produce Diels-Alder protected unsaturated aromatic N-substituted cyclic imide.
5. The process of claim 2 wherein the Diels-Alder protected unsaturated aromatic N-substituted cyclic imide of transimidating step (i) is separated from water prior to conducting step (ii).
6. The process of claim 2 wherein the Diels-Alder protected unsaturated aromatic N-substituted cyclic imide of transimidating step (i) is separated from water by azeotropic distillation prior to conducting step (ii).
7. The process of claim 2 wherein the regenerated diene of step (ii) is recycled to process.
8. The process of claim 3 wherein the primary aromatic amine is a primary arylamine or a primary heteroarylamine.
9. The process of claim 8 wherein the primary aromatic amine is at least one member selected from the group consisting of aniline, ring substituted anilines, 2-amino pyridine, amino naphthalenes, and amino anthracenes.
10. The process of claim 3 wherein the diene is at least one member selected from the group consisting of furan, substituted furans, fulvene, substituted fulvenes, anthracene and substituted anthracenes.
11. The process of claim 3 wherein the regenerated diene of step (ii) is at least one member selected from the group consisting furan, substituted furans, fulvene, substituted fulvenes, anthracene and substituted anthracenes, and the primary aromatic amine is selected from the group selected from a primary arylamine, a primary heteroarylamine, aniline, ring substituted anilines, 2-amino pyridine, amino naphthalenes, and amino anthracenes.
12. The process of claim 11 wherein the regenerated diene of step (ii) comprises substitution groups selected from the group consisting of alkyl chains having about 2 to about 20 carbons, methyl, ethyl, iso-propyl, tert-butyl, OH, SH, halogens, aryl, carboxyl, carbonyl, nitro, carboxyamido, keto, sulfoxide, sulfone, sulfonic acid, phosphoric acid and amino groups.
13. The process of claim 1 wherein transimidation is conducted employing at least one step (i) aminoalkoxy silane having the general formula:
wherein R 1 is an alkoxy, alkylene or cycloalkylene group of from 1 to about 20 carbon atoms or an arylene group of from 6 to about 20 carbon atoms, R 2 and R 3 each is independently is an alkoxy, alkyl or cycloalkyl group of from 1 to about 20 carbon atoms or an aryl group of from 6 to about 20 carbon atoms, and n is an integer from about 1 to about 20.
14. The process of claim 13 wherein R 1 is an alkoxy group of from 1 to 4 carbon atoms, and n is 3.
15. The process of claim 1 wherein transimidating step (i) is conducted employing at least one aminoalkoxysilane selected from the group consisting of aminomethyl-triethoxy-silane, (3-amino-propyl)triethoxy-silane, (3-amino-propyl)-methyl-diethoxy-silane, (3-amino-propyl)-phenyl-dimethoxy-silane, (4-amino-butyl)triethoxy-silane, (3-amino-2-methyl-propyl)-triethoxy-silane, (4-amino-butyl)-methyl-diethoxy-silane, (3-aminopropoxypropyl)-triethoxy-silane, (3-amino-propoxypropyl)-trimethoxy-silane, (3-amino-propoxypropyl)-methyl-diethoxysilane, (3-amino-propoxypropyl)-ethyl-diethoxy-silane, (p-aminophenyl)-triethoxy-silane, (2-amino-ethylaminomethyl)-(methoxyethoxy)-bis-(1-methylpropylidene aminoxy)-silane and [(.omega.-amino-alkylamino)-alkyl]-trialkoxy-silanes, and, especially, [3-(2-amino-ethylamino)-propyl]-trimethoxysilane, [3-(3-amino-propylamino)-propyl]-triethoxy-silane, [(2-amino-ethylamino)-methyl]-triethoxy-silane and [(6-aminohexylamino)-methyl]-trimethoxy-silane.
16. The process of claim 1 , wherein transimidating step (i) is carried out in the presence of solvent.
17. The process of claim 16 wherein the solvent forms an azeotrope with water.
18. The process of claim 17 wherein the solvent is at least one member selected from the group consisting of toluene, xylenes, orthodichlorobenzene, and mixture thereof.
19. The process of claim 13 wherein transimidating step (i) is carried out in the presence of catalyst.
20. The process of claim 19 wherein the catalyst is a Lewis acid.
21. The process of claim 13 wherein imidating step (a) is carried out at a pressure of from about 0.1 atm to about 20 atm and a temperature of from about 25° C. to about 200° C.
22. The process of claim 2 wherein the deprotecting step (ii) is carried out in the presence of solvent.
23. The process of claim 22 wherein solvent is a Lewis Acid.
24. The process of claim 22 wherein deprotecting step (ii) is carried out in the presence of catalyst.
25. The process of claim 24 wherein the catalyst is a Lewis acid.
26. The process of claim 22 wherein deprotecting step (ii) is carried out at a pressure of from about 0.1 atm to about 20 atm and a temperature of from about 25° C. to about 200° C.
27. The process of claim 4 wherein the protecting step is carried out in an organic solvent at a temperature above about 60° Celsius and below the boiling point of the organic solvent.