Gem cyclodialkylation of amines and amides

Abstract

Amines and amides are N,N-cyclodialkylated by reaction with an unstrained cyclic ether in the presence of a B-subgroup metal oxide alkylation catalyst, preferably a Group IV-B metal oxide such as titanium dioxide.

I claim: 
     
       1. The process of converting an N,N-dialkylatable amino or amido group into an N,N-cyclodialkylated amino or amido group which comprises reacting a compound containing at least one N,N-dialkylatable amino or amido group with an unstrained cyclic ether co-reactive therewith in the presence of a viable B-subgroup metal oxide alkylation catalyst other than a Group I-B metal oxide so that at least one such N,N-dialkylatable amino or amido group is transformed into an N,N-cyclodialkylated amino or amido group, respectively.[...]..Iadd., such that when said group being transformed in an amino group, said cyclic ether has a furan ring system, a dihydrofuran ring system, a pyran ring system or a dihydropyran ring system. .Iaddend. .[.2. A process of claim 1 wherein the ether has a single oxygen atom and 
     
     
        at least four carbon atoms in the ring..]. 3. A process of claim 1 wherein said compound has at least one N,N-dialkylatable primary amino group in 
     
     
        the molecule. 4. A process of claim 1 wherein the reaction is conducted in the vapor phase by contacting a vapor phase mixture of the reactants with 
     
     
        a bed of the catalyst. 5. A process of claim 1 wherein the reaction is 
     
     
        conducted in the liquid phase in the presence of the catalyst. 6. A process of claim 1 wherein the reaction is conducted at a temperature of at least about 200° C. but below that at which the catalyst becomes 
     
     
        inactive. 7. A process of claim 1 wherein the catalyst is composed predominantly or entirely of one or more oxides of one or more Group IV-B 
     
     
        metals. 8. A process of claim 7 wherein the catalyst is composed 
     
     
        predominantly or entirely of titanium dioxide. 9. The process of converting an N,N-dialkylatable amino group into an N,N-cyclodialkylated amino group which comprises reacting a compound containing at least one N,N-dialkylatable amino group with an unstrained cyclic ether co-reactive therewith in the presence of a viable B-subgroup metal oxide alkylation catalyst other than a Group I-B metal oxide at a temperature of at least about 200° C. but below that at which the catalyst becomes inactive, so that at least one such N,N-dialkylatable amino group is transformed into an N,N-cyclodialkylated amino group.[...]..Iadd., said cyclic ether having a furan ring system, a dihydrofuran ring system, a pyran ring system or a dihydropyran ring system. .Iaddend. .[.10. A process of claim 9 wherein the ether has but a single ring composed of a furan ring system, a dihydrofuran ring system, a tetrahydrofuran ring 
     
     
        system or a dihydropyran ring system..]. 11. A process of claim 9 wherein said compound has at least one N,N-dialkylatable primary amino group in 
     
     
        the molecule. 12. A process of claim 11 wherein said compound is a primary 
     
     
        aromatic amine. 13. A process of claim 12 wherein the amine is a mononuclear primary aromatic amine having one or two amino groups on one 
     
     
        or two aromatic rings. 14. A process of claim 11 wherein said compound is 
     
     
        a primary aliphatic amine. 15. A process of claim 14 wherein said amine is 
     
     
        a monoalkyl amine. 16. A process of claim 9 wherein the catalyst is composed predominantly or entirely of a dioxide of one or more Group IV-B 
     
     
        metals. 17. A process of claim 16 wherein the ether is furan, a dihydrofuran, .[.tetrahydrofuran, a mono- or polyalkyl substituted tetrahydrofuran,.]. furfuryl alcohol, a dihydrofurfuryl alcohol, .[.tetrahydrofurfuryl alcohol, an alkoxytetrahydrofuran, a hydroxytetrahydrofuran,.]. furaldehyde, furfurylamine,.Iadd.or 
     
     
        .Iaddend.dihydropyran.[., or tetrahydropyran..]..Iadd.. .Iaddend. 18. A process of claim 17 wherein said compound is a primary aromatic amine or a 
     
     
        primary aliphatic amine. 19. A process for the production of imidazolidones which comprises heating a compound containing at least one N,N-dialkylatable primary amino group with an oxazolidone in the presence of a viable catalyst consisting essentially of a dioxide of at least one Group IV-B metal so that N,N-cyclodialkylation of the amino group takes 
     
     
        place. 20. A process of claim 19 wherein said compound is a primary aromatic or aliphatic amine, said oxazolidone is 2-oxazolidone and said 
     
     
        catalyst consists essentially of titanium dioxide. 21. A process for the production of N,N-cyclodialkylated amines which comprises reacting N,N-cyclodialkylatable .[.primary or.]. secondary aliphatic amine or N,N-cyclodialkylatable .[.primary or.]. secondary aromatic amine with an unstrained cyclic ether co-reactive therewith in the presence of a viable B-subgroup metal oxide catalyst other than a group I-B metal oxide at a temperature of at least about 200° C., but below that at which the catalyst becomes inactive, so that N,N-cyclodialkylated amine is produced. 
     
     
        2. A process of claim 21 .[.wherein the amine used in the reaction is a primary alkyl amine or a primary aromatic amine,.]. wherein the ether has but a single ring composed of a furan ring system, a dihydrofuran ring system, a tetrahydrofuran ring system, or a dihydropyran ring system and wherein the catalyst is composed predominantly or entirely of titanium 
     
     
        dioxide or zirconium dioxide. 23. A process of claim 22 wherein the reaction is conducted in the vapor phase by contact a vapor phase mixture of the reactants with a bed of the catalyst.