Process for preparing ortho substituted phenylamines
A process is disclosed for preparing ortho substituted phenylamines comprising contacting phenylhydroxylamine, optionally substituted with at least one inert substituent, with a nucleophilic reagent in the presence of a manganese oxide at a temperature between about 10° C. and about 170° C. and a pressure from subatmospheric to superatmospheric such that an ortho substituted phenylamine, optionally correspondingly substituted with at least one inert substituent, is predominantly formed.
1. A process of preparing ortho substituted phenylamines comprising contacting phenylhydroxylamine, optionally substituted with at least one inert substituent, with a nucleophilic reagent in the presence of a manganese oxide at a temperature between about 10° C. and about 170° C. and a pressure from subatmospheric to superatmospheric such that an ortho substituted phenylamine, optionally correspondingly substituted with at least one inert substituent, is formed.
2. The process of claim 1 wherein the phenylhydroxylamine is unsubstituted phenylhydroxylamine.
3. The process of claim 1 wherein the phenylhydroxylamine is substituted with at least one member selected from the group consisting of C 1 -C 10 alkyl, C 6 -C 10 aryl, and C 6 -C 10 alkaryl moieties.
4. The process of claim 1 wherein the nucleophilic reagent is selected from the group consisting of ammonia, water, C 1 -C 20 aliphatic alcohols, phenols, halides, and amines having the formula R′ 2 NH wherein each R′ may independently be a hydrogen, C 1 -C 20 aliphatic, C 4 -C 8 alicyclic, or C 6 -C 15 aryl or alkaryl moiety.
5. The process of claim 1 wherein the nucleophilic reagent is an amine represented by the formula R′ 2 NH wherein each R′ is independently a hydrogen, C 1 -C 5 alkyl, or C 6 -C 10 phenyl or alkyl-substituted phenyl moiety.
6. The process of claim 5 wherein the nucleophilic reagent is aniline.
7. The process of claim 1 wherein the molar ratio of nucleophilic reagent to phenylhydroxylamine ranges from about 2 to about 100.
8. A process for preparing ortho substituted phenylamines comprising contracting phenylhydroxylamine, optionally substituted with at least one inert substituent, with a nucleophilic reagent, the molar ratio of nucleophilic reagent to phenylhydroxylamine ranging from about 2 to about 100, the contacting of the phenylhydroxylamine and nucleophilic reagent being conducted in the absence of oxygen and in the presence of a catalyst that is a cryptomelane-type manganese oxide Octahedral Molecular Sieve, with a composition of KMn 8 O 16 .nH 2 O (n=0.5-10) in which said molecular sieve comprises MnO 6 octahedral structural units that are edge and corner shared to form a 4.6×4.6 tunnels as a result of 2×2 arrangement of octahedra, in which the potassium ions are present in the tunnels with water and said potassium ions are ion-exchanged by H + ions using nitric acid to obtain the acidic form of said sieve at temperatures ranging from about 70° C. to about 120° C., whereby an optionally-substituted ortho substituted phenylamine is formed.
9. The process of claim 8 wherein the phenylhydroxylamine is unsubstituted phenylhydroxylamine.
10. The process of claim 8 wherein the nucleophilic reagent is selected from the group consisting of ammonia, water, C 1 -C 20 aliphatic alcohols, phenols, halides, and amines having the formula R′ 2 NH wherein each R′ may independently be a hydrogen, C 1 -C 20 aliphatic, C 4 -C 8 alicyclic, or C 6 -C 15 aryl or alkaryl moiety.
11. The process of claim 8 wherein the nucleophilic reagent is aniline.
12. The process of claim 8 wherein the ortho substituted phenylamine is represented by the formula:
wherein R 2 is hydrogen or at least one C 1 -C 10 alkyl moiety, and X is selected from hydroxy, halo, C 1 -C 20 alkoxy, phenoxy, and amino of the formula —NR′ 2 wherein each R′ is independently a C 1 -C 20 aliphatic, C 4 -C 8 alicyclic, or C 6 -C 15 aryl or alkaryl moiety.
13. The process of claim 12 wherein X is amino and the ortho substituted phenylamine is a o-phenylenediamine.
14. The process of claim 13 wherein the ortho substituted phenylamine is o-aminodiphenylamine represented by the formula: