Preparation of cyclic amines

• US 5,663,438 A
• Filed: 08/17/1995
• Issued: 09/02/1997
• Est. Priority Date: 08/16/1994
• Status: Expired due to Term

• Current Assignee: BASF AG (BASF SE)
• Original Assignee: BASF AG (BASF SE)
• Inventors: Pape, Frank-Friedrich, Hesse, Michael, Kohler, Ulrich, Polanek, Peter, Irgang, Matthias, Wulff-Doring, Joachim
• Primary Examiner(s): O SULLIVAN, PETER G
• Application Number:
  US08/516,147
• Time in Patent Office: 747 Days
• Field of Search: 564/305, 564/307, 564/402
• US Class Current: 564/305
• CPC Class Codes: C07C 209/16 with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
• CPC Class Codes: C07C 209/68 from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton

Abstract

A process for the preparation of a phenyl amine which may be substituted by alkyl or cycloalkyl in which the corresponding cyolohexylamine is reduced at temperatures of 150° to 300° C. and pressures of 0.01 to 50 bar in the presence of a heterogeneous dehydrogenation catalyst consisting essentially of palladium or a palladium/platinum mixture supported on carrier consisting of the oxides of rare earth metals and and metals of Group IVb of the Periodic Table of Elements, with the proviso that the palladium/platinum mixture may also be supported on an alumina carrier. The cyclohexylamine reactant can be advantageously prepared by reacting the corresponding phenol with ammonia and hydrogen at 100° to 250° C. in the presence of the same heterogeneous catalyst as a preliminary step to provide a two stage process using the same catalyst in both stages.

Claims

1. A process for the preparation of aromatic amines of the formula I ##STR4## where R¹, R², R³, R⁴ and R⁵ are each hydrogen, C₁ -C₁₂ -alkyl or C₃ -C₁₂ -cycloalkyl, from aliphatic amines of the formula II ##STR5## where R¹, R², R³, R⁴ and R⁵ have the abovementioned meanings, at from 150°

to 300°

C. and from 0.01 to 50 bar in the presence of a heterogeneous catalyst, wherein the heterogeneous catalyst consists of from 30 to 100% by weight of

a) palladium on oxides of the rare earth elements or on oxides of metals of Group IVb or

b) platinum/palladium mixtures on alumina or oxides of the rare earth element or oxides of metals of Group IVb

and from 0 to 70% by weight of alkali metal or alkaline earth metal oxide.

2. A process for the preparation of aromatic amines of the formula I as claimed in claim 1, wherein the aliphatic amines of the formula II are prepared by reacting phenols of the formula III ##STR6## where R¹, R², R³, R⁴ and R⁵ have the abovementioned meanings, with ammonia and hydrogen at from 100°

to 250°

C. and from 0.01 to 50 bar in the presence of a catalyst of claim 1.

3. A process for the preparation of aromatic amines of the formula I as claimed in claim 1, wherein a heterogeneous catalyst which consists of from 50 to 100% by weight of

a) palladium on oxides of the rare earth elements or on oxides of metals of Group IVb or

b) platinum/palladium mixtures on alumina or oxides of the rare earth elements or oxides of metals of Group IVb

and from 0 to 50% by weight of alkali metal or alkaline earth metal oxide is used.

4. A process for the preparation of aromatic amines of the formula I as claimed in claim 1, wherein a heterogeneous catalyst which consists of from 70 to 100% by weight of

a) palladium on oxides of the rare earth elements or on oxides of metals of Group IVb or

b) platinum/palladium mixtures on alumina or oxides of the rare earth element or oxides of metals of Group IVb

and from 0 to 30% by weight of alkali metal or alkaline earth metal oxide is used.

5. A process for the preparation of aromatic amines of the formula I as claimed in claim 1, wherein a heterogeneous catalyst which consists of from 30 to 100% by weight of CeO₂ as an oxide of the rare earth elements is used.

6. A process for the preparation of aromatic amines of the formula I as claimed in claim 1, wherein a heterogeneous catalyst which consists of from 30 to 100% by weight of ZrO₂ as an oxide of the rare earth elements is used.

7. A process for the preparation of aromatic amines of the formula I as claimed in claim 1, wherein R¹, R², R³, R⁴ and R⁵ are each hydrogen, C₁ -C₈ -alkyl or C₅ -C₈ -cycloalkyl.

8. A process for the preparation of aromatic amines of the formula I as claimed in claim 1, wherein R¹, R², R³, R⁴ and R⁵ are each hydrogen, C₁ -C₄ -alkyl or C₅ - or C₆ -cycloalkyl.