Chemistry of hydrocarbon compounds – Adding hydrogen to unsaturated bond of hydrocarbon – i.e.,... – With preliminary diverse conversion
Reexamination Certificate
2000-11-30
2002-05-14
O'Sullivan, Peter (Department: 1621)
Chemistry of hydrocarbon compounds
Adding hydrogen to unsaturated bond of hydrocarbon, i.e.,...
With preliminary diverse conversion
C585S255000, C585S273000, C585S274000, C585S275000, C585S276000, C528S490000, C526S335000, C526S340000, C526S340100, C526S340400, C526S341000, C526S342000
Reexamination Certificate
active
06388149
ABSTRACT:
The present invention relates to a process for reacting an organic compound in the presence of a catalyst which comprises ruthenium and optionally one or more further Group Ib, VIIb, or VIIIb metals, applied to a porous support, as active metal(s).
In one embodiment the present invention relates to a process for the reaction, preferably hydrogenation, of an aromatic compound in which at least one hydroxyl group is attached to an aromatic core, where preferably at least one optionally substituted C
1
-C
10
-alkyl group and/or at least one C
1
-C
10
-alkoxy group is attached to an aromatic core in addition to said at least one hydroxyl group. Furthermore, monoalkyl-substituted phenols are preferably used in the process of the invention.
The mononuclear or polynuclear aromatic compounds are preferably hydrogenated in the presence of the catalyst that is described herein to produce the corresponding cycloaliphatic compounds, during which process the hydroxyl group remains intact.
Cycloaliphatic alcohols, and particularly alkylcyclohexanols, are important intermediates for the preparation of various perfumes, medicines and other organic fine chemicals. The above cycloaliphatic alcohols are readily obtained by catalytic hydrogenation of the corresponding aromatic precursors.
The method of preparing alkylcyclohexanols by catalytic hydrogenation of the corresponding alkylphenols is known. The hydrogenation of alkylphenols to form the corresponding alkylcyclohexanols in the presence of hydrogenation catalysts, particularly catalysts that are applied to supports, has been described in many places.
The catalysts used are metallic rhodium, rhodium/platinum and rhodium/ruthenium alloys, and also ruthenium, palladium, or nickel on catalyst supports. The catalyst supports used are carbon, barium carbonate, and, particularly, aluminum oxide.
PL 137,526 describes the hydrogenation of p-tert-butylphenol to form p-tert-butylcyclohexanol using a nickel catalyst.
DE-A 3,401,343 and EP 0,141,054 describe a process for the preparation of 2- and 4-tert-butylcyclohexanol from 2- and 4-tert-butylphenol by catalytic hydrogenation. The hydrogenation is carried out in two stages, a palladium catalyst on a Al
2
O
3
support being used in the first stage and a ruthenium catalyst on a Al
2
O
3
support being used in the second stage. The metal content on the support is from 0.1 to 5 wt.-%. The supports are not specified. The process is carried out under a pressure of 300 bar with recycling of the product, and there are preferably obtained the cis-tert-butylphenols, during which process from 0.1 to 0.5% of by-products are formed.
U.S. Pat. No. 2,927,127 describes a process for the preparation of p-tert-butylcyclohexanol and esters thereof by catalytic hydrogenation of p-tert-butylphenol. The catalysts used are 5% of rhodium on carbon, 5% of palladium on barium carbonate and 5% of ruthenium on carbon. When using ruthenium on carbon the process has been carried out under a pressure of from 70 to 120 bar and at a temperature of from 74° C. to 93° C. The hydrogenation product obtained comprised 66% of cis-isomer.
DE-A 2,909,663 describes a process for the preparation of cis-alkylcyclohexanols by catalytic hydrogenation of the corresponding alkylphenols. The catalyst used was ruthenium on a Al
2
O
3
support. The process was carried out under pressures of 40, 60, and 80 bar. The products obtained were predominantly cis-alkylcyclohexanols, whilst the by-product obtained comprised from 0.1 to 1% of alkyl benzenes.
In a further embodiment the present invention relates to a process for the reaction, preferably hydrogenation, of an aromatic compound in which at least one amino group is attached to an aromatic core, where preferably at least one optionally substituted C
1
-C
10
alkyl group and/or at least one C
1
-C
10
alkoxy group is attached to an aromatic core in addition to said at least one amino group. In particular, monoallyl-substituted amines are preferably used.
The mononuclear or polynuclear aromatic compounds are preferably hydrogenated to the corresponding cycloaliphatic compounds in the presence of the catalyst that is described herein, during which process the amino group remains intact.
Cycloaliphatic amines, and particularly optionally substituted cyclohexylamines and dicyclohexylamines, are used for the preparation of age protectors for caoutchoucs and plastics materials, as anticorrosive agents and also as intermediates for plant protectants and textile auxiliaries. Moreover cycloaliphatic diamines are used in the manufacture of polyamide and polyurethane resins and are also used as curing agents for epoxy resins.
It is known to be possible to prepare cycloaliphatic amines by catalytic hydrogenation of the corresponding mononuclear or polynuclear aromatic amines. The hydrogenation of aromatic amines to form the corresponding cycloaliphatic amines in the presence of hydrogenation catalysts, particularly catalysts that are applied to supports, has been described in many places.
The catalysts used are for example Raney cobalt containing basic additives (JP 43/3180), nickel catalysts (U.S. Pat. No. 4,914,239, DE 805,518), rhodium catalysts (BE 739,376, JP 7,019,901, JP 7,235,424), and also palladium catalysts (U.S. Pat. No. 3,520,928, EP 501,265, EP 53,818, JP 59/196843). In most cases, however, catalysts containing ruthenium are used.
DE 2,132,547 describes a process for the hydrogenation of mononuclear or polynuclear aromatic diamines to produce the corresponding cycloaliphatic amines which is carried out in the presence of a suspended ruthenium catalyst.
EP 67,058 describes a process for the preparation of cyclohexylamine by catalytic hydrogenation of the corresponding aromatic amine. The catalyst used is ruthenium metal in a finely divided state on activated aluminum pellets. After four recyclings the catalyst began to lose its activity.
EP 324,984 relates to a process for the preparation of a mixture of optionally substituted cyclohexylamine and optionally substituted dicyclohexylamine by hydrogenation of optionally substituted aniline using a catalyst containing ruthenium and palladium on a support which, moreover, contains an alkaline reacting alkali metal compound acting as modifier. A basically similar process is described in EP 501,265, where the catalyst contains niobic acid, tantalic acid, or a mixture of the two, as modifier.
U.S. Pat. No. 2,606,925 describes a process for the preparation of an aminocyclohexyl compound by hydrogenation of a corresponding aromatic compound where a ruthenium catalyst is used, whose active catalytic component is selected from elementary ruthenium, ruthenium oxides, and ruthenium salts in which the ruthenium is present in the anion or in the cation. As revealed by the examples of said process, the catalyst is prepared and dried in a separate stage and is intoduced into the reaction vessel after a relatively long drying time.
A further process for the preparation of cyclohexylamine is described in U.S. Pat. No. 2,822,392, and the main feature of this patent specification involves the use of a specific reactor in which the aniline and hydrogen used as starting products are caused to react with each other countercurrently.
U.S. Pat. Nos. 3,636,108 and 3,697,449 relate to the catalytic hydrogenation of aromatic compounds containing nitrogen using a ruthenium catalyst which additionally contains an alkali metal compound acting as modifier.
Common to all of the above processes is the use of mesoporous supports having surface areas (BET) which are typically between 50 and more than 1000 m
2
/g in order to achieve a high activity of the catalyst.
Furthermore, apart from the high cost of the catalyst, it has been found to be a disadvantage, particularly during hydrogenation using a rhodium-containing catalyst, that relatively large amounts of alkyl benzenes and other, unidentifiable compounds which are formed as decomposition products or by-products during hydrogenation frequently occur during such reactions. These by-products restrain working-up and purification of th
Breitscheidel Boris
Gausepohl Hermann
Henkelmann Jochem
Henne Andreas
Knoll Konrad
BASF - Aktiengesellschaft
Keil & Weinkauf
O'Sullivan Peter
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