Noble metal raney catalysts and preparation of hydrogenated...

Details Noble metal raney catalysts and preparation of hydrogenated... Noble metal raney catalysts and preparation of hydrogenated...

1999-11-30

2001-04-10

Wilson, James O. (Department: 1623)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S864000, C568S885000

Reexamination Certificate

active

06215030

ABSTRACT:

BACKGROUND OF THE INVENTION
This invention relates to catalysts for hydrogenation and to hydrogenation reactions therewith. More particularly, this invention relates to noble metal Raney catalysts which can efficiently hydrogenate aromaticity-exhibiting ring portions and carbonyloxy portions of organic compounds and aromatic nitrile compounds and the like under conditions milder than conventional methods and to methods for the preparation of hydrogenated compounds with such catalysts.
DESCRIPTION OF RELATED ART
1) Hydrogenation reaction of aromaticity-exhibiting ring portions
There are many organic compounds which contain in their molecule rings which exhibit aromaticity. Hydrogenation reactions of such organic compounds generally are conducted under severe conditions, i.e., at high temperatures and at high hydrogen pressures.
Examples of prior art on catalysts for use in the hydrogenation of the aromaticity-exhibiting ring portions are described along with catalysts, compounds to be hydrogenated, and reaction conditions (reaction temperature and hydrogen pressure)
As the catalyst, there have been used Raney catalysts such as Raney Ni or Co, noble metal carried type catalysts such as Pd, Rh, Ru, etc. and base metal carried type catalysts. Reaction conditions therefor may depend on the natures of catalysts and compounds to be hydrogenated but generally comprise temperatures of 60 to 200° C. and pressures of 25-280 Kg/cm
2
.
TABLE
Compound
Reaction
Hydrogen
to be
Temperature
Pressure
Reference
Catalyst
hydrogenated
(° C.)
(kg/cm
2
G)
JP-A-48-032845
Co/CaO/Al2O3
xylylene diamine
130
200
JP-B-51-007659
Ru/carbon
xylylene diamine
105
200
JP-A-53-079840
R/carbon
xylylene diamine
110
125
JP-B-60-034526
Ru/Al2O3
4-tert-butylphenol
60-80
80
JP-A-53-119855
Ru/carbon
isopropylidene diphenol
155
120
JP-A-06-279339
Ni/diatomaceous
bisphenol A
200
25
earth
(12 hours)
JP-A-42-001423
Raney Ni
bisphenols
200
80
JP-A-45-035300
carried type Rh
bisphenols
75
50
JP-A-06-009461
Ru/carbon
bisphenols
140
50
JP-A-06-279368
Ru/Al2O3
aromatic dinitrile
140
150
JP-A-06-306019
Ru/Co/Al2O3
methylene diamine
180
58
JP-A-56-012348
Raney Ni
carbomethoxybenzaldehyde
150
90
oxime
JP-A-04-018935
Co oxide/
phenylene diamine
165
5
carried Rh
JP-A-04-247056
Ru/Co/Mn
bis(4-aminophenyl)methane
140
260
Al2O3
JP-A-63-295533
Ru/carbon
pyridine
160
80
JP-A-03-002162
Ru/carbon
picolic acid
80-160
30-50
JP-A-58-108439
Pd/Ru/carbon
terephthalic acid
150
100
USSR Patent No. 706398 (1979) discloses hydrogenation of 4,4′-diaminodiphenylmethane into 4,4′-diaminodicyclohexyl-methane can be achieved under the conditions of a temperature of 60 to 140° C. and a hydrogen pressure of 40 to 130 atm. in the presence of skeleton Ru catalyst obtained by development of ruthenium-aluminum alloy with aqueous 20% sodium hydroxide solution.
As for the reaction conditions in concrete examples of the USSR patent, it was reported that 98.7% of 4,4′-diaminodicyclohexylmethane was obtained by 30 minute's reaction under severe conditions, i.e., a temperature of 140° C. and a hydrogen pressure of 120 atm. in isopropyl alcohol. However, only a brief description was made and no detailed explanation was given. In the experiments conducted by the present inventors, yield of 71.4% was obtained even after 4 hours' reaction. In the above mentioned prior art reference, there is recited only one species of 4,4′-diamino-diphenylmethane as a compound to be hydrogenated.
Japanese Patent Publication (Kokoku) No. 55-35177 (JP-B-55-035177) and Japanese Patent Publication (Kokai) (JP-A-02-258064) disclose that Raney ruthenium catalysts are effective as catalysts for ammonia synthesis. Japanese Patent Publication (Kokai) No. 5-253468 (JP-A-05-253468) discloses that Raney ruthenium catalysts are effective as catalysts for methanol synthesis. However, none of these references discloses effectiveness of the Raney ruthenium catalysts for hydrogenation reactions.
In contrast, by the use of the Raney ruthenium catalyst of the present invention described in detail hereinafter, ring portions of various aromatic compounds can be hydrogenated efficiently at a hydrogen pressure of 5 to 10 kg/cm
2
, which is much lower than the condition described in the above-listed prior art references, at a temperature mostly around room temperature and at most about 100° C. None of the above publications can be said to be valid prior art which could render obvious to one skilled in the art the present invention directed to catalysts that allow hydrogenation of ring portions of a wide variety of aromatic compounds under mild conditions and to methods for the preparation of hydrogenated compounds with such catalysts.
2) Hydrogenation of carboxylic acids and their esters
Many methods have been known in which compounds having a carbonyloxy group (—CO—O—) are reacted with hydrogen to produce corresponding alcohols or the like.
For example, as a method for hydrogenating carboxylic acids, a method using a rhenium oxide catalyst is disclosed in J. Org. Chem. 24, 1847 (1959). This method involves a reaction which must be carried out for a long time at high pressures and whose product contains many by-products.
Use of cobalt-yttrium-palladium catalysts in hydrogenation of lauric acid into lauryl alcohol is known (Japanese Patent Publication (Kokoku) No. 4-36140 (JP-B-04-036140)). However, the method uses severe reaction conditions, i.e., a temperature of 225° C. and a hydrogen pressure of 250 kg/cm
2
.
As methods of hydrogenation of carboxylic acid esters, there have been known a method in which the ester group of a cyclohexane dicarboxylic ester is hydrogenated with a copper-chromium catalyst at a reaction temperature of 220° C. at a reaction pressure of 150 kg/cm
2
as disclosed in Japanese Patent Publication (Kokai) No. 52-242 (JP-A-52-000242), a method in which the benzene skeleton of dimethyl terephthalate is hydrogenated, followed by hydrogenation of the ester portion of the product with a copper-chromium catalyst (CuO—Cr
2
O
3
—BaO) at a reaction temperature of 120-220° C. at a reaction pressure of 300 Bar as disclosed in U.S. Pat. No. 5,030,771, and so on. These reactions each must be carried out under severe conditions.
Further, there is known a method in which a catalyst containing ruthenium and tin carried on titania is used for hydrogenating dimethyl 1,4-cyclohexanedicarboxylate at a temperature of 270-280° C. at a pressure of 90-100 kg/cm
2
to obtain 1,4-cyclohexanedimethanol as disclosed in Japanese Patent Publication (Kokai) No. 6-228028. The reaction conditions used in this method is also severe. Also, there is known a method in which a catalyst containing ruthenium and tin carried on titania is used for hydrogenating dimethyl dimerate at a temperature of 250° C. at a pressure of 100 kg/cm
2
into an alcohol as disclosed in Japanese Patent Publication (Kokai) No. 6-228027. Also, the reaction conditions used are severe and unsatisfactory.
Many prior art references have been known on the use of Raney catalysts as a catalyst for the hydrogenation of compounds having a carbonyloxy group. For example, there are known use of Raney nickel, Raney rhenium, and Raney copper catalysts (Japanese Patent Publication (Kokai) No. 5-345735), use of Raney nickel catalyst (Japanese Patent Publication (Kokai) No. 55-40685), and so on.
As examples of use of noble metal catalysts, there are disclosed hydrogenation reactions in the presence of compound (alloy) catalysts comprising at least one noble metal selected from noble metal elements belonging to the period 5 or 6 in the groups VIII, IX, and X and an alloy of such noble metal with other metal(s) (Japanese Patent Publication (Kohyo) Nos. 1-503459 and 3-500657).
However, the former Raney catalysts do not suggest the noble metal Raney catalysts. In addition, the latter noble metal-other metal alloy catalysts are carried type catalysts. In either of the cases, a problem arises in that high reaction temperatures and high reaction pressures are used.
Catalyst systems thus far known need severe reaction conditions such as

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