Process for producing alicyclic monoketones and process for...

Details Process for producing alicyclic monoketones and process for... Process for producing alicyclic monoketones and process for...

1999-09-02

2001-11-06

Padmanabhan, Sreeni (Department: 1621)

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

Organic compounds

Oxygen containing

C568S322000, C568S324000, C568S329000, C568S338000, C568S362000

Reexamination Certificate

active

06313351

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a process for producing alicyclic monoketones (hydroxyphenylcyclohexanone derivatives) and a process for producing alicyclic diketones. More particularly, the invention relates to a process for producing alicyclic monoketones in which alicyclic monoketones can be obtained in high yields by hydrogenating (reducing) substituted bisphenols in an organic solvent and to a process for producing diketones in which alicyclic diketones can be obtained in high yields by hydrogenating (reducing) substituted bisphenols in an organic solvent.
BACKGROUND OF THE INVENTION
Alicyclic diketones such as 2,2-bis(4-oxocyclohexyl)propane are useful compounds as intermediates of materials of medicines, materials of industrial chemicals, materials of polymers, polymerization initiators, heat resistance improvers, antioxidants and the like.
As a process for producing alicyclic diketones, a process comprising oxidizing alicyclic diol to produce alicyclic diketones has be en known for a long time. For example, Japanese Patent Laid-Open Publication No. 59742/1992 describes a process for producing 2,2-bis(4-oxocyclohexyl)propane, which comprises oxidizing 2,2-bis(4-hydroxycyclohexyl)propane by hypochlorous acid and the like in the presence of a solvent.
The process described in Japanese Patent Laid-Open Publication No. 59742/1992, however, has a problem of using expensive alicyclic diol. If 2,2-bis(4-hydroxyphenyl)propane that is relatively inexpensive is used as a starting material, reactions of two steps, namely, hydrogenation reaction of 2,2-bis(4-hydroxyphenyl)propane and oxidation reaction of 2,2-bis(4-hydroxycyclohexyl)propane obtained by the hydrogenation reaction, must be conducted to produce 2,2-bis(4-oxocyclohexyl)propane, so that the process becomes complicated.
Similarly to the alicyclic diketones, alicyclic monoketones (hydroxyphenylcyclohexanone derivatives) such as 4-(4′-hydroxyphenyl)cyclohexanone and 2-(4-oxocyclohexyl)-2-(4-hydroxyphenyl)propane are also useful as intermediates of materials of medicines, materials of industrial chemicals, materials of polymers, polymerization initiators, heat resistance improvers, antioxidants, liquid crystal compounds for display and the like. However, the aforesaid alicyclic diketones such as 2,2-bis(4-oxocyclohexyl)propane are commonly used as the intermediates, and any literature on the technique to produce alicyclic monoketones was not found as far as the present inventor investigated.
Accordingly, there has been desired development of a process for producing alicyclic diketones by which alicyclic diketones such as 2,2-bis(4-oxocyclohexyl)propane can be obtained in high yields through simple steps using inexpensive materials.
There has been also desired development of a process for producing alicyclic monoketones by which alicyclic monoketones such as 4-(4′-hydroxyphenyl)cyclohexanone and 2-(4-oxocyclohexyl)-2-(4-hydroxyphenyl)propane can be obtained in high yields through simple steps using inexpensive materials.
In connection with the above, Japanese Patent Laid-Open Publication No. 134009/1996 describes a process for producing alicyclic diketones such as 2-(4-oxocyclohexyl)-2-(4-hydroxycyclohexyl)propane, which comprises hydrogenating bisphenols such as bisphenol A in a liquid phase in the presence of a palladium type hydrogenation catalyst and an alkali metal compound with heating under pressure.
OBJECT OF THE INVENTION
It is an object of the present invention to provide a process for producing alicyclic monoketones (hydroxyphenylcyclohexanone derivatives) by which alicyclic monoketones can be obtained with high selectivity and in high yields through simple steps using inexpensive materials. It is another object of the invention to provide a process for producing alicyclic diketones by which alicyclic diketones can be obtained with high selectivity and in high yields through simple steps using inexpensive materials.
SUMMARY OF THE INVENTION
The process for producing alicyclic monoketones (hydroxyphenylcyclohexanone derivatives) according to the present invention comprises hydrogenating substituted bisphenols represented by the following formula (I) in a solvent in the presence of a palladium/alkali metal catalyst in which palladium and an alkali metal are both supported on a carrier, to obtain alicyclic monoketones represented by the following formula (II);
wherein X is a single bond, —CH
2
—, —C(CH
3
)
2
—, —O— or —SO
2
—; R
1
and R
2
are each independently a hydrogen atom or an alkyl group of 1 to 6 carbon atoms; and m and n are each an integer of 0 to 2 and are the same or different;
wherein X, R
1
, R
2
, m and n have the same meanings as those of X, R
1
, R
2
, m and n in the formula (I).
The process for producing alicyclic diketones according to the present invention comprises hydrogenating substituted bisphenols represented by the above formula (I) in a solvent in the presence of a palladium/alkali metal catalyst in which palladium and an alkali metal are both supported on a carrier, to obtain alicyclic diketones represented by the following formula (III):
wherein X, R
1
, R
2
, m and n have the same meanings as those of X, R
1
, R
2
, m and n in the formula (I).
The palladium/alkali metal catalyst in which palladium and an alkali metal are both supported on a carrier is preferably one in which 1 to 10% by weight of palladium and 0.5 to 5% by weight of an alkali metal are both supported on a carrier.
The solvent is preferably a saturated alcohol of 3 or more carbon atoms, particularly preferably a monohydric saturated aliphatic alcohol of 3 to 12 carbon atoms.
The other process for producing alicyclic monoketones according to the present invention comprises hydrogenating substituted biphenols represented by the following formula (I-1) in an organic solvent in the presence of a palladium catalyst in which 10 to 30% by weight of palladium is supported on a carrier, to obtain alicyclic monoketones represented by the following formula (II-1);
wherein R
1
and R
2
are each independently a hydrogen atom or an alkyl group of 1 to 6 carbon atoms; and m and n are each an integer of 0 to 2 and are the same or different;
wherein R
1
, R
2
, m and n have the same meanings as those of R
1
, R
2
, m and n in the formula (I-1).
The organic solvent is preferably a monohydric saturated aliphatic alcohol of 3 to 12 carbon atoms.
In order to obtain alicyclic monoketones represented by the above formula (II) wherein X is a single bond, namely, alicyclic monoketones represented by the above formula (II-1), the latter process for producing alicyclic monoketones according to the invention is preferable because high-purity alicyclic monoketones can be obtained with high selectivity and in high yields.
DETAILED DESCRIPTION OF THE INVENTION
The process for producing alicyclic monoketones (hydroxyphenylcyclohexanone derivaties) and the process for producing alicyclic diketones according to the invention are described in detail hereinafter.
In the process for producing alicyclic monoketones or the process for producing alicyclic diketones according to the invention, hydrogenation of specific substituted bisphenols is carried out in a solvent in the presence of a palladium/alkali metal catalyst in which palladium and an alkali metal are both supported on a carrier, to obtain the desired alicyclic monoketones or alicyclic diketones.
In the other process for producing alicyclic monoketones according to the invention, specific substituted biphenols are selectively hydrogenated with hydrogen in an organic solvent, particularly preferably a monohydric alcohol solvent of 3 or more carbon atoms, in the presence of a palladium catalyst in which palladium is supported on a carrier in a high concentration, to obtain the desired alicyclic monoketones.
Substituted Bisphenols
The substituted bisphenols used as starting materials in the process for producing alicyclic monoketones and the process for producing alicyclic diketones according to the invention are represented by the following formula (I). The

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