Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2002-10-28
2004-08-24
Richter, Johann (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
Reexamination Certificate
active
06781016
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to processes for producing an alicyclic ketone and an alkyl-substituted alicyclic ester. More specifically, it relates to a process for producing an alicyclic ketone such as adamantanone and a process for producing an alkyl-substituted alicyclic ester from an alicyclic ketone obtained by the above process.
DESCRIPTION OF THE PRIOR ART
An alkyl-substituted alicyclic ester is a useful compound as a raw material for electronic materials and an intermediate for medicines and agricultural chemicals. For example, it is reported that a resist obtained from an alkyladamantyl ester which is an alkyl-substituted alicyclic ester has high resistance to dry etching in a semiconductor production process (JP-A 5-265212) (the term “JP-A” as used herein means an “unexamined published Japanese patent application”) and attracts attention as a potential resist material for semiconductors.
An alicyclic ketone such as adamantanone is an important compound as a raw material for the above alkyl-substituted alicyclic ester and required to have high purity from its application fields.
Since a competition is becoming keen in the field of electronic materials and a great reduction in production cost is strongly desired, it is extremely important to obtain a high-purity product from an inexpensive raw material by a simple method. For example, a process for obtaining high-purity adamantanone directly and easily from adamantane without using a derivative such as adamantanol is desired in the production of adamantanone.
As means of producing adamantanone from adamantane, there has been known a process in which adamantane is oxidized using hydroxyphthalimide as a catalyst (JP-A 10-309469). However, the production process is not satisfactory because the yield of adamantanone is low at about 30%.
There has also been known a process for obtaining adamantanone at a relatively high yield by oxidizing adamantane with concentrated sulfuric acid and then purifying oxidized adamantane by steam distillation (Organic Synthesis, vol. 53. pp. 8, 1973). In this process, an object can be obtained at a relatively high yield of 47 to 48%. However, this process needs a complicated purification step, that is, steam distillation. It is also reported that specific reaction conditions are employed to improve the reaction yield of the process in which adamantane is oxidized with sulfuric acid (JP-A 11-189564).
Although a process for producing adamantanone by oxidizing adamantane with concentrated sulfuric acid or fuming sulfuric acid (to be referred to as “concentrated sulfuric acid process” hereinafter) is a very promising process because a high yield is expected and an inexpensive raw material is used, a process for obtaining a high-purity product with ease has yet to be established.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a process for producing such a high purity alicyclic ketone that a purification step is substantially unnecessary by a simple extraction operation in the above concentrated sulfuric acid process.
It is another object of the present invention to provide the above method in which the alicyclic ketone is adamantanone.
It is still another object of the present invention to provide a process for producing a useful alkyl-substituted alicyclic ester from a high-purity alicyclic ketone obtained by the above method.
Other objects and advantages of the present invention will be obvious from the following description.
According to the present invention, firstly, the above objects and advantages of the present invention are attained by a process for producing an alicyclic ketone, comprising the steps of:
oxidizing an alicyclic hydrocarbon with concentrated sulfuric acid or fuming sulfuric acid to obtain a mixture containing an alicyclic ketone and concentrated sulfuric acid or fuming sulfuric acid;
mixing the obtained mixture with water and an organic solvent;
separating an organic layer containing the alicyclic ketone from a water layer; and
recovering the alicyclic ketone from the separated organic layer, wherein
the concentration of sulfuric acid in the water layer is adjusted to 60 to 90 wt % when the organic layer is to be separated.
According to the present invention, secondly, the above objects and advantages of the present invention are attained by a process for producing an alkyl-substituted alicyclic ester, comprising the steps of:
reacting an alicyclic ketone obtained by the above process of the present invention with at least one alkylating reagent selected from an alkyl lithium, Grignard reagent and a combination of a haloalkyl compound and metal lithium to obtain an alkyl-substituted alicyclic alkoxide; and
reacting the obtained alkyl-substituted alicyclic alkoxide with an acid halide to produce an alkyl-substituted alicyclic ester.
THE PREFERRED EMBODIMENT OF THE INVENTION
In the process for producing an alicyclic ketone of the present invention, an alicyclic hydrocarbon is first oxidized with concentrated sulfuric acid or fuming sulfuric acid to obtain a mixture containing an alicyclic ketone and concentrated sulfuric acid or fuming sulfuric acid.
Any alicyclic hydrocarbon may be used as a raw material compound if it is a cyclic hydrocarbon and compound having no unsaturated bond. However, it is preferably a saturated alicyclic hydrocarbon having high symmetry because the position to be oxidized is limited and a single alicyclic ketone is easily obtained. Preferred examples of the alicyclic hydrocarbon include adamantane and cyclohexane. Out of these compounds, adamantane is most preferred because an oxidation reaction proceeds selectively and efficiently, an alicyclic ketone obtained therefrom is useful as an intermediate for medicines, agricultural chemicals and electronic materials, and high purity is desired.
The process for obtaining an alicyclic ketone by contacting the above alicyclic hydrocarbon with concentrated sulfuric acid or fuming sulfuric acid to oxidize the alicyclic hydrocarbon is identical to the conventional concentrated sulfuric acid process for producing an alicyclic ketone compound. Therefore, the process described at page 8 of Organic Synthesis vol. 53, 1973, the process disclosed by JP-A 11-189564 and known processes can be applied without restriction.
The oxidation of the alicyclic hydrocarbon can be advantageously carried out by mixing and stirring an alicyclic hydrocarbon and concentrated sulfuric acid in the absence of a solvent and heating. The concentration of concentrated sulfuric acid at this point is preferably 96 wt % or more and fuming sulfuric acid may also be used. The amount of the alicyclic hydrocarbon is not particularly limited but preferably 0.1 to 5 mols based on 1 kg of the concentrated sulfuric acid or fuming sulfuric acid. As for the reaction temperature and the reaction time which differ according to the type of the alicyclic hydrocarbon to be oxidized, the alicyclic hydrocarbon is preferably reacted at 50 to 100° C. for 0.5 to 48 hours. More preferably, the temperature is elevated by checking the proceeding of the reaction.
The reaction temperature may be changed in two stages. For example, the first stage of the reaction is carried out at 50 to 60° C. and then the second stage of the reaction is carried out at 60 to 100° C. The formation of a resin-like substance in particular can be suppressed by this two-stage reaction.
A reaction solution which is a mixture containing an alicyclic ketone (object) having a —C(═O)— group formed by oxidizing a —CH
2
— group contained in the alicyclic hydrocarbon and concentrated sulfuric acid or fuming sulfuric acid can be obtained by the above reaction.
In the present invention, after the thus obtained reaction solution, water and an organic solvent are mixed together, a water layer and an organic layer containing an alicyclic ketone compound are separated from each other. The concentration of sulfuric acid in the water layer (defined as wt % of sulfuric acid based on the total weight of water and sulfuric acid) at this point is c
Hirota Yoshihiro
Kadokura Atsushi
Kikuchi Hideki
Matsumura Takashi
Yamaguchi Masao
Richter Johann
Tokuyama Corporation
Zucker Paul A.
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