Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2001-08-08
2002-10-29
Keys, Rosalynd (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S628000
Reexamination Certificate
active
06472567
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a process for the production of a styrene compound, and a styrene compound free from biphenyl. More particularly, the present invention relates to a process for the production of a styrene compound which comprises reacting a Grignard reagent prepared from an aromatic halogen compound with a vinyl halide in the presence of a catalyst, and styrene compound free from biphenyl.
BACKGROUND OF THE INVENTION
A styrene derivative towards which the present invention is directed is very useful as a raw material of functional high molecular compounds, medicines, agricultural chemicals, etc. For example, para-tertiary butoxystyrene (hereinafter referred to as “PTBS”) is known to be extremely useful as a raw material of a resist for use in super LSI's, etc. (JP-A-59-199705 (The term “JP-A” as used herein means an “unexamined published Japanese patent application”), JP-A-3-277608). Further, meta-tertiary butoxystyrene (hereinafter referred to as “MTBS”) is known to be useful as an intermediate raw material of functional high molecular compounds, medicines, agricultural chemicals, etc. (JP-A-2-160739).
Two processes for the production of a styrene derivative such as PTBS and MTBS have been heretofore known.
U.S. Pat. No. 4,603,101 and JP-A-59-199705 disclose a process involving the reaction of a Grignard reagent prepared from halostyrene with perbenzoic acid tertiary butyl ester. However, this production process gives a low reaction yield. In addition, this production process is disadvantageous in that it requires the use of a perbenzoic acid tertiary butyl ester, which is difficult to be available in a large amount and is explosive. Thus, this production process leaves something to be desired in mass production of a styrene derivative such as PTBS and MTBS.
On the other hand, JP-B-4-71896 (The term “JP-A” as used herein means an “unexamined published Japanese patent application”) and JP-A-2-160739 disclose a process involving the reaction of a Grignard reagent prepared from a tertiary butoxyphenyl halide with a vinyl halide in the presence of a nickel-phosphine complex catalyst. However, this production process is disadvantageous in that it requires the use of a nickel-phosphine complex catalyst which is expensive and very toxic, although providing some improvement in reaction yield. The above cited patent applications describe that bidentate phosphine complexes such as dichloro[1, 2-bis (diphenylphosphino)ethane]nickel and dichloro[1, 3-bis (diphenylphosphino)propane] nickel are effective for the progress of this reaction in a high yield. However, these catalysts are expensive and very toxic. Accordingly, even if this production process is used, it is difficult to produce a styrene derivative such as PTBS and MTBS economically and safely. Thus, this production process, too, leaves something to be desired in mass production of a styrene derivative such as PTBS and MTBS.
Further, the present inventors have found that in the case of producing tertiary-butoxystyrene by those processes, biphenyl is produced as a reaction by-product. Biphenyl has the characteristic of having strong absorption to far ultraviolet light of excimer laser or the like used in super LSI. For this reason, if biphenyl is present in a resist resin, there are the problems that the presence decreases light permeability and also decreases resolution of a resist, thus inducing unfavorable trouble. In other words, it is preferable for tertiary-butoxystyrene used in resist to not contain biphenyl as an impurity. However, boiling points of tertiary-butoxystyrene and biphenyl are very close, and thus it is extremely difficult to remove biphenyl once produced, by general distillation operation.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a process for the production of a styrene compound giving improvements over the prior art, and a styrene compound free from biphenyl. More particularly, the object of the present invention is to provide a process for the production of a styrene compound such as PTBS and MTBS which gives solution to the prior art problems and hence provides excellent economy and safety, and also provide a high quality tertiary butoxystyrene free from biphenyl.
The above object of the present invention will become more apparent from the following detailed description and examples.
The inventors made extensive studies of solution to the prior art problems. As a result, it was found that the use of a specific catalyst in a process for the production of a styrene compound such as PTBS and MTBS involving the reaction of a Grignard reagent prepared from tertiary butoxyphenyl halide with a vinyl halide in the presence of a catalyst makes it possible to produce such a styrene compound economically and safely on an industrial basis. It was further found that using this catalytic process makes it possible to achieve a reaction which does not form biphenyl by-product at all. Thus, the present invention has been worked out.
That is, the present invention provides a process for the production of a styrene compound which comprises reacting a Grignard reagent prepared from a tertiary butoxyphenyl halide represented by the following formula (I):
wherein X represents a halogen atom, with a vinyl halide in the presence of a catalyst, wherein said catalyst is at least one member selected from the group consisting of a manganese catalyst, an iron catalyst, a cobalt catalyst and a rhodium catalyst.
The present invention also provides a styrene compound free from biphenyl, obtained using this process.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be further described with reference to the production of PTBS.
The Grignard reagent to be used in the production process of the present invention is not specifically limited so far as it is prepared from an aromatic halogen compound. Thus, the Grignard reagent of the present invention can be easily prepared by any ordinary method. In other words, the Grignard reagent of the present invention can be easily prepared, e.g., by a process which comprises the reaction of metallic magnesium with para-tertiary butoxyphenyl halide in a solvent. If activated metallic magnesium is used in this preparation process, particularly good results can be given. Examples of effective methods for activating metallic magnesium include a method involving heating of a suspension of metallic magnesium in a solvent with stirring and a method involving stirring of such a suspension mixed with a slight amount of iodine, iodide such as methyl iodide, bromide such as dibromoethane or the like.
In accordance with the production process of the present invention, the reaction of a Grignard reagent prepared by the above method with a vinyl halide in the presence of one or more catalysts selected from the group consisting of manganese catalyst, iron catalyst, cobalt catalyst and rhodium catalyst makes it possible to produce PTBS safely in a high yield at a low cost.
Examples of the vinyl halide used in the production process of the present invention include vinyl fluoride, vinyl chloride, vinyl bromide, and vinyl iodide. These vinyl halides may be used singly or in admixture. In general, vinyl chloride gas and/or vinyl bromide gas are selected taking into account the economy and availability.
The catalyst used herein comprises one or more catalysts selected from the group consisting of manganese catalyst, iron catalyst, cobalt catalyst and rhodium catalyst.
The term “manganese catalyst” as used herein means to indicate a catalyst comprising manganese element as an effective component. Thus, the manganese catalyst used herein is not specifically limited. In practice, however, manganese powder, manganese compounds such as manganese chloride (II), manganese bromide (II), manganese iodide (II), manganese fluoride (II), manganese acetate (II), manganese acetate (III), manganese formate (II), manganese oxalate (II), manganese benzoate (II), manganese stearate (II), manganese borate (II), mang
Eguchi Hisao
Ishikawa Shin-ichi
Keys Rosalynd
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
Tosoh Corporation
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