Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1981-09-23
1985-11-05
Reamer, James H.
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C07C 4546
Patent
active
045515549
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to a new process for production of 2-haloacetylphenols.
BACKGROUND ART
The objective compounds in the present invention, 2-haloacetylphenols (I) are important as intermediates in preparation of drugs, agricultural chemicals, perfumes, dyes, etc. A sufficient process for production thereof, however, has not been established. In the prior art, the Friedel-Crafts reaction of phenols (II) and the Fries rearrangement of haloacetoxybenzenes (III) have been utilized. These reactions, however, have the common disadvantage that the substitution occurs at both ortho and para position and moreover the para-substituted compounds (IV) are the main products. ##STR3##
DISCLOSURE OF INVENTION
The present invention relates to a new process for production of 2-haloacetylphenols, which comprises reacting phenols having the general formula ##STR4## (wherein, X is hydrogen, C.sub.1 -C.sub.5 alkyl, C.sub.3 -C.sub.6 cycloalkyl, C.sub.1 -C.sub.5 alkoxy or halogen atom and; ##STR5## (wherein, R is halogen atom and; general formula ##STR6## (wherein, X, Y, m and m each has the same meaning as mentioned above).
The following are explanations of the terms used in the above definition:
C.sub.1 -C.sub.5 alkyl; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, etc.
C.sub.3 -C.sub.6 cycloalkyl; cyclopropyl, cyclopentyl, cyclohexyl, etc.
C.sub.1 -C.sub.5 alkoxy; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy, etc.
C.sub.6 -C.sub.10 aryl; phenyl, tolyl, xylyl, naphthyl, etc.
As halogen atom, fluoro, chloro, bromo, iodo, etc. are mentioned.
The halogen atoms in boron halide compounds (VI), however, mean chloro and bromo, particularly chloro is preferred.
This reaction may be conducted in the presence of condensing coagents in a suitable inert solvent at a temperature of 0.degree.-150.degree. C., preferably at room temperature or under heating at approximately the boiling point of the solvent employed. As a condensing coagent, Lewis acids such as aluminum chloride, zinc chloride, titanium tetrachloride, tin tetrachloride, ferric chloride, etc. are exemplified, particularly aluminum chloride is preferred. As a solvent, methylene chloride, 1,2-dichloroethane, benzene, toluene, xylene, etc. are employed. The condensing coagents may be used in an amount of about 0.1-1.5 mole, preferably about 0.1-0.5 mole, per 1 mole of the starting phenol.
The starting phenols (II) may have the same or different kind of 1-2 substituents selected from alkyl, cycloalkyl, alkoxy, and halogen atom on the benzene ring. At least one site of the ortho-positions of the benzene ring, however, must be vacant in order that the reaction occurs. Practically, phenol, alkylphenol, cycloalkylphenol, alkoxyphenol, halophenol, 2,3-dihalophenol, 2,4-dialkylphenol, 3-cycloalkyl-4-halophenol, etc. are mentioned.
And as haloacetonitriles (V), monohaloacetonitrile (chloroacetonitrile, bromoacetonitrile, iodoacetonitrile, etc.), dihaloacetonitrile (dichloroacetonitrile, dibromoacetonitrile, etc.) and trihaloacetonitrile (trichloroacetonitrile, etc.) are mentioned.
As boron halide compounds (IV), boron trihalide such as boron trichloride and boron tribromide, and hydrocarbon boron dihalide such as butylboron dichloride, phenylboron dichloride and phenylboron dibromide are mentioned, particularly boron trichloride is preferred.
Haloacetonitriles (V) and boron halide compounds (VI) may be used in an amount of about 1.0-1.2 mole preferably about 1.0-1.1 mole per 1 mole of the starting phenol.
CAPABILITY OF EXPLOITATION IN INDUSTRY
The resulting objective compounds (I) in the present invention are useful as raw materials for drugs, agricultural chemicals, perfumes, dyes, etc. For example, 4-chloro-2-(2-chloroacetyl)-5-cyclohexylphenol is treated with sodium acetate to cyclize, and reduced with sodium borohydride, in order to convert the oxo group to the hydroxy group, followed by catalytic hydrogenation with palladium/carbon in hydrogen atomosphere, eliminating the hydroxy group to give 5-chloro-6-cyclo
REFERENCES:
Ruske, Friedel Crafts & Related Reactions, vol. III, pp. 403-410, 416-419, 439, 450, (1963).
Sugasawa et al., J. Org. Chem., vol. 44, #4, pp. 578-586, (1979).
Booth et al., J.C.S. Perkin Tran. I, pp. 2894-2900, (1980).
Sasakura Kazuyuki
Sugasawa Tsutomu
Toyoda Tatsuo
Reamer James H.
Shionogi & Co. Ltd.
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