Organic compounds -- part of the class 532-570 series – Organic compounds – Sulfur containing
Reexamination Certificate
2003-06-30
2004-10-19
Vollano, Jean F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Sulfur containing
C568S028000
Reexamination Certificate
active
06806387
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a process for producing an allyl sulfone derivative which is a starting material for vitamin A derivatives and various terpene compounds to be used for medicament, feed additives, food additives, etc., and an intermediate for producing it.
BACKGROUND ART
As a process for producing a vitamin A derivative, there has been known a process using an intermediate compound obtained by reacting a halogen compound, which is derived from a C10 alcohol compound such as linalool, geraniol, or the like by a reaction step using an expensive Pd catalyst and a ligand, with a C10 sulfone (a compound represented by the formula (7) described below) to introduce a C10 side chain (EP 900785 A).
DISCLOSURE OF THE INVENTION
According to the process of the present invention, an allyl sulfone derivative represented by the formula (3) described below which is useful as an intermediate for producing vitamin A derivatives and the like, can be industrially and advantageously produced from a halide compound (a compound represented by the formula (8) described below) without requiring an expensive Pd catalyst and a ligand, thereby requiring no recovery step thereof.
That is, the present invention provides:
1. An allyl halide derivative represented by the formula (1):
wherein Ar is an optionally substituted aryl group, X is a halogen atom, and the corrugated line means either one of E/Z geometrical isomers or a mixture thereof;
2. A process for producing an allyl sulfone derivative represented by the formula (3):
wherein Ar and the corrugated line are as defined above, which comprises reacting an aryl sulfinic acid or a salt thereof, represented by the formula (2):
ArSO
2
M (2)
wherein Ar is as defined above, and M is hydrogen atom, sodium atom or potassium atom, with an allyl halide derivative represented by the formula (1):
wherein Ar, X and the corrugated line are as defined above; and
3. A process for producing the above allyl halide represented by the formula (1) which comprises subjecting an allyl alcohol derivative represented by the formula (5):
wherein Ar and the corrugated line are as defined above, to a halogenation reaction.
MODE FOR CARRYING OUT THE INVENTION
Detailed explanation of the present invention will be set forth hereinafter.
Ar of the compounds represented by respective formulas in the present invention is an optionally substituted aryl group. Examples of the aryl group include phenyl group, naphthyl group, and the like, and examples of the substituent thereof include a C1 to C5 straight or branched chain alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, etc.), a C1 to C5 straight or branched chain alkoxy group (methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, etc.), a halogen atom (fluorine, chlorine, bromine, iodine), nitro group, and the like. Specifically, there are phenyl, naphthyl, o-tolyl, m-tolyl, p-tolyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-bromophenyl, m-bromophenyl, p-bromophenyl, o-iodophenyl, m-iodophenyl, p-iodophenyl, o-fluorophenyl, m-fluorophenyl, p-fluorophenyl, o-nitrophenyl, m-nitrophenyl, p-nitrophenyl, and the like.
Further, the substituent X represents a halogen atom and, specifically, there are chlorine atom, bromine atom and iodine atom.
In the present invention, the allyl halide derivative (1) can be produced by reacting a halogenation agent with the allyl alcohol derivative of the above formula (5).
The halogenation agent is not specifically limited and, for example, reactive halides such as a group 4 transition metal halide, a sulfur, phosphorus or boron halide, an acid chloride, and the like can be exemplified. These halogenation agents can be reacted in the presence of a formamide compound. Of course, the halogenation reaction can be carried out in the presence of a Vilsmeyer complex formed by the above halogenation agent and a formamide compound.
As to respective halogenation agents, more detailed explanation will be set forth hereinafter.
Examples of the group 4 transition metal halide include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, dichlorotitanium diisopropoxide, chlorotitanium triisopropoxide, zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide, hafnium tetrachloride, hafnium tetrabromide, hafnium tetraiodide, and the like. Usually, the amount thereof to be used is about 0.3 to 5 mole, preferably about 1 to 3 mole per 1 mole of the ally alcohol derivative (5). Usually, a solvent is used for this reaction. Examples of such solvent include ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, anisole, etc.; hydrocarbon solvents such as n-hexane, cyclohexane, n-pentane, benzene, toluene, xylene, etc.; halogenated hydrocarbon solvents such as chloroform, dichloromethane, 1,2-dichloroethane, monochlorobenzene, o-dichlorobenzene, etc.; ketone solvents such as acetone, methyl ethyl ketone., methyl isobutyl ketone, acetylacetone, etc.; or aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, hexamethylphosphoric triamide, etc. They may be used alone or in the form of a mixed solvent of two or more thereof.
Preferably, the above halogenation reaction is carried out, for example, in the presence a coordination compound such as an ether compound inclusive the above ether solvent or a ketone compound inclusive the above ketone solvent. They may be used alone or in the form of a mixture of two or more thereof.
Examples of the coordination compound include C2 to C10 straight or branched ether compounds and ketone compounds. Specifically, as the ether compounds, there are dimethyl ether, methyl ethyl ether, diethyl ether, methyl t-butyl ether, methyl cellosolve, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, and the like; and as the ketone compounds, there are acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl t-butyl ketone, cyclopentenone, cyclohexanone, and the like.
The amount of the coordination compound to be used may be that sufficient to serve as a solvent regardless of a halogenation agent to be used and the addition of about 5 mole thereof per 1 mole of the allyl alcohol derivative (5) is sufficient. Usually, the reaction temperature can be freely selected within the range of −78° C. to the boiling point of a solvent but, preferably, within the range of about −20 to 80° C.
Examples of the sulfur, phosphorus or boron halide and the acid chloride include thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxytrichloride, phosphorus tribromide, phosphorus pentabromide, phosphorus triiodie, boron trichloride, boron tribromide, boron triiodie, phosgene, oxalyl chloride, and the like. Usually, the amount thereof to be used is about 0.3 to 5 moles, preferably, about 1 to 3 moles per 1 mole of the allyl alcohol derivative (5).
Usually, a solvent is used for this reaction. Examples of such solvent include ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, anisole, etc.; hydrocarbon solvents such as n-hexane, cyclohexane, n-pentane, benzene, toluene, xylene, etc.; halogenated hydrocarbon solvents such as chloroform, dichloromethane, 1,2-dichloroethane, monochlorobenzene, o-dichlorobenzene, etc.; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, etc.; or aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, N,N-dimethylacetamide, hexamethylphosphoric triamide, etc. The reaction temperature can be freely selected within the range of −78° C. to the boiling point of a solvent but, preferably, within the range of about −20 to 80° C.
A Vilsmeyer complex can be formed by coexisting a halogenation agent such as thionyl chloride, thionyl bromide, phosphorus trichloride,
Kakiya Hirotada
Seko Shinzo
Takahashi Toshiya
Sumitomo Chemical Company Limited
Vollano Jean F.
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