JPH10147578A - Production of n-aryl-2-oxazolidone derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound that is useful as a cocatalyst in the synthesis of a polymer material such as polyamide by reaction of an N- aryl-β-chloroethyl carbamate derivative with an inorganic base in an organic solvent. SOLUTION: The objective compound of formula II, typically N-phenyl-2- oxazolidone, is obtained in an industrial scale, by carrying out the reaction of an N-aryl-β-chloroethyl carbamate derivative of formula I [R<1> -R<5> are each H, a halogen, nitro, a (substituted) alkyl, an aryloxy] with an inorganic base of the formula: An X (A is an alkali metal; X is a carbonate group, hydrogen carbonate group; n is 1, 2) preferably potassium carbonate or sodium carbonate, preferably at a molar ratio of 1/(1.0-5.0) in an organic solvent such as acetonitrile, acetone, methyl ethyl ketone, preferably at 40-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION
N-aryl-2 such as phenyl-2-oxazolidone
The present invention relates to a process for producing oxazolidone derivatives. The N-aryl-2-oxazolidone derivative is useful as a co-catalyst when synthesizing a polymer material (particularly polyamide).

Among the target compounds obtained by the production method of the present invention, for example, 3-phenyl-2-oxazolidone is a solution of ε-caprolactam and lithium hydride as described in JP-A-50-132094. , Acts as a cocatalyst.

[0003]

2. Description of the Related Art As a conventional method for producing an N-aryl-2-oxazolidone derivative, there is the following method. 1) Journal of Organic Chemistry
(Journal of Organic Chemis
try, Vol. 36, No. 21, pp. 3071-3076,
1971) describes a method of reacting an N-aryl-β-chloroethylcarbamate derivative with sodium hydride in acetone. However, this method uses sodium hydride, which is hygroscopic and decomposable, and is industrially difficult to handle due to the generation of hydrogen during the reaction, and further requires the decomposition treatment of excess sodium halide. There was a problem that is.

[0004] 2) Bulletin of Chemical Society of Japan
medical Society of Japan, 3rd
5, No. 8, pages 1309-1312, 1962) describes a method for reacting an N-aryl-β-chloroethylcarbamate derivative with sodium ethylate in ethanol. I have. However, this method uses sodium ethylate which is industrially difficult to handle due to its corrosiveness, hygroscopicity and decomposability, and furthermore, the decomposition treatment of excess sodium ethylate Was necessary.

[0005] Therefore, any of the known techniques 1) and 2) have been unsatisfactory as an industrial production method for producing an N-aryl-2-oxazolidone derivative.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have attempted to solve the problems in the known production method by using N-aryl
As a result of intensive studies on the production method of the 2-oxazolidone derivative, the use of an alkali metal carbonate or bicarbonate as an inorganic base is convenient and requires no post-treatment, and N-
The present inventors have found that an aryl-2-oxazolidone derivative is produced, and have completed this reaction.

According to the present invention, an N-aryl-β-chloroethylcarbamate derivative and an inorganic base are dissolved in an organic solvent.
An object of the present invention is to provide a method for producing an N-aryl-2-oxazolidone derivative to be reacted.

[0008]

According to the present invention, there is provided a compound represented by the general formula (1):

[0009]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵
Are the same or different and are a hydrogen atom, a halogen group, a nitro group, a cyano group, a carboxyl group, an alkyl group which may have a substituent, an alkoxy group, an alkylcarbonyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group , An aryloxy group, an aryloxycarbonyl group, or an arylcarbonyloxy group), and an N-aryl-β-chloroethylcarbamate derivative represented by the general formula (2):

[0011]

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Wherein A represents an alkali metal, X represents a carbonate group or a hydrogen carbonate group, and n represents an integer of 1 or 2 in an organic solvent. General formula (3)

[0013]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ have the same meanings as described above)
The present invention relates to a method for producing an oxazolidone derivative.

The reaction in the production method of the present invention is, for example, the following reaction formula (1)

[0016]

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## EQU1 ##

The N-aryl-β-chloroethyl carba represented by the general formula (1) used in the production method of the present invention.
In the bamate derivative (hereinafter also referred to as compound (1)), R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may be the same or different and are a hydrogen atom, a nitro group, a cyano group, a carboxyl group, a halogen group, A linear or branched alkyl group having 1 to 10 carbon atoms which may have a group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent 1 carbon atom with a branched alkyl group
10 to 10 alkoxy groups, 1 to 10 carbon atoms which may have a substituent, 2 carbon atoms having a linear or branched alkyl group moiety
1 to 11 alkylcarbonyl groups, 1 to 10 carbon atoms which may have a substituent, and 2 carbon atoms having a linear or branched alkyl group moiety
1 to 11 alkylcarbonyloxy groups, 1 to 10 carbon atoms which may have a substituent, and 2 carbon atoms having a linear or branched alkyl group moiety
To 11 alkyloxycarbonyl groups, an aryloxy group having an aryl group portion which may have a substituent, an arylcarbonyl group having an aryl group portion which may have a substituent An arylcarbonyloxy group having an aryl group portion which may have a substituent;-(2) an aryl group having an aryl group portion which may have a substituent. -Yloxycarbonyl group.

The halogen group may be fluorine, chlorine, bromine or iodine.

Examples of the alkyl group having 1 to 10 carbon atoms which may have a substituent include an alkyl group having 1 to 10 carbon atoms which has no substituent and a substituent having Alkyl groups having 1 to 10 carbon atoms.

Unsubstituted C 1 -C 10
The alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms (particularly 1 to 5 carbon atoms), for example, a methyl group, an ethyl group, a propyl group ( Butyl group (including isomers), pentyl group (including isomers), hexyl group (including isomers), heptyl group (including isomers), octyl group (including isomers) , A nonyl group (including an isomer), a decyl group (including an isomer), and the like, preferably a methyl group, an ethyl group, a propyl group (including an isomer), and a butyl group (including an isomer). , A pentyl group (including an isomer), a hexyl group (including an isomer), a heptyl group (including an isomer), and an octyl group (including an isomer), and particularly preferably a methyl group, an ethyl group, and a propyl group. (Including isomer), butyl group (isomer Free), a pentyl group (including isomers).

The above "substituent having 1 carbon atom"
As a substituent of the `` -10 alkyl groups '', a hydroxyl group, a phenyl group, a nitro group, a carboxyl group, the above-mentioned halogen group, which may be substituted at any position of the alkyl group portion,
For example, methoxy, ethoxy, propoxy (including isomers), butoxy (including isomers), pentyloxy (including isomers), hexyloxy (including isomers), heptyloxy (including isomers) An alkoxy group having 1 to 10 carbon atoms such as an octyloxy group (including an isomer), a nonyloxy group (including an isomer), a decyloxy group (including an isomer),

C 1-5 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl (including isomers), butoxycarbonyl (including isomers), and pentoxycarbonyl (including isomers) Having 2 carbon atoms having a linear or branched alkyl group moiety of
Straight-chain having 1 to 5 carbon atoms such as alkoxycarbonyl group, acetyl group, propionyl group (including isomer), butanoyl group (including isomer), pentanoyl group (including isomer); An alkylcarbonyl group having 2 to 6 carbon atoms having a branched alkyl group portion,

Examples include an optionally substituted phenylcarbonyl group, an optionally substituted phenoxycarbonyl group, and an optionally substituted phenyl group.

Examples of the phenylcarbonyl group which may be substituted include a phenylcarbonyl group having no substituent (2) and a phenylcarbonyl group having a substituent (2). Examples of the phenoxycarbonyl group which may be substituted include a phenoxycarbonyl group having no substituent (2) and a phenoxycarbonyl group having a substituent (2).

Examples of the phenyl group which may be substituted include a phenyl group having no substituent (2) and a phenyl group having a substituent (2). ]

The substituents (2) of the phenylcarbonyl group having the substituent (2), the phenoxycarbonyl group having the substituent (2), and the phenyl group having the substituent (2) include a hydroxyl group, a phenyl group, and a nitro group. Group, carboxyl group,
Examples thereof include a phenylcarbonyl group, a phenoxycarbonyl group, the aforementioned alkoxy group, the aforementioned halogen group, the aforementioned alkylcarbonyl group, and the aforementioned alkyloxycarbonyl group.

The above-mentioned "optionally substituted alkoxy group having 1 to 10 carbon atoms and having a linear or branched alkyl group moiety having 1 to 10 carbon atoms" includes: "A carbon atom having 1 to 10 carbon atoms which has no substituent and which has a linear or branched alkyl group moiety;
10 to 10 alkoxy groups "and" 1 to 10 carbon atom alkoxy groups having a linear or branched alkyl group moiety having 1 to 10 carbon atoms having a substituent ". be able to.

"C1-C1 having no substituent"
Examples of the "alkoxy group having 1 to 10 carbon atoms having 0 straight-chain or branched alkyl group moieties" include the aforementioned alkoxy groups.

"Substituents having 1 to 10 carbon atoms
Examples of the substituent of the "alkoxy group having 1 to 10 carbon atoms having a linear or branched alkyl group portion" include the substituents of the above-mentioned alkyl group.

As the above-mentioned "optionally substituted alkylcarbonyl group having 1 to 10 carbon atoms and having a linear or branched alkyl group portion having 2 to 11 carbon atoms", , "1 to 1 carbon atoms having no substituents"
An alkylcarbonyl group having 2 to 11 carbon atoms having 10 linear or branched alkyl groups, "a linear or branched alkylcarbonyl group having 1 to 10 carbon atoms having a substituent. An alkylcarbonyl group having 2 to 11 carbon atoms having a branched alkyl group portion "can be mentioned.

"C1-C1 having no substituent"
As an alkylcarbonyl group having 2 to 11 carbon atoms having 0 linear or branched alkyl group portions,
The alkylcarbonyl group having the above-mentioned "unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms" in the alkyl group portion can be mentioned.

"Substituents having 1 to 10 carbon atoms
Examples of the substituent of the "alkylcarbonyl group having 2 to 11 carbon atoms having a linear or branched alkyl group portion" include the substituents of the aforementioned alkyl groups.

The above-mentioned “optionally substituted alkylcarbonyloxy group having 2 to 11 carbon atoms and having a linear or branched alkyl group having 1 to 10 carbon atoms” Are “unsubstituted alkylcarbonyloxy groups having 1 to 10 carbon atoms and having a linear or branched alkyl group moiety having 2 to 11 carbon atoms”; 2 carbon atoms having a linear or branched alkyl group portion having 1 to 10 carbon atoms
To 11 alkylcarbonyloxy groups ".

"C1-C1 having no substituent"
Examples of the “C 2-11 alkylcarbonyloxy group having 0 straight-chain or branched alkyl group moieties” include the aforementioned “unsubstituted carbon atom having 1 carbon atom” in the alkyl group moiety. And alkylcarbonyloxy groups having from "10 straight-chain or branched alkyl groups".

"C1-C10 having a substituent"
Examples of the substituent of the “alkylcarbonyloxy group having 2 to 11 carbon atoms having a linear or branched alkyl group portion” include the substituents of the aforementioned alkyl group.

As the above-mentioned "optionally substituted alkyloxycarbonyl group having 1 to 10 carbon atoms and having a linear or branched alkyl group portion having 2 to 11 carbon atoms". Are "unsubstituted alkyloxycarbonyl groups having 1 to 10 carbon atoms and having a linear or branched alkyl group moiety having 2 to 11 carbon atoms"; 2 carbon atoms having a linear or branched alkyl group portion having 1 to 10 carbon atoms
To 11 alkyloxycarbonyl groups ".

"C1-C1 having no substituent"
Examples of the “alkyloxycarbonyl group having 2 to 11 carbon atoms having 0 linear or branched alkyl group portions” include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group (including isomers) , Butoxycarbonyl group (including isomer), pentyloxycarbonyl group (including isomer), hexyloxycarbonyl group (including isomer), heptyloxycarbonyl group (including isomer), octyloxycarbonyl group (including isomer) And a nonyloxycarbonyl group (including isomers) and an alkyloxycarbonyl group having 2 to 11 carbon atoms such as a decyloxycarbonyl group (including isomers). 2 carbon atoms
It is six alkoxycarbonyl groups, particularly preferably a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group (including isomers).

"Substituents having 1 to 10 carbon atoms
Examples of the substituent of the "alkyloxycarbonyl group having 2 to 11 carbon atoms having a linear or branched alkyl group portion" include the substituents of the aforementioned alkyl group.

The above-mentioned "aryloxy group having an aryl group portion which may have a substituent" includes "an aryloxy group having an aryl group portion having no substituent". And an "aryloxy group having an aryl group portion having a substituent".

Examples of the aryl group in the "aryloxy group having an aryl group portion having no substituent" include a phenyl group, a naphthyl group and an anthryl group. Group, a naphthyl group,
Particularly preferred is a phenyl group.

The substituent of the "aryloxy group having an aryl group having a substituent" is a substituent of the above-mentioned alkyl group which may be substituted at any position of the aryl group. Substituents can be mentioned.

The above-mentioned "arylcarbonyl group having an aryl group portion which may have a substituent" includes:
An "arylcarbonyl group having an aryl group portion having no substituent" and an "arylcarbonyl group having an aryl group portion having a substituent" can be given.

As the substituent of the "arylcarbonyl group having an aryl group part having a substituent", the alkyl group which may be substituted at any position of the aryl group part Can be mentioned.

The above-mentioned "(1)" arylcarbonyloxy group having an aryl group part which may have a substituent "
As an "arylcarbonyloxy group having an aryl group portion having no substituent"; and an "arylcarbonyloxy group having an aryl group portion having a substituent".
Can be mentioned.

As the substituent of the "arylcarbonyloxy group having an aryl group part having a substituent", the above-mentioned alkyl, which may be substituted at any position of the aryl group part, may be used. Substituents of groups can be mentioned.

The above-mentioned "(2) aryloxycarbonyl group having an aryl group part which may have a substituent"
As an "aryloxycarbonyl group having an aryl group portion having no substituent"; and an "aryloxycarbonyl group having an aryl group portion having a substituent".
Can be mentioned.

As the substituent of the "aryloxycarbonyl group having an aryl group part having a substituent", the above-mentioned alkyl which may be substituted at any position of the aryl group part Substituents of groups can be mentioned.

R ¹ , R ² , R ³ , R ⁴ , R
⁵ is the same or different, preferably a hydrogen atom, a carboxyl group, a nitro group, an alkyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a halogen group, an alkoxy group, a phenoxy group,
Particularly preferably, a hydrogen atom, a carboxyl group, a nitro group,
Alkyl group, alkyloxycarbonyl group, cyano group,
A halogen group and an alkoxy group.

The N-aryl-β-chloroethyl carbamate derivatives represented by the general formula (1) used in the production method of the present invention include, for example, N-phenyl-β-chloroethyl carbamate, N- (p -Carboxyphenyl) -β
-Chloroethyl carbamate, N- (o-carboxyphenyl) -β-chloroethyl carbamate, N- (p-
Nitrophenyl) -β-chloroethylcarbamate, N
-(O-nitrophenyl) -β-chloroethylcarbamate, N- (p-methylphenyl) -β-chloroethylcarbamate, N- (o-methylphenyl) -β-chloroethylcarbamate, N- (p-ethyl Phenyl)-
β-chloroethyl carbamate, N- (o-ethylphenyl) -β-chloroethyl carbamate, N- (p-methoxycarbonylphenyl) -β-chloroethyl carbamate,

N- (p-ethoxycarbonylphenyl)
-Β-chloroethylcarbamate, N- (p-phenoxycarbonylphenyl) -β-chloroethylcarbamate, N- (o-methoxycarbonylphenyl) -β-chloroethylcarbamate, N- (o-ethoxycarbonylphenyl) -β -Chloroethyl carbamate, N-
(O-phenoxycarbonylphenyl) -β-chloroethylcarbamate, N- (p-cyanophenyl) -β-
Chloroethyl carbamate, N- (o-cyanophenyl) -β-chloroethyl carbamate, N- (p-chlorophenyl) -β-chloroethyl carbamate, N-
(P-bromophenyl) -β-chloroethyl carbamate, N- (p-iodophenyl) -β-chloroethyl carbamate,

N- (o-chlorophenyl) -β-chloroethylcarbamate, N- (o-bromophenyl) -β
-Chloroethyl carbamate, N- (o-iodophenyl) -β-chloroethyl carbamate, N- (p-methoxyphenyl) -β-chloroethyl carbamate, N-
(P-ethoxyphenyl) -β-chloroethylcarbamate, N- (o-methoxyphenyl) -β-chloroethylcarbamate, N- (o-ethoxyphenyl) -β-
Chloroethyl carbamate, N- (p-phenoxyphenyl) -β-chloroethyl carbamate, N- (o-phenoxyphenyl) -β-chloroethyl carbamate can be mentioned,

Preferably, N-phenyl-β-chloroethylcarbamate, N- (p-carboxyphenyl) -β
-Chloroethyl carbamate, N- (p-nitrophenyl) -β-chloroethyl carbamate, N- (p-methylphenyl) -β-chloroethyl carbamate, N-
(P-ethylphenyl) -β-chloroethylcarbamate, N- (o-methylphenyl) -β-chloroethylcarbamate, N- (o-ethylphenyl) -β-chloroethylcarbamate,

N- (p-methoxycarbonylphenyl)
-Β-chloroethylcarbamate, N- (p-ethoxycarbonylphenyl) -β-chloroethylcarbamate, N- (p-phenoxycarbonylphenyl) -β-
Chloroethyl carbamate, N- (p-cyanophenyl) -β-chloroethyl carbamate, N- (p-chlorophenyl) -β-chloroethyl carbamate, N-
(P-bromophenyl) -β-chloroethylcarbamate, N- (p-methoxyphenyl) -β-chloroethylcarbamate, N- (p-ethoxyphenyl) -β-chloroethylcarbamate, N- (p-phenoxyphenyl ) -Β-chloroethylcarbamate;

Particularly preferred are N-phenyl-β-chloroethylcarbamate, N- (p-carboxyphenyl)
-Β-chloroethyl carbamate, N- (p-nitrophenyl) -β-chloroethyl carbamate, N- (o-
Methylphenyl) -β-chloroethylcarbamate, N
-(O-ethylphenyl) -β-chloroethylcarbamate, N- (p-methoxycarbonylphenyl) -β-
Chloroethyl carbamate, N- (p-ethoxycarbonylphenyl) -β-chloroethyl carbamate, N-
(P-cyanophenyl) -β-chloroethylcarbamate and N- (p-chlorophenyl) -β-chloroethylcarbamate.

The N-aryl-β-chloroethylcarbamate derivative represented by the general formula (1) used in the production method of the present invention is, for example, Bulletin of Chemical Society of Japan (Bulletin of Chem.).
Ial Societyof Japan, 35th
Vol. 8, No. 1, pp. 1309-1312, 1962), by reacting β-chloroethylchloroformate with the corresponding aniline derivative,
It is derived by reacting chloroethanol with the corresponding phenyl isocyanate derivative. Further details will be described in a reference example.

The inorganic base A represented by the general formula (2) used in the production method of the present invention includes, for example, alkali metals such as lithium, sodium and potassium, and is preferably potassium or sodium. is there.

X of the inorganic base represented by the general formula (2) used in the production method of the present invention includes, for example, a hydrogen carbonate group and a carbonate group, and is preferably a carbonate group.

The n of the inorganic base represented by the general formula (2) used in the production method of the present invention can be, for example, an integer of 1 or 2, and is preferably 2.

Examples of such inorganic bases represented by A, n, and X include potassium carbonate, sodium carbonate, lithium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate. Sodium carbonate.

The amount of the inorganic base represented by the general formula (2) used in the production method of the present invention is usually 0.8 to 10 mol per 1 mol of the compound (1). Is particularly preferable, and an amount that gives a ratio of 1.0 to 5.0 mol is particularly preferable.

The organic solvent used in the production method of the present invention is not particularly limited as long as it does not participate in the reaction. For example, nitrile organic solvents such as acetonitrile and benzonitrile, N, N-dimethylformamide,
N, N-dimethylacetamide, N-methylpyridone,
Amide polar organic solvents such as dimethylimidazolidone,
Ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol
And aliphatic alcohol-based organic solvents such as n-propanol, isopropanol and butanol, preferably a nitrile-based organic solvent and a ketone-based organic solvent, and particularly preferably acetonitrile. , Acetone and methyl ethyl ketone.

The amount of the organic solvent used in the production method of the present invention is usually 0.01 to 0.9 times the amount of the compound (1) [normal compound (1) weight / volume of the organic solvent]. The ratio is preferably an amount which is 0.05 to 0.4 times [normal compound (1) weight / volume of organic solvent]. The reaction temperature in the production method of the present invention may be a temperature up to the boiling point of a commonly used organic polar solvent, but is preferably in the range of 0 to 200 ° C, particularly preferably in the range of 40 to 100 ° C.

The reaction time in the production method of the present invention is significantly affected by the reaction temperature, but the reaction is usually completed in 20 hours.

The N-aryl-2-oxazolidone derivative of the target compound represented by the general formula (3) obtained by the above-mentioned production method of the present invention is a compound of the formula (1)
-Defined by aryl-β-chloroethyl carbamate derivatives. Examples of the N-aryl-2-oxazolidone derivatives of the target compound include N-phenyl-2-oxazolidone, N- (p-carboxyphenyl) -2-oxazolidone, and N- (o-carboxyphenyl)- 2-oxazolidone, N- (p-nitrophenyl) -2-oxazolidone, N- (o-nitrophenyl) -2-oxazolidone, N- (p-methylphenyl) -2-oxazolidone, N- (p-ethylphenyl ) -2-oxazolidone, N- (o-methylphenyl) -2-oxazolidone, N- (o-ethylphenyl) -2-oxazolidone, N- (p-methoxycarbonylphenyl) -2-oxazolidone,

N- (p-ethoxycarbonylphenyl)
-2-oxazolidone, N- (p-phenoxycarbonylphenyl) -2-oxazolidone, N- (o-methoxycarbonylphenyl) -2-oxazolidone, N-
(O-ethoxycarbonylphenyl) -2-oxazolidone, N- (o-phenoxycarbonylphenyl) -2
-Oxazolidone, N- (p-cyanophenyl) -2-
Oxazolidone, N- (o-cyanophenyl) -2-oxazolidone, N- (p-chlorophenyl) -2-oxazolidone, N- (p-bromophenyl) -2-oxazolidone,

N- (p-iodophenyl) -2-oxazolidone, N- (o-chlorophenyl) -2-oxazolidone, N- (o-bromophenyl) -2-oxazolidone, N- (o-iodophenyl) ) -2-oxazolidone, N- (p-methoxyphenyl) -2-oxazolidone, N- (p-ethoxyphenyl) -2-oxazolidone, N- (o-methoxyphenyl) -2-oxazolidone, N- (o- Ethoxyphenyl) -2-oxazolidone, N- (p-phenoxyphenyl) -2-oxazolidone, N- (o-phenoxyphenyl) -2-oxazolidone;

Preferably, N-phenyl-2-oxazolidone, N- (p-carboxyphenyl) -2-oxazolidone, N- (p-nitrophenyl) -2-oxazolidone, N- (p-methylphenyl) -2 -Oxazolidone, N- (p-ethylphenyl) -2-oxazolidone, N- (o-methylphenyl) -2-oxazolidone, N- (o-ethylphenyl) -2-oxazolidone, N- (p-methoxycarbonylphenyl) ) -2-oxazolidone;

N- (p-ethoxycarbonylphenyl)
-2-oxazolidone, N- (p-phenoxycarbonylphenyl) -2-oxazolidone, N- (p-cyanophenyl) -2-oxazolidone, N- (p-chlorophenyl) -2-oxazolidone, N- (p-bromo Phenyl) -2-oxazolidone, N- (p-methoxyphenyl) -2-oxazolidone, N- (p-ethoxyphenyl) -2-oxazolidone, N- (p-phenoxyphenyl) -2-oxazolidone;

Particularly preferably, N-phenyl-2-oxazolidone, N- (p-carboxyphenyl) -2-oxazolidone, N- (p-nitrophenyl) -2-oxazolidone, N- (o-methylphenyl) -2 -Oxazolidone, N- (o-ethylphenyl) -2-oxazolidone, N- (p-methoxycarbonylphenyl) -2-
Oxazolidone,

N- (p-ethoxycarbonylphenyl)
-2-oxazolidone, N- (p-phenoxycarbonylphenyl) -2-oxazolidone, N- (p-cyanophenyl) -2-oxazolidone, N- (p-chlorophenyl) -2-oxazolidone.

In the production method of the present invention, a method of obtaining a reaction mixture containing the produced N-aryl-2-oxazolidone derivative may be performed by a combination of ordinary washing operation and separation operation. After adding a solvent and filtering off an insoluble inorganic salt or removing an inorganic base by washing with water or the like, a crude product is obtained by solvent extraction and concentration under reduced pressure. In the case of further purification, purification may be performed by, for example, column chromatography or the like, and a purification method may be appropriately selected for each compound.

[0073]

According to the present invention, according to the general formula (1),
If the aryl-β-chloroethylcarbamate derivative is reacted with an inorganic base of the general formula (2) in an organic solvent, the handling is convenient and N-aryl-2 is unnecessary without post-treatment.
-Oxazolidone derivatives can be produced.

[0074]

EXAMPLES Examples and reference examples are shown below.

Example 1 150 g of N- (p-methoxycarbonylphenyl) -β-chloroethylcarbamate
(0.58 mol) and 88.2 g of potassium carbonate (0.6
4 mol) was suspended in 577 ml of acetonitrile, and the resulting acetonitrile suspension was reacted by stirring at 70 ° C. for 6 hours.

The resulting reaction solution was filtered while hot, and the obtained filtrate was concentrated under reduced pressure to obtain 128 g of colorless needle-like 3- (p-methoxycarbonylphenyl) -2-oxazolidone.
(0.58 mol). [Yield based on N- (p-methoxycarbonylphenyl) -β-chloroethylcarbamate: 99.4%] Melting point: 140-141 ° C. ¹ H-NMR (CDCl ₃ ) δ = 3.89 (s, 3); 4.08 (dd, 2);
52 (dd, 2), 7.62 (d, 2), 8.05
(D, 2)

Example 2 Instead of acetonitrile, 557 ml of acetone was used, and the amount of potassium carbonate used was changed to 120.2 g (0.87 g).
Mol) in the same manner as in Example 1, except that 3- (p-methoxycarbonylphenyl) -2-oxazolidone 12
4 g (0.56 mol) were obtained. [Yield based on N- (p-methoxycarbonylphenyl) -β-chloroethylcarbamate: 97%]

Example 3 In the same manner as in Example 2 except that the amount of acetone used was changed to 1744 ml, 123 g (0.56 mol) of 3- (p-methoxycarbonylphenyl) -2-oxazolidone was obtained. [Yield for N- (p-methoxycarbonylphenyl) -β-chloroethylcarbamate: 9
7%]

Example 4 3- (p-methoxycarbonylphenyl) -2-oxazolidone 12 was prepared in the same manner as in Example 2 except that potassium carbonate was replaced with 92.2 g (0.87 mol) of sodium carbonate.
6 g (0.57 mol) were obtained. [Yield based on N- (p-methoxycarbonylphenyl) -β-chloroethylcarbamate: 98%]

Example 5 123 g of 3- (p-methoxycarbonylphenyl) -2-oxazolidone (0.5 g) was prepared in the same manner as in Example 1 except that acetonitrile was replaced with 577 ml of acetone.
6 mol). [Y-N- (p-methoxycarbonylphenyl) -β-chloroethylcarbamate yield:
97%]

Example 6 3- (p-methoxycarbonylphenyl) -2-oxazolidone 123 was prepared in the same manner as in Example 1, except that 577 ml of methyl ethyl ketone was used instead of acetonitrile.
g (0.56 mol) were obtained. [Yield based on N- (p-methoxycarbonylphenyl) -β-chloroethylcarbamate: 97%]

Example 7 158 g (0.58 mol) of N- (p-ethoxycarbonylphenyl) -β-chloroethylcarbamate and 120.2 g (0.87 mol) of potassium carbonate were added to acetone 57
The suspension was suspended in 7 ml, and the obtained acetone suspension solution was stirred at 70 ° C. for 5 hours to react.

The resulting reaction solution was filtered while hot, and the obtained filtrate was concentrated under reduced pressure to give 135 g of colorless needle-like 3- (p-ethoxycarbonylphenyl) -2-oxazolidone.
(0.57 mol). [Yield for N- (p-ethoxycarbonylphenyl) -β-chloroethylcarbamate: 98%] Melting point: 109-110 ° C ¹ H-NMR (CDCl ₃ ) δ = 1.97 (t, 3); 38 to 1.62 (m,
2) 1.70 to 1.82 (m, 2), 4.10 (d
d, 2), 4.31 (t, 2), 4.52 (dd,
2), 7.62 (d, 2), 8.05 (d, 2)

Example 8 116 g of N-phenyl-β-chloroethylcarbamate
(0.58 mol) and 120.2 g (0.8
7 mol) was suspended in 577 ml of acetone, and the resulting acetone suspension was stirred at 70 ° C. for 3 hours to react. The obtained reaction solution was filtered while hot, and the obtained filtrate was concentrated under reduced pressure to obtain 94.5 g (0.58 mol) of 3-phenyl-2-oxazolidone as a colorless needle. (Yield for N-phenyl-β-chloroethylcarbamate:
99.7%) Boiling point: 160 ° C./5 mmHg

Example 9 N- (p-nitrophenyl) -β-chloroethyl carbamate 142.4 g (0.58 mol) and potassium carbonate 1
20.2 g (0.87 mol) were suspended in 577 ml of acetone, and the resulting acetone suspension was stirred at 70 ° C. for 7 hours to react.

The obtained reaction solution was filtered while hot, and the obtained filtrate was concentrated under reduced pressure to obtain 117 g (0.56 mol) of 3- (p-nitrophenyl) -2-oxazolidone as colorless needles.
I got [Yield against N- (p-nitrophenyl) -β-chloroethylcarbamate: 97%) Melting point: 117-118 ° C

Example 10 N- (o-methylphenyl) -β-chloroethyl carbamate 124.4 g (0.58 mol) and potassium carbonate 1
20.2 g (0.87 mol) were suspended in 577 ml of acetone, and the resulting acetone suspension was stirred at 70 ° C. for 2 hours to react.

The resulting reaction solution was filtered while hot, and the obtained filtrate was concentrated under reduced pressure to obtain 102 g (0.58 mol) of 3- (o-methylphenyl) -2-oxazolidone as colorless needles.
I got [Yield of N- (o-methylphenyl) -β-chloroethylcarbamate: 99%] Melting point: 44 to 45 ° C

REFERENCE EXAMPLE 1 90.7 g (0.6 mol) of methyl p-aminobenzoate and 94.4 g of β-chloroethylchloroformate (0.
66 mol) in 600 ml of toluene,
The obtained toluene solution was refluxed for 1.5 hours to react. The obtained reaction solution was cooled to room temperature (20 ° C.) and filtered, and the collected matter was dried under reduced pressure to give N- (p-
Methoxycarbonylphenyl) -β-chloroethylca
152 g (0.59 mol) of bamate were obtained. (Yield based on methyl p-aminobenzoate: 98%)

Example 11 1.41 g (5.79 mmol) of N- (p-phenoxycarbonylphenyl) -β-chloroethylcarbamate
And 0.88 g (6.40 mmol) of potassium carbonate were suspended in 6 ml of acetonitrile, and the resulting acetonitrile suspension was stirred and reacted at 60 ° C. for 6 hours.

The obtained reaction solution was filtered while hot, and the obtained filtrate was concentrated under reduced pressure to give 3- (p-phenoxycarbonylphenyl) -2-oxazolidone 1.41 as a colorless powder.
g (4.98 mmol) were obtained. [Yield for N- (p-phenoxycarbonylphenyl) -β-chloroethylcarbamate = 86.2%) ¹ H-NMR (CDCl ₃ ) δ = 4.09 (dd, 2), 4.52 (dd, 2),
7.05 to 7.48 (m, 5), 8.05 (d, 2)

Example 12 1.41 g (5.79 mmol) of N- (p-carboxyphenyl) -β-chloroethylcarbamate and 0.88 g (6.40 mmol) of potassium carbonate were mixed with N, N-dimethylformamide 4 The suspension was suspended in milliliters, and the obtained N, N-dimethylformamide suspension was reacted by stirring at 60 ° C. for 6 hours.

The obtained reaction solution was filtered while hot, the filtrate was concentrated under reduced pressure, and the obtained residue was separated and purified by silica gel chromatography (separation liquid; ethyl acetate: methanol = 10: 1). The obtained separated solution was concentrated under reduced pressure to obtain 0.86 g (4.15 mmol) of 3- (p-carboxyphenyl) -2-oxazolidone as a colorless powder. [N-
(P-carboxyphenyl) -β-chloroethyl carbamate yield = 71.6%) ¹ H-NMR (CDCl ₃ ) δ = 4.10 (dd, 2), 4.47 (dd, 2),
7.66 (d, 2), 7.98 (d, 2), 12.70
~ 12.95 (br, 1)

Example 13 7.87 g (35.0 mmol) of N- (p-cyanophenyl) -β-chloroethylcarbamate and 7.26 g (52.6 mmol) of potassium carbonate were suspended in 30 ml of methyl ethyl ketone. The resulting methyl ethyl ketone suspension was refluxed for 6 hours to react.

The obtained reaction solution was filtered while hot, and the filtrate was concentrated under reduced pressure to give 3- (p-cyanophenyl)-colorless powder.
4.83 g (25.9 mmol) of 2-oxazolidone were obtained. [Yield based on N- (p-cyanophenyl) -β-chloroethylcarbamate = 74.0%) Melting point: 146 to 148 ° C. ¹ H-NMR (CDCl ₃ ) δ = 4.09 (dd, 2), 4 .53 (dd, 2),
7.45 to 7.81 (m, 4)

Example 14 8.20 g (35.0 mmol) of N- (p-chlorophenyl) -β-chloroethylcarbamate and 7.26 g (52.6 mmol) of potassium carbonate were suspended in 30 ml of methyl ethyl ketone. The obtained methyl ethyl ketone suspension was refluxed for 6 hours to react.

The resulting reaction solution was filtered while hot, and the filtrate was concentrated under reduced pressure to give 3- (p-chlorophenyl)-as a colorless powder.
6.15 g (31.1 mmol) of 2-oxazolidone were obtained. [Yield for N- (p-chlorophenyl) -β-chloroethylcarbamate = 88.9%) Melting point: 120-121 ° C.

Preferred embodiments of the present invention are as follows. 1. General formula (1)

[0099]

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(Wherein R ¹ is hydrogen, halogen, nitro, cyano, carboxyl, alkyl, alkoxy, alkylcarbonyl, alkyloxycarbonyl, alkylcarbonyloxy, aryloxy, aryl) An aryloxycarbonyl group or an arylcarbonyloxy group, wherein R ² , R ³ , R ⁴ and R ⁵ represent hydrogen) and an N-aryl-β-chloroethylcarbamate derivative represented by the general formula: Equation (2)

[0101]

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(Wherein, A represents an alkali metal, X represents a carbonate group or a hydrogen carbonate group, and n represents an integer of 1 or 2) in an organic solvent. General formula (3)

[0103]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , and R ⁵ have the same meanings as described above)
A method for producing an oxazolidone derivative.

2. In the general formula (1), R ¹ is hydrogen,
Nitro group, cyano group, carboxyl group, alkyl group, alkoxy group, alkyloxycarbonyl group, aryloxycarbonyl group, phenoxy group, halogen group,
^2. The method according to the above 1, wherein R ² , R ³ , R ⁴ and R ⁵ are hydrogen.

3. In the general formula (1), R ¹ is hydrogen,
^2. The method according to the above 1, wherein the nitro group, cyano group, carboxyl group, alkyl group, alkoxy group, alkyloxycarbonyl group, and halogen group, and R ² , R ³ , R ⁴ , and R ⁵ are hydrogen.

4. In the general formula (2), A represents an alkali metal, X represents a carbonate group, and n is an inorganic base showing an integer of 2.

5. In the general formula (2), A represents potassium or sodium, X represents a carbonate group, and n is an inorganic base represented by an integer of 2.

6. 3. In the general formula (2), A represents an alkali metal, X represents a carbonate group, and n is an inorganic base showing an integer of 2.

7. In the general formula (2), A represents an alkali metal, X represents a carbonate group, and n is an inorganic base showing an integer of 2.

8. In the general formula (2), A represents potassium or sodium, X represents a carbonate group, and n is an inorganic base showing an integer of 2.

9. In the general formula (2), A represents potassium or sodium, X represents a carbonate group, and n is an inorganic base showing an integer of 2.

Continuation of the front page (72) Inventor Mizuho Oda 5 in 1978 Kogushi, Ube-shi, Yamaguchi Ube Kosan Co., Ltd. Ube Laboratory

Claims (1)

[Claims] 1. A compound of the general formula (1) (In the formula, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same or different and each represents a hydrogen atom, a halogen group, a nitro group, a cyano group, a carboxyl group, or an alkyl which may have a substituent. Group, alkoxy group, alkylcarbonyl group, alkyloxycarbonyl group, alkylcarbonyloxy group, aryloxy group, aryloxycarbonyl group, aryl-
An N-aryl-β-chloroethylcarbamate derivative represented by the formula (2): (Wherein A represents an alkali metal, X represents a carbonate group or a hydrogen carbonate group, and n represents an integer of 1 or 2) with an inorganic base represented by the following general formula: (3) (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above). [0001]