JP2003321471A - Lactam compound and method of production for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lactam compound useful as a colorless dye and to provide a method for producing the lactam in a mild condition with a high generality. <P>SOLUTION: The lactam compound expressed by general formula (1) and method of production for the same. (R<SP>1</SP>, R<SP>2</SP>are each H, an alkyl or an aryl excluding H in the same time. R<SP>3</SP>is H, an alkyl, an alkoxy, an aryloxy or -NHCOR<SP>7</SP>, R<SP>7</SP>is an alkyl or an aryl, R<SP>4</SP>, R<SP>5</SP>are each H, an alkyl or an aryl, R<SP>6</SP>is H, an alkyl, an aryl, a heterocyclic ring, -COR<SP>8</SP>, -SO<SB>2</SB>R<SP>9</SP>or CSR<SP>10</SP>, R<SP>8</SP>-R<SP>10</SP>are an alkyl, an aryl, a heterocyclic ring, an alkylamino, an arylamino, an alkoxy or an aryloxy, Y<SP>1</SP>, Y<SP>2</SP>, Y<SP>3</SP>or Y<SP>4</SP>are each CH or each of either one or two of Y<SP>1</SP>, Y<SP>2</SP>, Y<SP>3</SP>or Y<SP>4</SP>is N and the rest is CH.). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel lactam compound and a method for producing the same. The lactam compound of the present invention is useful as a recording material using an electron-donating colorless dye and an electron-accepting compound, particularly as an electron-donating colorless dye for a recording material such as a pressure-sensitive recording material and a heat-sensitive recording material.

[0002]

2. Description of the Related Art Conventionally, electron-donating colorless dyes have been variously studied because they are useful as recording materials such as heat-sensitive paper, pressure-sensitive paper, light-sensitive pressure-sensitive paper, heat-sensitive recording paper, and heat-sensitive transfer paper. For example, British Patent No. 2,140,449, U.S. Patent Nos. 4,480,052, 4,436,920, JP-B-60-23992, and JP-A-57-179836,
For details, see Nos. 60-123556 and 60-123557. However, among the electron-donating colorless dyes used in these, most of those exhibiting blue to cyan colors are triarylmethane type dyes, and various production methods have been reported. For example, JP-A-8-337727, JP-A-10-338686, JP-A-8-276654, JP-A-8-313355, and JP-A-8-313356,
The details are described in JP-A-8-31357 and JP-A-9-31345. However, at present, these are phthalide type dyes and lactam type dyes are not well known. Further, among the methods for producing a lactam compound of an electron-donating colorless dye, a method for producing a phthalide compound and an aniline by heating is already known in German Patent DE81958 and the like, but this method requires heating, and There is a problem that only aniline derivatives can be produced.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel lactam compound which is useful as an electron-donating colorless dye, and a method for producing a lactam compound which has mild reaction conditions and is highly versatile. To do.

[0004]

The above-mentioned object has been achieved by the present invention described below. That is, the present invention is <1> a lactam compound represented by the following general formula (1).

[0005]

[Chemical 5]

(In the general formula (1), R¹, R²Each is German
It represents a hydrogen atom, an alkyl group, or an aryl group.
However, R¹And R²Does not represent a hydrogen atom at the same time. R
³Is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group
A xy group or -NHCOR ⁷Represents a group, R⁷Is alkyl
Represents a group or an aryl group. R^Four, R^FiveAre independent
Represents a hydrogen atom, an alkyl group, or an aryl group. R
⁶Is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
COR⁸Group, -SO₂R⁹Group, or -CSR^TenTable
And R⁸, R⁹, R^TenIs an alkyl group, aryl group, heterocycle
Group, alkylamino group, arylamino group, alkoxy
Represents a group or an aryloxy group. Y¹, Y², Y³，
Y^FourAre all CH or Y¹, Y², Y³, Y
^FourAny one or two of them represents N and the other represents CH.
You )

<2> The lactam compound according to <1>, wherein the lactam compound represented by the general formula (1) is a lactam compound represented by the following general formula (2).

[0008]

[Chemical 6]

(In the general formula (2), R¹, R²Each is German
It represents a hydrogen atom, an alkyl group, or an aryl group.
However, R¹And R²Does not represent a hydrogen atom at the same time. R
³Is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group
A xy group or -NHCOR ⁷Represents a group, R⁷Is alkyl
Represents a group or an aryl group. R^Four, R^FiveAre independent
Represents a hydrogen atom, an alkyl group, or an aryl group. R
⁶Is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
COR⁸Group, -SO₂R⁹Group, or -CSR^TenTable
And R⁸, R⁹, R^TenIs an alkyl group, aryl group, heterocycle
Group, alkylamino group, arylamino group, alkoxy
Group or an aryloxy group)

<3> An indylphthalide compound represented by the following general formula (3) is reacted with a halogenating agent to produce an acid halide represented by the following general formula (5) as an intermediate. Further, the acid halide represented by the general formula (4) is reacted with an amine compound represented by the following general formula (6) to obtain a lactam compound represented by the general formula (1). A method for producing a characteristic lactam compound.

[0011]

[Chemical 7]

(In the general formula (3) and the general formula (4), R
¹, R²Are each independently a hydrogen atom, an alkyl group, or
Represents an aryl group. However, R¹And R²At the same time hydrogen atom
There is no representation. R³Is a hydrogen atom, an alkyl group, an alcohol
An oxy group, an aryloxy group, or -NHCOR⁷Base
Represent, R⁷Represents an alkyl group or an aryl group.
R ^Four, R^FiveAre each independently a hydrogen atom, an alkyl group, or
Represents an aryl group. Y¹, Y², Y³, Y^FourIs all CH
Or Y¹, Y², Y³, Y^FourAny one of the young
More specifically, two represent N and the other represent CH. Also the general formula
In (4), X represents a halogen atom. In the general formula (5),
R⁶Is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
-COR⁸Group, -SO₂R⁹Group, or -CSR^TenTable
And R⁸, R⁹, R^TenIs an alkyl group, aryl group, heterocycle
Group, alkylamino group, arylamino group, alkoxy
Represents a group or an aryloxy group. )

<4> The method for producing a lactam compound according to <3>, wherein the halogenating agent is oxalyl chloride.

<5> An acid halide represented by the general formula (4) is produced in the presence of an acid <3>
Alternatively, it is the method for producing a lactam compound according to <4>.

<6> The method for producing a lactam compound according to <5>, wherein the acid is any one of methanesulfonic acid, toluenesulfonic acid and benzenesulfonic acid.

<7> A lactam compound represented by the following general formula (6) is reacted with an electrophile to obtain a lactam compound represented by the above general formula (1). It is a manufacturing method.

[0017]

[Chemical 8]

(In the general formula (6), R¹, R²Each is German
It represents a hydrogen atom, an alkyl group, or an aryl group.
However, R¹And R²Does not represent a hydrogen atom at the same time. R
³Is a hydrogen atom, an alkyl group, an alkoxy group, an aryl group
A xy group or -NHCOR ⁷Represents a group, R⁷Is alkyl
Represents a group or an aryl group. R^Four, R^FiveAre independent
Represents a hydrogen atom, an alkyl group, or an aryl group. Y
¹, Y², Y³, Y^FourAre all CH, or
Y¹, Y², Y³, Y^FourEither one or two of them represents N
And the other represents CH. )

<8> The method for producing a lactam compound according to <7>, wherein the electrophile is any one of acid halide, sulfonyl halide, isocyanate and thioisocyanate.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The lactam compound of the present invention is a lactam compound represented by the following general formula (1).

[0021]

[Chemical 9]

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group. However, R ¹ and R ² do not represent hydrogen atoms at the same time. R ³
Represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, or a —NHCOR ⁷ group, and R ⁷ represents an alkyl group or an aryl group. R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group, or an aryl group. R
⁶ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,-
Represents a COR ⁸ group, a —SO ₂ R ⁹ group, or a —CSR ¹⁰ group, wherein R ⁸ , R ⁹ and R ¹⁰ are an alkyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group, an alkoxy group, or Represents an aryloxy group. Y ¹ , Y ² , Y ³ ,
Y ⁴ all represent CH, or Y ¹ , Y ² , Y ³ , Y
Any one or two of ⁴ represents N and the other represents CH.

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and among them, an alkyl group having 1 to 18 carbon atoms and a carbon number 6
The aryl group having 20 to 20 carbon atoms is preferable, and the alkyl group having 1 to 12 carbon atoms and the aryl group having 6 to 12 carbon atoms are more preferable.
The alkyl group represented by R ¹ and R ² also includes a cycloalkyl group corresponding to a cyclic alkyl group and an aralkyl group corresponding to an alkyl group having a substituent. As the cycloalkyl group, a cycloalkyl group having 4 to 12 carbon atoms is preferable, and a cycloalkyl group having 5 to 6 carbon atoms is more preferable. The aralkyl group has 7 to 7 carbon atoms.
An aralkyl group having 18 carbon atoms is preferable, and an aralkyl group having 7 to 12 carbon atoms is more preferable. R ¹ and R ² are each an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a halogen atom, or the like. It may be substituted.
However, R ¹ and R ² do not represent hydrogen atoms at the same time.

Specific examples of R ¹ and R ² in the general formula (1) include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and sec-butyl group. , N-pentyl group, i-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group, benzyl group, 2-phenethyl group , 1-phenethyl group, phenyl group, p-tolyl group, p-methoxyphenyl group, p-chlorophenyl group, 2-methoxyethyl group, 2- (2-methoxyethoxy) ethyl group, 2-phenoxyethyl group, 2- Examples thereof include a phenoxypropyl group and a 3-phenoxypropyl group.

R ¹ and R ² in the general formula (1) may be bonded to each other to form a cyclic amino structure, and specific examples of the cyclic amino include a 1-pyrrolidinyl group, a piperidinino group,
A morpholino group etc. are mentioned.

In the general formula (1), R ³ is a hydrogen atom,
It represents an alkyl group, an alkoxy group, an aryloxy group, or a —NHCOR ⁷ group, and R ⁷ represents an alkyl group or an aryl group. When R ³ represents a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group, it has 1 to 1 carbon atoms.
An alkyl group having 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms are preferable, and 1 carbon atom.
~ 12 alkyl groups, C 1-12 alkoxy groups,
An aryloxy group having 6 to 18 carbon atoms is more preferable. These may be further substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a halogen atom or the like. . On the other hand, in the general formula (1), R ³
Represents an —NHCOR ⁷ group, R ⁷ is preferably an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms,
Preferably, an alkyl group having 1 to 12 carbon atoms, 6 to 1 carbon atoms
An aryl group of 0 is more preferred. R ⁷ is further substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a halogen atom or the like. Good.

Specific examples of R ³ in the general formula (1) include methyl group, ethyl group, i-propyl group, n-butyl group, n-hexyl group, octyl group, 2-ethylhexyl group and n-decyl group. , N-dodecyl group, cyclohexyl group, benzyl group, 2-phenethyl group, phenyl group, p-
Tolyl group, p-methoxyphenyl group, p-chlorophenyl group, 2-methoxyphenyl group, p-bromophenyl group, p-nitrophenyl group, 2-nitrophenyl group,
2,5-dimethoxyphenyl group, 2-methoxyethoxy-5-ethylphenyl group, methoxy group, ethoxy group, n
-Propyloxy group, I-propyloxy group, n-butoxy group, hexyloxy group, 2-ethylhexyloxy group, n-decyloxy group, phenoxy group, p-tolyloxy group, p-methoxyphenoxy group, p-chlorophenoxy group , 2-methoxyphenoxy group, p-bromophenoxy group, p-nitrophenoxy group, 2-nitrophenoxy group, 2,5-dimethoxyphenoxy group, 2-methoxyethoxy-5-ethylphenoxy group, aminoacyl group,
Aminocarbonylbutyl group, aminobenzyl group, aminobenzoyl group and aminocarbonylnaphthyl group are preferred.

In the general formula (1), R ^4's each independently represent a hydrogen atom, an alkyl group or an aryl group,
Among these, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferable, and a hydrogen atom, an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms are more preferable. R ⁴ in the general formula (1) is further an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms,
It may be substituted with an aryloxy group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a halogen atom and the like.

Specific examples of R ⁴ in the general formula (1) include methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group, phenyl group and p-tolyl group. , P-methoxyphenyl group, ethoxybutyl group and p-chlorophenyl group are preferred.

In the general formula (1), each R ⁵ independently represents a hydrogen atom, an alkyl group or an aryl group,
Among these, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferable, and a hydrogen atom, an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms are more preferable. R ⁵ is further substituted with an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a halogen atom or the like. Good. Specific examples of R ⁵ include methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group, phenyl group, p-tolyl group, p-methoxyphenyl, ethoxybutyl. Group, p-chlorophenyl group and the like.

In the general formula (1), R ⁶ is a hydrogen atom,
Alkyl group, aryl group, heterocyclic group, -COR ⁸ group,-
R ₂ represents a SO ₂ R ⁹ group or a —CSR ¹⁰ group, and R ⁶ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group;
⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and 6 carbon atoms
To an aryl group having 3 to 20 carbon atoms and a heterocyclic group having 3 to 20 carbon atoms are preferable, and a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a heterocyclic group having 3 to 12 carbon atoms are more preferable. preferable. Further, R ⁶ is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms,
It may be substituted with a halogen atom or the like. Specific examples of R ⁶ include hydrogen atom, methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group, phenyl group, p-tolyl group, p.
-Methoxyphenyl group, ethoxybutyl group, p-chlorophenyl group, 2,5-dimethoxyphenyl group, p-nitrophenyl group, 2-nitrophenyl group, pyridine ring, thiophene ring, furan ring, imidazole ring, pyrazole ring, triazole Ring, benzothiazole ring, benzimidazole ring and the like.

On the other hand, in the general formula (1), R ⁶ is -C.
When representing an OR ⁸ group, a —SO ₂ R ⁹ group, or a —CSR ¹⁰ group. R ⁸ , R ⁹ and R ¹⁰ are an alkyl group, an aryl group,
It represents a heterocyclic group, an alkylamino group, an arylamino group, an alkoxy group, or an aryloxy group, and among these, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a heterocyclic ring having 3 to 20 carbon atoms. Group, an alkylamino group having 1 to 18 carbon atoms, an arylamino group having 6 to 20 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. Alkyl group, C6-12 aryl group, C3-12 heterocyclic group, C1-12 alkylamino group, C6
-12 arylamino groups, C1-C12 alkoxy groups, and C6-C12 aryloxy groups are preferable.
Further, R ⁸ , R ⁹ and R ¹⁰ are each an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms,
It may be substituted with a halogen atom or the like.

Specific examples of R ⁸ , R ⁹ and R ¹⁰ include a methyl group, a trifluoromethyl group, an ethyl group and i-
Propyl group, n-butyl group, perfluorobutyl group, n
-Hexyl group, octyl group, 2-ethylhexyl group, perfluorooctyl group, n-decyl group, n-dodecyl group, cyclohexyl group, benzyl group, 2-phenethyl group, phenyl group, p-tolyl group, p-methoxyphenyl group Group, p-chlorophenyl group, 2-methoxyphenyl group,
p-bromophenyl group, p-nitrophenyl group, 2-nitrophenyl group, 2,5-dimethoxyphenyl group, 2-
Methoxyethoxy-5-ethylphenyl group, 2-hydroxy-5-ethylphenyl group, 2-methoxyethoxy-5-ethylphenyl group, 2-ethylthio-5-ethylphenyl group, methylamino group, ethylamino group, dimethylamino Group, 2-ethylhexylamino group, aminophenyl group, amino-4-nitrophenyl group, amino-4-chlorophenyl group, methoxy group, ethoxy group, n-propyloxy group, I-propyloxy group, n-butoxy group,
Hexyloxy group, 2-ethylhexyloxy group, n-
Decyloxy group, phenoxy group, p-tolyloxy group,
p-methoxyphenoxy group, p-chlorophenoxy group,
2-methoxyphenoxy group, p-bromophenoxy group,
p-nitrophenoxy group, 2-nitrophenoxy group,
A 2,5-dimethoxyphenoxy group, a 2-methoxyethoxy-5-ethylphenoxy group, a pyridine ring, a thiophene ring, a furan ring, an imidazole ring, a pyrazole ring, a triazole ring, a benzothiazole ring and a benzimidazole ring are preferable.

In the general formula (1), Y¹, Y², Y³，
Y^FourAre all CH or Y¹, Y², Y³, Y
^FourAny one or two of them represents N and the other represents CH.
Then Y ¹, Y², Y³, Y^FourWhen any two of the above represent N,
Y¹And Y^FourIs preferably N. In general formula (1)
Wait Y¹, Y², Y³, Y^FourWhen any one of N represents N,
Y¹Or Y^FourIs preferably N. General formula
In (1), Y¹, Y², Y³, Y^FourAll represent CH
In this case, any CH hydrogen atom is an alkyl group or a halo.
It may be substituted with a gen atom.

The lactam compound represented by the general formula (1) is preferably a lactam compound represented by the following general formula (2).

[0036]

[Chemical 10]

R ¹ , R ² , R ³ in the general formula (2),
R ⁴ , R ⁵ , and R ⁶ are each R ¹ in the general formula (1),
It is the same as R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ .

Specific examples of the lactam compounds represented by the general formulas (1) and (2) (No. 1 to No. 58) are as follows.
However, the present invention is not limited to these.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

[Table 5]

[0044]

[Table 6]

[0045]

[Table 7]

[0046]

[Table 8]

[0047]

[Chemical 11]

<Method for Producing Lactam Compound> The basic reaction mechanism of the method for producing the lactam compound represented by the general formula (1) is that R ⁶ is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Is represented by the following reaction formula (1)
Represented by Further, R ⁶ is a —COR ⁸ group, —S
The O ₂ R ⁹ group or the -CSR ¹⁰ group is represented by the following reaction formula (2).

[0049]

[Chemical 12]

[0050]

[Chemical 13]

First, the reaction formula (1) will be described. In the production method represented by the reaction formula (1), the indolyl phthalide compound represented by the general formula (3) is dissolved or dispersed in an organic solvent, and then a halogenating agent is added, and the general formula ( The acid halide represented by 4) is produced as an intermediate. The acid halide represented by the general formula (4) is preferably produced in the presence of an acid. Further, the amine compound represented by the general formula (5) is added to the obtained acid halide represented by the general formula (4) to produce the lactam compound represented by the general formula (1). be able to.

As the organic solvent, aprotic solvents such as acetonitrile, ethyl acetate, tetrahydrofuran, chloroform, dichloromethane, dichloroethane, tetrahydrofuran, dimethylformamide, dimethylacetamide, diethyl ether, toluene and benzene can be used. Among them, acetonitrile, ethyl acetate, tetrahydrofuran, dimethylformamide, and toluene are preferable in terms of environment and cost.

As the concentration of the indolylphthalide compound represented by the general formula (3) in the reaction formula (1), any concentration of 0.01 to 10 mol / l can be used, and preferably 0. 0.1 to 2.0 mol / l is preferable. As the acid, Bronsted acid can be used, and examples thereof include methanesulfonic acid, paratoluenesulfonic acid, sulfuric acid, hydrochloric acid, phosphoric acid, toluenesulfonic acid, benzenesulfonic acid, and the like, preferably methanesulfonic acid and paratoluene. Among these, sulfonic acid and sulfuric acid, but in the present invention, methanesulfonic acid, toluenesulfonic acid, and benzenesulfonic acid are particularly preferable. The equivalent amount of the acid used is preferably 0.1 to 3 equivalents, particularly preferably 0.5 to 1.5 equivalents, relative to the phthalide compound.

As the halogenating agent, a halogenating agent capable of inducing a carboxylic acid into a carboxylic acid halide can be used. Examples thereof include oxalic acid chloride, thionyl chloride, sulfuryl chloride, phosphorus oxychloride, phosphorus oxybromide, trivalent and 5
Valuable phosphorus chloride, phosphorus bromide, oxalyl chloride and the like can be mentioned. Among these, oxalic chloride, thionyl chloride, phosphorus oxychloride, trivalent and pentavalent phosphorus chloride are preferable, and oxalyl chloride is particularly preferable in the present invention. The equivalent of the halogenating agent to be used is preferably 1 to 5 equivalents relative to the phthalide compound, and particularly preferably 1 to 3 equivalents. The equivalent of the amine represented by the general formula (5) is preferably 1 to 10 equivalents, particularly preferably 1 to 3 equivalents. Although the reaction temperature varies depending on the kind of the halogenating agent used, it is preferably -20 ° C to 100 ° C,
Particularly preferably -5 ° C to 30 ° C.

Next, the reaction formula (2) will be described. In the production method represented by the reaction formula (2), the lactam compound represented by the general formula (6) is dissolved or dispersed in an organic solvent, and finally an electrophilic agent is added to the general formula (1). The lactam compound represented by these can be manufactured. Further, in the production method represented by the reaction formula (2), it is preferable to add a base before adding the electrophile. As the organic solvent, acetonitrile, ethyl acetate, tetrahydrofuran, chloroform,
An aprotic solvent such as dichloromethane, dichloroethane, tetrahydrofuran, dimethylformamide, dimethylacetamide, diethyl ether, toluene can be used. Of these, acetonitrile, ethyl acetate, tetrahydrofuran, dimethylformamide, and dimethylacetamide are particularly preferable in terms of environment and cost.

Examples of the base include metal hydrides such as sodium hydride, potassium hydride, lithium hydride and calcium hydride and organic metals such as butyl lithium, ethyl magnesium bromide, lithium diisopropylamide and potassium hexamethyldisilazide. And organic bases,
Examples thereof include dimethylaminopyridine, DBU, triethylamine and the like. Particularly preferred are metal hydrides such as sodium hydride, potassium hydride, lithium hydride and calcium hydride from the viewpoint of basicity. The equivalent of the base used is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, based on the lactam compound represented by the general formula (6).

[0057] As the electrophilic agent differs depending on the type of R ^6, when R ⁶ represents a COR ^8, may be used acid anhydrides, carbonyl halides, isocyanates. R ⁶ is S
When representing O ₂ R ⁹ , a sulfonyl halide can be used. When R ⁶ represents CSR ¹⁰ , thiocarbonyl halide and thioisocyanate can be used. The amount of these is preferably 1 to 5 equivalents, particularly preferably 1 to 3 equivalents, relative to the compound of the general formula (4). The reaction temperature varies depending on the type of base and electrophile used, but it is -20
C. to 100.degree. C. is preferable, and -5.degree. C. to 60 is particularly preferable.
C is preferred.

[0058]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. still,
The general formula (3) as a raw material of the lactam compound of the present invention
The indolyl phthalide compound represented by
37727, JP-A-9-31345, JP-A-8-2
It can be synthesized by the synthesis method described in JP-A No. 76654 and JP-A No. 8-313355.

Example 1 A solution of 45.3 g of the compound (A) represented by the following structural formula in acetonitrile (200 ml) was cooled to 0 ° C., and stirred with methanesulfonic acid 9.6.
g was added. Further, 25.2 g of oxalyl chloride was added and the mixture was stirred at the same temperature for 30 minutes to obtain an intermediate A represented by the following structural formula. Further, the reaction solution containing the intermediate A was poured into 28% ammonia water (200 ml), and then 200 ml of water was added to precipitate the intended product. The target substance was collected by filtration and recrystallized from 200 ml of acetonitrile to obtain 25.5 g of the lactam compound of the present invention (Exemplified Compound 1).

[0060]

[Chemical 14]

As a result of NMR analysis of the obtained compound, ¹ H-NMR (300 MHz, CDCl ₃ ) δ1.1
(T, 6H), 1.2 (t, 3H), 2.05 (s, 3
H), 2.1 (S, 3H), 3.3 (q, 4H), 4.
1 (q, 2H), 6.4 (d, 1H), 6.5 (S, 1
H), 6.9 (t, 1H), 7.0 (s, 1H), 7.
05-7.1 (m, 2H), 7.2 (s, 1H), 7.
25 (d, 1H), 7.35 (d, 1H), 8.1
The values were (d, 1H) and 8.7 (d, 1H).

Example 2 A solution of 10 g of the lactam compound of the present invention (Exemplary Compound 1) of the present invention obtained in Example 1 in dimethylacetamide (100 ml) was added with sodium hydride 1.1.
g was added and stirred for 30 minutes, and 2 g of acetyl chloride was further added. After confirming the completion of the reaction by TLC (silica thin layer chromatography), water (200 ml) was added for crystallization. The crystallized product was collected by filtration and produced by silica gel chromatography to obtain 5.5 g of the lactam compound of the present invention (Exemplified Compound 2).

As a result of NMR analysis of the obtained compound, ¹ H-NMR (300 MHz, CDCl ₃ ) δ1.1
(T, 6H), 1.3 (t, 3H), 2.2 (s, 3)
H), 2.3 (S, 3H), 2.6 (s, 3H), 3.
3 (q, 4H), 4.1 (q, 2H), 6.1 (d, 1
H), 6.4 (S, 1H), 6.45 (d, 1H),
6.8 (t, 1H), 7.0 (t, 1H), 7.2-
7.3 (m, 2H), 7.4 (d, 1H), 8.2
The values were (d, 1H) and 8.7 (d, 1H).

Example 3 A solution of 10 g of the lactam compound of the present invention (Exemplified Compound 1) of the present invention obtained in Example 1 in dimethylacetamide (100 ml) was added with 1.1 parts of sodium hydride.
g and stirred for 30 minutes, and further 3.4 g of phenyl isothiocyanate was added. After confirming the completion of the reaction by TLC, water (200 ml) was added for crystallization. The lactam compound of the present invention (Exemplified Compound 3) was obtained by collecting the crystallized product by filtration and producing it by silica gel chromatography.
0 g was obtained.

As a result of NMR analysis of the obtained compound, ¹ H-NMR (300 MHz, CDCl ₃ ) δ1.1
(T, 6H), 1.3 (t, 3H), 1.8 (s, 3
H), 2.4 (S, 3H), 3.3 (q, 4H), 4.
1 (q, 2H), 6.3-6.5 (m, 2H), 7.0
-7.4 (m, 10H), 7.7 (d, 1H), 8.2
The values were (d, 1H) and 8.8 (d, 1H).

Example 4 A solution of 10 g of the lactam compound of the present invention (Exemplified Compound 1) of the present invention obtained in Example 1 in dimethylacetamide (100 ml) was added with 1.1 parts of sodium hydride.
g was added and stirred for 30 minutes, and then 2.9 g of methanesulfonyl chloride was added. After confirming the completion of the reaction by TLC, water (200 ml) was added for crystallization. The lactam compound of the present invention (Exemplified Compound 4) was obtained by collecting the crystallized product by filtration and producing it by silica gel chromatography.
2 g was obtained.

As a result of NMR analysis of the obtained compound, ¹ H-NMR (300 MHz, CDCl ₃ ) δ1.1
(T, 6H), 1.3 (t, 3H), 2.2 (s, 3)
H), 2.4 (S, 3H), 2.5 (s, 3H), 3.
3 (q, 4H), 4.2 (q, 2H), 5.8 (bs,
1H), 6.4-6.6 (m, 2H), 6.7 (t, 1
H), 7.0 (t, 1H), 7.25 (d, 1H),
7.4 (d, 1H), 7.7 (d, 1H), 8.2
The values were (d, 1H) and 8.7 (d, 1H).

Example 5 A solution of 10 g of the lactam compound of the present invention (Exemplified Compound 1) obtained in Example 1 in dimethylacetamide (100 ml) was added with 1.1 parts of sodium hydride.
g was added and the mixture was stirred for 30 minutes, and further 4.8 g of p-toluenesulfonyl chloride was added. After confirming the completion of the reaction by TLC, water (200 ml) was added for crystallization. A lactam compound of the present invention (Exemplified Compound 6) is obtained by collecting the crystallized product by filtration and producing it by silica gel chromatography.
Was obtained.

As a result of NMR analysis of the obtained compound, ¹ H-NMR (300 MHz, CDCl ₃ ) δ1.1
(T, 6H), 1.2 (t, 3H), 2.05 (s, 3
H), 2.1 (S, 3H), 2.3 (s, 3H), 3.
3 (q, 4H), 4.0 (q, 2H), 6.2 (d, 1)
H), 6.4 (S, 1H), 6.6 (d, 1H), 6.
8 (t, 1H), 7.0 (d, 1H), 7.05 (d,
2H), 7.2 (d, 1H), 7.25 (d, 1H),
7.8 (d, 1H), 7.9 (d, 2H), 8.6
(D, 1H).

Example 6 A solution of 10 g of the lactam compound of the present invention (Exemplified Compound 1) of the present invention obtained in Example 1 in dimethylacetamide (100 ml) was added with 1.1 parts of sodium hydride.
g was added and stirred for 30 minutes, and then 5.9 g of 2,5-dimethoxybenzenesulfonyl chloride was added. After confirming the completion of the reaction by TLC, water (200 ml) was added for crystallization. The crystallized product was collected by filtration and produced by silica gel chromatography to obtain 11.2 g of the lactam compound of the present invention (Exemplified Compound 9).

As a result of NMR analysis of the obtained compound, ¹ H-NMR (300 MHz, CDCl ₃ ) δ1.1
(T, 6H), 1.2 (t, 3H), 1.8 (s, 3)
H), 2.1 (s, 3H), 3.3 (q, 4H), 3.
6 (s, 3H), 3.65 (s, 3H), 4.0 (q,
2H), 6.2 (d, 1H), 6.3 (S, 1H),
6.5 (d, 1H), 6.6 (d, 1H), 6.8
(T, 1H), 6.9 (d, 1H), 6.9-7.1
(M, 2H), 7.2 (d, 1H), 7.3 (d, 1)
H), 7.4 (s, 1H), 7.9 (d, 1H), 8.
It was 6 (d, 1H).

Example 7 A solution of 10 g of the lactam compound of the present invention (Exemplified Compound 1) of the present invention obtained in Example 1 in dimethylacetamide (100 ml) was added with 1.1 parts of sodium hydride.
g was added and the mixture was stirred for 30 minutes, and then 4.4 g of 2-chlorosulfonylpyridine was added. After confirming the completion of the reaction by TLC, water (200 ml) was added for crystallization. The crystallized product was collected by filtration and produced by silica gel chromatography to obtain 8.3 g of the lactam compound of the present invention (Exemplified compound 53).

As a result of NMR analysis of the obtained compound, ¹ H-NMR (300 MHz, CDCl ₃ ) δ1.2
(T, 6H), 1.3 (t, 3H), 1.9 (s, 3)
H), 2.1 (s, 3H), 3.3 (q, 4H), 4.
0 (q, 2H), 6.2 (d, 1H), 6.3 (s, 1
H), 6.6 (d, 1H), 6.8 (t, 1H), 7.
0-7.2 (m, 4H), 7.3 (t, 1H), 7.5
(T, 1H), 7.9 (d, 1H), 8.1 (d, 1)
H), 8.4 (d, 1H) and 8.6 (d, 1H).

(Example 8) A solution of 10 g of the lactam compound of the present invention (Exemplified Compound 1) obtained in Example 1 in dimethylacetamide (100 ml) was added with sodium hydride 1.1.
g was added and the mixture was stirred for 30 minutes, and further 3.7 g of 2-thiophenecarbonyl chloride was added. Completion of reaction by TLC
After confirming by (1), water (200 ml) was added for crystallization. The crystallized product was collected by filtration and produced by silica gel chromatography to produce the lactam compound of the present invention (Exemplified Compound 5
6.5 g of 8) was obtained.

As a result of NMR analysis of the obtained compound, ¹ H-NMR (300 MHz, CDCl ₃ ) δ1.1
(T, 6H), 1.3 (t, 3H), 2.2 (s, 6)
H), 3.3 (q, 4H), 4.1 (q, 2H), 6.
3 (d, 1H), 6.5 (d, 1H), 6.8 (t, 1
H), 7.0-7.3 (m, 6H), 7.7 (d, 2)
H), 8.1 (s, 1H) and 8.6 (d, 1H).

[0076]

INDUSTRIAL APPLICABILITY The present invention can provide a novel lactam compound which is useful as an electron-donating colorless dye, and a method for producing a lactam compound which has mild reaction conditions and is highly versatile.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H026 AA07 BB02                 2H085 AA07 BB02                 4C065 AA04 BB04 CC01 DD02 EE02                       HH01 JJ01 KK05 LL04 LL10                       PP03 PP09 QQ02                 4H039 CA50 CA65 CD30 CE20 CH60

Claims (8)

[Claims] 1. A lactamization represented by the following general formula (1):
Compound [Chemical 1] (In the general formula (1), R¹, R²Are independent hydrogen
Represents a child, an alkyl group, or an aryl group. However, R¹
And R²Does not represent a hydrogen atom at the same time. R³Is hydrogen
Child, alkyl group, alkoxy group, aryloxy group,
Or -NHCOR ⁷Represents a group, R⁷Is an alkyl group, or
Represents an aryl group. R^Four, R^FiveAre independent hydrogen
Represents a child, an alkyl group, or an aryl group. R⁶Is hydrogen
Atom, alkyl group, aryl group, heterocyclic group, -COR⁸
Group, -SO₂R⁹Group, or -CSR^TenRepresents a group, R⁸，
R⁹, R^TenIs an alkyl group, an aryl group, a heterocyclic group,
Killamino group, arylamino group, alkoxy group,
Represents an aryloxy group. Y¹, Y², Y³, Y^FourIs all
Represents CH, or Y¹, Y², Y³, Y^FourOne of
One or two represent N and the other represent CH. ) 2. A lactamization represented by the general formula (1)
The compound is a lactam compound represented by the following general formula (2)
The lactam compound according to claim 1, wherein
object. [Chemical 2] (In the general formula (2), R¹, R²Are independent hydrogen
Represents a child, an alkyl group, or an aryl group. However, R¹
And R²Does not represent a hydrogen atom at the same time. R³Is hydrogen
Child, alkyl group, alkoxy group, aryloxy group,
Or -NHCOR ⁷Represents a group, R⁷Is an alkyl group, or
Represents an aryl group. R^Four, R^FiveAre independent hydrogen
Represents a child, an alkyl group, or an aryl group. R⁶Is hydrogen
Atom, alkyl group, aryl group, heterocyclic group, -COR⁸
Group, -SO₂R⁹Group, or -CSR^TenRepresents a group, R⁸，
R⁹, R^TenIs an alkyl group, an aryl group, a heterocyclic group,
Killamino group, arylamino group, alkoxy group,
Represents an aryloxy group. ) 3. An indrill represented by the following general formula (3):
For reacting phthalide compounds with halogenating agents
From the acid halide represented by the following general formula (4) as an intermediate
And generate Furthermore, an acid halide represented by the general formula (4) and one of the following
By reacting with an amine compound represented by the general formula (5),
It is characterized in that a lactam compound represented by the general formula (1) is obtained.
A method for producing a lactam compound. [Chemical 3] (In general formula (3) and general formula (4), R¹, R²Is it
Each independently represents a hydrogen atom, an alkyl group, or an aryl group.
Represent However, R¹And R²Does not represent a hydrogen atom at the same time.
Yes. R³Is a hydrogen atom, alkyl group, alkoxy group, ant
Group, or -NHCOR⁷Represents a group, R⁷A
It represents a alkyl group or an aryl group. R ^Four, R^FiveIs that
Independently represent a hydrogen atom, an alkyl group, or an aryl group.
You Y¹, Y², Y³, Y^FourAll represent CH, or
Is Y¹, Y², Y³, Y^FourEither one or two is N
And CH represents CH. In general formula (4), X is a
Represents a logen atom. R in the general formula (5)⁶Is a hydrogen atom,
Alkyl group, aryl group, heterocyclic group, -COR⁸Group,-
SO₂R⁹Group, or -CSR^TenRepresents a group, R⁸, R⁹, R
^TenIs an alkyl group, an aryl group, a heterocyclic group, an alkylami
Group, arylamino group, alkoxy group, or aryl
Represents a luoxy group. ) 4. The method for producing a lactam compound according to claim 3, wherein the halogenating agent is oxalyl chloride. 5. The method for producing a lactam compound according to claim 3, wherein the acid halide represented by the general formula (4) is produced in the presence of an acid. 6. The method for producing a lactam compound according to claim 5, wherein the acid is any one of methanesulfonic acid, toluenesulfonic acid and benzenesulfonic acid. 7. A lactamization represented by the following general formula (6):
The compound represented by the general formula (1) is obtained by reacting the compound with an electrophile.
Lactam characterized by obtaining a lactam compound
Method for producing compound. [Chemical 4] (In the general formula (6), R¹, R²Are independent hydrogen
Represents a child, an alkyl group, or an aryl group. However, R¹
And R²Does not represent a hydrogen atom at the same time. R³Is hydrogen
Child, alkyl group, alkoxy group, aryloxy group,
Or -NHCOR ⁷Represents a group, R⁷Is an alkyl group, or
Represents an aryl group. R^Four, R^FiveAre independent hydrogen
Represents a child, an alkyl group, or an aryl group. Y¹, Y²，
Y³, Y^FourAre all CH or Y¹, Y², Y
³, Y^FourAny one or two of them represents N, and the other is CH
Represents ) 8. The method for producing a lactam compound according to claim 7, wherein the electrophile is any one of acid halide, sulfonyl halide, isocyanate and thioisocyanate.