JPH08325470A - Pyrazolone compound - Google Patents

Abstract

PURPOSE: To obtain a novel bis-1-substd.-5-pyrazolone compd. which is an intermediate for the preparation of a polymer dye and can provide a dye causing no diffusion of a photosensitive material from a hydrophilic binder layer into other layer(s). CONSTITUTION: This pyrazolone compd. is represented by the formula (wherein X represents a 1-6C methylene, phenylene, pyridin-diyl; R<1> represents H or a halogen; Y represents a 1-6C alkyl or hydroxyl group; and (n) and (m) are 1 or 2). In the formula, the 1-substd.-pyrazolone-3-yl is pref. in a meta or para position on the phenyl ring relative to the NHCO-X-CONH. In the formula, this compd. is represented as having a 5-pyrazolone ring. However, the compd. embraces also a compound having a 5-hydroxy-pyrazole ring due to tautomerism. The compd. is a novel compd. useful as an intermediate for the preparation of a polymer dye. The polymer dye prepared from this intermediate is hydrophilic and suitable for a photosensitive material.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a pyrazolone compound. More specifically, the present invention relates to a novel pyrazolone compound useful as a production intermediate for the production of polymer dyes.

[0002]

2. Description of the Related Art 1-Substituted-5-hydroxy-pyrazoles are described in "Theory and Manufacturing Dye Chemistry" by Yutaka Hosoda (published by Gihodo.
1957), it is a compound useful as an intermediate for dyes. Also, 1-substituted-5-hydroxy-
Dyes containing pyrazoles as a production intermediate are useful as dyes added to silver halide photographic light-sensitive materials, and are known to have a function of controlling spectral sensitivity and preventing irradiation and halation. ing. Specifically, U.S. Pat.No. 2,274,782, JP-A-51-77327, JP-A-54-118247, JP-A-3-288841,
Also, the dyes described in Japanese Examined Patent Publication No. 4-8466 are found. However, when a dye having these pyrazoles as an intermediate is contained in a hydrophilic binder layer such as gelatin of a light-sensitive material, there is a problem that the dye easily diffuses to another layer.

[0003]

The object of the present invention is to provide a useful intermediate for producing a dye which does not diffuse into other layers when incorporated in a hydrophilic binder layer such as a light-sensitive material. , To provide novel 1-substituted-5-hydroxy-pyrazoles.

[0004]

As a result of diligent efforts to solve the above problems, the present inventor has developed a novel bis-1-substituted-5-hydroxy-pyrazole (bis-1- Substituted-5-pyrazolone) compounds are useful as intermediates for the production of polymer-based dyes, and even when the obtained polymer-based dyes are contained in a hydrophilic binder layer, they do not diffuse into other layers and It has been found to have excellent properties as a dye for manufacturing. The present invention has been completed based on the above findings.

That is, the present invention provides the following formula:

Embedded image (In the formula, X represents a linear or branched methylene group having 1 to 6 carbon atoms, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted pyridinediyl group, and R ^1's each independently represent a hydrogen atom or Represents a halogen atom, Y represents each independently a linear or branched alkyl group having 1 to 6 carbon atoms or a hydroxyl group, and n and m each independently represent 1 or
The present invention provides a pyrazolone compound represented by 2).

The compound of the present invention has two (1-substituted-pyrazolon-3-yl) -phenyl groups which are the same or non-identical and which are —NHC.
It is a so-called bis-type compound bonded by an OX-CONH- group, and preferably two identical (1-substituted-pyrazolone-3
-Yl) -phenyl group is a compound bonded by -NHCO-X-CONH- group. In the above formula, X represents a linear or branched methylene group having 1 to 6 carbon atoms, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted pyridinediyl group. Examples of the methylene group include -CH _2- , -CH ₂ CH ₂ -,-
(CH ₂ ) ₃ -,-(CH ₂ ) ₄ -,-(CH ₂ ) ₅ -,-(CH ₂ ) _6- , -CH (CH ₃ ) CH ₂
-, -CH ₂ CH (CH ₃ )-, -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH _2- ,
-CH ₂ CH ₂ CH (CH ₃ )-, -CH (CH ₂ CH ₃ ) CH ₂ CH _2- , -CH (CH ₃ ) CH (C
H ₃ ) CH _2- , and -CH (CH ₂ CH ₃ ) CH (CH ₃ ) CH _2- can be exemplified, but the present invention is not limited thereto. Of these, a linear methylene group having 3 to 5 carbon atoms is preferable,
- (CH _{2) 4} - group is particularly preferred.

The phenylene group is an o-phenylene group,
Either an m-phenylene group or a p-phenylene group may be used, but an m-phenylene group or a p-phenylene group is preferred. The pyridinediyl group represents a divalent group formed by removing a hydrogen atom from two different ring carbon atoms of pyridine. For example, 2,3-pyridinediyl group, 2,4-pyridinediyl group, 2,5-pyridinediyl group, 2,6-pyridinediyl group, 3,4-pyridinediyl group, 3,5-pyridinediyl group Either may be used. These phenylene groups or pyridinediyl groups may have one or two or more optional substituents. Such a substituent has 1 to 10 carbon atoms.
A 6 straight-chain or branched-chain alkyl group, a straight-chain or branched-chain alkoxy group having 1 to 6 carbon atoms, or a halogen atom can be used.

Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group,
tert-butyl group, n-pentyl group, neopentyl group, or
An n-hexyl group or the like can be used. 1 to 6 carbon atoms
Examples of the linear or branched alkoxy group include, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group. Group or n-
A hexoxy group or the like can be used. As the halogen atom, any of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom may be used.

In the above formula, the 1-substituted-pyrazolon-3-yl group substituted on the phenyl group to which the -NHCO-X-CONH- group is bonded may be substituted at any position on the phenyl ring. Is preferably m- or p-substituted with respect to the -NHCO-X-CONH- group on the phenyl ring, and particularly preferably p-substituted. R ¹ independently represents a hydrogen atom or a halogen atom, and the halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Of these, R ¹ is preferably a hydrogen atom or a chlorine atom. Y is independently hydroxyl group or carbon number
1 to 6 represents a linear or branched alkyl group. When Y ₂ represents a hydroxyl group, —SO ₂ Y represents a sulfonic acid group.
As the linear or branched alkyl group having 1 to 6 carbon atoms, those exemplified above can be used, but a methyl group or an ethyl group is preferable.

N and m each independently represent 1 or 2, but when these are 1, a group represented by --SO ₂ Y is substituted on the phenyl group substituted at the 1-position of pyrazolone. In the case of 2, it means that two groups represented by -SO ₂ Y are substituted on the phenyl group substituted at the 1-position of pyrazolone. R ¹ on the phenyl group substituting the 1-position of pyrazolone
And each of 1 or 2 —SO ₂ Y may be substituted at any position on the phenyl ring.

The compound of the present invention may exist as an acid addition salt or a base addition salt, and the compound in the free form or the above salt may exist as a hydrate or a solvate. Also included within the scope of the invention. As the acid addition salt, for example, hydrochloride, sulfate,
Mineral salts such as hydrobromide, hydroiodide and nitrate,
Organic acid salts such as paratoluene sulfonate, methane sulfonate, camphor sulfonate, tartrate and citrate may be mentioned. Examples of the base addition salt include metal salts such as sodium salt, potassium salt, magnesium salt, calcium salt and ammonium salt, methylamine salt,
Examples thereof include organic amine salts such as dimethylamine salt and triethylamine salt.

The compound of the present invention is, depending on the kind of the substituent,
It may have one or more asymmetric carbons, but any optical isomer based on such one or more asymmetric carbons, or any diastereomer based on two or more asymmetric carbons All isomers are included within the scope of the invention.
Further, all the isomers in the pure form of the above optical isomers or diastereoisomers, arbitrary mixtures, racemates and the like are also included in the scope of the present invention. Furthermore, although the compound of the present invention contains the 5-pyrazolone skeleton as a partial structure,
It will be apparent to those skilled in the art that the pyrazolone ring may exist as a 5-hydroxy-pyrazole ring due to tautomerism. Although the above general formula has been described for a compound having a 5-pyrazolone ring for the sake of convenience, all of these tautomers are included in the scope of the present invention regardless of whether or not they have the same physicochemical properties. Needless to say.

Preferred compounds of the present invention include, for example, (a) X is a linear methylene group having 3 to 5 carbon atoms, an unsubstituted phenylene group, or an unsubstituted pyridinediyl group; R ¹ is independently a hydrogen atom or a halogen atom; Y is a hydroxyl group; and compounds wherein n and m are each independently 1 or 2; (b) X is - (CH _{2) 4} -, unsubstituted m- or p -A phenylene group or an unsubstituted 2,6-pyridinediyl group; -NHCO-
A pyrazolon-3-yl group substituted on the phenyl group to which the X-CONH- group is bonded is m- or p-substituted on the phenyl ring with respect to the -NHCO-X-CONH- group; R ¹ is independent Is a hydrogen atom or a chlorine atom; Y is a hydroxyl group; and n and m are each independently 1 or 2, and (c) in the compound of the above (b) group, pyrazolone-3-yl Mention may be made of compounds in which the group is p-substituted on the phenyl ring with respect to the -NHCO-X-CONH- group.

Preferred compounds among the compounds included in the above-mentioned group (C) are illustrated in Table 1 below, but the scope of the present invention is not limited thereto (in the table, compound numbers are added. The compound is the compound described in Preparation Examples in Examples). In the table below, “sulfo” indicates a sulfonic acid group in a free form or salt form, and “disulfo” indicates that two sulfonic acid groups are both released. Forms, including one sulfonic acid group in free form and the other sulfonic acid group in salt form, and two sulfonic acid groups both in the same or different base addition salt form .

[Table 1] ───────────────────────────── XR ^1- (SO ₃ H) _n ───────── ─────────────────────-(CH ₂ ) ₄ --H 4-sulfo (Compound 8) 〃 -H 3-sulfo 〃 -H 2-sulfo 〃 -H 2,5-disulfo (compound 9) 〃 -H 2,4-disulfo 〃 4-Cl 3-sulfo (compound 2) 〃 3-Cl 4-sulfo 〃 2-Cl 4-sulfo 〃 2-Cl 3- Sulfo 〃 2-Cl 5-sulfo 〃 4-Cl 2,5-disulfo 〃 3-Cl 2,5-disulfo m-phenylene group -H 4-sulfo (Compound 5) 〃 -H 3-sulfo 〃 -H 2- Sulfo 〃 -H 2,5-disulfo (compound 6) 〃 -H 2,4-disulfo 〃 4-Cl 3-sulfo 〃 3-Cl 4-sulfo 〃 2-Cl 4-sulfo 〃 2-Cl 3-sulfo 〃 2-Cl 5-sulfo 〃 4-Cl 2,5-disulfo 〃 3-Cl 2,5-disulfo p-phenylene group -H 4-sulfo (Compound 3) 〃 -H 3-sulfo 〃 -H 2-sulfo 〃 -H 2,5-disulfo (Compound 4) 〃 -H 2,4-dis White 4-Cl 3-Sulfo (Compound 1) White 3-Cl 4-Sulfo 2-Cl 4-Sulfo 2-Cl 3-Sulfo 2-Cl 5-Sulfo 4-Cl 2,5-Disulfo 〃 3-Cl 2,5-disulfo 2,6-pyridinediyl group -H 4-sulfo 〃 -H 3-sulfo 〃 -H 2-sulfo 〃 -H 2,5-disulfo (Compound 7) 〃 -H 2,4 -Disulfo 〃 4-Cl 3-Sulfo 〃 3-Cl 4-Sulfo 〃 2-Cl 4-Sulfo 〃 2-Cl 3-Sulfo 〃 2-Cl 5-Sulfo 〃 4-Cl 2,5-Disulfo 〃 3-Cl 2,5-Disulfo ────────────────────────────

The process for preparing the compounds of the present invention is described in Table 1 above.
Representative compounds of the compounds shown in are described in detail in the Examples. An example of the production method of the present invention according to the production method of the example is shown in the following scheme (the compound numbers in the scheme are the compounds 1 to 9 of the present invention).
(Corresponding to the compound numbers described in Examples in Table 1 and Example numbers above, and reaction reagents and starting materials, Ar in the scheme represents R ¹ and a phenyl group substituted with a sulfonic acid group) . Those skilled in the art can easily produce the compounds included in the above general formula by referring to these Examples or by appropriately modifying or modifying the starting compounds, reaction reagents, reaction conditions, etc. used. You can

As a method for constructing a partial structure containing a pyrazolone ring, a condensation ring-closing reaction between a corresponding phenylhydrazine derivative and a β-keto acid ester ("The Chemistry of Hete
rocyclic Compounds ”ed. A. Weissberger, Vol.20, P.
9. (see 1964)). The method for producing the compound of the present invention is not limited to these, and compounds produced by any method are included in the scope of the present invention.

[0017]

Embedded image

The compound of the present invention is useful as an intermediate for the production of polymer-based dyes, which has not hitherto been known for the dye obtained by using pyrazoles as an intermediate for production.
The polymer dye produced by using the compound of the present invention as a production intermediate is hydrophilic and has better compatibility with a hydrophilic binder (eg gelatin) than conventional hydrophobic polymer dyes. When incorporated in a photographic light-sensitive material, it does not diffuse into other layers, and it is possible to enhance the product stability of the light-sensitive material. As a method for converting into a polymer dye, for example, the methods described in JP-A No. 4-130429, JP-A No. 3-288841, US Pat. No. 2,274,782 and the like can be adopted.

[0019]

The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples. The structures of the compounds referred to in this example are:
It is as follows.

[Chemical 4]

Example 1 (Synthesis of Compound 11) Under a nitrogen stream, iron (23.7 g), ammonium chloride (2.4 g),
1 solution of water (24 ml) in isopropyl alcohol (170 ml)
Heated to reflux for 5 minutes. 4-Nitrobenzoyl ethyl acetate (1
0) (23.7 g) was added, and the mixture was heated under reflux for 40 min. The reaction solution was filtered through Celite, and the crystals precipitated from the mother liquor were collected by filtration to obtain the compound (11) (21.3 g, 90%). Example 2 (Synthesis of Compound 13) Pyridine (4 ml) was added to a solution of compound (2) (8.28 g) in acetonitrile (100 ml) to prepare terephthaloyl chloride (12).
(4.06 g) was added and stirred for 1 hour. 1N hydrochloric acid (100 m
l) was added and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and dried to obtain compound (13) (10.8 g, 99%).

Example 3 (Synthesis of compound 15) Pyridine (4 ml) was added to a solution of compound (2) (8.28 g) in acetonitrile (100 ml) to prepare isophthaloyl chloride (14).
(4.06 g) was added and stirred for 1 hour. 1N hydrochloric acid (100 m
l) was added and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and dried to obtain compound (15) (10.2 g, 94%). Example 4 (Synthesis of Compound 17) Pyridine (4 ml) was added to a solution of compound (2) (8.28 g) in acetonitrile (100 ml), and 2,6-pyridinedicarbonyldichloride (16) (4.08 g) was added. And stirred for 1 hour. 1N Hydrochloric acid (100 ml) was added and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and dried to obtain compound (17) (10.0 g, 92%).

Example 5 (Synthesis of Compound 19) Pyridine (4 ml) was added to a solution of compound (2) (8.28 g) in acetonitrile (100 ml), and adipic acid chloride (18) (3.66) was added.
g) was added and stirred for 1 hour. 1N hydrochloric acid (100 ml) was added, and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and dried to obtain compound (19) (9.9 g, 78%).

Example 6 (Synthesis of Compound 1) Compound (13) (3.15 g) and phenylhydrazine compound (2
0) (3.10 g) to N, N-dimethylacetamide (DMAc: 30 ml)
It was heated to reflux for 3 hours. The solvent was distilled off, isopropyl alcohol (80 ml) was added to the residue, and the precipitated crystals were collected by filtration. The obtained crystals were washed with isopropyl alcohol to give compound (1) (5.27 g, 38%, mp> 300 ° C). NMR (δ ppm, CDCl ₃ ) 2.55 (4H, d), 7.88 (6H, m), 7.7
9 (4H, s), 8.13 (8H, s), 10.50 (2H, s), 10.72 (2H, s)

Example 7 (Synthesis of Compound 2) Compound (19) (1.05 g) and phenylhydrazine compound (2
0) (1.03 g) was added to N, N-dimethylacetamide (10 ml) and the mixture was heated under reflux for 3 hours. The solvent was distilled off, isopropyl alcohol (50 ml) was added to the residue, and the precipitated crystals were collected by filtration. The obtained crystals were washed with isopropyl alcohol to obtain compound (2) (0.27 g, 16%, mp> 300 ° C). NMR
(δ ppm, CDCl ₃ ) 2.57 (4H, s), 7.49 (2H, d), 7.67 (2H,
d), 7.76 (8H, d), 8.40 (2H, s), 10.00 (2H, s)

Example 8 (Synthesis of Compound 3) Compound (13) (1.09 g) and phenylhydrazine compound (2
1) (0.76 g) was added to N, N-dimethylacetamide (10 ml), and the mixture was heated under reflux for 2 hours. The solvent was distilled off, isopropyl alcohol (50 ml) was added to the residue, and the precipitated crystals were collected by filtration. The obtained crystals were washed with isopropyl alcohol to give compound (3) (0.18 g, 10%, mp> 300 ° C). NMR
(δ ppm, CDCl ₃ ) 2.55 (4H, s), 7.90 (4H, m), 8.04 (8H,
s), 8.18 (8H, s), 10.75 (2H, s)

Example 9 (Synthesis of Compound 4) Compound (13) (1.09 g) and phenylhydrazine compound (2
2) (1.10 g) was added to N, N-dimethylacetamide (10 ml), and the mixture was heated under reflux for 2 hours. The precipitated crystals were collected by filtration and washed with isopropyl alcohol to give compound (4) (0.50 g, 26%,
mp> 300 ° C.). NMR (δ ppm, CDCl ₃ ) 2.56 (4H,
d), 7.85 (4H, m), 7.99 (8H, s), 8.10 (2H, br), 8.13 (8H,
s), 10.72 (2H, s)

Example 10 (Synthesis of Compound 5) Compound (15) (1.09 g) and phenylhydrazine compound (2
0) (0.75 g) was added to N, N-dimethylacetamide (10 ml) and the mixture was heated under reflux for 2 hours. The solvent was distilled off, isopropyl alcohol (50 ml) was added to the residue, and the precipitated crystals were collected by filtration. The obtained crystals were washed with isopropyl alcohol to give compound (5) (0.26 g, 16%, mp> 300 ° C). NMR
(δ ppm, CDCl ₃ ) 2.56 (4H, d), 7.72 (5H, m), 7.86 (12H,
m), 8.18 (2H, d), 8.59 (1H, s), 10.54 (2H, s)

Example 11 (Synthesis of Compound 6) Compound (15) (1.09 g) and phenylhydrazine compound (2
2) (1.10 g) was added to N, N-dimethylacetamide (10 ml) and the mixture was heated under reflux for 2 hours. The solvent was distilled off, isopropyl alcohol (50 ml) was added to the residue, and the precipitated crystals were collected by filtration. The obtained crystals were washed with isopropyl alcohol to obtain compound (6) (0.22 g, 12%, mp> 300 ° C). NMR
(δ ppm, CDCl ₃ ) 2.55 (4H, d), 7.75 (5H, m), 7.99 (8H,
s), 8.17 (4H, m), 8.59 (1H, s), 10.58 (2H, br), 10.75 (2
H, s)

Example 12 (Synthesis of Compound 7) Compound (17) (1.09 g) and phenylhydrazine compound (2
2) (1.10 g) was added to N, N-dimethylacetamide (10 ml), and the mixture was heated under reflux for 2 hours. The solvent was distilled off, isopropyl alcohol (50 ml) was added, and the precipitated crystals were collected by filtration.
The obtained crystals were washed with isopropyl alcohol to give compound (7) (0.19 g, 10%, mp> 300 ° C). NMR (δ p
pm, CDCl ₃ ) 2.55 (4H, d), 7.89 (4H, d), 8.00 (4H, d), 8.2
6 (6H, br), 8.33 (1H, t), 8.42 (2H, d), 11.83 (2H, s)

Example 13 (Synthesis of Compound 8) Compound (19) (1.05 g) and phenylhydrazine compound (2
1) (0.75 g) was added to N, N-dimethylacetamide (10 ml) and the mixture was heated under reflux for 2 hours. The solvent was distilled off, isopropyl alcohol (50 ml) was added, and the precipitated crystals were collected by filtration.
The obtained crystals were washed with isopropyl alcohol to give compound (8) (0.24 g, 16%, mp> 300 ° C). NMR (δ p
pm, CDCl ₃ ) 1.65 (4H, br), 2.31 (4H, br), 2.57 (4H, d),
7.70 (16H, m), 10.23 (2H, s)

Example 14 (Synthesis of Compound 9) Compound (19) (1.05 g) and phenylhydrazine compound (2
2) (1.16 g) was added to N, N-dimethylacetamide (10 ml) and the mixture was heated under reflux for 2 hours. The solvent was evaporated, isopropyl alcohol (50 ml) was added, and the precipitated crystals were filtered.
The obtained crystals were washed with isopropyl alcohol to obtain compound (9) (0.20g, 11%, mp> 300 ° C). NMR (δ pp
m, CDCl ₃ ) 1.66 (4H, br), 2.38 (4H, br), 2.55 (4H, d), 7.
63 (10H, m), 7.90 (2H, br), 8.14 (2H, br), 10.04 (2H, m),
10.25 (2H, s)

[0032]

INDUSTRIAL APPLICABILITY The present invention provides a novel compound useful as an intermediate for the production of polymer dyes. The polymer dyes produced using the compound of the present invention as a production intermediate are hydrophilic and are useful dyes because they enhance the product stability of the light-sensitive material.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 30, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

Example 1 (Synthesis of Compound 11) Under a nitrogen stream, iron (23.7 g), ammonium chloride (2.4 g),
1 solution of water (24 ml) in isopropyl alcohol (170 ml)
Heated to reflux for 5 minutes. 4-Nitrobenzoyl ethyl acetate (1
0) (23.7 g) was added, and the mixture was heated under reflux for 40 min. After cooling, the reaction solution was filtered through Celite, and the crystals precipitated from the mother liquor were collected by filtration to obtain the compound (11) (21.3 g, 90%). Example 2 (Synthesis of Compound 13) Pyridine (4 ml) was added to a solution of compound (11) (8.28 g) in acetonitrile (100 ml) to prepare terephthaloyl chloride (12).
(4.06 g) was added and stirred for 1 hour. 1N hydrochloric acid (100 m
l) was added and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and dried to obtain compound (13) (10.8 g, 99%).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

Example 3 (Synthesis of Compound 15) Pyridine (4 ml) was added to a solution of compound (11) (8.28 g) in acetonitrile (100 ml) to prepare isophthaloyl chloride (14).
(4.06 g) was added and stirred for 1 hour. 1N hydrochloric acid (100 m
l) was added and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and dried to obtain compound (15) (10.2 g, 94%). Example 4 (Synthesis of Compound 17) Pyridine (4 ml) was added to a solution of compound (11) (8.28 g) in acetonitrile (100 ml), and 2,6-pyridinedicarbonyldichloride (16) (4.08 g) was added. And stirred for 1 hour. 1N Hydrochloric acid (100 ml) was added and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and dried to obtain compound (17) (10.0 g, 92%).

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

Example 5 (Synthesis of Compound 19) Pyridine (4 ml) was added to a solution of the compound (11) (8.28 g) in acetonitrile (100 ml), and adipic acid chloride (18) (3.66) was added.
g) was added and stirred for 1 hour. 1N hydrochloric acid (100 ml) was added, and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and dried to obtain compound (19) (9.9 g, 78%).

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

Example 10 (Synthesis of Compound 5) Compound (15) (1.09 g) and phenylhydrazine compound (2
1) (0.75 g) was added to N, N-dimethylacetamide (10 ml), and the mixture was heated under reflux for 2 hours. The solvent was distilled off, isopropyl alcohol (50 ml) was added to the residue, and the precipitated crystals were collected by filtration. The obtained crystals were washed with isopropyl alcohol to give compound (5) (0.26 g, 16%, mp> 300 ° C). NMR
(δ ppm, CDCl ₃ ) 2.56 (4H, d), 7.72 (5H, m), 7.86 (12H,
m), 8.18 (2H, d), 8.59 (1H, s), 10.54 (2H, s)

Claims (4)

[Claims] 1. The following formula: (In the formula, X represents a linear or branched methylene group having 1 to 6 carbon atoms, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted pyridinediyl group; R ¹ is independently a hydrogen atom or Represents a halogen atom; Y represents each independently a linear or branched alkyl group having 1 to 6 carbon atoms or a hydroxyl group; n and m each independently represent 1 or
A pyrazolone compound represented by 2). 2. X is a straight-chain methylene group having 3 to 5 carbon atoms,
An unsubstituted phenylene group or an unsubstituted pyridinediyl group; R ¹ is independently a hydrogen atom or a halogen atom;
Y is a hydroxyl group; n and m are each independently 1 or 2
The compound of claim 1, which is Wherein X is - (CH _{2) 4} -, it is unsubstituted m- or p- phenylene, or unsubstituted 2,6-pyridine-diyl group; -NHCO-X-CONH- group is bonded A substituted pyrazolon-3-yl group on the phenyl group is -NHCO-X-CO
M- or p-substituted with respect to the NH- group; R ¹ is independently a hydrogen atom or a chlorine atom; Y is a hydroxyl group; n and m
The compound according to claim 2, wherein each independently is 1 or 2. 4. The compound according to claim 3, wherein the pyrazolon-3-yl group is p-substituted on the phenyl ring with respect to the -NHCO-X-CONH- group.