JPH0393767A - Production of hydrazine compound having semicarbazide group - Google Patents

Abstract

NEW MATERIAL:The new hydrazine compound having semicarbazido group and expressed by formula I (both A<1> and A<2> are H or one of the groups is H and the other is acyl, sulfonyl or oxalyl; X is bivalent aromatic residue or heterocyclic residue; R<1> to R<3> are H, alkyl, alkenyl, alkynyl, aryl, heterocyclic group, acyl, sulfonyl, carbamoyl, etc.; R<1> and R<2> and/or R<1> and R<3> may together form a ring, etc.; R<4> is H or alkyl; G is carbonyl, sulfonyl, sulfoxy, phosphoryl, etc.; R<5> is H, alkyl, aryl, alkoxy, heterocyclic group, OH, etc.; R<6> is H, alkyl, aryl or heterocyclic group). EXAMPLE:The compound of formula II. USE:A contrasting agent and fogging agent in the field of photosensitive material. It has high performance and excellent properties. PREPARATION:The compound of formula I can be produced by condensing a hydrazine derivative of formula III with a compound of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a novel hydrazine compound having a semirubazide group.

[Background of the invention]

Hydrazine compounds have been used in various fields. For example, in the field of photographic light-sensitive materials, it is used as a contrast enhancer or a fogging agent.

For example, regarding hydrazine compounds used as contrast enhancing agents, there is a desire for compounds that exhibit even better contrast enhancing effects.

Based on the above background, the present inventors have made various studies and have proceeded with research into the development of a new hydrazine compound that can exhibit better performance than conventional ones.

[Object of the Invention] An object of the present invention is to develop a novel hydrazine compound that can exhibit good performance, and to provide a method for producing the same.

[Structure of the invention]

The present invention is characterized in that a hydrazine derivative represented by the following general formula [II] is condensed with a compound represented by the following general formula (lI[), which is represented by the following general formula [I]. This is a method for producing a hydrazine compound having a segocarbazide group.

General formula [■] General formula CI! ) General formula (III) The present invention will be explained in more detail below.

According to the present invention, a hydrazine compound represented by the above general formula [I] is provided.

In the general formula (1), A I and A f both represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. X represents a divalent aromatic residue or a heterocyclic residue.

R', R'' and R3 each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a thioacyl group, a sulfonyl group, a carbamoyl group, or a thiocarbamoyl group. R2 and/or R'' and R3 may form a ring, and R1 and R
2 may form an alkylidene group.

R4 represents a hydrogen atom or an alkyl group.

G represents a carbonyl group, sulfonyl group, sulfoxy group, phosphoryl group, thiocarbonyl group, or iminomethylene group, and RS represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a hydroxy group, Represents an amino group, an alkoxycarbonyl group, an alkenyloxycarbonyl group, an alkynyloxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group.

To explain the general formula (1) in more detail, A I
, A! are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (e.g., acetyl, trifluoroacetyl, benzoyl, etc.) or a sulfonyl group (e.g., ethane, methanesulfonyl, benzenesulfonyl, toluenesulfonyl, etc.) each group), or an oxalyl group (for example, a group such as ethoxalyl). AI, A
! is most preferably a hydrogen atom.

and represents each group or those with substituents, etc.). X is preferably a phenylene group or a naphthylene group, particularly 1,4-phenylene? is preferred.

Rl. R2 and R3 each represent a hydrogen atom, an alkyl group (e.g., methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, 2(2.4-di-alphenoxy)ethyl, benzyl, trifluoroethyl, etc.); ), alkenyl groups (e.g., allyl, butenyl, bentenyl, pentadienyl, etc.), alkynyl groups (e.g., eha, propargyl, putynyl, pentynyl, etc.), aryl groups (e.g., phenyl, naphthyl,
cyanophenyl, methoxyphenyl, etc.), heterocyclic groups (e.g., pyridine, thiophene, furan, tetrahydrofuran, sulfolane, etc.), acyl groups (e.g., acetyl, benzoyl, 2-(2,4-di), t-amylphenoxy)butanoyl, etc.), thioacyl groups (e.g., thioacetyl, thiobenzoyl, etc.), sulfonyl groups (e.g., methanesulfonyl, ethanesulfonyl, benzenesulfonyl, etc.), carbamoyl groups (e.g., unsubstituted carbamoyl, methylcarbamoyl, provirylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, penzylcarbamoyl, etc.), thiocarbamoyl groups (for example, unsubstituted thiocarbamoyl, methylthiocarbamoyl, ethylthiocarbamoyl, butylthiocarbamoyl, octylthiocarbamoyl, phenyl) thiocarbamoyl, pendylthiocarbamoyl, cyclohexylthiocarbamoyl, etc.), and R' and R2 and/or R1 and R3 together with the nitrogen atom form a heterocycle (for example, a ring such as biperidine, biperazine, morpholine, etc.). Alternatively, Rl and R2 may form an alkylidene group such as penzylidene or an alkylidene group having a substituent.

R4 represents a hydrogen atom or an alkyl group (eg, methyl, ethyl, benzyl, etc.).

-C In formula [1), when G is a carbonyl group, RS is a hydrogen atom, an alkyl group (e.g. methyl, trifluoromethyl, 2,4-di-t-amylphenoxymethyl, methoxymethyl, phenoxymethyl, hydroxy methyl, cyanomethyl, methylthiomethyl, phenylthiomethyl, etc.), aryl groups (e.g., phenyl, chlorophenyl, etc.), alkoxy groups (e.g., ethoxy, penzyloxy, etc.), aryloxy groups (e.g., phenoxy, etc.) ), heterocyclic groups (e.g., biridyl, chenyl, furyl, etc.), hydroxy groups, amino groups (e.g., ξ-no, methyl-aξ-no, dimethylamino, anilino, etc.), alkoxy carbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, tetradecyloxycarbonyl, etc.), alkenyloxycarbonyl groups (e.g., allyloxycarbonyl, etc.), alkynyloxycarbonyl groups (e.g., propargyloxycarbonyl, etc.), aryloxycarbonyl groups (e.g., groups such as phenoxycarponyl), carbamoyl groups (e.g. carbamoyl, methylcarbamoyl, ethylcarbamoyl, methoxyethylcarbamoyl, cyanoethylcarbamoyl, hydroxyethylcarbamoyl, 4-(2,4-di-t-amylphenoxy)butylcarbamoyl, pendylcarbamoyl), rucarbamoyl, trifluoroethylcarbamoyl, allylcarbamoyl, pentadienylcarbamoyl, propargylcarbamoyl, phenylcarbamoyl, cyanophenylcarbamoyl, naphthylcarbamoyl, pyridylcarbamoyl, furylcarbamoyl, tetrahydrofurylcarbamoyl, hydroxycarbamoyl, methoxycarbamoyl,
Allyloxycarbamoyl, propargyloxycarbamoyl, ryoryloxycarbamoyl, pyridyloxycarbamoyl, biperidinocarbonyl, morpholinocarbonyl, (2,2,6,6-tetramethylpiperidine-
4-yl)carbamoyl, etc.). When G is a sulfonyl group, R5 is an alkyl group (e.g. methyl, ethyl, etc.), an aryl group (e.g. phenyl, tolyl,
4-dodecyloxyphenyl, etc.), heterocyclic groups (e.g., pyridyl, furyl, chenyl, etc.), amino groups (e.g., amino, methylamino, morpholino, etc.)
is preferred. When G is a sulfoxy group, R5 is preferably an alkyl group (for example, a group such as cyanobenzyl). When G is a phosphoryl group, Rs is preferably an aryl group (for example, a group such as phenyl), an alkoxy group (for example, a group such as methoxy or ethoxy), or an aryloxy group (for example, a group such as phenoxy).

When G is a thiocarbonyl group, Rs is preferably a hydrogen atom, an alkyl group (for example, a group such as methyl), or an aryl group (for example, a group such as phenyl). When G is an ξnomethylene group, R% is an alkyl group (for example, a group such as methyl or ethyl),
Aryl groups (eg, groups such as phenyl) are preferred.

In the present invention, more preferred compounds are those in general formula (1) in which G is a carbonyl group and RS is a hydrogen atom, an alkyl group, or a carbamoyl group.

In the production method of the present invention, the hydrazine compound represented by the general formula [I] is combined with the compound represented by the general formula [II] (hereinafter also referred to as "compound [II] J" as appropriate) and the general formula [II]. Compound represented by formula (III) (hereinafter referred to as "
It is produced by condensing a compound (sometimes referred to as "■").

In the general formula (n) (III), R t, Rz, R
i, Ra, R', X, A', A'' and G have the same meanings as above.

Rh is a hydrogen atom, an alkyl group (for example, methyl, ethyl, methoxyethyl, benzyl, etc.), an aryl M (
For example, phenyl, chlorophenyl, etc.) or a heterocyclic group (eg, pyridyl, etc.), and among these, phenyl is the most preferred.

In the condensation reaction between compound [II] and compound (III), it is advantageous to use a solvent that has the property of dissolving compound (1). For example, acetonitrile, pyridine, benzene, toluene, chlorobenzene, ethyl acetate, or amides (eg, acetamide, dimethylformamide, dimethylacetate ξF, etc.) are suitable.

In this condensation reaction, compounds [■], (I[[
] or in the presence of a base (for example, triethylamine, pyridine, idazole, etc.), and generally it is suitable to carry out the reaction at a temperature ranging from room temperature to the boiling point of the solvent.

However, the production method of the present invention is not limited to the above reaction conditions. The hydrazine derivative represented by the general formula [II] can be produced manually by commercially available products, or by the following reaction formulas (IVY.(V), (VIE
or the Journal of the Chemical Society4
elIIical Society) 1961, the following reaction formula [■] as described in No. 1743-1748 and JP-A-1-132561. It is possible to practice the precepts using the method shown in [■].

Margin below Reaction formula (IV) N}IJHz・H,0 Reaction formula [V] Reaction formula (Vl) Reaction formula [■] Reaction formula [■] Specific compound examples (1) (3) In the above, Et represents an ethyl group, and Ac represents an acetyl group.

In the compound represented by the general formula [I], for example, G in the formula is a carbonyl group, AI, A2, R4, RS are hydrogen atoms,
Regarding compounds in which R& is a phenyl group, JP-A-62-27
It can be synthesized by the known method described in No. 0948, and other compounds (III) can be synthesized in the same manner.

Representative examples of the compound represented by general formula [I] produced by the present invention are shown below. However, the specific compound of general formula (1) obtained by the present invention is not limited to these compounds.

(5) (11) (7) (12) (8) (9) <14) (lO) (15) (16) (17) (l8) (l9) (25) (27) (20) (2l ) (22) (29) (3l) (32) (33) (34) (35) (36) (38) (44) (39) (42) (53) (55) (56) (57) ( 5 days) (64) (66) (67) (59) (60) (62) (63) (68) (70) CI. (72) (73) (74) (75) (76) (8I) (84> (77) (78) (79) (85) (86) (87) ■3 * NHNIICOCONIICI12CIhOCI13N
HCSNIICzlls (90) (9l) (92) (93) (9 days) (100) C2HS (94) (95> (96) (97) (+02) (103) Among the above, exemplified compound (2).( 3).(5) can also be obtained by reacting compound (1) with 2-(2,4-di-t-agorphenoxy)butanoic acid chloride, methylisothiocyanate, and dodecyl isocyanate, respectively. Exemplary compound (1) is also effective as a synthetic intermediate for the compound of general formula (1).

The compound represented by the general formula [■] produced by the present invention can be used in various fields that use this type of hydrazine compound.

For example, it can be used as a contrast agent in the field of silver halide photographic materials. It can also be used as a fogging agent.

It is particularly effective as a contrast enhancer.

That is, for example, in the photographic reproduction of a continuous tone image using a halftone image in a printing plate-making process, or the reproduction of a line drawing, a silver halide photographic light-sensitive material having high contrast photographic properties is required. For this purpose, hydrazine compounds were added to silver halide photographic emulsions in JP-A No. 56-10
This method is disclosed in Japanese Patent No. 6244 and US Pat. No. 4,686.167. The hydrazine produced in the present invention exhibits particularly excellent performance as a hydrazine used for the above purpose, a so-called high contrast agent. [Examples] The present invention will be explained below using examples. However, the following examples are merely examples of the present invention, and the present invention is of course not limited thereto. Example 1 Exemplary compound (1), the Gakai compound (1), is obtained from the compound (a) synthesized according to the Gawai method below and commercially available hydrazine hydrate. (In the above, Pd/C is a palladium-carbon catalyst).

Acetonitrile 200#ll! 20.0 g of the compound (a) obtained above was added to the suspension, and 4.0 d of hydrazine hydrate was added to the suspension while stirring in 100 g of acetonitrile.
When the solution diluted with d is added dropwise and refluxed, compound (a)
dissolves. After about 10 minutes, white crystals begin to precipitate and eventually become full of precipitates. After stirring under reflux for 4 hours, the mixture was cooled to room temperature, and the precipitated crystals were collected by suction filtration, washed with 100% acetonitrile, and dried to obtain 15.7 g of compound (1).

Compound (1) turned brown and decomposed at 210''C.

Exemplary compound (2). (3), (5), (64), etc. can be obtained by preparing compound (1) by the following method in addition to the production method of the present invention.
easily obtained from.

Example 2 Compound (2) of Exemplified Compound (2) is obtained from compound (a) of Example 1 and compound (b) which is synthesized according to the following method.

10.0 g of compound (a) and 10.5 g of compound (b) are added to 100 d of pyridine, and the mixture is refluxed with stirring. After 5 hours of reaction, the reaction solution is concentrated and then poured into water 5001d to precipitate crude crystals. The crystals are collected by suction filtration, washed with water, and then dried. This was heated and dissolved in 30d of toluene, cooled to room temperature, and this solution was dissolved in 100d of hexane.
When injected into ll, white crystals precipitate. This was collected by suction filtration, washed with 20#t1l of hexane, dried, and the compound (
1.3 g of 2N was obtained. The melting point was 113.5°C.

Example 3 Exemplified compound (3), compound (3), is obtained from compound (a) of example 1 and commercially available methylthiosemicerubazide.

10.0 g of compound (a) in 100 d of acetonitrile
and 4.0 g of methylthiosecarbazide were added, and 10 d of triethylamine was added dropwise with stirring, followed by refluxing.

After reacting for 7 hours, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by suction filtration. These crystals are heated and dissolved in a mixed solution of 70 d of DMF (dimethylformamide) and 70 IR of acetonitrile, and then cooled to O''C to precipitate white crystals. These are collected by suction filtration, washed with 20 d of acetonitrile, and dried to form compound (3). ) 7.6g was obtained.Melting point was 212
．． The temperature was 5°C.

Example 4 Synthesis of Exemplified Compound (6) Compound (6) is obtained from compound (a) of Example 1 and 1,1-dibenzylhydrazine combined according to the following synthesis method.

Compound (a) 12.6g to chlorobenzene 63d
and 7.3 g of 1,1-dibenzylhydrazine were added, and the mixture was refluxed with stirring. After 2 hours of reaction, about 50 parts of chlorobenzene was distilled off, 50 ml of ethyl acetate was added, and the temperature was cooled to O''C to precipitate white crystals. These crystals were collected by suction filtration, washed with 20 parts of hexane, and dried to obtain the compound ( 6) 9.6 g was obtained.The melting point was 154.5°C.Example 5 Synthesis of Exemplified Compound (12) Compound (12) was a known compound described in JP-A No. 62-270948 etc. Compounds that are permitted according to the following legal laws (
C) and hydrazine hydrate.

Compound (12) 14.7 was prepared in the same manner as in Example 1 from 20.0 g of compound (c) and 4.3 d of hydrazine hydrate.
I got g.

Example 6 Compound (38) of Exemplary Compound (38) is a compound (e) synthesized by the following synthesis method from the following compound (d) described in U.S. Patent No. 4,686.167. is obtained from commercially available methylthioseξcarbazide. Below margin -・''・'t'? Procedural amendment (self-button (d) Compound (e) in acetonitrile 100-10.0
After adding 3.8 g of methylthiosemicarbazide and 10 d of triethylamine with stirring, 6.4 g of compound (3B) was obtained in the same manner as in Example 3. [Effects of the Invention] According to the present invention, a novel hydrazine compound useful as, for example, a contrast enhancer can be provided.

Claims (1)

[Claims] 1. A hydrazine derivative represented by the following general formula [II];
A method for producing a hydrazine compound having a semicarbazide group represented by the following general formula [I], which comprises condensing the compound with a compound represented by the following general formula [III]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A^ 1 and A^2 both represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. X represents a divalent aromatic residue or a heterocyclic residue. R^1, R^2 and R^3 each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a thioacyl group, a sulfonyl group, a carbamoyl group, or a thiocarbamoyl group. represent. R^1
and R^2 and/or R^1 and R^3 may form a ring, or R^1 and R^2 may form an alkylidene group. R^4 represents a hydrogen atom or an alkyl group. G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, a thiocarbonyl group, or an iminomethylene group. R^5 is a hydrogen atom, an alkyl group, an aryl group,
Heterocyclic group, alkoxy group, aryloxy group, hydroxy group, amino group, alkoxycarbonyl group, alkenyloxycarbonyl group, alkynyloxycarbonyl group,
Represents an aryloxycarbonyl group or a carbamoyl group. R^6 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.