JPH09160167A - Silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photosensitive material prevented from deterioration of color tone and sensitivity and low in fog by incorporating at least one king of specified compound. SOLUTION: This silver halide photosensitive material contains at least one kind of compound represented by the formula in which R is an aliphatic hydrocarbon or aryl or heterocyclic group; L is a divalent arylene or heterocyclic group; A is an H or halogen atom or an electron withdrawing group; the aliphatic hydrocarbon group represented by R is a straight or branched or cyclic alkyl or alkenyl group or the like each optionally substituted; the aryl group represented by R is a phenyl or 4-methylphenyl group or the like; and the hetero-cyclic group represented by R is a 3- to 10-membered saturated or unsaturated heterocyclic group having at least one of N, O, and S atoms.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silver halide photosensitive material and a photothermographic material.

[0002]

2. Description of the Related Art A photothermographic material for forming a photographic image by using a heat development processing method is disclosed, for example, in US Pat. No. 3,152,904.
No. 3457075 and D.C. Morgan and B.A. "Thermally Processed Silver Systems" by Shely
(Imaging Processes and Materials Neblette 8
Edition, Sturge, V. Walworth
th), A. Edited by Shepp, page 2, 1969
Year). Such a photothermographic material is
It contains a reducible silver source (eg organic silver salt), a catalytically active amount of photocatalyst (eg silver halide), a toning agent controlling the color tone of silver and a reducing agent, usually dispersed in an (organic) binder matrix. ing. The photothermographic material is stable at room temperature, but it is a reducible silver source (functions as an oxidizing agent) when heated to a high temperature (for example, 80 ° C or higher) after exposure.
Silver is produced through a redox reaction between a reducing agent and a reducing agent.
This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver produced by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas and forms the image.

The most effective conventional fog prevention technique has been a method using a mercury compound as an antifoggant. The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat. No. 3,589,990.
No. 3. However, mercury compounds are not environmentally preferable, and development of a non-mercury antifoggant has been desired. As non-mercury antifoggants, various polyhalogen compounds have hitherto been disclosed (for example, US Pat. No. 3,874,946).
No. 4,756,999, No. 5,340,712, European Patent Nos. 605981A1, 622666A1, 6
31176A1, JP-B-54-165, JP-A-7-
No. 2781). However, these compounds have problems that the effect of preventing fogging is low and that the color tone of silver is deteriorated. Further, those having a high antifogging effect have problems such as lowering of sensitivity, and thus need to be improved.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide light-sensitive material and a photothermographic material which are free from deterioration of color tone and sensitivity and have low fog.

[0005]

The above-mentioned objects can be achieved by the following means. (1) A silver halide light-sensitive material containing at least one compound represented by the following general formula (I). General formula (I)

[0006]

Embedded image

(In the formula, R represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. L represents a divalent arylene group or a divalent heterocyclic group. X ₁ and X ₂ are each a halogen. Represents an atom, and A represents a hydrogen atom, a halogen atom or an electron-withdrawing group.)

(2) A photothermographic material containing at least one compound represented by the general formula (I).

(3) A photothermographic material comprising at least one compound represented by the general formula (I) and at least one compound represented by the following general formula (II). General formula (II)

[0010]

Embedded image

(In the formula, R ₁ and R ₂ represent an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. N is 0 to 4).
Represents an integer. (4) The photothermographic material according to (2) or (3), which is for infrared laser exposure.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION First, the compound represented by formula (I) will be described in detail. The aliphatic hydrocarbon group represented by R is a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and further preferably 1 to 12), an alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 and even more preferably 2
To 12), an alkynyl group (preferably having 2 to 20 carbon atoms,
It is more preferably 2 to 16 and even more preferably 2 to 12) and may have a substituent.

The substituent is, for example, an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms,
Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl. ), An amino group (preferably having a carbon number of 0 to 20, more preferably 0 to 10, particularly preferably 0 to 6, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.), Alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, etc.), aryloxy group (preferably 6 to 2 carbon atoms
It has 0, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples include phenyloxy and 2-naphthyloxy. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, acetyl,
Examples thereof include benzoyl, formyl and pivaloyl. ), An alkoxycarbonyl group (preferably having 2 carbon atoms)
-20, more preferably 2-16 carbon atoms, particularly preferably 2-12 carbon atoms, for example, methoxycarbonyl,
Ethoxycarbonyl and the like. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, and particularly preferably having 7 to 1 carbon atoms.
0, for example, phenyloxycarbonyl and the like. ), An acyloxy group (preferably having 1 to 2 carbon atoms)
It has 0, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). (Preferably having 2 to 20 carbon atoms,
More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 carbon atoms)
To 16, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino,
Benzenesulfonylamino, methanesulfonamide, octylsulfonylamino, dodecanesulfonamide, naphthylsulfonylamino, toluenesulfonylamino,
p-methoxyphenylsulfonylamino, 2,4,6-
Trimethylphenylsulfonylamino and the like can be mentioned. ), A sulfamoyl group (preferably having a carbon number of 0 to 2)
It has 0, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and phenylsulfamoyl. ), A carbamoyl group (preferably having 1 to 20 carbon atoms, and more preferably having 1 to 1 carbon atoms).
6, particularly preferably 1 to 12 carbon atoms, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), An ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms,
Examples thereof include ureido, methylureido, phenylureido and the like. ), An alkylthio group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 16 and particularly preferably a carbon number of 1 to 12 and examples thereof include methylthio and ethylthio), and an arylthio group (preferably carbon). Number 6 to 20, more preferably carbon number 6 to 16,
Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenylthio. ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl), and a sulfinyl group (preferably carbon). It has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl).
Phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms)
And examples thereof include diethylphosphoric acid amide and phenylphosphoric acid amide. ), Hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxy group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, heterocyclic group (For example, imidazolyl, pyridyl, furyl, piperidyl, morpholino and the like can be mentioned.) And the like. These substituents may be further substituted. When there are two or more substituents, they may be the same or different.

The substituent of the aliphatic hydrocarbon group represented by R is preferably an aryl group, an alkoxy group or a heterocyclic group, more preferably an aryl group or a heterocyclic group. The aliphatic hydrocarbon group represented by R is preferably an alkyl group, and more preferably a chain alkyl group.

The aryl group represented by R is preferably a monocyclic or condensed ring aryl group having 6 to 30 carbon atoms, and more preferably a monocyclic or condensed ring aryl group having 6 to 20 carbon atoms. Examples thereof include phenyl and naphthyl, and phenyl is particularly preferable. The aryl group represented by R may have a substituent, and examples of the substituent include those exemplified as the substituents of the aliphatic hydrocarbon group represented by R, and an alkyl group (preferably having a carbon number of 1 to 1). 20, more preferably 1 to 12 carbon atoms, particularly preferably 1 carbon atom
To 8 and examples thereof include methyl, ethyl, iso-propyl, tert-butyl, n-octyl, tert-amyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), Alkynyl group (preferably having 2 to 2 carbon atoms)
It preferably has 20 carbon atoms, more preferably has 2 to 12 carbon atoms, and particularly preferably has 2 to 8 carbon atoms, and examples thereof include propargyl and 3-pentynyl. ) Etc. can be applied.

The substituent of the aryl group represented by R is preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group,
Acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group,
Ureido group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, phosphoramide group, halogen atom, cyano group, nitro group, heterocyclic group, more preferably an alkyl group, an alkoxy group, an aryloxy group,
Acyl group, alkoxycarbonyl group, acyloxy group,
Acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group,
Sulfamoyl group, carbamoyl group, ureido group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, phosphoramide group, heterocyclic group, more preferably an alkyl group, an alkoxy group, an aryloxy group,
Acylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group, phosphoric acid amide group, a heterocyclic group, particularly preferably an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonylamino group, a sulfamoyl group, A carbamoyl group and an ureido group.

Specific examples of the aryl group represented by R include phenyl, 4-methylphenyl and naphthyl.

The heterocyclic group represented by R is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one N, O or S atom, which may be a monocyclic ring. , And may form a condensed ring with another ring. The heterocyclic group is preferably a 5- to 6-membered heterocyclic group, more preferably a 5- to 6-membered heterocyclic group containing a nitrogen atom, and further preferably 1 to 2 nitrogen atoms.
It is a 5- or 6-membered aromatic heterocyclic group containing atoms.

Specific examples of the heterocyclic group include thienyl, furyl, pyranyl, 2H-pyrrolyl, pyrrolyl,
Imidazolyl, pyrazolyl, isothiazolyl, isoxazolyl, thiazolyl, oxazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-
Oxadiazolyl, 1,3,4-thiadiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, indolyl, 1H-indazolyl, purinyl, 4H-quinolidinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, Cinnolinyl, pteridinyl, carbazolyl, β-carbonylyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, phenalsazinyl, phenothiazinyl, flazanyl, phenoxazinyl, isochromanyl, chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolidinyl, pyridolinidinyl, imidazolidinyl, pyridolinidinyl, imidazolinyl, , Piperidyl, piperazinyl, indolinyl, isoin Examples thereof include linyl, quinuclidinyl, morpholinyl, tetrazolyl, benzimidazolyl, benzoxazolyl, benzthiazolyl, benztriazolyl, triazinyl and the like, preferably pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, 1,2,3-triazolyl, 1 , 2,4-triazolyl, 1,3,4-oxadiazolyl, 1,3,4-
Thiadiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, 1H-indazolyl,
Purinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, tetrazolyl, benzimidazolyl, benzoxazolyl, benzthiazolyl, benztriazolyl, triazinyl, and more preferable imidazolyl, pyrazolyl, thiazolyl, thioazolyl.
1,2,3-triazolyl, 1,2,4-triazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, 1H-indazolyl, purinyl, quinolyl, Phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, tetrazolyl, benzimidazolyl, benzoxazolyl, benzthiazolyl, benztriazolyl, triazinyl, particularly preferably imidazolyl, thiazolyl, oxazolyl, 1,2,4-triazolyl, 1,
3,4-oxadiazolyl, 1,3,4-thiadiazolyl, pyridyl, quinolyl, tetrazolyl, benzimidazolyl, benzoxazolyl, benzthiazolyl, benztriazolyl, triazinyl and the like can be mentioned.

The heterocyclic group represented by R may have a substituent, and examples of the substituent include those exemplified as the substituent of the aliphatic hydrocarbon group represented by R, and an alkyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms
2, particularly preferably C 1-8, such as methyl, ethyl, iso-propyl, tert-butyl, n
-Octyl, tert-amyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 2 carbon atoms).
It preferably has 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include propargyl and 3-pentynyl).
Can be applied.

The substituent of the heterocyclic group represented by R is preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group,
Acyloxy group, acylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, ureido group,
Alkylthio group, sulfonyl group, sulfinyl group, halogen atom, cyano group, nitro group, a heterocyclic group, more preferably an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonylamino group, Sulfamoyl group, carbamoyl group, a heterocyclic group, more preferably an alkyl group, an aryl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group,
It is an ureido group or a heterocyclic group.

The divalent arylene group represented by L is preferably an arylene group having 6 to 30 carbon atoms, more preferably a monocyclic or condensed ring arylene group having 6 to 20 carbon atoms, and further preferably Is phenylene or naphthylene, particularly preferably phenylene.

The divalent heterocyclic group represented by L is N, O
Or a 3- to 10-membered saturated or unsaturated heterocycle containing at least one S atom, which may be a monocycle or may form a condensed ring with another ring.
The heterocycle is preferably a 5- to 6-membered aromatic heterocycle, more preferably 5 to 6 containing a nitrogen atom.
A 5-membered aromatic heterocycle, more preferably a 5- to 6-membered aromatic heterocycle containing 1 to 3 nitrogen atoms.

Specific examples of the heterocycle include pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole,
Pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline,
Pteridine, acridine, phenanthroline, phenazine, thiazole, oxazole, benzimidazole,
Examples thereof include benzoxazole and benzthiazole. The heterocycle is preferably thiophene, furan,
Pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, thiazole, oxazole, benzimidazole, benzoxazole, Benzthiazole, indolenine, more preferably pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, thiadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole, indolenine. , And particularly preferably, thiadiazole.

The divalent arylene group and divalent heterocyclic group represented by L may have a substituent, and examples of the substituent include the substituents of the aliphatic hydrocarbon group represented by R. In addition to the above, an alkyl group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 12 carbon atoms, and particularly preferably 1 carbon atom.
To 8 and examples thereof include methyl, ethyl, iso-propyl, tert-butyl, n-octyl, tert-amyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), Alkynyl group (preferably having 2 to 2 carbon atoms)
It preferably has 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include propargyl and 3-pentenyl. ) Etc. are applicable.

The substituent of the divalent arylene group or divalent heterocyclic group represented by L is preferably an alkyl group, an aryl group or a halogen atom, more preferably an alkyl group having 1 to 10 carbon atoms, 6 to 12 aryl groups and halogen atoms. L is preferably a phenylene group, 1,
It is a 3,4-thiadiazolyl group.

The halogen atoms represented by X ₁ and X ₂ may be the same or different and are a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, Chlorine atom and bromine atom are more preferable, and bromine atom is particularly preferable.

The halogen atom represented by A is a fluorine atom,
Chlorine atom, bromine atom and iodine atom are preferable, chlorine atom, bromine atom and iodine atom are more preferable, chlorine atom and bromine atom are more preferable, and bromine atom is particularly preferable. The electron withdrawing group represented by A is preferably σ
Substituent having _ap value of 0.01 or more, more preferably σ
It is a substituent having _ap value of 0.1 or more. Examples of the electron-withdrawing group include trihalomethyl group, cyano group, nitro group, aliphatic aryl group or heterocyclic sulfonyl group, aliphatic group
Examples thereof include an aryl or heterocyclic acyl group, an alkenyl group, an alkynyl group, an aliphatic aryl or heterocyclic oxycarbonyl group, a carbamoyl group, a sulfamoyl group, etc., preferably an aliphatic aryl or heterocyclic sulfonyl group, an aliphatic aryl. Alternatively, it is a heterocyclic acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. A is preferably a halogen atom,
A chlorine atom, a bromine atom and an iodine atom are more preferable, a chlorine atom and a bromine atom are still more preferable, and a bromine atom is particularly preferable.

Of the compounds represented by the general formula (I), the compounds represented by the general formula (Ia) are preferable. General formula (Ia)

[0030]

Embedded image

In the formula, L has the same meaning as in formula (I), and the preferred range is also the same. X ₃ and X
₄ has the same meaning as X ₁ and X ₂ in formula (I), respectively, and the preferred range is also the same. Aa has the same meaning as A in formula (I), and the preferred range is also the same.

Of the compounds represented by the general formula (I), the compounds represented by the general formula (Ib) are preferable. General formula (Ib)

[0033]

[Chemical 6]

In the formula, L has the same meaning as in formula (I), and the preferred range is also the same. Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited thereto.

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

The compound represented by the general formula (I) of the present invention can be synthesized according to the method described in, for example, JP-A-5-239015.

Specific examples of the synthesis of the compound represented by formula (I) are shown below. Synthesis Example 1 Synthesis of Compound I-2 Synthesis of [4- (phenylthio) phenylthio] acetic acid 2-phenylthiobenzenethiol 21.9 g (0.1
(0 mol), ethanol (30 ml) and water (50 ml) are stirred at room temperature, and then sodium hydroxide (5.2 g) is added.
An aqueous solution of (0.13 mol) / 10 ml of water was added dropwise. 2
After stirring for 0 minutes, sodium monochloroacetate 15.1 g
(0.13 mol) was added and heated to 40 ° C. 5.2 g of sodium hydroxide while stirring at the same temperature
An aqueous solution of (0.13 mol) / 10 ml of water was slowly added dropwise. After stirring at 40 ° C. for 6 hours, it was cooled to room temperature and the pH was adjusted to about 2 with concentrated hydrochloric acid. The precipitated solid was collected by filtration, and
By recrystallizing with propanol, a white solid [4
2 (1.6 g) of-(phenylthio) phenylthio] acetic acid
(0.078 mol) was obtained. Yield 78%

Synthesis of Compound I-2 13.8 g (0.05 mol) of [4- (phenylthio) phenylthio] acetic acid obtained in the above reaction and 60 ml of water were stirred, and 18.0 g of sodium hydroxide was added.
An aqueous solution of (0.45 mol) / water (30 ml) was added dropwise. Under ice cooling, 24.0 g (0.15 mol) of bromine was slowly added dropwise, the mixture was stirred for 2 hours, and then left overnight at room temperature. The precipitated crystals were collected by filtration and recrystallized from acetonitrile to give 16.5 g (0.0
31 mol) was obtained. Yield 62% Melting point 217-218 ° C

Next, the compound represented by formula (II) will be described in detail. The aliphatic hydrocarbon group represented by R ₁ and R ₂ has the same meaning as in the case where R in the general formula (I) is an aliphatic hydrocarbon group, and the preferred range is also the same.
The aryl group represented by R ₁ and R ₂ has the same meaning as in the case where R in the general formula (I) is an aryl group, and the preferred range is also the same. The substituent of the aryl group represented by R ₁ and R ₂ is preferably an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, a ureido group or a phosphoric acid amide group, more preferably an acylamino group or a sulfonylamino group. , A sulfamoyl group,
A carbamoyl group and a ureido group are preferable, and a sulfonylamino group is particularly preferable. The heterocyclic group represented by R ₁ and R ₂ has the same meaning as in the case where R in the general formula (I) is a heterocyclic group, and the preferred range is also the same.

N represents an integer of 0 to 4, preferably 0.
Or 1, and more preferably 0.

Among the compounds represented by the general formula (II), the compounds represented by the general formula (II-a) are preferable. General formula (II-a)

[0046]

Embedded image

(Wherein R _a1 , R _a2 , R _a3 , R _a4 , R _a5 ,
R _b1 , R _b2 , R _b3 , R _b4 and R _b5 each represent a hydrogen atom or a substituent. As the substituents represented by R _{a1 to} R _b5 , those exemplified as the substituents which R in the general formula (I) may have when R is an aryl group can be applied, and the preferred range is also the same. is there. )

Among the compounds represented by the general formula (II), the compounds represented by the general formula (II-b) are preferable. General formula (II-b)

[0049]

Embedded image

(In the formula, R _2a1 and R _2a2 each represent an aliphatic hydrocarbon group, an aryl group or a heterocyclic group.
_2a3 and R _2a4 each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. )

The aliphatic hydrocarbon group represented by R _2a1 and R _{2a2 has the same meaning as the case} where R in the general formula (I) is an aliphatic hydrocarbon group. The aliphatic hydrocarbon group represented by R _2a1 and R _2a2 is preferably an alkyl group, more preferably 1 to 30 carbon atoms, and further preferably 1 to 2 carbon atoms.
0, particularly preferably an alkyl group having 1 to 16 carbon atoms. Specific preferred examples of the aliphatic hydrocarbon group include n-
Butyl, tert-butyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl, n-undecyl and the like can be mentioned. The aryl group represented by R _2a1 and R _{2a2 has the same meaning as} in the case where R in the general formula (I) is an aryl group, and the preferred range is also the same. The heterocyclic group represented by R _2a1 and R _{2a2 has the same meaning as} in the case where R in the general formula (I) is a heterocyclic group, and the preferred range is also the same. R _2a1 and R _2a2 are preferably alkyl groups.

[0052] aliphatic hydrocarbon group represented by R _2a3 and R _2a4, an aryl group, a heterocyclic group are the same as those represented by R _2a1, R _2a2, and the preferred ranges are also the same. R _2a3 and R _2a4 are preferably a hydrogen atom or an aliphatic hydrocarbon group, and more preferably a hydrogen atom or an alkyl group.

Of the compounds represented by the general formula (II), the compound represented by the general formula (II-c) is more preferable. General formula (II-c)

[0054]

Embedded image

(In the formula, R _2a1 and R _2a2 are represented by the general formula (II
It has the same meaning as those in -b), and the preferred range is also the same. ) Specific examples of the compound represented by formula (II) are shown below, but the invention is not limited thereto.

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

The compound represented by the general formula (II) of the present invention is, for example, as described in New Experimental Chemistry Course (edited by The Chemical Society of Japan, Maruzen) 1
4-III, Chapter 8 8.4 or ORANIC FUNCTIONAL GR
OUP PREPARATIONS (Sandler, Karo, ACADEMIC PRESS Ne
w York and London) It can be synthesized by various methods such as those described in I-Chapt.18. The synthesis methods are roughly classified as follows. (1) Method by oxidation of corresponding mercaptan (2) Method by nucleophilic substitution of corresponding alkyl (aryl) halide with alkali metal polysulfide salt (3) Conversion of corresponding aniline derivative into diazinium salt and then alkali polysulfide Method for nucleophilic substitution reaction with metal salt

With respect to the mercaptans used in the method (1), there is no particular limitation on both alkyl and aryl mercaptans, and as oxidation means, there are air oxidation (oxygen oxidation), dimethyl sulfoxide oxidation, hydrogen peroxide oxidation. , Hypochlorous acid oxidation and the like. When performing these methods, the reaction can be accelerated by making the reaction system alkaline. It is also known that the reaction can be accelerated by adding a metal catalyst such as copper or iron.

The alkyl halide that can be used in the method (2) is preferably one having no functional group (eg, ketone, aldehyde, enone, etc.) which is susceptible to nucleophilic attack in its molecule. As for the series, the first class has the highest reactivity, and the reactivity decreases in the order of the second class and the third class. The aryl halide that can be used in the method (2) is generally preferably one having an electron-withdrawing character, and a benzene ring-type halide having a substituent such as halogen or nitro is highly reactive. It is preferable in that the target product can be obtained efficiently. In the case of a heteroaromatic halide having a hetero atom in the aromatic ring, it is more electron-withdrawing than a benzene ring, so that the target product can be obtained without particularly having an electron-withdrawing group in the heteroaromatic ring. Many. Further, as in the case of the alkyl halide, it is preferable that these aryl halides do not have a functional group (for example, ketone, aldehyde, enone, etc.) which is susceptible to nucleophilic attack in the molecule.

The aniline derivative which can be used in the method (3) is not particularly limited, but for the convenience of forming a diazonium salt and reacting it with an alkali metal polysulfide salt under aqueous conditions, the aniline derivative And the diazonium salt formed is water-soluble.
When using an aniline derivative which has relatively low water solubility and does not efficiently form a diazonium salt, it is also possible to use a mixture of alcohols with water as a solvent. Also,
Hydrochloric acid and sulfuric acid are generally used as the acid for forming the diazonium salt, but borofluoric acid may be used for the purpose of improving the stability of the salt formed.

As a method of synthesizing the mercaptans used in the method (1), a new experimental chemistry course (edited by the Chemical Society of Japan, Maruzen)
14-III, Chapter 8, 8.1, ORANIC FUNCTIONAL GROUP PR
EPARATIONS (Sandler, Karo, ACADEMIC PRESS New York
and London) I-Chapt.18 or THE CHEMISTRY OF F
UNCTINONAL GROUPS (Patai, JONE WILLY & SONS) "
It can be synthesized by various methods as described in The Chemistry of the thiol group "-Chapt. 4. Next, typical synthetic examples of the compound represented by the general formula (II) of the present invention Indicates.

Synthesis Example 2 Synthesis of Compound II-13 25.0 g (0.1 mol) of 2,2'-dithioaniline was dissolved in 250 ml of acetonitrile, and 15.6 ml (0.2 20.4 g (0.2 mol) of acetyl chloride
Was slowly added dropwise. After stirring for 2 hours at room temperature,
Since the target substance was precipitated, 150 ml of acetonitrile was added, heated and dissolved, and then ice-cooled and recrystallized. The precipitate was collected by filtration and 28.0 g (0.0
84 mol) was obtained. Yield 84.2% Melting point 167-168 ° C

Synthesis Example 3 Synthesis of compound II-21 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 9.2 g (0.040 mol) of pentafluorobenzoyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from dimethylformamide / isopropyl alcohol to obtain 10.5 g (0.016 mol) of the target compound II-21. Yield 8
2.7% melting point 218-219 ° C

Synthesis Example 4 Synthesis of Compound II-45 5.0 g (0.020 mol) of 4,4'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring, pyridine 3.4 ml
(0.044 mol) was added, and 7.4 g (0.042 mol) of benzenesulfonyl chloride was added to the reaction solution at 10 ° C.
It was dropped so that it would not exceed. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours.
The reaction solution was poured into water and 250 ml of ethyl acetate was added for extraction. After the extract was dried and concentrated, the starting compound was removed and purified by silica gel chromatography (ethyl acetate / hexane = 1/1) to give the desired compound II-45.
3 g (0.017 mol) was obtained. Yield 87.7% Melting point 166-167 ° C

Synthesis Example 5 Synthesis of compound II-46 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring, pyridine 3.4 ml
(0.044 mol) was added, and 7.4 g (0.042 mol) of benzenesulfonyl chloride was added to the reaction solution at 15 ° C.
It was dropped so that it would not exceed. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours.
The reaction solution was poured into water, and the precipitated solid was collected by filtration and recrystallized from ethyl acetate / isopropyl alcohol to obtain 8.4 g (0.016 mol) of the target compound II-46. Yield 79.0% Melting point 148-149 ° C

Synthesis Example 6 Synthesis of compound II-48 5.0 g (0.020 mol) of 4,4'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 10.7 g (0.040 mol) of diphenylphosphoric acid chloride was added to the reaction liquid at 15 ° C.
It was dropped so that it would not exceed. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours.
The reaction solution was poured into water, the precipitated solid was collected by filtration, and recrystallized from dimethylformamide / isopropyl alcohol to obtain 8.9 g (0.012) of the target compound II-48.
Mol). Yield 62.2% Melting point 183-185
° C

Synthesis Example 7 Synthesis of compound II-6 7.45 g (0.030 mol) of 2,2'-dithioaniline was dissolved in 50 ml of acetonitrile, cooled to 5 ° C or lower under a nitrogen atmosphere, and stirred with phenyl. 7.14 g (0.060 mol) of isocyanate was added to the reaction solution at 15 ° C.
It was dropped so that it would not exceed. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited.
The precipitate is collected by filtration and washed with acetonitrile. Target compound II
-1 was obtained (13.6 g, 0.028 mol). Yield 93.
0% melting point 209-211 ° C

Synthesis Example 8 Synthesis of compound II-60 7.45 g (0.030 mol) of 4,4'-dithioaniline was dissolved in 50 ml of acetonitrile, cooled to 5 ° C or lower under a nitrogen atmosphere, and stirred with phenyl. 7.14 g (0.060 mol) of isocyanate was added to the reaction solution at 15 ° C.
It was dropped so that it would not exceed. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited.
The precipitate is collected by filtration and washed with acetonitrile. Target compound II
-60 was obtained (14.0 g, 0.029 mol). Yield 95.
9% melting point 250 ° C or higher

Synthesis Example 9 Synthesis of compound II-61 5.0 g (0.020 mol) of 4,4'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 12.4 g (0.040 mol) of pentafluoropropionic anhydride was added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from ethyl acetate / ethyl alcohol to give the target compound II-61 (4.6).
g (0.0085 mol) was obtained. Yield 42.6% Melting point
210-211 ° C

Synthesis Example 10 Synthesis of compound II-62 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 12.4 g (0.040 mol) of pentafluoropropionic anhydride was added dropwise so that the reaction liquid did not exceed 15 ° C. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. The reaction solution was poured into water, and the precipitated solid was collected by filtration and recrystallized from ethyl alcohol / water to obtain 6.0 g (0.011 mol) of the target compound II-62. Yield 5
6.0% melting point 97-97.5 ° C

Synthesis Example 11 Synthesis of compound II-63 5.0 g (0.020 mol) of 4,4'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 9.2 g (0.040 mol) of pentafluorobenzoyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from dimethylformamide / isopropyl alcohol to obtain 8.2 g (0.013 mol) of target compound II-63. Yield 6
4.6% melting point 236-238 ° C

Synthesis Example 12 Synthesis of Compound II-64 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 9.1 g (0.040 mol) of 1-naphthalenesulfonyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from dimethylformamide / isopropyl alcohol to obtain 5.4 g (0.0086 mol) of the target compound II-64. Yield 4
2.8% melting point 220-222 ° C

Synthesis Example 13 Synthesis of compound II-65 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 9.1 g (0.040 mol) of 2-naphthalenesulfonyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. The reaction solution was poured into water and the precipitated solid was collected by filtration and recrystallized from dimethylformamide / isopropyl alcohol to obtain 8.3 g (0.01%) of the target compound II-65.
3 mol) was obtained. Yield 65.9% Melting point 171-17
2 ℃

Synthesis Example 14 Synthesis of Compound II-66 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 7.6 g (0.040 mol) of p-toluenesulfonyl chloride was added to the reaction solution to give 1
It was added dropwise so as not to exceed 5 ° C. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. The reaction solution was poured into water and 250 ml of ethyl acetate was added for extraction. When the extract was dried and concentrated, the target product was precipitated. The precipitate was collected by filtration and recrystallized from ethyl acetate / hexane to give 9.0 g (0.0) of the target compound II-66.
16 mol) was obtained. Yield 80.8% Melting point 164-166 ° C

Synthesis Example 15 Synthesis of compound II-68 5.0 g (0.020 mol) of 2,2'-dithioaniline
Is dissolved in 100 ml of acetonitrile, and under a nitrogen atmosphere,
Cool to below 5 ° C and agitate 3.1 ml of pyridine
(0.040 mol) was added, and 8.3 g (0.040 mol) of p-methoxybenzenesulfonyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After dropping,
The temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. Pour the reaction mixture into water and add 250 ml of ethyl acetate.
And extracted. The extract was dried and concentrated, the obtained oily product was dissolved in ethyl acetate, and then hexane was added to cause crystallization to give 6.8 of the target compound II-68.
g (0.012 mol) was obtained. Yield 58.0% Melting point 1
31-132 ° C

Synthesis Example 16 Synthesis of Compound II-69 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 11.2 g (0.04 mol) of 2,4,5-trichlorobenzenesulfonyl chloride was further added.
0 mol) was added dropwise so that the reaction liquid did not exceed 15 ° C.
After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. The reaction solution was poured into water and the precipitated solid was collected by filtration and recrystallized from dimethylformamide / isopropyl alcohol to obtain 9.9 g (0.013 mol) of the target compound II-69. Yield 67.3% Melting point 228-229 ° C

Synthesis Example 17 Synthesis of compound II-70 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 8.7 g (0.040 mol) of 2-mesitylene sulfonyl chloride was further added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring and left overnight,
The target substance was deposited. The precipitate was collected by filtration and recrystallized from ethyl acetate / isopropyl alcohol to obtain 8.2 g (0.013 mol) of the target compound II-70. Yield 6
6.7% melting point 140-141 ° C

Synthesis Example 18 Synthesis of compound II-71 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and further 7.6 g (0.040 mol) of 2-naphthalenecarboxylic acid chloride was added dropwise so that the reaction liquid did not exceed 15 ° C. After completion of the dropping, the temperature was gradually raised to room temperature with stirring and the reaction was carried out for 2 hours, whereupon the target product was precipitated. 50m acetonitrile in the precipitate
1 was added, heated and dissolved, and then ice-cooled and recrystallized. The precipitate was collected by filtration, and 10.6 g of the target compound II-71 was obtained.
(0.019 mol) was obtained. Yield 95.5% Melting point 1
78-179 ° C

Synthesis Example 19 Synthesis of compound II-72 5.0 g (0.020 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
Cool down below ℃, and with stirring 3.1 ml pyridine
(0.040 mol) was added, and 10.7 g (0.040 mol) of diphenylphosphoric acid chloride was added to the reaction liquid at 15 ° C.
It was dropped so that it would not exceed. After the completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was allowed to proceed for 2 hours. Acetonitrile 50 for precipitate
After adding ml, heating and dissolving, ice-cooling and recrystallization were performed. The precipitate was collected by filtration and 4.6 g of the target compound II-72 was obtained.
(0.0065 mol) was obtained. Yield 32.2% Melting point
121-123 ° C

Synthesis Example 20 Synthesis of compound II-73 1) Synthesis of (2,2'-diamino-5,5'-dichlorodiphenyl) disulfide 50 g of potassium hydroxide and 100 ml of ethylene glycol
Was added and dissolved by heating at 90 ° C., and then 2-amino-6-
Chlorobenzothiazole 10.3 g (0.056 mol)
Was added to the alkaline solution. The reaction solution was heated to 165 ° C. and reacted for 24 hours. The reaction solution was allowed to cool to room temperature, 1.5 l of water was added for dilution, and then air was passed through for 24 hours for oxidation. After filtering off the precipitate, hydrochloric acid was added to adjust the pH to 6
Adjusted to -7, the precipitated solid was collected by filtration and recrystallized with ethyl alcohol / water to obtain 5.6 g (0.01
8 mol) was obtained. 63% yield

2) Synthesis of II-73 2 g (0.0063 mol) of (2,2'-diamino-5,5'-dichlorodiphenyl) disulfide was dissolved in 25 ml of acetonitrile and cooled to 5 ° C or lower under a nitrogen atmosphere. And, with stirring, 1 ml of pyridine (0.013 mol)
Was added, and benzoyl chloride 1.8 g (0.01
28 mol) was added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from dimethylformamide / ethyl alcohol to obtain 3.3 g (0.0063 mol) of target compound II-73. Yield 99.7% Melting point 192-193 ° C

Synthesis Example 21 Synthesis of Compound II-74 (2,2'-diamino-5,5 'was synthesized in the section of II-73.
-Dichlorodiphenyl) disulfide 2 g (0.006
3 mol) in 25 ml of acetonitrile, cooled to 5 ° C. or lower under a nitrogen atmosphere, and stirred with 1 ml of pyridine.
(0.013 mol) was added, and 2.2 g (0.0125 mol) of benzenesulfonyl chloride was added to the reaction solution to give 15
It was added dropwise so as not to exceed ℃. After the dropwise addition was completed, the temperature was gradually raised to room temperature with stirring, and the mixture was allowed to stand overnight, whereupon the target substance was precipitated. The precipitate was collected by filtration, and ethyl acetate /
By recrystallization from methyl alcohol, 1.2 g (0.0020 mol) of the target compound II-74 was obtained. Yield 3
1.8% melting point 175-178 ° C

Synthesis Example 22 Synthesis of Compound II-75 1) Synthesis of (2,2'-diamino-5,5'-dimethyldiphenyl) disulfide 50 g of potassium hydroxide and 100 ml of ethylene glycol
Was added and dissolved by heating at 90 ° C., and then 2-amino-6-
Methylbenzothiazole 10.0 g (0.061 mol)
Was added to the alkaline solution. The reaction solution was heated to 165 ° C. and reacted for 24 hours. The reaction solution was allowed to cool to room temperature, 1.5 l of water was added for dilution, and then air was passed through for 24 hours for oxidation. The precipitate was filtered off and 4.1 g (0.01
5 mol). Yield 49%

2) Synthesis of II-75 Dissolve 2 g (0.0072 mol) of (2,2'-diamino-5,5'-dimethyldiphenyl) disulfide in 25 ml of acetonitrile and cool to 5 ° C or lower under a nitrogen atmosphere. Then, 1.1 ml of pyridine (0.0144) with stirring.
Mol), and further 2.0 g of benzoyl chloride
(0.0144 mol) was added dropwise so that the reaction liquid did not exceed 15 ° C. After the dropping was completed, the temperature was gradually raised to room temperature with stirring, and the target substance was deposited. The precipitate was collected by filtration and recrystallized from dimethylformamide / ethyl alcohol to give 3.0 g (0.
(0062 mol) was obtained. Yield 86.0% Melting point 158
-159 ° C

Synthesis Example 23 Synthesis of Compound II-76 Synthesized in the section of II-75 (2,2′-diamino-5,5 ′).
-Dimethyldiphenyl) disulfide 2 g (0.007
2 mol) in 25 ml of acetonitrile, cooled to 5 ° C. or lower under a nitrogen atmosphere, and stirred with pyridine 1.1.
ml (0.0144 mol) was added, and 2.5 g (0.0144 mol) of benzenesulfonyl chloride was further added dropwise so that the temperature of the reaction solution did not exceed 15 ° C. After completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was continued for 2 hours. The reaction solution was poured into water, and the precipitated solid was collected by filtration and recrystallized from dimethylformamide / ethyl alcohol to give 3.6 g (0.006) of the target compound II-76.
5 mol). Yield 89.8% Melting point 164-16
5 ℃

Synthesis Example 24 Synthesis of Compound II-77 9.2 g (0.030 mol) of 2,2'-dithiobenzoic acid
Is suspended in 100 ml of toluene, and 1 m of pyridine is added with stirring.
1, thionyl chloride 4.8 ml (0.066 mol) were added. The reaction solution was heated to 80 ° C. and reacted for 3 hours, and then the pressure in the reaction system was reduced to distill off toluene to dryness. After cooling the obtained solid, 50 ml of acetonitrile and 50 ml of tetrahydrofuran were added and dissolved, and 6.6 g (0.060 mol) of aniline and 4.7 ml of pyridine were added thereto.
(0.060 mol) in acetonitrile (50 ml)
Was dripped. After reacting at room temperature for 3 hours, the reaction solution was poured into water, and the precipitated solid was recrystallized from dimethylformamide / ethyl alcohol to give the target compound II-77 as 1
0.8 g was obtained. Yield 78.8% Melting point 239-242
° C.

Synthesis Example 25 Synthesis of Compound II-78 8.7 g (0.035 mol) of 2,2'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
The reaction liquid was cooled to below 1 ° C and stirred with 12.4 g (0.0735 mol) of 1-naphthalene isocyanate.
It was added dropwise so as not to exceed ℃. After the dropwise addition was completed, the temperature was gradually raised to room temperature with stirring, and the mixture was allowed to stand overnight, whereupon the target substance was precipitated. The precipitate was collected by filtration and washed with acetonitrile to obtain 18.2 g (0.031) of the target compound II-78.
Mol). Yield 88.8% Melting point 220-224 ° C

Synthesis Example 26 Synthesis of Compound II-79 8.7 g (0.035 mol) of 4,4'-dithioaniline
Was dissolved in 50 ml of acetonitrile, and was dissolved in a nitrogen atmosphere for 5
The reaction liquid was cooled to below 1 ° C and stirred with 12.4 g (0.0735 mol) of 1-naphthalene isocyanate.
It was added dropwise so as not to exceed ℃. After the completion of the dropping, the temperature was gradually raised to room temperature with stirring, and the reaction was allowed to proceed for 2 hours. The precipitate was collected by filtration, and washed with acetonitrile. 18.8 g (0.0) of the target compound II-79 was washed.
32 mol) was obtained. Yield 91.7% Melting point 256-259 ° C

The compound represented by formula (I) or (II) of the present invention can be added in either the light-sensitive layer or the non-light-sensitive layer. It is preferably a photosensitive layer. The compounds represented by the general formulas (I) and (II) of the present invention also differ depending on the desired purpose, but are from 10 ⁻⁴ mol to 1 mol / Ag mol, preferably 1 mol.
It is advisable to add 0 ⁻³ mol to 0.3 mol / Ag mol. It is preferable that any compound be dissolved in an organic solvent and added.

The photothermographic material of the present invention is preferably a monosheet type (a type in which all the materials donated to form an image are completed as an image sheet to be observed) because of its goodness to the earth. is there. Further, it is preferably a photothermographic material for infrared laser exposure. Further, the wavelength of infrared laser exposure is 750 nm or more, more preferably 800 nm or more. In order to be compatible with a laser in such a wavelength range, it is necessary to be spectrally sensitized so as to have sensitivity in these wavelength ranges, that is, in the infrared range. Known infrared sensitizing dyes may be used.

The photothermographic material of the present invention forms a photographic image using a photothermographic method. Such a photothermographic material is disclosed in, for example, US Pat.
No. 152904, 3457075, and D.C. Morgan and B.A. "Thermally Processed SilverSy" by Shely
stems) "(Imaging Processors and
Materials (Imaging Processes and Materials) Neb
lette 8th edition, Sturge, V. Walworth, A. Edited by Shepp, page 2,
1969) and the like.

The heat-developable light-sensitive material of the present invention may be any one capable of forming a photographic image by using a heat-development treatment, including a reducible silver source (eg organic silver salt) and a catalytically active amount of photocatalyst (eg halogen). It is preferably a photothermographic material containing silver halide), a color tone controlling agent for controlling the color tone of silver, and a reducing agent in a state of being normally dispersed in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature,
After exposure, development is performed by heating to a high temperature (for example, 80 ° C. or higher). Heating produces silver through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

The photothermographic material of the invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. A filter layer may be formed on the same side or on the opposite side of the photosensitive layer in order to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or a pigment. The photosensitive layer may be composed of multiple layers, and the sensitivity is high for adjusting the gradation.
It may be a low sensitive layer or a low sensitive layer / high sensitive layer. Various additives may be added to any of the light-sensitive layer, the non-light-sensitive layer, and other forming layers.

The support applicable to the photothermographic material of the present invention includes, for example, paper, polyethylene-coated paper, polypropylene-coated paper, parchment, cloth, etc .;
Sheets or films of metals such as aluminum, copper, magnesium, zinc; glass or chromium alloy, steel,
Glass coated with a metal such as silver, gold, platinum; poly (alkyl methacrylates) (eg, poly (methyl methacrylate)), poly (esters) (eg, poly (ethylene terephthalate)), poly (vinyl acetal) ), Poly (amides) (eg, nylon), and cellulose esters (eg, cellulose nitrate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate). The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

Each binder layer (for example, synthetic polymer) together with chemicals in the photothermographic material of the present invention may form a self-supporting film. The support is made of known auxiliary materials, for example, vinylidene chloride, acrylic acid monomers (for example, acrylonitrile and methyl acrylate)
And copolymers and terpolymers of unsaturated dicarboxylic acids (eg, itaconic acid, acrylic acid), carboxymethylcellulose, poly (acrylamide); and similar polymeric materials.

Suitable binders are transparent or translucent, generally colorless, and include natural polymeric synthetic resins, polymers and copolymers, and other film-forming media such as:
Gelatin, gum arabic, poly (vinyl alcohol),
Hydroxyethyl cellulose, cellulose acetate,
Cellulose acetate butyrate, poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (Styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal)
(Eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), There are poly (vinyl acetate), cellulose esters, and poly (amide) s. The binder may be coated from water or an organic solvent or an emulsion.

The addition of toning agents is highly desirable. Examples of suitable toning agents are disclosed in Research Report No. 17029,
There are the following: imides (eg, phthalimide);
Cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline, and 2,4-thiazolidinedione); naphthalimides (eg, , N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3-mercapto-1,2,4-triazole); N
-(Aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide);
Blocked pyrazoles, isothiuronium (isot
hiuronium) derivatives and certain photobleaching combinations (eg, N, N'hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-
A combination of dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl-2-benzothia) Zolinylidene (benzothiazolinylidene) -1
-Methylethylidene) -2-thio-2,4-oxazolidinedione); phthalazinone, phthalazinone derivatives or metal salts of these derivatives (e.g.,
4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1,4-phthalazinedione); phthalazone; a combination of phthalazinone and a sulfinic acid derivative (For example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); a combination of phthalazine + phthalic acid; phthalazine (including an adduct of phthalazine) and maleic anhydride, And at least one selected from phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivative and its anhydride (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride). Combination with two compounds; quinazolinediones, benzene Oxazine, Narutokisajin derivatives; benzoxazine-2,4-diones (e.g.,
1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg, 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg, 3,6-dimerocapto-1, 4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene.

[0112]

Embedded image

And more preferably phthalazine. The reducing agent may contain a so-called photographic developer, for example, phenidone, hydroquinones, catechol and the like, but hindered phenol is preferred. US Patent No. 4
A color light-sensitive material as disclosed in 460681 is also conceivable in the realization of the present invention.

Examples of suitable reducing agents are described in US Pat. No. 3,770.
Nos. 448, 3773512, 3959633, and Research Disclosure Nos. 17029 and 29.
963, and include: aminohydroxycycloalkenone compounds (eg, 2-hydroxy-piperidino-2-cyclohexenone); aminoreductones esters (eg, Piperidinohexose reductone monoacetate); N-hydroxyurea derivatives (for example, Np-
Methylphenyl-N-hydroxyurea); aldehyde or ketone hydrazones (eg, anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone) , Isopropylhydroquinone and (2,5-dihydroxy-phenyl) methyl sulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamide anilines (eg, 4- (N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Tetrahydroquinoxaline); amidooxins; azines (for example, aliphatic carboxylic acid aryl hydrazides and ascorbic acid); polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; hydroxanoic acids; azines and sulfones Combination of amidophenols; α-cyanophenylacetic acid derivative; bis-β-naphthol and 1,3-
5-pyrazolones; sulfonamidophenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridines (e.g., 2,6-dimethoxy-3) , 5-dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-
Hydroxy-3-t-butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4 -Ethylidene-bis (2
-T-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Preferred developers are hindered phenols of the general formula (A):

[0115]

Embedded image

Here; R is a hydrogen atom or 1 carbon atom.
To 10 alkyl groups (for example, -C _FourH₉, 2,4,4
-Trimethylpentyl);^FiveAnd R⁶Is carbon source
An alkyl group having 1 to 5 children (for example, methyl, ethyl, t
-Butyl).

A silver halide useful as a catalytically active amount of a photocatalyst is any photosensitive silver halide (eg, silver bromide, silver iodide, silver silver, silver chlorobromide, silver iodobromide, chloroiodo). However, it is preferable that the iodide ion is contained. The silver halide may be added to the imaging layer in any manner, with the silver halide being placed in close proximity to the reducible silver source. In general, it is preferred that the silver halide contains from 0.75 to 30% by weight, based on the reducible silver source. Silver halide may be prepared by conversion of the silver soap portion by reaction with a halide ion, may be preformed and added during the generation of the soap, or a combination of these methods is possible. The latter is preferred.

The reducible silver source can be any material containing a source of reducible silver ions. Silver salts of organic and heteroorganic acids, especially long chains (10-30, preferably 15-25
) Aliphatic carboxylic acids are preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of suitable silver salts are described in Research Disclosure No. 1702.
9 and 29996, and include the following:
Salts of organic acids (eg gallic acid, oxalic acid, behenic acid,
Stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salt of silver (for example, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea); aldehyde Silver complexes (e.g., aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids (e.g., salicylic acid, benzoic acid, 3,5-
Dihydroxybenzoic acid, 5,5-thiodisalicylic acid),
Silver salts or complexes of thioenes (eg, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thioene and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole ,
Urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-
Complexes or salts of silver and nitrogen acids selected from triazoles and benzotriazoles; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are stearic acid and silver behenate, with behenic acid being especially preferred. The reducible silver source preferably has a silver content of 3 g / m ² or less. More preferably, it is 2 g / m ² or less.

The photothermographic material of the present invention includes, for example, JP-A Nos. 63-159841, 60-140335, 63-231437, 63-259651 and 6-63.
Nos. 3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, and 4,419.
Sensitizing dyes described in JP-A Nos. 66, 4751175 and 48335096 can be used. General formula (I) of the present invention
The compound represented by can be used in ordinary silver halide light-sensitive materials. Any silver halide light-sensitive material may be used as long as it has a light-sensitive silver halide emulsion layer on a support.

[0120]

【Example】

Example 1 Preparation of Photosensitive Emulsion A Solution Stearic acid 135 g Behenic acid 635 g Distilled water 13 liter Mixed at 15 minutes at 85 ° C. Solution NaOH 89 g Distilled water 1500 ml Solution concentrated HNO ₃ 21 ml Distilled water 50 ml Solution AgNO ₃ 365 g Distilled water 2500 ml Solution polyvinyl butyral 86 g Ethyl acetate 4300 ml solution Polyvinyl butyral 290 g Isopropanol 3580 ml solution N-Bromosuccinimide 9.7 g Acetone 700 ml

The solution was added over 5 minutes with vigorous stirring while the temperature was kept at 85 ° C., and then the solution was added to 2
Add over 5 minutes. After stirring for 20 minutes as it is, 35
Cool down to ° C. Add the solution over 5 minutes with more vigorous stirring at 35 ° C. and continue stirring for 90 minutes.
Then, the solution was added, and the mixture was left without stirring, and the aqueous phase was removed together with the salt contained therein to obtain an oil phase, which was desolvated to remove traces of water, and then the solution was added and vigorously stirred at 50 ° C. Then, the solution was added over 20 minutes and stirred for 105 minutes to obtain a photosensitive emulsion A.

The following layers were sequentially formed on a biaxially stretched 175 μm thick polyethylene terephthalate support (without an undercoat layer) which was colored blue with Dye-A. Drying was performed at 75 ° C. for 5 minutes each.

<Back side coating> ○ Antihalation layer (wet thickness 80 micron) Polyvinyl butyral (10% isopropanol solution) 150 ml Dye-C (solvent DMF) 70 mg

<Photosensitive layer side coating> ○ Photosensitive layer (wet thickness 140 micron) Photosensitive emulsion A 73 g Sensitizing dye-1 (0.1% DMF solution) 2 ml Antifoggant-1 (0.01% methanol solution) ) 3 ml Phthalazone (4.5% DMF solution) 8 ml Reducing agent-1 (10% acetone solution) 13 ml Compounds described in Tables 1 and 2.

Surface protection layer (wet thickness 100 micron) Acetone 175 ml 2-Propanol 40 ml Methanol 15 ml Cellulose acetate 8.0 g Phthalazine 1.0 g 4-Methylphthalic acid 0.72 g Tetrachlorophthalic acid 0.22 g Tetrachlorophthalic anhydride Thing 0.5g

[0126]

Embedded image

[0127]

Embedded image

Cesitometry The photothermographic material prepared above was processed into a half-cut size,
An 830 nm laser diode was exposed with a beam tilted 13 ° from the vertical. Then use a heat drum for 1
Heat development treatment was carried out at 20 ° C. for 10 seconds and 125 ° C. for 15 seconds. Then, the fog value at that time was measured and the color tone was visually evaluated. Further, when the maximum concentration of Sample No. 1 in Table 1 was set to 100, the maximum concentration of each sample was evaluated as a relative value. The results are shown in Tables 1 and 2.

[0129]

[Table 1]

[0130]

[Table 2]

[0131]

Embedded image

From Tables 1 and 2, it is understood that the samples of the present invention have sufficient sensitivity, low fog, and good black color tone.

Example 2 Preparation of Photosensitive Emulsion B Solution Stearic acid 135 g Behenic acid 635 g Distilled water 13 liters 85 ° C. mixing for 15 minutes Solution A Preformed cubic AgBrI (I = 4 mol%) 0.06 μ (as Ag) 0.22 mole) distilled water 1250ml solution NaOH 89 g distilled water 1500ml solution of concentrated HNO ₃ 19 ml of distilled water 50ml solution AgNO ₃ 365 g distilled water 2500ml solution polyvinylbutyral 86g ethyl acetate 4300ml solution polyvinylbutyral 290g isopropanol 3580ml

Solution A was added over 10 minutes with vigorous stirring while keeping the solution at 85 ° C., followed by addition of solution over 5 minutes, and then over 25 minutes. After stirring for 20 minutes as it is, the temperature is lowered to 35 ° C. Add the solution over 5 minutes with more vigorous stirring at 35 ° C. and continue stirring for 90 minutes. Thereafter, the solution was added, the stirring was stopped and the mixture was left to stand, and the aqueous phase was extracted together with the salt contained therein to obtain an oil phase. After removing the traces of water by removing the solvent, the solution was added and the mixture was stirred vigorously at 50 ° C. Later, 10
Emulsion B was obtained by stirring for 5 minutes.

A test was conducted in the same manner as in Example 1, except that the antihalation layer was provided below the photosensitive layer on the side of the photosensitive layer. As in the case of Example 1, the sample using the compound of the present invention had good fog and black color tone.

[0136]

The light-sensitive material of the present invention has high sensitivity, low fog and good color tone.

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

[Procedure amendment]

[Submission date] January 4, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction contents]

[0060]

Embedded image

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0112

[Correction method] Change

[Correction contents]

[0112]

Embedded image

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0117

[Correction method] Change

[Correction contents]

A silver halide useful as a catalytically active amount of a photocatalyst is any photosensitive silver halide (eg, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc.). However, it is preferable that iodine ions are contained. The silver halide may be added to the imaging layer in any manner, with the silver halide being placed in close proximity to the reducible silver source. In general, it is preferred that the silver halide contains from 0.75 to 30% by weight, based on the reducible silver source. The silver halide may be prepared by conversion of the silver soap part by reaction with halogen ions,
It may be preformed and added as the soap evolves, or a combination of these methods is possible. The latter is preferred.

Claims (4)

[Claims] 1. A silver halide light-sensitive material containing at least one compound represented by the following general formula (I). General formula (I) (In the formula, R represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. L represents a divalent arylene group or a divalent heterocyclic group. X ₁ and X ₂ each represent a halogen atom. A represents a hydrogen atom, a halogen atom or an electron-withdrawing group.) 2. A photothermographic material comprising at least one compound represented by formula (I) according to claim 1. 3. A photothermographic material comprising at least one compound represented by the general formula (I) according to claim 1 and at least one compound represented by the following general formula (II). . General formula (II) (In the formula, R ₁ and R ₂ represent an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. N represents an integer of 0 to 4.) 4. The photothermographic material according to claim 2, which is for infrared laser exposure.