JP2557726B2 - Phenylmercaptoazole compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel phenylmercaptoazole compound, and more specifically to a novel phenylmercaptoazole compound having a phosphonic acid moiety and a salt or lower alkyl ester thereof.

(Prior Art) As a phenylmercaptoazole compound, substitution of a hydroxyl group, a sulfonic acid group, a carboxyl group, a nitro group, a cyano group, an amino group, a sulfamoyl group, a carbamoyl group, an amide group, a sulfonamide group, or a halogen atom on an aromatic ring. Those having a group are disclosed in JP-A-60-192936 and JP-A-64-8095 as antifoggants for silver halide photographic light-sensitive materials.
It is described in No. 1.

Furthermore, as a phenylmercaptoazole compound having a phosphonic acid moiety, the following compound Is described in European Patent 283041A as a compound having a function of fogging silver halide in order to directly obtain a positive image.

(Problems to be Solved by the Invention) It is an object of the present invention to provide a novel phenylmercaptoazole compound capable of effectively suppressing the occurrence of fog while reducing the sensitivity decrease in a silver halide photographic light-sensitive material. .

(Means for Solving the Problems) As a result of various studies, the present inventor has found that the following general formula [I] (In the formula [I], A represents -CH = or -N =, and B represents -CH = or -N =.
CH =, Or represents -N =, and X is And Y represents an alkylene chain having 2 or 3 carbon atoms. n represents 0 or 1, and m represents 0 or 1. In the phenyl group The bonding position of is 3 or 4 position with respect to the heterocycle. ), A novel phenylmercaptoazole compound represented by the formula (1) and a salt thereof, or a methyl ester or an ethyl ester thereof was found, and it was found that the compound exhibits an excellent antifoggant action in a silver halide photographic light-sensitive material.

In the formula [I], Y is preferably an alkylene chain having 3 carbon atoms. Moreover, it is preferable that both n and m are 0 or both are 1 from the viewpoint of ease of synthesis.

Furthermore, because of the ready availability of starting materials, when A is -CH =, B is -CH = or And when A is -N =, B is Alternatively, -N = is preferable, and when both A and B are -N =, it is preferable that both n and m are 1.

Further, the present invention includes a salt of a phenylmercaptoazole compound having a phosphonic acid moiety represented by the formula [I] or a lower alkyl ester (methyl ester or ethyl ester) thereof.

Examples of salts include ammonium salts, metal salts (eg sodium salt, potassium salt) and the like.

 Next, the synthetic method of the compound of the present invention will be described.

There are roughly two synthesizing methods. One is a method particularly convenient for the synthesis of arylphosphonic acid mercaptoazoles, which is a method of synthesizing an aromatic compound having a phosphonic acid or a phosphonate ester moiety as a starting material.
The other method is particularly convenient for the synthesis of compounds containing a linking group, and is a method of separately synthesizing a phenylmercaptoazole compound and an alkylphosphonic acid moiety and finally linking them.

For the synthesis of mercapto-substituted heterocycles, see Berichte der Deutschen Chemische Gesellschaf.
t), 22 , 568 pages (1889), 29 , 2483 pages (1896)
), Journal of Chemical Society (J.Cem.Soc.), 1932, p. 1806, Journal of
American Chemical Society (J.Am.Cem.So
c.), 71 , 4000 (1949), U.S. Patent No. 2,585,388,
2,541,924, Advances in Heterocyclic Chemistry.
mistry), 9 , 165 (1968), Organic Synthesis IV (Org.Synth.IV), 569 (1963), Berichte der Deutschen Chemische Gesellschaf
t), 9 , p. 465 (1876), Journal of American Chemical Society (J. Am. Chem. Soc.),
45 , p. 2390 (1923), Katricky and Lace (Katrit
Comprehensive Heterocyclic Chemi by zky and Rees
stry), 2, 3, 4, 5, and 6. In particular, Comprehensive Heterocyclic Chemistry by Katritzky and Rees
ive Heterocyclic Chemistry), which is exhaustive and helpful.

The synthesis of the phosphonic acid moiety will be described separately for alkylphosphonic acid and arylphosphonic acid.

Alkylphosphonic acid is generally obtained by reacting an alkyl halide with a phosphite, a so-called Arbuzov reaction.
Reaction) can synthesize an alkylphosphonate. An alkylphosphonic acid can be synthesized by subjecting this phosphonate to a general hydrolysis reaction with an acid or alkali. For details of the method, Synthesis, 1979, 6
Page 15, Chemical Review, 1981
Year, 81 volumes, 415 pages, Journal of Organic
The method described in Chemistry (J. of Org. Chem.) Can be referred to.

For arylphosphonic acids, use Synthesi
s), 1979, p. 21, a method of reacting a cyclic-phosphorous chlorite with a diazonium salt to form an arylphosphonate followed by hydrolysis, Journal of
Organic Chemistry (J. of Org. Chem.), 24
Vol. 3612, (1974), a method of reacting an aryl iodide with a dialkyl phosphite under light irradiation to form an aryl phosphonate, followed by hydrolysis is known. Can be synthesized relatively easily with.

The compound of the present invention can be made into a highly purified product by performing column chromatography or recrystallization, if necessary.

Next, specific examples of the compounds of the present invention, their melting points and ¹ H-NMR
The data are shown in Table 1 below, but the invention is not limited to these specific examples.

(Example) Next, a production example of the compound of the present invention will be shown as an example.
The compound example numbers obtained in the following examples correspond to the compound example numbers in Table 1 above.

Example 1 Synthesis of 4- (3-phosphonophenyl) -3-methyl-5-mercaptotriazole (Compound Example 4) (Synthesis Example 1-1) 3-nitrobenzenephosphonic acid (1a)
Synthesis of Concentrated nitric acid (250 ml) and concentrated sulfuric acid (250 ml) were mixed under ice cooling and the temperature was adjusted to 20
200 g of benzenephosphonic acid was added little by little while maintaining at -30 ° C. After the addition was completed, the mixture was stirred at room temperature for 2 hours, and poured into ice water 2 after the reaction was completed. Under ice-cooling, 288 g of sodium hydroxide was added for neutralization, and sodium chloride was further added for saturation. The saturated aqueous solution was extracted with ethyl acetate, the extract was dried over magnesium sulfate, and concentrated by a rotary evaporator. 200 ml of chloroform was added to the concentrate, and the inside of the container was rubbed with a glass rod to crystallize. The generated crystals were filtered and dried under reduced pressure to obtain 156 g of 3-nitrobenzenephosphonic acid (1a).

(Synthesis example 1-2) Synthesis of 3-diethylphosphononitrobenzene (1b) 400 ml of acetonitrile was added to 50 g of 3-nitrobenzenephosphonic acid (1a) and suspended. 50 ml of phosphorus oxychloride was added at room temperature, and the mixture was heated under reflux for 2 hours after the addition. The reaction solution was poured into 300 ml of ethanol under ice cooling and stirred for 30 minutes, and then ethanol was distilled off with a rotary evaporator. The concentrate was diluted with ethyl acetate, saturated aqueous sodium hydrogen carbonate solution,
The extract was washed with saturated brine, added with magnesium sulfate and dried, and then concentrated with a rotary evaporator. The residue was purified by column chromatography (silica gel) to obtain 17 g of 3-diethylphosphononitrobenzene (1b). Yield 5
0% (Synthesis example 1-3) 3-diethylphosphonoaniline (1c)
Synthesis of 3-diethylphosphononitrobenzene (1b) 17g dissolved in 250ml ethanol, ammonium chloride 6g water 100ml
An aqueous solution dissolved in was added and heated. 20 g of iron powder was added little by little under heating, and the mixture was heated under reflux for 30 minutes. After completion of the reaction, iron powder was removed by Celite filtration, and ethanol was distilled off with a rotary evaporator. The obtained concentrate was extracted with ethyl acetate, the extract was washed with saturated brine, dried over magnesium sulfate, and then concentrated with a rotary evaporator to give 3-diethylphosphonoaniline (1c) 14 g. . Yield 94% (Synthesis Example 1-4) Synthesis of 3-diethylphosphonophenyl isothiocyanate (1d) 15 g of 3-diethylphosphonoaniline (1c) was dissolved in 50 ml of acetonitrile, and 9 ml of thiophosgene and 100 ml of water were suspended. Dropped into the liquid. After completion of dropping, the mixture was stirred for 30 minutes, and after confirming the completion of the reaction, 45 ml of triethylamine was added and stirred for 10 minutes. The mixture was extracted with ethyl acetate, the extract was washed with saturated brine, dried over magnesium sulfate, and concentrated with a rotary evaporator. The residue was purified by column chromatography to obtain 11 g of 3-diethylphosphonophenyl isothiocyanate (1d). Yield 62% (Synthesis example 1-5) 4- (3-phosphonophenyl) -3-
Synthesis of Methyl-5-mercaptotriazole (Compound Example 4) 2.1 g of 3-diethylphosphonophenyl isothiocyanate (1d), 0.8 g of acetohydrazide and 50 ml of ethanol were mixed and reacted at room temperature for 1 hour. After concentrating with a rotary evaporator, the residue was purified by column chromatography to obtain 1- (3-phosphonophenyl) -3 as an intermediate.
-2.4 g of acetylaminosemicarbazide was obtained. The obtained 1- (3-phosphonophenyl) -3-acetylaminosemicarbazide was dissolved in 20 ml of ethanol, 10 ml of a 10% aqueous solution of potassium hydroxide was added, and the mixture was heated under reflux for 3 hours. After completion of the reaction, dilute hydrochloric acid was added to adjust the pH to 6 to 7, and then ethanol was removed by a rotary evaporator. Concentrated hydrochloric acid (50 ml) was added to the obtained concentrated liquid and the mixture was heated under reflux for 5 hours, and then water was removed by a rotary evaporator. The residue was purified by column chromatography (Sephadex) to obtain 4- (3-phosphonophenyl) -3-methyl-5-mercaptotriazole (Compound Example 4). Yield 1.0g, 43%.

Example 2 Synthesis of 4- (4-phosphonophenyl) -3-methyl-5-mercaptotriazole (Compound Example 3) (Synthesis Example 2-1) Synthesis of 4-diethylphosphononitrobenzene (2a) 4-nitrobenzenediazonium 48 g of tetrafluoroborate was suspended in 300 ml of ethyl acetate, 33 g of phosphorus trichloride and 4 g of cuprous bromide were added and stirred at room temperature. When the mixture was heated to 50 ° C, it reacted violently and evolved a gas. After the reaction,
Under ice-cooling, add 100 ml of ethanol and stir for 10 minutes.
After adding ml, excess ethanol was removed on a rotary evaporator. The obtained concentrate was extracted with ethyl acetate, the extract was washed with aqueous ammonia and saturated brine, dried over magnesium sulfate, and the solvent was removed by a rotary evaporator to remove 4-diethylphosphononitrobenzene (2a).
I got 15g. Yield 33% (Synthesis example 2-2) 4-diethylphosphonoaniline (2b)
Synthesis of 4-diethylphosphononitrobenzene (2a) 16 g was dissolved in 250 ml of ethanol, and 80 ml of an aqueous solution of 4.2 g of ammonium chloride was added and heated. Under heating, 17 g of iron powder was added little by little and heated under reflux for 20 minutes. After completion of the reaction, iron powder was removed by Celite filtration, ethanol was distilled off under reduced pressure with a rotary evaporator, and the obtained concentrate was extracted with ethyl acetate. The extract was washed with saturated brine, dried over magnesium sulfate, and the solvent was removed by a rotary evaporator to obtain 13.5 g of 4-diethylphosphonoaniline (2b).
96% yield.

(Synthesis Example 2-3) Synthesis of 4-diethylphosphonophenylisothiocyanate (2c) 5.0 g of 4-diethylphosphonoaniline (2b) was dissolved in 30 ml of acetonitrile, and a suspension of 3.8 ml of thiophosgene and 50 ml of water was prepared. It was added dropwise under ice cooling. After reacting at 10 ° C. or lower for about 1 hour, after confirming disappearance of raw materials, 17 ml of triethylamine was added and stirred at room temperature for 30 minutes. The mixture was extracted with ethyl acetate, the extract was washed with saturated brine, dried over magnesium sulfate, and concentrated with a rotary evaporator. The concentrated liquid was purified by a silica gel column to obtain 3.2 g of 4-diethylphosphonophenyl isothiocyanate (2c). Yield 53% (Synthesis example 2-4) 4- (4-phosphonophenyl) -3-
Synthesis of methyl-5-mercaptotriazole (Compound Example 3) 1.2 g of 4-diethylphosphonophenyl isothiocyanate (2c) was dissolved in 20 ml of ethanol to prepare acetohydrazide.
0.4 g was added and reacted at room temperature for 1 hour. 10% in the reaction solution
10 ml of an aqueous potassium hydroxide solution was added, and the mixture was heated under reflux for 4 hours.
After completion of the reaction, the mixture was neutralized to pH 5 with diluted hydrochloric acid, and concentrated with a rotary evaporator. 70 ml of concentrated hydrochloric acid was added to the concentrated solution, heated under reflux for 4 hours, and again concentrated by a rotary evaporator to obtain a crude product. The oily substance obtained was purified by column chromatography to give 4- (4-phosphonophenyl) -3.
-Methyl-5-mercaptotriazole (Compound Example 3)
I got Yield 0.5 g. Yield 37%. Example 3 4- [3- {3- (3-phosphonopropyl) ureido}
Synthesis of Phenyl] -3-methyl-5-mercaptotriazole (Compound Example 5) (Synthesis Example 3-1) N- (3-acetylaminophenyl)
Synthesis of triethylamine dithiocarbamate (3a) 600 g of 3-aminoacetanilide and 4 of acetonitrile
Was added and dissolved, and then 800 ml of triethylamine was added. While cooling this mixture with ice water and keeping it below 20 ° C,
360 ml of carbon disulfide was added dropwise. After about 1.5 hours, the completion of the reaction was confirmed, and the precipitated crystals were collected by filtration to obtain 1170 g (yield 90%) of N- (3-acetylaminophenyl) dithiocarbamic acid triethylamine salt (3a). The crystals were used for the next reaction without further purification.

(Synthesis example 3-2) Synthesis of 3-acetylaminophenyl isothiocyanate (3b) 800 ml of acetone was suspended in 270 g of N- (3-acetylaminophenyl) dithiocarbamic acid triethylamine salt (3a). The mixture was cooled with ice water under a nitrogen stream, and 100 ml of ethyl chlorocarbonate was added dropwise while maintaining the temperature at 10 ° C or lower. The generated gas was captured by an aqueous solution of sodium hypochlorite. After the dropping was completed, the crystals were filtered. Water 1 was added to the filtrate, and the precipitated crystals were collected by filtration. The obtained crystals were combined, washed with water, dried, and recrystallized from acetonitrile to obtain 115 g of 3-acetylaminophenyl isothiocyanate (3b). Yield 76%, melting point 148 ° C (Synthesis example 3-3) 1- (3-acetylaminophenyl)
Synthesis of 3-acetylthiosemicarbazide (3c) 3-Acetylaminophenyl isothiocyanate (3
b) To 30 g, 400 ml of ethanol was added, then 13 g of acetohydrazide was added, and the mixture was stirred at room temperature. Crystals began to precipitate in about 30 minutes. After 4 hours, the precipitated crystals were collected by filtration and dried to 1
42 g of-(3-acetylaminophenyl) -3-acetylthiosemicarbazide (3c) was obtained. Yield 100% (Synthesis example 3-4) 4- (3-acetylaminophenyl)
Synthesis of 3-methyl-5-mercaptotriazole (3d) 70 g of 1- (3-acetylaminophenyl) -3-acetylthiosemicarbazide (3c) was mixed with 250 ml of ethanol and 500 ml of potassium hydroxide (10%), and 2 Heated to reflux for hours. After cooling, the pH was adjusted to 6 to 7 using diluted hydrochloric acid, and crystals were precipitated. The crystals were filtered by suction and dried to obtain 53 g of 4- (3-acetylaminophenyl) -3-methyl-5-mercaptotriazole (3d). Yield 81%, melting point 225 ° C (Synthesis example 3-5) Synthesis of 4- (3-phenoxycarbonylaminophenyl) -3-methyl-5-mercaptotriazole (3f) 4- (3-acetylaminophenyl) -3 -Methyl-
5-mercaptotriazole (3d) in 10g 12N hydrochloric acid 150
Then, the mixture was heated and refluxed. After 3 hours, the mixture was cooled, water was distilled off with a rotary evaporator, and 4- (3-aminophenyl) -3-methyl-5-mercaptotriazole (3
e) Crude crystals of hydrochloride were obtained. Acetonitrile 1 in this crystal
00 ml was added, and then 12 g of pyridine was added and stirred.
Next, the mixture was cooled with ice water, and 7.5 g of phenyl chlorocarbonate was added dropwise while maintaining the temperature at 5 ° C. or lower. After the reaction was completed for 10 minutes after completion of the dropwise addition, 20 ml of water was added to the reaction solution, and the solvent was removed with a rotary evaporator. The obtained concentrate was extracted with ethyl acetate, and the extract was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain crude crystals of 4- (3-phenoxycarbonylaminophenyl) -3-methyl-5-mercaptotriazole (3f). The crude crystals were recrystallized from ethyl acetate to obtain 13 g of compound (3f).

Yield 98%, melting point 188 ° C. (Synthesis example 3-6) Synthesis of N- (3-bromopropyl) phthalimide (3 g) 90 g of potassium phthalimide was added to 300 ml of dimethylacetamide.
And stirred. Then 74 ml of 1,3-dibromopropane
Was added and reacted at 120 ° C. for 4 hours. The reaction solution was poured into water 1 and the precipitated crystals were suction filtered. The crude crystals were recrystallized from ethanol to obtain 100 g of N- (3-bromopropyl) phthalimide (3 g). Yield 77%, melting point 65 ° C. (Synthesis example 3-7) Synthesis of diethyl 3-aminopropylphosphonate (3h) N- (3-bromopropyl) phthalimide (3g) 40g
To the mixture was added 70 ml of triethyl phosphite and heated to 140 ° C. Ethyl bromide produced as a by-product was removed by distillation. After heating for 4 hours, the pressure was reduced by an aspirator, and excess triethyl phosphite was distilled off. Ethanol and 9 ml of hydrazine hydrate were added to the concentrate, and the mixture was heated under reflux for 20 minutes. The formed crystals were removed by filtration, and oxalic acid / acetone (10 g / 50 ml) was added to the filtrate. The crystals formed again were filtered off and the filtrate was concentrated. A small amount of water and acetone were added to the residue, and the precipitated crystals were separated by filtration. When the obtained filtrate was cooled, 3
Crystals of the oxalate salt of diethyl aminopropylphosphonate (3h) precipitated. The crystals were collected by filtration, dried under reduced pressure with a vacuum pump, and diethyl 3-aminopropylphosphonate (3h).
Was obtained as the oxalate. 12g yield, 34% yield, melting point 54
(Synthesis example 3-8) 4- [3- {3- (3-diethylphosphonopropyl) ureido} phenyl] -3-methyl-5
-Synthesis of mercaptotriazole (3i) To 5.0 g of 4- (3-phenoxycarbonylaminophenyl) -3-methyl-5-mercaptotriazole (3f) synthesized in (Synthesis Example 3-5), 40 ml of acetonitrile was added, and triethylamine 8.2 was added. g, and then (Synthesis example 3)
4.1 g of oxalate salt of diethyl 3-aminopropylphosphonate (3h) synthesized in -7) was added and reacted at 50 ° C for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 100 ml of water was added to the residue and the mixture was stirred. 4- [3- {3- (3-diethylphosphonopropyl) ureido} phenyl] -3-methyl-
Crystals of 5-mercaptotriazole (3i) were deposited.
The crystals were suction filtered and dried. Yield 6.2 g, yield 94%, melting point 128 ° C. (Synthesis example 3-9) 4- [3- {3- (3-phosphonopropyl) ureido} phenyl] -3-methyl-5-mercaptotriazole (Compound example) Synthesis of 5) 4- [3- {3- (3-diethylphosphonopropyl)
Ureido} phenyl] -3-methyl-5-mercaptotriazole (3i) 2.0 g, 12N hydrochloric acid 80 ml was added for 8 hours.
The reaction was performed at 90 ° C. After the reaction, hydrochloric acid was distilled off under reduced pressure, and then water 20
ml was added and dissolved by heating. When salt was added little by little to the solution, crystals precipitated. Salt was added until the solution became slightly cloudy. Then, the cloudy solution was heated to make it homogeneous again, filtered naturally, and left to stand.
Crystals of [3- {3- (3-phosphonopropyl) ureido} phenyl] -3-methyl-5-mercaptotriazole (Compound Example 5) were precipitated. It was suction filtered and dried. Yield 0.58 g, yield 33%, melting point 195 ° C. Next, it is shown that the compound of the present invention is useful as an antifoggant for silver halide photographic light-sensitive materials.

A silver bromide gelatin emulsion composed of monodisperse tetradecahedral grains (average grain size of silver halide grains: about 0.8 µ) was ripened by adding diphenylthiourea, potassium chloroaurate and rhodan ammonium. To the obtained emulsion, 0.1 mol% of potassium iodide was added, and then 3,3'-disulfopropyl-5,5'-dichloro-9-ethyl-oxacarbocyanine sodium salt was added. And the comparative compound are added as shown in Table 2, a coating aid (sodium dodecylbenzene sulfonate) and a film hardener (2,4-dichloro-6-hydroxy-s-triazine) are added to support cellulose triacetate. It was applied on the body and dried to obtain Samples 101 to 104. These samples were exposed using a sensitometer through an optical wedge equipped with a yellow filter (1/20 seconds), developed with a developer having the composition below at 35 ° C for 35 seconds, and then fixed by a usual method. After washing with water and drying,
The photographic properties (sensitivity and fog) were measured and the results shown in Table 2 were obtained.

The photographic sensitivity is represented by the reciprocal of the logarithm of the exposure amount required to obtain an optical density of fog value +0.2. In Table 2, the sensitivity of sample 101 is 100 and the others are relatively represented. It was

* Compound A is shown below, and compound examples (5) and (2) correspond to the compound numbers of the compounds according to the present invention described above.

As is clear from Table 2, the compound of the present invention is effective without lowering the relative sensitivity as compared with the case of not using the compound of the present invention and further using Comparative Compound A which is a known antifoggant. It can be seen that the fog density is lowered.

(Effect of the Invention) According to the present invention, it is possible to provide a novel phenylmercaptoazole compound represented by the formula [I] and a salt thereof or a lower alkyl ester thereof. The compound according to the present invention is useful as an antifoggant for a silver halide light-sensitive material.

Claims (3)

(57) [Claims] 1. The following general formula [I] (In the formula [I], A represents -CH = or -N =, and B represents -CH = or -N =.
CH =, Or represents -N =, and X is And Y represents an alkylene chain having 2 or 3 carbon atoms. n represents 0 or 1, and m represents 0 or 1. In the phenyl group The bonding position of is 3 or 4 position with respect to the heterocycle. ) A phenylmercaptoazole compound represented by: and its salt, or its methyl ester or ethyl ester. 2. A phenylmercaptoazole compound according to claim 1, wherein n is 0 and m is 0 in the general formula [I], its salt or its methyl ester or ethyl ester. 3. A phenylmercaptoazole compound according to claim 1, wherein n is 1 and m is 1 in the general formula [I], and a salt thereof or a methyl ester or ethyl ester thereof.