JP2709774B2 - New dicarbamoyl telluride compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel tellurium compound, a dicarbamoyl telluride compound.
The present invention relates to a novel dicarbamoyl telluride compound useful as a pharmaceutical, a pesticide, a photographic compound, and a synthetic intermediate thereof.

[0002]

2. Description of the Related Art Conventionally, diacyl tellurides and tellurodicarboxylic acid diesters are known as similar compounds, and are known from the Bulletin of the Chemical Society of Japan.
apan), 62, 2117 (1989), Journal
Journal of Organometallic Chemistry
Organometallic Chemistry), 338, 9 (198
8), Zeitschrf Fair Chemie
ift fuer Chemie), 26, 179 (1986), Indian Journal of Chemistry, Section A, 2
5A, 57 (1986), Angevante Chemie (Ang
ewandte Chemie), vol. 97, 1051 (1985), Spectrochimica A, Part A (Spectrochimica A)
cta, Part A) 38A, 185 (1982), Organic Preparations and Procedu International
res International), vol. 10, 289 (1978), and the like, as well as synthesis methods and the like, but dicarbamoyl telluride has not been known so far. Further, diacyl telluride, tellurodicarboxylic acid, and diester have poor stability, and cause a problem when used as a photographic compound requiring stability.

[0003]

SUMMARY OF THE INVENTION The present invention relates to medical, agricultural,
Provided are a photographic compound and a novel tellurium compound which is a synthetic intermediate thereof.

[0004]

The present invention has been achieved by a tellurium compound represented by the general formula (I). General formula (I)

[0005]

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In the formula, R ₁ and R ₂ represent an aliphatic group or an aromatic group. Next, the general formula (I) will be described in detail.

The substituted or unsubstituted aliphatic groups represented by R ₁ and R ₂ in the general formula (I) are linear, branched or cyclic alkyl, alkenyl, alkynyl and aralkyl groups. Examples of the alkyl group, alkenyl group, alkynyl group, and aralkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group,
and n-octyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, propargyl, benzyl and the like.

The substituted or unsubstituted aromatic group represented by R ₁ and R ₂ in the general formula (I) is a monocyclic or condensed aryl group, such as a phenyl group and a naphthyl group.

The above alkyl, alkenyl, alkynyl, aralkyl and aryl groups may be substituted. Examples of the substituent include a halogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, a substituted amino group, an acylamino group, a sulfonylamino group, an ureido group, a urethane group, a carbamoyl group, a sulfamoyl group, and an alkylthio group. , Arylthio, sulfonyl, hydroxy, cyano, sulfo, carboxy, nitro and the like.

Such a dicarbamoyl telluride compound of the present invention can be used, for example, as a tellurium sensitizer used in a silver halide photographic light-sensitive material, and is a halogenated compound having better photographic characteristics than conventional ones. A silver photographic light-sensitive material can be obtained. In the general formula (I), when the carbon number of R ₁ or R ₂ exceeds 30, the affinity for water becomes poor, and it becomes difficult to industrially use the silver halide photographic material. Thus, the type of substituent on the nitrogen of dicarbamoyl telluride greatly affects the properties of dicarbamoyl telluride. Therefore, when the compound of the present invention is used industrially, the substituent on the nitrogen can be selected according to the purpose, but the ease of synthesis, stability,
Preferred substituents in view of industrial utility are as follows.

In the general formula (I), the substituted or unsubstituted aliphatic group represented by R ₁ and R ₂ preferably has 1 to 30 carbon atoms, and particularly has 1 to 10 carbon atoms. Group. In the general formula (I), the substituted or unsubstituted aromatic group represented by R ₁ and R ₂ preferably has 6 to 30 carbon atoms, particularly an aryl group having 6 to 20 carbon atoms. .

Hereinafter, specific examples of the compound of the present invention will be listed, but the scope of the present invention is not limited thereto.

[0013]

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[0014]

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[0015]

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The dicarbamoyl telluride of the present invention can be generally synthesized by reacting a reagent (Na ₂ Ten) prepared by reducing tellurium with sodium hydride or the like and carbamoyl chloride. R ₁ R ₂ NCOCl + Na ₂ Ten → (R ₁ R ₂ NCO) ₂ Te In the formula, R ₁ and R ₂ have the same meaning as in the general formula (I), and n represents a natural number.

The reaction in the present invention is usually performed in a solvent. The solvent is not limited as long as it does not participate in the reaction, but it is advantageous to use dimethylformamide. Examples of the reducing agent that reduces tellurium include alkali metal hydrides such as sodium hydride, metal sodium, and metal potassium, alkali metals, and lithium triethylpolyhydride. These reducing agents are used in an amount of 1 to 2.5 equivalents relative to tellurium. Tellurium is used in an amount of 0.4 to 1.5 equivalents to carbamoyl chloride. The reaction between the reagent prepared by reducing tellurium and carbamoyl chloride is performed at 0 ° C.
It proceeds at -100C, preferably 10-50C.

[0018]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples. Example 1 Synthesis of Compound Example 1 In a well-dried three-necked flask, 80 ml of dried DM was added.
F, 6.38 g of tellurium powder and 2.2 g of sodium hydride (60% assay in oil) were added, and the inside of the reaction vessel was set to an argon atmosphere. 90 to 10 under argon stream
The mixture was heated to 0 ° C. and stirred for 3 hours. Cool the reaction to 0 ° C.
11.6 g of N, N-diphenylcarbamoyl chloride dissolved in 50 ml of dry dimethylformamide (DMF) were added dropwise. After stirring at room temperature for 12 hours, DMF was distilled off under reduced pressure until the reaction solution became 70 cc, 70 cc of methylene chloride was added, and the resulting white precipitate was collected by filtration. The filtrate is concentrated,
After drying, 30 cc of methylene chloride was added and the resulting white precipitate was collected by filtration. This was combined with the above white precipitate, dissolved in 200 ml of methylene chloride, and the insoluble matter was removed by filtration. Then, methylene chloride was distilled off under reduced pressure to obtain 7.6 g of crude crystals. Recrystallization from 300 cc of acetonitrile gave 5.2 g (40%) of white crystals. Melting point 194-195 [deg.] C (dec.). ¹ H-NMR (CDCl ₃ ) δ (ppm) δ 7.18-7.38 (s, 20H) IR (KBr) (cm ⁻¹ ) 3052, 1681, 1485, 1238, 1126,
752, 697, 595

Example 2 Synthesis of Compound Example 2 In a well-dried three-necked flask, 100 ml of dried DM was added.
F was added, and 7.65 g of tellurium powder was added thereto and dried to obtain a suspension. Replace the inside of the system with argon, and quickly add 2.64 g of sodium hydride (60% assay in oil)
Was added. After stirring at room temperature for 1 hour, the temperature was gradually raised and the mixture was stirred at 90-100 ° C for 3 hours. After returning the reaction solution to room temperature, it was further cooled to −10 ° C., and 50 ml of dry DM was added.
10.2 g of N-methyl-N-phenylcarbamoyl chloride dissolved in F was added dropwise. After the reaction solution was returned to room temperature and stirred for 5 hours, the solvent was distilled off under reduced pressure. The resulting mixture of crystals and oil was filtered under reduced pressure to separate crystals and oil. The obtained oil was purified using silica gel column chromatography (methylene chloride / ethyl acetate = 20/1) to obtain white crystals (4.2 g). This was recrystallized using a mixed solvent (100 ml) of methanol / n-hexane = 1/9 to obtain 3.5 g of white crystals (29 g).
%). 134-135.5 ° C (dec.). ¹ H-NMR (CDCl ₃ ) δ (ppm) δ 7.27-7.38 (m 6H) δ 7.11-7.20 (m 4H) δ 3.33 (s 6H) IR (KBr) (cm ^-1 ) 3055, 2925, 1687, 1640, 1235,
1094,826,696,546

Hereinafter, other compounds were synthesized by the same experimental procedure.

Next, the industrial utility of the compound of the present invention will be described with reference to application examples. Application example Application example to silver halide photographic light-sensitive material

First, a silver halide emulsion was prepared as follows to prepare a silver halide photographic film. While stirring into 1 liter of an aqueous solution containing 0.05 g of potassium bromide and 30 g of gelatin kept at 75 ° C. and kept at pH 2 with nitric acid, 75 ml of an aqueous solution of silver nitrate (1 M) and an aqueous solution of potassium bromide (1 M) were simultaneously added. The silver potential was added over 4 minutes while maintaining the potential at 0 mV with respect to the saturated calomel electrode.

Thereafter, an aqueous silver nitrate solution (1M) 67
5 ml and an aqueous potassium bromide solution (1 M) were added to a silver potential of -3.
The addition was carried out simultaneously for 36 minutes while maintaining 0 mV.

After the completion of the particle formation, the mixture was desalted and washed with a usual flocculation method, and gelatin and water were added to adjust the pH to 6.4 and the pAg to 8.6.

The resulting silver bromide emulsion has a grain diameter of 0.2
This is a monodispersed octahedral emulsion having a size of 5 μm and a variation coefficient of the grain diameter of 11%.

After this emulsion was divided into small portions, the temperature was raised to 60 ° C., and a sensitizer was added as shown in Table 1, followed by chemical ripening for 60 minutes. The addition amount of the sensitizer is an optimum addition amount having the highest reaching sensitivity. Then, gelatin, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene, potassium poly-styrenesulfonate and sodium dodecylbenzenesulfonate were added to form a triacetylcellulose film having an undercoat layer on a support. Co-extrusion was applied with a protective layer containing methacrylate particles and sodium 2,4-dichloro-6-hydroxy-s-triazine. These samples were exposed to sensitometric exposure (10 seconds) through an optical wedge, developed with a MAA-1 developer having the following formulation at 20 ° C. for 10 minutes, then stopped, fixed, and washed in a conventional manner. , Dried and measured for density.

The relative sensitivity is represented by the reciprocal of the exposure required to obtain an optical density of fog value + 0.2. The results are shown in Table 1.

MAA-1 developer Metol 2.5 g Ascorbic acid 10 g Nabox 35 g Potassium bromide 1 g Add water to make 1 liter

[0029]

[Table 1]

The compound of the present invention can be used as a sensitizer, and as shown in Table 1, the sensitivity of a silver halide photographic material can be improved. The relative sensitivity when no sensitizer was used was 10 or less. As is evident from Table 1, when the compound of the present invention was used as a sensitizer, much higher sensitivity was obtained than in the case of sodium thiosulfate, which has been well known and has high industrial utility value. . This indicates that the compound of the present invention exhibits excellent photographic characteristics.

[0031]

The present invention can provide a tellurium compound useful as a photographic compound, a medicine, a pesticide, and a synthetic intermediate thereof.

Claims (1)

(57) [Claims] 1. A tellurium compound represented by the general formula (I): In the formula, R ₁ and R ₂ represent an aliphatic group or an aromatic group.