JPS6029390B2 - Benzotriazole compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a penzotriazole compound and a method for producing the same.

Penzotriazole compounds are conventionally known to be useful as photographic development inhibitors and as leaving groups in development inhibitor releasing couplers (DIR couplers). The DIR coupler invented in Tokusekki No. 49-122335 has significantly improved image tone, fine grained images, improved sharpness of images (by edge effect), color reproduction (by multilayer effect), etc. Although improved, there is a practical need for the development of new benzotriazole compounds that further improve various properties including an improvement in the reaction activity of DIR couplers.

Therefore, an object of the present invention is to provide a compound which is essential as an intermediate for DIR coupler synthesis and which has outstandingly improved physical properties as described above.

The above object can be effectively achieved by the following general formula (1).

[In the formula, R represents an alkyl group having 5 to 11 carbon atoms.

] When a compound in which R in formula (1) is an alkyl group having 7 to 9 carbon atoms is introduced into a coupler, the performance of the coupler as a DIR coupler is particularly excellent.

The compound of the present invention is reacted with a photographic coupler to obtain a DIR coupler, and the "DIR coupler" exhibits outstandingly superior performance compared to those obtained by reacting known penzotriazole compounds.

Furthermore, when the compound of the present invention was itself added to a photographic emulsion, it exhibited an excellent development inhibitory effect that could not be expected from conventionally known compounds with similar measures.

That is, it can be used as an anti-fogging agent. Specific examples of the compounds of the present invention are shown below.

<・) Melting point 210-11℃ 5{6)-hexanoamide benzotriazole※※(2
) Melting point 204~5℃ 5{6)-Octanoamide benzotriazole (3) Melting point 202~400 5'6}-Decanoamide benzotriazole Melting point 19
9-200℃ Pentapod-(3,5,5-trimethylhexanoamide)-penzotriazole Melting point 19 is ○ 5[6}-(2-ethylhexanoamide)-benzotriazole Example 1 (Compound [ Synthesis of 1') Aminobenzotriazole 45.6 moles (0.34 mol)
Pour the mixture and acetonitrile into a 3-necked flask equipped with a condenser, rope strainer, and thermometer, and completely dissolve at room temperature.

After adding 34.3 moles (0.34 mol) of triethylamine to this, 51.1 moles (0.38 mol) of caproic acid chloride was added dropwise over 1 hour. Approximately 1 hour after the completion of the dropwise addition, yellow crystals begin to precipitate. This is taken in a furnace, washed with benzene, and then recrystallized from ethyl acetate. Melting point 210
~11°C, yield 42 min (55.3%). Example 2 (Synthesis of compound ①) p-Nitro-m-phenylenediamine 91.8 hours (0.
6 moles) and 720' of methyl isobutyl ketone were charged into a two-hole flask equipped with a reflux condenser, a Kashiyo machine, and a thermometer.
To this is added 121 moles (1.2 moles) of triethylamine.

When 195 mg (1.2 mol) of caprylic acid chloride is dropped under the rope over 1 hour, crystals are precipitated. 6 after completion of dripping
Continuing to sail for 2 hours at 5°C, 160 ml of methanol was added, and after cooling with water, the crystals were collected in a furnace and thoroughly washed with 900 w' of methanol to obtain yellow crystals of 2,4-dioctanoamidenitrobenzene with a melting point of 155-65°C. Yield: 200 yen (82%).
Pour 125 μm of iron powder, 125 μl of water, and 600 μl of inpropyl alcohol into a 2-k flask equipped with a reflux condenser, rope heater, and thermometer, heat to 70 μm, add 5 μm of ammonium chloride under rope, Add 10 drops of acetic acid.

At 80°C, 200 g (0.5 mol) of 2,4-dioctanoamidonitrobenzene was added in portions for 1 hour.

After finishing, add boiling inpropyl alcohol 600ml,
Further, it is neutralized with a sodium methoxide-methanol solution and filtered in a hot oven. The furnace liquid is cooled with water and the precipitated crystals are collected in the furnace. 2,4-dioctanoamide aniline.

Melting point 215-6.5 qo. Yield: 150 yen (80%). 2
・150 parts (0.4 mol) of 4-dioctanoamide aniline, 24 parts of concentrated sulfuric acid, 80 parts of water, 400 parts of acetone
Pour into 2 flasks and add 36 liters of sodium nitrite under the rope at room temperature.
．． A concentrated aqueous solution was added dropwise over 1 hour on August 8th, and the rope was continued for another 2 hours after completion.

The generated crystals are taken out of the furnace and washed with water and methanol. 1
-6-dioctanoamide benzotriazole.

Melting point 129-30°C. Yield: 147 evenings (93%). Elemental analysis value (0, 2 days, 6N4 0) ○ (*) N section)
N (Shigeru) calculated value 62.08 6.89 2.4
．． 14 Actual value 61.85 6.81 24.0
01,6-dioctanoamide benzotriazole 147
In the evening (0.37 mol), 22 ml of a saturated solution of Z sodium toxide and methanol in 700 methanol was charged into a 2-ml flask equipped with a reflux condenser, a hawk, and a thermometer.
After completely melting at ℃, add 7.5 tons of decolorizing charcoal and heat in a furnace.

15' of acetic acid is added to the furnace liquid, and after cooling with water, the precipitated crystals are collected in the furnace to obtain 5[6}-octanoamide benzotriazole. Melting point 204-500. Yield 78 evenings (80%). Elemental analysis value (022 Day 34 N4 02) ○(Tsutomu) H section) N section) Calculated value 68.36 8.87
14.50 Actual value 68.14 8.78 14
．． 73 Example 3 (Synthesis of Compound [3') 200 ml of pyridine was charged into a 500' 3-necked flask equipped with a thermometer, a evaporator, and a reflux condenser, and 35.2 ml of aminobenzotriazole (0.0 ml) was added to this. 2625 mol) is added.

50 minutes of capric acid chloride (o.2
625 mol) was added dropwise between each powder. 30 minutes after the completion of the addition, the mixture was returned to room temperature and heated for another 5 hours. The reaction mixture is added to ice water, and the precipitated crystals are collected in a furnace, washed with water and ethyl acetate, and then recrystallized from ethanol. Melting point 202
~4℃. Yield: 49 evenings (64.8%). Elemental analysis value
(0,4 days 20N 4 0) ○ (difficult) days (purple)
N (omitted) Calculated value 64.62 7.69 21.
54 actual value 64.74 7.77 21.52
Example 4 (Synthesis of Compound '4}) In a 500' three-necked flask equipped with a thermometer, a thermometer, and a reflux condenser, aminotriazole 27 (0.2 mol),
Acetonitrile 300%, triethylamine 23% (
0.23 mol) of 3.5,5-trimethylhexanoyl chloride was added dropwise, and after the completion of the reaction, the mixture was heated under reflux for 3 hours.

After the reaction is complete, the solvent is distilled off, water is added to the residue, and the mixture is extracted with ethyl acetate. Ethyl acetate is driven off, the remaining oil is crystallized from acetone-hexane, and the crystals obtained are recrystallized from ether. Yield 7 nights (13%). Melting point 199-2
0000. Elemental analysis value 0 16 days 24 N
400 (%) Day (%) N (%) Calculated value 66.67
8.33 19.44 Actual value 67.07 8.
61 18.62 Example 5 (Synthesis of Compound ■) In a 500' 3-necked flask equipped with a thermometer, a steamer, and a reflux condenser, 54 mm (0.4 mol) of aminobenzotriazole and 300 mm of pyridine were charged. 70 moles (0.43 mol) of 2-ethylhexanoyl chloride was added dropwise to an ice-cold tube.

After completion of the dropwise addition, the mixture was kept at room temperature for 3 hours, then added to ice water, and the precipitated white crystals were collected in a furnace and recrystallized with ether. Melting point: 19〆○. Yield 47 evenings (45%). element. Analysis value (0.5 days 22 N 4 0) ○ (omitted) days (%) N (%) Calculated value 65.66 8.0
8 20.42 Actual value 65.52 8.08
20.21 elemental analysis value (0.4 days 20N4
0)○(male)day(%)N-co)calculated value 64.59
7.74 21.52 Actual value 64.50
7.76 The spectrum of infrared absorption spectra of compounds '1' to (2) of 21.74 or higher, measured by the Nujol method, are shown in FIGS. 1 to 5.

The compound obtained by introducing the compound of the present invention into the active methylene group of an acetoacetanilide coupler according to the synthesis method described in Hakama Kai 52-82424, for example, is excellent as a DIR coupler. It has excellent performance.

That is, they bring about a much better effect in improving image quality (improving graininess, improving edge effects, etc.) than known DIR couplers. Specific examples of compounds synthesized using the compounds of the present invention are shown below.

Furthermore, these compounds exhibit great development inhibitory properties when added to emulsions or developers, and act as excellent fog removers when used for color correction.

The effects of the compounds of the present invention will be explained below using reference examples. Reference Example 1 - Synthesis of Compound (1) 55.1 parts of Q-(4-octadecyloxybenzoyl)-2-ethoxyacetanilide was dissolved in 200 parts of chloroform.

To this solution, 16.5 tons of bromine was added dropwise at 5°C. After the dropping was completed, the plate was washed with 500 g of water. Add this solution to the compound'
21 54.7 evening, triethylamine 20.2 evening 20
Add 20~ to a solution of 0M dimethylformamide.
It was dropped at 23:00. The reaction mixture was washed with a 3% aqueous sodium hydroxide solution, then with a 5% aqueous hydrochloric acid solution, and then with water. This solution was concentrated under reduced pressure,
The residue was recrystallized from a mixed solvent of isopropanol and ethyl acetate to obtain the desired product with a yield of 36.0 mm. The melting point is 141
It was ~3°C. Reference Example 2 Synthesis of Compound {q 53.7 mg of Q-(4-octadecyloxybenzoyl)-2-methoxyacetanilide was dissolved in 200 g of chloroform.

To this solution, 16.5 ml of bromine was added dropwise at 5°C. After the dropping was completed, it was washed with 500 ml of water. Add this solution to compound '4' for 57.2 hours and triethylamine for 20.2 hours.
2 in a solution of dimethylformamide of 00
It was dropped between 0 and 23:00. After 1 hour of dropping, the reaction mixture was washed with 3% sodium hydroxide aqueous solution, and then washed with 5% sodium hydroxide solution.
% aqueous hydrochloric acid solution and then water. This solution was concentrated under reduced pressure, and the residue was recrystallized from a mixed solvent of isopropanol and ethyl acetate to obtain the desired product in 36.3 days. Melting point is 144
It was ~6°C. Reference Example 3 Sample 101: The first to fourth layers were coated on a transparent cellulose triacetate film support in this order and dried to obtain a sample.

The composition of the coating liquid used for each layer and its preparation are as follows. 1st layer: Red-sensitive emulsion layer: A high-sensitivity silver iodobromide emulsion lk9 (silver amount: 0.6 mol, iodine content: 6 mol%) prepared by a conventional method is taken, and this is increased. 4 x 10-5 mol of sensitizing dye 1/1 mol of silver and 1 x 10-5 mol of sensitizing dye 0
Spectral sensitization was performed using 5 moles/1 mole of silver.

100 parts of coupler A to 1 part of tricresyl phosphate
Dissolve 00 in 200 ml of ethyl acetate and add 1 ml of this solution.
Add 550 g of "Emulsion 1" obtained by emulsifying and dispersing 0% gelatin aqueous solution lK9 using 4 g of sodium nonylbenzenesulfonate (surfactant) to the previously spectrally sensitized silver iodobromide emulsion. This was then treated with 2,4-dichloro-6-hydroxytriazine sodium as a hardening agent.
The mixture was added as an aqueous solution. The coating solution thus prepared was coated onto a transparent cellulose triacetate film support at a silver coating weight of 1.5/l. Second
Layer: Middle layer: 50% of 2,5-di-t-octylhydroquinone and 100% of tricresyl phosphate
The mixture was dissolved in water and emulsified and dispersed in 1 kg of a 10% aqueous gelatin solution in the same manner as Emulsion 1.

250 ml of this emulsion and 2 ml of sodium 2,4-dichloro-6-hydroxytriazine (as an aqueous solution) were added to a 10% aqueous gelatin solution LK9. It was coated as a dry membrane to a thickness of 1.5 microns. 3rd layer: Green-sensitive emulsion layer...High-sensitivity silver iodobromide emulsion of lk9 (same as the 1st layer), 3 x 10-5 moles of sensitizing dye m/
Spectral sensitization was performed using 1 mol of silver and 1×10 −5 mol of sensitizing dye W/1 mol of silver.

"Emulsion 2" was prepared in the same manner as Emulsion 1 in Example 1 using coupler BIOO. After adding 700 g of the emulsion to the spectrally sensitized silver iodobromide emulsion, 2 g of sodium 2,4-dichloro-6-hydroxytriazine was added as an aqueous solution while stirring. 4th layer: protective layer...
...2,4-dichloro-6-hydroxytriazine sodium was added to a 10% gelatin aqueous solution LK9 and applied to a dry film thickness of 1.5 microns.

Samples 102 to 107: Oil of emulsion D of sample 101 (
coupler solvent) as shown in Table 1 below.
A sample was prepared in the same manner as sample 101 except that R coupler was added in an amount corresponding to 3 hol% of the amount of coupler B added, and the coating amount of the third layer was adjusted to have the same thickness as yG of sample 101.

Compounds used to prepare the samples Sensitizing dye 1: Anhydro-5,5-dichloro-3,3-disulfoprupyl-9-ethylthiacarbocyanine hydroxide pyridinium salt Sensitizing dye 0: Anhydro-
9-Ethyl-3,3'-di(3-sulfonepropyl)-
4,5,4'-5-dibenzothiacarbocyanine hydride 0
Oxide triethylamine sensitizing dye M: Anhydro-9-ethyl-5,5-dichloro-3,3-disulfopropyloxacarbocyanine sodium salt sensitizing dye W:
Anhydro 5,6,5,6-tetrachloro-1,1-diethyl-3,3-disulfopropoxyethoxyethylimidazolocarbocyanine hydroxide sodium salt coupler A: 1-hydroxy-N-[y-(2,4-di 2-naphthamide coupler B: 1-(2,4,6-trichlorophenyl)-3-(214-amylphenoxyacetamide)penzamide 15-pyrazolone (4
Equivalent coupler) Comparative DIR coupler D-1 Comparative DIR coupler D-2 After giving stepwise exposure to samples 101 to 107 with red light,
After uniform exposure with green light, 3
Development processing was performed at 8°C.

Furthermore, line image exposure of 4 skin widths and 10 mountain skin widths was performed using soft x line, and the same development process was performed. 1. Color development...
・3 minutes 19 sand 2. Bleaching...3/6 thighs 3. Washing...3 minutes 19 steps 4, Fixing...6 minutes 3 steps 5. Wash with water...3 minutes with sand6. Stable...3 minutes 1 second The composition of the processing solution used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0% Sodium sulfite. Thorium 4.0 Sodium carbonate 30.0 Potassium polybromide
1.4 Hydroxylamine sulfate 4-(N-ethyl-N-hydroxyethylamine/)-2-methyl-aniline
2.4 Sulfate
4.5 Add water 1. Bleach solution Ammonium bromide 160.0 t Ammonium water (28%) Ethylenediamine-tetraacetic acid
25.0' Sodium Iron Salt 1302** Glacial Acetic Acid
14 [Add water
1 Fixing solution Sodium tetrapolyphosphate 2.0 ta Sodium sulfite 4.0 Ammonium thiosulfate (70%) 175.0 Sodium bisulfite 4.6 ta Add water
1 Add stabilizer formalin 8.0 ml of water to the resulting characteristic curve, set the gradation of the red filter optical density - log (exposure amount) curve (corresponding to the first layer) to yR, and use the green filter. If the gradation of the optical density-log (exposure amount) curve (corresponding to the third layer) is yG, then the magnitude of yR/yo can be considered to represent the magnitude of the interlayer effect from the third layer to the first layer. .

(yR value is almost constant). That is, the more negative yR/yG and the larger the absolute value, the greater the multilayer effect. yR/yG of each sample
The values are shown in Table 1. Each sample obtained by line image exposure with soft X-rays was irradiated with red light and scanned with a microdensitometer to measure the density.

If the density of the line image of 10〃 is D; and the density of the paper image of 4 ribs is ○, then (D; - D)/D; is the magnitude of the edge effect of the sample when observed with red light. represent.

The (D; -D noon)/Df value of each sample is shown in Table 1. table
1 Note 1 Amount: Approximate molar relative to Coupler-B From the above results, it can be seen that Compound Kaze~Dish all have excellent performance as DIR couplers, and have large layer effects and edge effects that are related to image quality.

[Brief explanation of the drawing]

FIGS. 1 to 5 are infrared absorption spectra of compounds {1) to compound (2), respectively. All were measured by the Nujol method. 1st
Figure 2 Figure 3 Figure 4 Figure 5

Claims (1)

[Claims] 1. A benzotriazole compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R represents an alkyl group having 5 to 11 carbon atoms. 2. The compound according to claim 1, wherein R is an alkyl group having 7 to 9 carbon atoms. 3. The compound according to claim 1, wherein R is a straight chain alkyl group having 7 to 9 carbon atoms. 4. The compound according to claim 1, wherein R is a 2,4,4-trimethylamyl group. Claim 1 in which 5 R is a 1-ethyl amyl group
Compounds described in Section.