CN1037551C - Process for directly linking 3-anilino-pyrazolone and sulfoether - Google Patents
Process for directly linking 3-anilino-pyrazolone and sulfoether Download PDFInfo
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- CN1037551C CN1037551C CN91101071A CN91101071A CN1037551C CN 1037551 C CN1037551 C CN 1037551C CN 91101071 A CN91101071 A CN 91101071A CN 91101071 A CN91101071 A CN 91101071A CN 1037551 C CN1037551 C CN 1037551C
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Abstract
The present invention directly synthesizes a thioether type DIR pyrazolone magenta color former from a 3-anilino substituted parent color former (CO) by use of activated chlorides and activated disulfides. The present invention omits the steps for acylating, brominating and hydrolyzing the parent color and enables a DIR compound to be fully utilized.
Description
The invention belongs to the technical field of: the present invention belongs to the preparation of color sensitive material color former.
Pyrazolone used as a fuchsin color former applied to a color photosensitive material has the advantages of high activity, strong chromophoric ability, easy industrialization and the like, but has larger harmful absorption in a blue-sensitive area, and the harmfulabsorption of the pyrazolone substituted by anilino at the 1, 3-position is smaller, so the pyrazolone is practically applied [2].
Mercapto compounds have a development-inhibiting effect and are commonly used DIR groups. The mercapto compound is grafted to form thioether type DIR color formationReagents, the literature uses a precursor coupler first made into bromide. Prior to bromination, the anilino group is protected by acylation because it is quite basic and can also be brominated. After bromination is complete, hydrolysis is carried out to remove the protected acyl group [3]]Preparing dibromo colour former, and then reacting with 3 times mole ratio of mercapto compound [4]。For the thiol compound, only 1/3 was used to form the thioether-type DIR coupler, 2/3 formed a byproduct disulfide compound.
The purpose of the invention is as follows: the present invention makes it possible to attach DIR groups directly to the parent couplers of the following structure (C0) in relatively high yields using relatively simple methods, via sufficiently reactive forms.
Method 1. with reactive chlorides:
The yield of each step is higher. By using the method of our invention, it is not necessary to brominate the parent coupler first (acylation and deacylation are also omitted), and the DIR compound can be used completely in the synthesis of DIR coupler. Thus, the synthesis steps are simplified, and the DIR compound is fully utilized.
Synthesis examples example 1. synthesis of couplers where Ar is phenyl tetrazolyl:
(1) synthesis of intermediate I1:
adding 0.9 g (5mMol) phenyl mercapto tetrazole and 20ml carbon tetrachloride into a 100ml three-neck flask, adding a mixed solution of 0.5ml sulfonyl chloride and 5ml carbon tetrachloride while stirring, gradually heating, reacting for 1 hour when the temperature reaches 30 ℃, and heating to about 50 ℃ to completely remove acid gas. I1 was unstable and was used as soon as possible in the next reaction.
(2) Synthesis of color former C1:
in the flask, 3.4 g (5mMol) of coupler C0 was added, the coupler gradually dissolved with stirring and acid gas evolution, after 2 hours reaction at 60 ℃ the heating was stopped, cooling, the reaction solution was added in a trickle into 150ml petroleum ether, a large amount of solid precipitated, stirred, filtered, washed with petroleum ether and dried to give 4.3 g (99%) of light pink powder. Recrystallization from organic solvents gives a white solid. Melting point: 74-76 deg.CNuclear magnetism (CDCl)3): 0.85-0.95, t, 3 hydrogen; 1.35, s, 18 hydrogen; 1.53, s, 9 hydrogen; 1.60.1.70, m, 2 hydrogen; 1.90-2.05, m, 2 hydrogen; 4.55-4.65, t, 1 hydrogen; 6.65, s, 2 hydrogen; 6.95-7.05, d, 2 hydrogen; 7.30-7.75, m, 8 hydrogen; 8.10-8.40, m, 2 hydrogen. Example 2. method of synthesis of coupler with Ar as benzyl: 
the synthesis method of the intermediate I2 comprises the following steps:
37.8 g of benzyl chloride (0.3Mol), 22.8 g of thiourea (0.3Mol) and 70ml of 95% ethanol are added into a 250ml three-neck flask, heating and refluxing are carried out for 30 minutes to obtain a transparent colorless liquid, then a solution prepared from 24 g of NaOH and 100ml of water is added, the reaction liquid becomes turbid, a white solid is separated out, the solution is refluxed again, and the reaction liquid is gradually addedClarifying, refluxing for 2 hr, naturally cooling to room temperature, adding 15ml concentrated hydrochloric acid and 82 g FeCl3·6H2And O, stirring, precipitating a large amount of solid, filtering, washing with water, and drying to obtain an off-white solid with the weight of 45 g. Recrystallizing with ethanol to obtain white needle crystal. Melting point: nuclear magnetic (CDCl) at 70-71 deg.c3): 3.60-3.65, s, 4 hydrogen; 7.25-7.45, m, 10 hydrogen. Mass Spectrum (M +/e): 246.
synthesis method of color former C2:
in a 100ml three-neck flask, 3.4 g (5mMol) of color former C0 and 0.62 g (2.5mMol) of I2 were added, 50ml of DMF was added, stirred and dissolved at normal temperature, and 0.4 g of Br was added dropwise2And 10ml of DMF, and the dropwise addition is completed within 10 minutes. Heating the reaction solution to 50 ℃ by using a water bath, reacting at the temperature for 2 hours, cooling toroom temperature, slowly pouring into 200ml of distilled water under stirring, separating out a large amount of white solid, filtering, washing with water, and drying a filter cake to obtain the white solid. Weight 4.0 g (yield 99%). melting point: 102 ℃ 103 ℃ Nuclear magnetism (CDCl)3): 0.90-0.95, t, 3 hydrogen; 1.32, s, 18 hydrogen; 1.52, s, 9 hydrogen; 1.60-1.70.m, 2 hydrogen; 1.90-2.00, m, 2 hydrogen; 3.78, s, 2 hydrogen; 4.55-4.65, t, 1 hydrogen; 6.65, s, 2 hydrogen; 6.95-7.05, d, 2 hydrogen; 7.20-7.65, m, 8 hydrogen; 7.98, s, 1 hydrogen; 8.18, s, 1 hydrogen.
Reference 1, Huang Zheng, photosensitive materials, 1985, sixth phase, page 12. 2. Sunshengye, doctor thesis, university of California, 1990, page 151. Machiele, U.S. patent, 3,962,273 (1976). 4. Ancient museum Xinsheng, Japanese Kokai, Sho 53-63377 (1978).
Claims (4)
1. Pyrazolone fuchsin coupler substituted by 3-anilino (C0)
Synthesis of pyrazolone DIR coupler (C)1)
Wherein Ar is
And R is alkyl, phenyl, etc., comprising the steps of:
a. reacting a mercapto compound (Ar-SH) with a sulfonyl chloride (SO)2Cl2) Reaction, Synthesis of intermediate (I)1)
(I1)
b. Reacting intermediate (I)1) Reaction with Co to synthesize color former (C)1)
(I1)
2. The method of synthesis according to claim 1, characterized in that step a
The method comprises the following steps: dripping 0.9 g (5mMol) phenyl mercapto tetrazole in 20ml carbon tetrachloride, dripping 0.5ml sulfonyl chloride and 5ml carbon tetrachloride mixed solution, heating to 30 ℃, reacting for 1 hour, heating to 50 ℃, completely removing acid gas to obtain an intermediate I1(ii) a The step b comprises the following steps: 3.0 g of the precursor coupler (C0) was added to the above vessel, reacted at 60 ℃ for 2 hours, cooled, and added to petroleum ether to obtain coupler (C)1) The yield of the crude product was 99%.
3. Pyrazolone fuchsin coupler substituted by 3-anilino (C0)Synthesis of pyrazolone DIR magenta coupler (C)2)
The method comprises the following steps: a. reacting benzyl chloride
With thiourea (S ═ C (NH)2)2) Reaction, Synthesis of intermediate (I)2)
b. Reacting intermediate (I)2) And C0And bromine (Br)2) Reaction, Synthesis of color coupler (C)2)
4. The method of synthesis according to claim 3, characterized in that step a comprises: 37.8 g of benzyl chloride (a3Mol), 22.8 g of thiourea (0.3Mol) and 70ml of 95% ethanol are heated and refluxed for 30 minutes, then a solution prepared from 24 g of NaOH and 100ml of water is added, after refluxing for 2 hours, the mixture is naturally cooled to room temperature, 15ml of concentrated hydrochloric acid and 82 g of Fel are added3·6H2O, a large amount of solid is separated out to obtain an intermediate I2(ii) a The step b comprises the following steps: 3.4 g (5mMol) of coupler (C0) and 0.62 g (2.5mMol) of intermediate (I)2) 50ml of DMF are added and 0.4 g of Br are added dropwise within 10 minutes2And 10ml DMF at 50 deg.C for 2 hr, cooling to room temperature, and pouring into distilled water under stirring to obtain color former (C)2) Precipitated out and weighed 4.0 g, yield 99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91101071A CN1037551C (en) | 1991-02-27 | 1991-02-27 | Process for directly linking 3-anilino-pyrazolone and sulfoether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91101071A CN1037551C (en) | 1991-02-27 | 1991-02-27 | Process for directly linking 3-anilino-pyrazolone and sulfoether |
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| Publication Number | Publication Date |
|---|---|
| CN1064555A CN1064555A (en) | 1992-09-16 |
| CN1037551C true CN1037551C (en) | 1998-02-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN91101071A Expired - Fee Related CN1037551C (en) | 1991-02-27 | 1991-02-27 | Process for directly linking 3-anilino-pyrazolone and sulfoether |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3962273A (en) * | 1972-09-01 | 1976-06-08 | Eastman Kodak Company | Novel method for the synthesis of 4-thio and 4-seleno ethers of 2-pyrazolin-5-ones |
| JPS5363377A (en) * | 1976-11-17 | 1978-06-06 | Fuji Photo Film Co Ltd | Preparation of 3-n-monosubstd. amino-4-monohalogeno-5-oxo-pyrazolines |
| EP0350286A2 (en) * | 1988-07-06 | 1990-01-10 | Konica Corporation | Silver halide photographic light-sensitive material |
| US4942116A (en) * | 1986-07-29 | 1990-07-17 | Agfa-Gevaert Aktiengesellschaft | Color photographic recording material containing 2-equivalent magenta couplers |
| US4952484A (en) * | 1988-02-18 | 1990-08-28 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
| US4983507A (en) * | 1985-12-25 | 1991-01-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic materials |
-
1991
- 1991-02-27 CN CN91101071A patent/CN1037551C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3962273A (en) * | 1972-09-01 | 1976-06-08 | Eastman Kodak Company | Novel method for the synthesis of 4-thio and 4-seleno ethers of 2-pyrazolin-5-ones |
| JPS5363377A (en) * | 1976-11-17 | 1978-06-06 | Fuji Photo Film Co Ltd | Preparation of 3-n-monosubstd. amino-4-monohalogeno-5-oxo-pyrazolines |
| US4983507A (en) * | 1985-12-25 | 1991-01-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic materials |
| US4942116A (en) * | 1986-07-29 | 1990-07-17 | Agfa-Gevaert Aktiengesellschaft | Color photographic recording material containing 2-equivalent magenta couplers |
| US4952484A (en) * | 1988-02-18 | 1990-08-28 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
| EP0350286A2 (en) * | 1988-07-06 | 1990-01-10 | Konica Corporation | Silver halide photographic light-sensitive material |
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| CN1064555A (en) | 1992-09-16 |
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