CN1349128A - Timely released development inhibiting primary yellow former and its prepn - Google Patents
Timely released development inhibiting primary yellow former and its prepn Download PDFInfo
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- CN1349128A CN1349128A CN 00123092 CN00123092A CN1349128A CN 1349128 A CN1349128 A CN 1349128A CN 00123092 CN00123092 CN 00123092 CN 00123092 A CN00123092 A CN 00123092A CN 1349128 A CN1349128 A CN 1349128A
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- yellow coupler
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Abstract
The invention relates to a coupling agent of restraining developed base yellow with timing released. Its molecular structural formula is: A-COC(-)HCONHB(-)(Timing)n-PUG Here A is as an alkyl, aromatic group or rsidue of heterocyclic compound containing N,S,O,C etc; B is as linear chain saturation alkyl, branched chain saturation alkyl and aromatic ring base group; Timing represents timing base; PUG is sulfhydryl commpound. Under certain condition Timing-PUG radical is cracked from 'Timing', generating PUG radical so as to improve performance of film. The invention provides features of reasonable synthesized technique, high purity of the product, high yield and easy to be refined.
Description
The present invention relates to a functional yellow colour-forming agent in the field of photographic chemistry, in particular, it is a timing-release development-inhibiting yellow colour-forming agent in negative silver halide photographic emulsion.
When the color former reacts with an oxidation product of the developer, a development inhibitor is released and has an improvement effect on the photosensitive property. For example: USP 3,227,554; 3,148,064, respectively; 3,933,500, respectively; 4,477,563 demonstrates that in negative-working photographic photosensitive materials, the DIR color former used to improve image definition and color reduction, when reacted with the oxidation product of the developer, the developer binds to the parent of the color former at the coupling site to form a dye, and the released development inhibitor can improve the silver halide granularity of the photosensitive material, creating intra-layer and edge effects. Further, Japanese patent Nos. JPK 03-189645, JPK 03-215869, JPK 03-127057 also describe release development inhibiting yellow couplers with a timed release base, and in particular, such couplers have the effect of reducing the graininess, improving the in-layer and interlayer effects of the film.
Although various researchers in various countries issue numerous patents, many of them have the defects of complicated process route, unsuitability for practical production and the like in the synthesis process. In the published type of time release development inhibiting yellow couplers, a sequential process is generally used, in which the coupler precursor is first bonded to the timing base and then bonded to the inhibiting base. The method has the defects of difficult industrialization in production, high impurity content of products, low yield, difficult product purification, high production cost and the like. For example: JPK 56-114946.
The invention aims to provide a yellow color former with a timed-release development inhibition function and a preparation method thereof, and the yellow color former has the advantages of reasonable synthesis process, high product purity, high yield and easiness in refining.
The invention provides a timed-release development inhibition yellow-based color former, which has the characteristic molecular structure as follows:
wherein n is 0 or 1;
a is the residue of a color former, which is alkyl or aryl with 1-20 carbon atoms and halogen atom substituent, or the residue of a heterocyclic compound consisting of N, S, O, C;
b is an oil-soluble group of the color former, which is a straight-chain saturated alkyl group or a branched-chain saturated alkyl group consisting of N, S, O and 1-30 carbon atoms, or an aromatic group with a saturated alkane substituent;
TIMING is a TIMING group which, under certain chemical reaction conditions, is detached from the molecule of the color former together with a development-inhibiting group PUG to generate a TIMING-PUG group;
the developing inhibition group PUG is a diazole sulfhydryl compound substituted by oxadiazole five-membered ring sulfhydryl compounds and aryl, substituted aryl, heteroatomsubstituted aryl and the like, and has a structural general formula as follows:
(CH3)3C-* (CH3)2CH-* CH3CH2-* CH3(CH2)3CH2-*
wherein: n-1-6
Wherein: n-4-18
Wherein: n is 1-5.
based on the aboveThe invention also provides a preparation method of the timed-release development inhibition yellow color former, which is characterized in that the synthesis route is as follows:
specifically, U.S. patent No. USP 4618571; USP No. 4770982; the synthesis methods described in Japanese patent laid-open Nos. 63-284159, 60-203943, and 63-23152. The invention overcomes the defects of the prior art and adopts a process route of a reverse grafting method to synthesize the compound, namely, a fixed time base (Timing) is firstly connected with an inhibiting base (PUG), and then the compound is connected with a parent color former. The method can ensure that the process is smoothly carried out, and has the advantages of high product purity, high yield, easy refining and the like. The present invention is described in detail below by way of examples.
FIG. 1 is a CP-T-ZB nuclear magnetic spectrum;
FIG. 2 shows a CP-ZB nuclear magnetic spectrum.
FIG. 3 is a CP-T-ZC nuclear magnetic spectrum;
example 1
Synthesis of N- [5- [ [4- [2, 4-bis (1, 1-dimethylpropyl) phenoxy]-1-oxobutyl]amino]-2-chlorophenyl]-4, 4-dimethyl-3-oxo-2- [ 4-nitro-2- [5- [ [ [ (4-methylphenoxy) methyl]-1, 3, 4-oxadiazol-2-yl]mercapto]methyl]phenoxy]-N-pentanamide (abbreviated to CP-T-ZB)
And (3) synthesis of an intermediate:
2- [5- [ (4-Methylphenoxy) methyl group]-1, 3, 4-oxadiazole-2-mercaptomethyl]-4-nitrophenol (T-Z13 for short) is synthesized by the following reaction formula:
the operation method comprises the following steps:
in a 125 ml three-necked flask equipped with a thermometer, a condenser, a dropping funnel and a stirring device, 2.6 g of ZBTA and 50 ml of acetone were added, and dissolved by stirring, and 20 ml of acetone solution containing 2.1 g of benzal chloride was slowly dropped. After the dropwise addition, the mixture was stirred for half an hour, heated to reflux, then thermally filtered to remove insoluble substances, cooled to precipitate a solid, filtered and dried to obtain 3.4 g of a white solid. Yield 91.2%, melting point mp: 159-160 ℃.
Synthesis of DIAR yellow coupler CP-T-ZB, reaction formula:
the operation method comprises the following steps:
adding 1.56 g of parent color former chloride, 0.94 g of T-ZB and 30 ml of acetonitrile into a 50 ml three-necked bottle provided with a thermometer, a condenser and a stirring device, stirring and dissolving, heating to 40 ℃, adding 0.4 ml of triethylamine, controlling the temperature to be about 40-50 ℃, cooling after 3.5 hours, and filtering. Putting the wet filter cake into a 50 ml three-necked bottle, adding 30 ml of methanol, carrying out hot melting, freezing, separating out, filtering and drying to obtain 1.5 g of a product. Yield 63.8%, melting point mp: 177 to 178 ℃. The actual values (%) of the elemental analysis of C, H, N were: 63.35; 6.57; 7.31. (theoretical values: 63.72; 6.37; 7.43, respectively)
Example 2
Synthesis of N- [5- [ [4- [2, 4-bis (1, 1-dimethylpropyl) phenoxy]-1-oxobutyl]amino]-2-chlorophenyl]-4, 4-dimethyl-3-oxo-2- [ [5- [ (4-methylphenoxy) methyl]-1, 3, 4-oxadiazol-2-yl]mercapto]-N-pentanamide (abbreviated to CP-ZB)
the operation method comprises the following steps:
adding 3.12 g of parent color former chloride, 1.12 g of ZB and 50 ml of acetonitrile into a 100 ml three-mouth bottle provided with a thermometer, a condenser and a stirring device, stirring and dissolving, heating to 40 ℃, adding 0.8 ml of triethylamine, controlling the temperature to be about 40-50 ℃, cooling after8 hours, pouring into water, filtering and drying to obtain brown solid. After dissolving the solid in ethyl acetate, the solution was washed with water to neutrality using a separatory funnel, and a little anhydrous magnesium sulfate was added thereto and allowed to stand overnight. The next day, the mixture is filtered, 30 ml of petroleum ether (bp: 60-90 ℃) is added, solid is gradually separated out the next day, and the product 1.5 g is obtained after filtration and drying. Melting point mp: 78-80 ℃. The actual values (%) of the elemental analysis of C, H, N were: 65.10; 6.87; 7.12. (theoretical values: 65.28; 6.96; 7.09 respectively)
Example 3
Synthesis of N- [5- [ [4- [2, 4-bis (1, 1-dimethylpropyl) phenoxy]-1-oxobutyl]amino]-2-chlorophenyl]-4, 4-dimethyl-3-oxo-2- [ 4-nitro-2- [5- [ [ [ (4-chlorophenoxy) methyl]-1, 3, 4-oxadiazol-2-yl]mercapto]methyl]phenoxy]-N-pentanamide (abbreviated to CP-T-ZC)
And (3) synthesis of an intermediate:
synthesis of 2- [5- [ (4-chlorophenoxy) methyl]-1, 3, 4-oxadiazole-2-mercaptomethyl]-4-nitrophenol (abbreviated as T-ZC):
the operation method comprises the following steps:
adding ZCNa 2.64 g and 50 ml of acetone into a 125 ml three-neck flask provided with a thermometer, a condenser, a dropping funnel and a stirring device, stirring and dissolving, slowly dropping 20 ml of acetone liquid containing 2.1 g of benzyl chloride, stirring for half an hour after dropping, heating to reflux, then carrying out hot filtration, removing insoluble substances, cooling to separate out solid, filtering, and drying to obtain 3.0 g of white solid. Yield 88%, melting point mp: 179-181 ℃.
Synthesis of DIAR yellow coupler CP-T-ZC:
the reaction formula is as follows:
the operation method comprises the following steps:
in a 50 ml three-necked flask equipped with a thermometer, condenser and stirring device, 1.56 g of the parent coupler chloride, 0.97 g of T-ZC and 30 ml of acetonitrile were added. The operation method refers to the synthetic method of CP-T-ZB. 1.48 g of product is obtained, yield 60.0%, melting point mp: 187-189 ℃. The actual values (%) of the elemental analysis of C, H, N were: 61.09; 5.89; 7.27. (theoretical values: 61.11; 5.92; 7.28, respectively)
The present invention also synthesizes the following compounds by a method similar to the above examples, but the present invention is not limited thereto.
Example 4
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 5
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 6
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 7
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
example 8
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
example 9
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 10
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 11
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 12
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 13
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
example 14
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
example 15
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 16
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
example 17
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 18
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 19
Following the procedure of example 3, using the corresponding intermediate, the following compound was prepared:
example 20
Preparation method according to example 3Using the corresponding intermediate, the following compounds were prepared:
example 21
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
example 22
Following the procedure of example 1, using the corresponding intermediate, the following compounds were prepared:
comparative example 1: synthesis of CP-T-ZB
the operation method comprises the following steps:
adding 7 g of 2-nitro-5-hydroxybenzyl alcohol, 12.16 g of compound (A) and 100 ml of acetone into a 250 ml three-neck flask provided with a thermometer, a condenser, a dropping funnel and a stirring device, stirring to fully dissolve, adding 3 ml of triethylamine, heating to 50 ℃, preserving heat for reacting for 8 hours, cooling to 10 ℃ after the reaction is finished, dropwise adding hydrochloric acid for neutralizing, adding 400 ml of water, stirring for separating out, standing for solidification, and filtering the mixture the next day to obtain a light yellow solid substance. And naturally drying, and leaching and drying the obtained solid in a funnel by using 30 ml of petroleum ether for three times to obtain 9.40 g of solid with a light yellow solid appearance. Liquid chromatography analysis, content 81%, melting point mp: 78-84 ℃.
Adding 9.40 g of the light yellow solid into a 250 ml three-mouth bottle provided with a thermometer, a condenser and a stirring device, adding 70 ml of dry chloroform, stirring and dissolving, keeping the internal temperature at 20 ℃, adding phosphorus pentachloride in small parts, reacting for 5 hours after half an hour until no hydrogen chloride gas is emitted. After stirring for 10 minutes with addition of 50 ml of water, the reaction solution was poured into a separatory funnel and washed with water until the pH of the solution became 7, and then 50 ml of chloroform was added thereto, and dried overnight with addition of anhydrous calcium chloride. The next day, the drying agent calcium chloride is removed, the chloroform is evaporated by pumping water under reduced pressure until the internal temperature does not exceed 50 ℃, the chloroform is evaporated until the temperature is all the time, 20 ml of acetone is added for dissolution, 10% hydrochloric acid and 200 ml of ice water are added, the pH value is adjusted to 2-3, and after solid is separated out, the filtration is carried out to obtain 2 g of light yellow solid. The yield is 12.5 percent, and the content is 94 percent by liquid chromatography detection.
Adding the prepared large parent benzyl chloride into a 150 ml three-neck flask provided with a stirrer, a condenser and a heating device, adding 40 ml of acetonitrile, 1.0 g of compound (B) and 0.4 ml of triethylamine, heating and stirring, refluxing for 4 hours, cooling the reaction solution, pouring into a beaker filled with 100 ml of ice water, and filtering after the solid is completely separated out to obtain a yellow solid. Silica gel column chromatography gave 0.3 g of a yellow oily product.
Claims (27)
wherein n is 0 or 1;
a is the residue of a color former, which is alkyl or aryl with 1-20 carbon atoms and halogen atom substituent, or the residue of a heterocyclic compound consisting of N, S, O, C;
b is an oil-soluble group of the color former, which is a straight-chain saturated alkyl group or a branched-chain saturated alkyl group consisting of N, S, O and 1-30 carbon atoms, or an aromatic group with a saturated alkane substituent;
TIMING is a TIMING group which, under certain chemical reaction conditions, is detached from the molecule of the color former together with a development-inhibiting group PUG to generate a TIMING-PUG group;
the method is characterized in that: the development inhibiting group PUG is a diazole sulfhydryl compound substituted by oxadiazole five-membered ring sulfhydryl compounds and aryl, substituted aryl, heteroatom substituted aryl and the like, and has a structural general formula as follows:
2. The timed release development-inhibiting yellow coupler according to claim 1 wherein a is one of the following groups:
(CH3)3C-* (CH3)2CH-* CH3CH2-* CH3(CH2)3CH2-*
3. the timed release development-inhibiting yellow-based color former according to claim 1, characterized in that B is one of the following groups:
wherein: n-1-6
Wherein: n-4-18
Wherein: n is 1-5.
13. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
15. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
16. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
17. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
22. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
24. the timed release development-inhibiting yellow coupler according to claim 1 wherein the yellow coupler has the formula:
27. a process for preparing a timed release development-inhibiting yellow coupler according to claim 1, characterized by the following synthetic route:
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CN1320403C (en) * | 2003-08-14 | 2007-06-06 | 中国乐凯胶片集团公司 | Yellow colour coupler |
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