CN1029922C - Synthesis method of colorless compound capable of releasing development enhancer - Google Patents
Synthesis method of colorless compound capable of releasing development enhancer Download PDFInfo
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- CN1029922C CN1029922C CN 89108704 CN89108704A CN1029922C CN 1029922 C CN1029922 C CN 1029922C CN 89108704 CN89108704 CN 89108704 CN 89108704 A CN89108704 A CN 89108704A CN 1029922 C CN1029922 C CN 1029922C
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- leucocompound
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- hydrogen atom
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- 150000001875 compounds Chemical class 0.000 title abstract description 25
- 238000011161 development Methods 0.000 title abstract description 8
- 239000003623 enhancer Substances 0.000 title 1
- 238000001308 synthesis method Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 150000004982 aromatic amines Chemical class 0.000 claims description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- 238000005859 coupling reaction Methods 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- -1 silver halide Chemical class 0.000 claims description 10
- 238000010189 synthetic method Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 230000008878 coupling Effects 0.000 claims description 9
- 238000010168 coupling process Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000002391 heterocyclic compounds Chemical group 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 46
- 235000019441 ethanol Nutrition 0.000 description 21
- 239000000047 product Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 229960004756 ethanol Drugs 0.000 description 18
- 238000001914 filtration Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 238000001953 recrystallisation Methods 0.000 description 12
- ADFXKUOMJKEIND-UHFFFAOYSA-N 1,3-dicyclohexylurea Chemical compound C1CCCCC1NC(=O)NC1CCCCC1 ADFXKUOMJKEIND-UHFFFAOYSA-N 0.000 description 10
- 206010034960 Photophobia Diseases 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 208000013469 light sensitivity Diseases 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 235000011167 hydrochloric acid Nutrition 0.000 description 4
- 229910000474 mercury oxide Inorganic materials 0.000 description 4
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 150000004075 acetic anhydrides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000007466 Corylus avellana Nutrition 0.000 description 1
- 240000003211 Corylus maxima Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- LQSIOKVOXUODFI-UHFFFAOYSA-N N-hydroxy-2-oxo-2-phenylethanimidoyl bromide Chemical class BrC(C(=O)C1=CC=CC=C1)=NO LQSIOKVOXUODFI-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- NEDVJZNVOSNSHF-ZNHDNBJUSA-N [(1r,5s)-8,8-dimethyl-8-azoniabicyclo[3.2.1]octan-3-yl] 3-hydroxy-2-phenylpropanoate;nitrate Chemical compound [O-][N+]([O-])=O.C([C@H]1CC[C@@H](C2)[N+]1(C)C)C2OC(=O)C(CO)C1=CC=CC=C1 NEDVJZNVOSNSHF-ZNHDNBJUSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical class Br* 0.000 description 1
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical class O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229920006304 triacetate fiber Polymers 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- KBMBVTRWEAAZEY-UHFFFAOYSA-N trisulfane Chemical compound SSS KBMBVTRWEAAZEY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a method for synthesizing A-type colorless compound capable of releasing development intensifier, which has the advantages of easily obtained raw material, simple and convenient synthesis process, high product yield and the like, thereby bringing great convenience to industrial production.
Description
The invention belongs to the field of organic synthesis, relate to a kind of functional organic synthetic method that can discharge developing promotor.
The photosensitive color negative material has entered high sense particulate, high definition and the high-quality reduction epoch at present, and photochrome almost reaches technicolour level, and the mankind are a a progressive step on solution light sensitivity and this a pair of contradiction of granularity.Except emulsion preparation, coating process, development processing technology are constantly progressive, have the employing of functional color coupler, make sensitive materials aspect the ISO and the high quality of image great breakthrough arranged.Here said functional color coupler is meant that a class is a raw material synthetic organism with the image coupler, coupled reaction can take place with the oxidation products quinondiimine (being called for short QDI) of photographic developer and generate dye image in it in the coupling development process, simultaneously, discharge a camera function base (as groups such as color developer, developing promotor, development restrainer, antifoggant, bleach boosters, photographic developer oxide removing agents) or self have a camera function base (as groups such as UV light absorber, photographic developer oxide removing agents).
Europen Patent 0117511 discloses a kind of A type coupler, be that a class is a raw material synthetic double-equivalent colour coupler with the image coupler, when it and QDI carry out coupled reaction (generation dye image), can discharge a developing promotor, make its contiguous silver halide particle form development center (information of photography gained obtains amplifying), thereby improved the light sensitivity of color film.But this class A type coupler has the following shortcoming:
(1) must with the image coupler of costliness raw material.
(2) yield of synthesis technique complexity, product is low, causes A type coupler cost too high.
(3) since A type coupler in developing process, when it and QDI coupling, must be mixed with dyestuff generates, therefore it can only with the supporting use of corresponding image coupler (as the A type coupler that becomes cyan can only with the supporting use of cyan image coupler, the rest may be inferred by analogy), so not only brought many difficulties to synthetic work, in case and improper use, can cause the color contamination of film, influence the quality of image.
The objective of the invention is to overcome the above-mentioned shortcoming of existing technology, a kind of synthetic method of leucocompound (abbreviation leucocompound) of energy releasing developing promotor is provided, have not only that synthesis technique is easy, raw material is cheap and easy to get, product yield advantages of higher but also owing to generate a kind of leucocompound when it and QDI coupling, therefore can be general in color film Huang, product, blue or green each silver emulsion coating, that has simplified film adds the production journey, brings great convenience to industrial production.
Design of the present invention is such: people use the purpose of A type coupler to be the micro-developing promotor that utilizes it to discharge usually, improve the light sensitivity of color film, and do not need the micro-dyestuff that it generated, opposite because the influence of these micro-dyestuffs, processing to film has brought many difficulties, and need the synthetic respectively A type coupler that adapts with Huang, product, blue or green image coupler, its synthetic work amount also is quite huge.For this reason, the contriver has conceived class leucocompound, it and QDI coupling generate a kind of leucocompound, discharge required developing promotor simultaneously, so both can prevent effectively because the color contamination of the film that improper use caused, and can be general in each layer silver emulsion that contains Huang, product, blue or green image coupler, thereby bring great convenience to industrial production.
The said leucocompound of the present invention can be represented with following general formula (1) by its function:
A-B （1）
Wherein: A is the parent fraction that contains active methylene radical, and the active position of this parent can generate leucocompound with photographic developer oxidation products quinondiimine ion (QDI ion) coupling;
The funtion part with development enhancement of B in the coupled reaction process, discharging, it can be for containing hydrazine class, aldehydes, the acetylene compound of electron-donating group, also can be for sulfonyl amine, Thiourea, the rhodanine compounds that contains the sulphur carboxyl, wherein best with the hydrazine class compound effect.
The present invention also is achieved in that
1. at first use the method for conventional organic synthesis, prepare carboxylic acid with (a) general formula and arylamine with (b) general formula.
A-X-COOH……（a）
Wherein: A is the parent fraction that contains active methylene radical, and it can generate leucocompound with photographic developer oxidation products QDI coupling, and suitable group has:
Wherein: R
1, R
2Can be hydrogen atom, C
1-C
2Alkyl, C
1-C
2Alkoxyl group, halogen atom (fluorine, chlorine, bromine, iodine).
Wherein: R
3, R
5Can be hydrogen atom, Cl, Br halogen atom, C
1-C
5Alkyl etc.R
4Be hydrogen atom.Also can be substituting groups such as Cl, Br.M, n are the substituting group number, m=0-4, the integer of n=0-5.But substituting group number commonly used is m=0-1, the integer of n=0-2.
Wherein: X often adopts silver halide is had adsorbing heterogeneous ring compound, as benzotriazole, phenyl mercapto tetrazole, dimercapto sulphur two pyrolles etc. for connecting a class group of parent fraction and developing promotor.
Wherein: Y is acyl group (as formyl radical, ethanoyl, propionyl, trifluoro acetyl, benzoyl etc.), sulfuryl (as methylsulfonyl, benzene sulfuryl etc.).
2. " carboxylic acid " that will make then and " arylamine " with etc. mole mix, with the effect of condensing agent, condensation makes the said A type of the present invention leucocompound in solvent, its condensation course is as shown in the formula institute
Wherein said solvent can be dimethyl formamide (DMF), pyridine, methylene dichloride, tetrahydrofuran (THF), N,N-DIMETHYLACETAMIDE, acetone etc.; Said condensing agent can be N, N '-dicyclohexylcarbodiimide (DCC).
Said carboxylic acid with general formula (a) structure, its preparation can be carried out according to prior art synthetic method routinely: for example:
(1) carboxylic acid of connection formula (a) A-X-COOH is when wherein
A is
X is
Form
(a
1) carboxylic acid of structure, can adopt hydrazine hydrate, dithiocarbonic anhydride etc. is raw material, and method is routinely synthesized, and its synthesis step is as follows:
1. compound (C
1) synthetic:
29.4 grams, 85% hydrazine hydrate (0.5mol) is added in 170 ml waters with 34 gram NaOH, and under 5～6 ℃ of the controlled temperature, agitation and dropping 68.4 gram dithiocarbonic anhydride (0.9mol) added in 2 hours.Be heated to 80 ℃ with water-bath then, stirring and refluxing one hour.Reactant is chilled to room temperature, adds 9.1 gram dithiocarbonic anhydride (0.12mol), press aforesaid operations and continue to reflux 2 hours, under reduced pressure boil off remaining dithiocarbonic anhydride, residue is acidified to PH=1 with concentrated hydrochloric acid, and the product precipitation is separated out.Filtration, washing, drying get the faint yellow solid crude product, use the dehydrated alcohol recrystallization, get faint yellow needle crystal 54 grams, productive rate 72%, fusing point: 166～168 ℃.
2. compound (d
1) synthetic:
With compound (C
1) 30 grams (0.2mol) are dissolved in 200 milliliters of dehydrated alcohols, stir to drip down and contain 11.2 gram KOH(0.2mol) and 40 milliliters of ethanolic solns.Reaction solution is chilled to 0～2 ℃ of slow down 24.6 gram ethyl chloroacetate (0.2mol) that drip added in about 1 hour, continue to stir 0.5 hour.Naturally be warming up to room temperature, at room temperature stirring reaction is 1 hour, boils off ethanol then, gets yellow mercury oxide, filters, washes, and gets crude product, uses the acetonitrile recrystallization, gets faint yellow needle crystal 45 and restrains, and productive rate 95%, fusing point are 68～70 ℃.
3. compound (e
1) synthetic:
With compound (d
1) 26.0 grams (0.11mol) are dissolved in 200 milliliters of ethanol, add 6.2 gram KOH(0.11mol).At room temperature stir and form suspension gradually, in this suspension, add 19.9 gram α bromo benzoylformaldoximes (0.1mol), generate a large amount of white precipitates immediately, temperature rising reflux half an hour, be cooled to room temperature then, the elimination inorganic salt.Under reduced pressure the ethanol in the filtrate is boiled off, the residuum ethyl alcohol recrystallization gets white crystals 30.8 grams.Productive rate 87%, fusing point: 90～92 ℃.
4. (a
1) preparation of carboxylic acid:
With 17.7 gram (e
1) compound (0.05mol) is dissolved in 50 ml methanol, adds the solution that 5.9 gram KOH and 30 ml waters are made into, and stirs 0.5 hour down at 40 ℃, then reaction solution poured in 400 ml waters that contain 20 milliliters of concentrated hydrochloric acids, separates out yellow mercury oxide.Filtration, drying get crude product.Use ethyl alcohol recrystallization, get faint yellow needle crystal 15.2 grams, productive rate 93%, fusing point: 169～170 ℃.
(2) and for example, by A be
,
X is
(a that is formed
2) carboxylic acid of structure, can adopt raw materials such as bromobenzene, aceticanhydride, method is routinely carried out organic synthesis, and its synthesis step is as follows:
1. compound (C
2) synthetic:
157 gram bromobenzenes (1.0mol) are added in 400 milliliters of exsiccant dithiocarbonic anhydride, add 300 milliliters of aluminum trichloride (anhydrous)s (2.20mol) again, be heated to reflux temperature, drip 82.0 gram aceticanhydrides (0.8mol), in 1 hour, add, continued reflux then 2 hours, boil off dithiocarbonic anhydride, with residuum cold slightly after, pour in the mixed solution of forming by 1600 milliliters of trash ices and 150 milliliters of concentrated hydrochloric acids, use the benzene extraction product, gained extraction liquid water, 10%NaOH solution respectively washes twice, and then washes with water to neutrality, restrains Calcium Chloride Powder Anhydrouss dry 1 hour with 15, boil off solvent, with remaining liquid underpressure distillation, receive 116-118 ℃ cut down in 7 mmhg, get oyster white crystallization 149 grams, productive rate 75%, fusing point: 49～50.5 ℃.
2. compound (d
2) synthetic:
Compound (C with above-mentioned gained
2) 50 grams (0.25mol) are dissolved in 100 milliliters of Glacial acetic acid, in temperature below 20 ℃, agitation and dropping 40 gram bromines (0.25mol) added in 30 minutes.Continued stirring reaction 0.5 hour.Then reactant is cooled off with frozen water, separate out product, after filtration, get crude product.Use ethyl alcohol recrystallization, get colourless acicular crystal 50 grams, productive rate 72%, fusing point: 108～109 ℃.
3. compound (e
2) synthetic:
Get 23.6 gram (d
2) compound (0.10mol) is dissolved in 250 milliliters of dehydrated alcohols, adds 5.6 gram KOH(0.10mol), stir and be suspension.In suspension, add 250 milliliters and contain 26.8 gram (d
1) ethanol solution of compound (0.10mol).Heating reflux reaction 1 hour.Filtered while hot is removed insolubles.After the filtrate cooling, separate out faint yellow needle-like crystal.After filtration, drying, product 37 gram, productive rate 88%.Fusing point: 94～96 ℃.
4. (a
2) preparation of carboxylic acid:
With compound (e
2) 36 grams (0.08mol) are dissolved in and add 250 milliliters in 500 milliliters the methyl alcohol and contain 8 gram KOH(0.14mol) and the aqueous solution, under 50～60 ℃, stirring reaction 0.5 hour.Reactant is poured in the mixed solution of 10 milliliters of concentrated hydrochloric acids and 500 ml waters, separated out yellow mercury oxide.After filtration, washing and ethyl alcohol recrystallization, obtain greenish orange look needle-like crystal 28 grams.Productive rate 85%, fusing point: 163～164 ℃.
Equally, also available above-mentioned method is prepared into the carboxylic acid that other has (a) structure, referring to table 1.
Table 1 has the carboxylic acid of A-X-COOH general formula
Continuous table 1
Continuous table 1
Continuous table 1
Continuous table 1
Table 2 has
The arylamine of general formula
Said preparation with arylamine of general formula (b) structure can be carried out according to prior art synthetic method routinely equally, for example:
(1) by R
1, R
2Be hydrogen atom, Y is
(the b that forms
1) arylamine of structure, can adopt raw materials such as paranitrophenylhydrazine, formic acid, method is routinely synthesized, and its synthesis step is as follows:
1. compound (f
1) synthetic:
45.9 gram paranitrophenylhydrazines (0.3mol) are dissolved in 160 milliliters of acetonitriles, add 32.2 gram formic acid (0.7mol) again, slowly heating, reaction solution is clarification gradually then, continuing reflux had crystallization to separate out after 0.5 hour, and then reflux 2 hours, reaction solution is cooled to below 5 ℃, filter, use the acetonitrile washing leaching cake, remove unreacted impurity, drying gets compound (f again
1) 51.0 grams, productive rate 94%, fusing point: 184～186 ℃.
2. (b
1) preparation of arylamine of structure:
In 500 milliliters ethanol, add 10 gram (f
1), be catalyzer with palladium-charcoal, at room temperature carry out hydrogenating reduction, the pressure during hydrogenation is 1～5kg/cm
2, the time is 1～3 hour, reaction product is removed pressure reducing and steaming ethanol behind the insolubles after filtration, filbert solid 7 grams, productive rate 87%, fusing point: 124～126 ℃.
(2) and for example, by R
1.R
2Be hydrogen atom, Y is-C-CH
3(the b that forms
2) arylamine of structure, also can adopt raw material methods routinely such as paranitrophenylhydrazine and aceticanhydride to synthesize, its synthesis step is as follows:
1. compound (f
2) synthetic:
Get in the acetonitrile of 100 milliliters of 15.3 gram paranitrophenylhydrazines (0.1mol) and 20 gram aceticanhydrides (0.2mol) addings, stirring heating refluxed 2 hours, separated out yellow needle-like crystal.Through cooling, filtration, acetonitrile washing, vacuum-drying, get compound (f
2) 18.0 grams, productive rate 91%, fusing point: 206～207 ℃.
2. (b
2) preparation of arylamine of structure:
In 500 milliliters ethanol, add 10 gram (f
2), be catalyzer with palladium-charcoal, at room temperature carry out hydrogenating reduction.Pressure during hydrogenation is 1～5kg/cm
2, hydrogenation time 1～3 hour.Reaction product is removed pressure reducing and steaming ethanol behind the insolubles after filtration, product 6.9 grams, productive rate 82%, fusing point: 140～142 ℃.
(3) for another example, R
1, R
2Be hydrogen atom, Y is
(the b that forms
3) arylamine of structure, also can adopt raw material methods routinely such as paranitrophenylhydrazine and Benzoyl chloride to synthesize, its synthesis step is as follows:
1. compound (f
3) synthetic:
Get 15.3 gram paranitrophenylhydrazines (0.1mol) and be added in 80 milliliters of pyridine solvents, below 10 ℃, restir drips 19.0 gram Benzoyl chlorides (0.1mol) in temperature, drips in 0.5 hour and finishes, and at room temperature stirring reaction spends the night then.Reactant is poured in 500 milliliters of dilute sulphuric acids (5%) aqueous solution, separated out yellow mercury oxide, more after filtration, washing, drying.Ethyl alcohol recrystallization gets pale brown look needle-like crystal 20 grams, productive rate 78%, fusing point: 196～198 ℃.
2. (b
3) preparation of arylamine of structure
Get 20 gram (f
3) compound is added in 1000 milliliters of dehydrated alcohols, is catalyzer with palladium-charcoal, in 5kg/cm
2Carried out hydro-reduction 1 hour.Reaction product is removed pressure reducing and steaming ethanol behind the insolubles after filtration, obtains red solid 12.2 grams, productive rate 75%, fusing point: 142-143 ℃.
Equally, available above-mentioned similar method makes the arylamine that other has general formula (b) structure, referring to table 2.
By the leucocompound that method of the present invention makes, the effect of sensitizing is all arranged, but the most remarkable with hydrazine class compound, its concrete structure is as shown in following (1)～(55) are various:
（1）
（2）
To further illustrate content of the present invention according to embodiment below:
Embodiment 1
Synthesizing of leucocompound (19):
(1) building-up reactions formula:
(2) synthetic method:
Get 9.8 gram (a
1) structure carboxylic acid (0.03mol) and 5.0 the gram (b
1) arylamine (0.03mol) of structure is dissolved among 70 milliliters of DMF, contains 6.2 gram DCC(0.03mol in 15 milliliters of-10～5 ℃ of following agitation and dropping) the DMF solution of condensing agent, drip off in half an hour.At room temperature continued stirring reaction then 2 hours.The elimination dicyclohexylurea (DCU).Filtrate is poured in 800 milliliters the water, separates out white precipitate.After filtration, washing, dry, ethyl alcohol recrystallization, product 8 grams.Productive rate 58%, fusing point: 188～190 ℃.
Ultimate analysis (C
1, H
17N
5O
3S
3):
C H N
Calculated value: 49.68 3.73 15.25
Measured value: 49.92 3.79 15.33
Embodiment 2
Synthesizing of leucocompound (24):
(1) building-up reactions formula:
(2) synthetic method:
Get 2.03 gram (a
2) structure carboxylic acid (5.1mmol) and 0.84 the gram (b
2) arylamine (5.1mmol) of structure is dissolved in 20 milliliters the pyridine.Under-10～5 ℃, 15 milliliters of agitation and dropping contain 1.05 gram DCC(5.1mmol) pyridine solution of condensing agent, drip off in half an hour.Naturally be warming up to room temperature, under this temperature, continued stirring reaction 2 hours.The elimination dicyclohexylurea (DCU).Filtrate is poured in 600 milliliters the water, separates out white precipitate.Washing more after filtration,, drying.Ethyl alcohol recrystallization gets product 1.37 grams (being faint yellow crystallization), productive rate 50%, fusing point: 207～208 ℃.
Ultimate analysis (C
20H
18BrN
5O
3S
3)
C H N
Calculated value: 43.47 3.26 12.68
Measured value: 42.90 3.31 12.49
Embodiment 3
Synthesizing of leucocompound (41):
(1) building-up reactions formula:
(2) synthetic method:
3.4 grams had (a
3) carboxylic acid (0.01mol) and 2.3 grams of structure have (a b
3) arylamine (0.01mol) of structure is dissolved among 50 milliliters the DMF, contains 2.1 gram DCC(0.01mol in 15 milliliters of-10～5 ℃ of following agitation and dropping) the DMF solution of condensing agent, continue again after adding to stir 1 hour.Naturally be warming up to room temperature then, continued stirring reaction 2 hours.Remove by filter dicyclohexylurea (DCU).Filtrate is poured in 500 ml waters, separates out white precipitate.Ethyl alcohol recrystallization after filtration.Get product (41) 2.8 grams, productive rate 50%.
Embodiment 4
Synthesizing of leucocompound (3):
(1) building-up reactions formula:
(2) synthetic method:
15.6 grams had (a
1) carboxylic acid (0.04mol) and 6.7 grams of structure have (a b
4) arylamine (0.04mol) of structure is dissolved among 80 milliliters of DMF, under-10～5 ℃, agitation and dropping contains 8.4 gram DCC(0.04mol for 20 milliliters) the DMF solution of condensing agent, add in half an hour, under this temperature, continue again to stir 1 hour.Naturally rise to room temperature then, continued stirring reaction 2 hours.Filter, remove dicyclohexylurea (DCU).Filtrate is poured in 800 ml waters, separate out white precipitate.Filtration, filter and dry back ethyl alcohol recrystallization get product 11 grams, productive rate 52%.
Embodiment 5
Synthesizing of leucocompound (36):
(1) building-up reactions formula:
(2) synthetic method:
7.00 grams had (a
5) carboxylic acid (0.016mol) and 2.6 grams of structure have (a b
5) arylamine (0.016mol) of structure is dissolved in 50 milliliters the methylene dichloride.Under-10～5 ℃, 20 milliliters of agitation and dropping contain 3.4 gram DCC(0.016mol) dichloromethane solution of condensing agent, drip off in 0.5 hour, under this temperature, continue to stir 1 hour.Naturally rise to room temperature then, at room temperature continued stirring reaction 2 hours.Filter, remove dicyclohexylurea (DCU).Filtrate is poured in 500 ml waters, separate out white precipitate.Drying more after filtration.With ethanol-sherwood oil of 1: 1,, get product (36) 5.2 grams, productive rate 56% at 60～90 ℃ of following recrystallizations.
By the foregoing description 1-5 as seen, the present invention is said, leucocompound, and its synthesis technique is easy, and therefore yield height (yield of A type coupler only is percentum) has the value of suitability for industrialized production.
The said leucocompound of the present invention have significant photograph effect.
As everyone knows, the multi layer colour sensitive materials all is made up of three basic silver halide emulsion layers, and therefore they be called the blue layer of sense, green layer and sense red beds respectively to blue light, green glow and red light sensitiveness.In three basic emulsion layers, add Huang, product, cyan colour coupler respectively.When coupling development, coupler and the coupling of photographic developer oxide compound generate dyestuff, and the superposition of three kinds of dyestuffs just forms colour picture.
Leucocompound are as a kind of functional compound, its photographic property finally is to be (employed image coupler can be commercially available various Huangs, product, cyan colour coupler) that the color development of image coupler obtains reflecting by common coupler, therefore must be through actual survey, could determine its quality, to prepare the leucocompound of gained by method of the present invention below, try out that obtainable effect is summarized as follows in color photographic material:
Leucocompound are dissolved in the ethyl acetate together by different mol ratios and image coupler, add high boiling solvent Tritolyl Phosphate or tributyl phosphate again, be scattered in the aqueous gelatin solution according to a conventional method then, be dispersed into uniform small-particle oil droplet dispersion through the high-pressure emulsification pump, coupler etc. by dispersed encapsulated in the high boiling solvent oil droplet-the coupler emulsion.
The coupler emulsion is mixed with silver halide than (mol ratio that refers to coupler and silver halide, commonly used is 0.02: 1) by certain look silver, coat then on the triacetate fiber sheet base, can obtain the single or multiple lift colour negative.
The single or multiple lift colour negative is exposed on the exposure instrument, and processing obtains single or multiple lift colorama key through developing.Measure photographic fog D with color densitometer.And colour density, be depicted as rational curve, just can measure the light sensitivity S and the contrast coefficient of colour negative.
, compare as benchmark with the individual layer colour negative that do not add leucocompound with the individual layer colour negative that contains leucocompound.The results are shown in Table 3, shown in the table 4, table 5.
Wherein: the mol ratio of leucocompound and image coupler is:
(0.1～0.2)/100, the content of leucocompound is 0.1～1.0%(mol% ratio in other words);
Look silver is than being: 0.02mol/molAgx.
Table 3
Leucocompound are to the influence of middling speed colour negative green layer photographic property
The other content mol% of sheet S(ASA) γ Do
Reference plate 0 132 1.62 0.33
Leucocompound 0.1 204 1.78 0.31
By table 3 as seen, the adding of leucocompound significantly improves the light sensitivity of middling speed colour negative green layer, and contrast also slightly increases, and photographic fog is constant substantially.
Table 4
Leucocompound are to the influence of high-speed color negative film green layer photographic property
(look silver ratio: 0.02mol/molAgx)
The other content mol% of sheet S(ASA) γ Do
Reference plate 0 204 1.22 0.26
Leucocompound 0.2 347 1.11 0.33
Leucocompound 0.8 490 0.98 0.53
Table 5
Leucocompound are to the influence of high-speed color negative film sense red beds photographic property
(look silver ratio: 0.02mol/molAgx)
The other content mol% of sheet S(ASA) γ Do
Reference plate 0 372 0.96 0.36
Leucocompound 0.2 724 0.97 0.54
The light sensitivity S that is given in [notes] above-mentioned table 3～5 represents with international standard light sensitivity unit (ASA).
By table 4, table 5 as seen:
1. the adding of leucocompound can make the green layer of high-speed color negative film and the light sensitivity of sense red beds be significantly increased, and contrast is constant substantially.
2. the consumption that increases leucocompound can improve light sensitivity, but photographic fog rises to some extent, and therefore the suitable consumption of restriction leucocompound perhaps increases the auxiliary agent that suppresses photographic fog.
In a word, by the said method synthetic of the present invention leucocompound are a kind of more satisfactory developing promotors, not only raw material is easy to get, synthesis technique is easy for it, the yield height of product, and (can be general in emulsion layer of all kinds) easy to use, be expected to bring obvious improvement for sensitive materials industry.
Claims (2)
1, a kind of synthetic method of leucocompound of energy releasing developing promotor can form in solvent usually in condensation, the invention is characterized in: said leucocompound are by the carboxylic acid with general formula A-X-COOH structure and have general formula
NHNH-Y
The arylamine of structure mixes to wait mole, and with condensing agent N, the effect condensation of N '-dicyclohexylcarbodiimide (DCC) makes in solvent,
Wherein: A is the parent fraction that contains active methylene radical, and it and QDI coupling generate leucocompound, and suitable group is:
Wherein: R
3, R
5Can be hydrogen atom, Cl, Br halogen atom, C
1-C
5Alkyl, n is the integer of O-2, R
4Be hydrogen atom;
Wherein: X is to the adsorption of silver halide tool and for linking the heterocyclic compound group of parent fraction and developing promotor;
Wherein: R
1, R
2Be hydrogen atom, low carbon chain alkyl, low carbon chain alcoxyl base, halogen atom;
Wherein: Y is acyl group, sulfuryl;
Condensation course can carry out under atmospheric pressure at room, but agitation and dropping must be carried out under-10～5 ℃ when containing the solution of condensing agent DCC.
2, the method for claim 1 is characterized in that said solvent is dimethyl formamide (DMF), pyridine, methylene dichloride, tetrahydrofuran (THF), N,N-DIMETHYLACETAMIDE or acetone.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108704 CN1029922C (en) | 1989-11-22 | 1989-11-22 | Synthesis method of colorless compound capable of releasing development enhancer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108704 CN1029922C (en) | 1989-11-22 | 1989-11-22 | Synthesis method of colorless compound capable of releasing development enhancer |
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| Publication Number | Publication Date |
|---|---|
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| CN1029922C true CN1029922C (en) | 1995-10-04 |
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ID=4857706
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|---|---|---|---|
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| Country | Link |
|---|---|
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1989
- 1989-11-22 CN CN 89108704 patent/CN1029922C/en not_active Expired - Fee Related
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