CN106916470A - A kind of preparation method of symmetrical anti-halo dye - Google Patents
A kind of preparation method of symmetrical anti-halo dye Download PDFInfo
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- CN106916470A CN106916470A CN201510981151.4A CN201510981151A CN106916470A CN 106916470 A CN106916470 A CN 106916470A CN 201510981151 A CN201510981151 A CN 201510981151A CN 106916470 A CN106916470 A CN 106916470A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
- C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
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Abstract
The present invention relates to photosensitive material field, specially a kind of preparation method of symmetrical anti-halo dye, solves complex process, high cost present in prior art, the problems such as being difficult to large-scale production, the characteristic for possessing the stabilization in film using anti-halo dye of the present invention in green X-ray is felt.With pentadienal contracting diphenylamine hydrochloride and 1- (4'- sulphenyls) -3- carboxyl -5- pyrazolones as initiation material, triethylamine and sylvite are added, again by ethanol or acetone refining after reaction, obtain target dyestuff.The present invention puies forward the synthetic method of magenta water solubility anti-halo dye, and the method has process is simple, and low cost is easy to implement large-scale production.
Description
Technical field
The present invention relates to photosensitive material field, specially a kind of preparation method of symmetrical anti-halo dye.
Background technology
The world consumes about billions square metres of X-ray film every year, and domestic annual consumption is medical and industrial
Also nearly 100,000,000 square metres of film, up to more than 10,000,000,000 yuan, this is a very huge market to consumption figure.With
Chinese national economy level and growth in the living standard, people also gradually step up to the attention rate of health, with pre-
Health idea based on anti-has been rooted in the hearts of the people, and medical film expense is significantly increased.X-ray film city at home
It is medical and industrial more than about 50,000,000 square metres in.The medically green X-ray of use feeling, for animal
The sense indigo plant X-ray of medical treatment and industrial flaw detection is progressively felt green X-ray substitution, and feeling green X-ray has such as
Radiation intensity is low, image definition is high, dynamically discriminating ability is strong, accuracy is high, and film silver content is low, manufacture
Low cost and other advantages.
Though the antihalation layer in photosensitive material is not photosensitive layer, critically important effect is also played, it is therein effective
Composition is anti-halo dye or pigment.It receives when photosensitive material exposes and is not passed through by absorption into emulsion layer
Light, to eliminate reflection and diffusion phenomenon, so as to improve the definition of image and prevent the generation of halation.
The content of the invention
It is an object of the invention to provide a kind of preparation method of symmetrical anti-halo dye, solution is deposited in the prior art
Complex process, high cost, it is difficult to realize large-scale production the problems such as.
The technical scheme is that：
A kind of preparation method of symmetrical anti-halo dye, with pentadienal contracting diphenylamine hydrochloride and 1- (4'- sulfonic acid benzene
Base) -3- carboxyl -5- pyrazolones be initiation material, add triethylamine and sylvite, again by ethanol or third after reaction
Ketone is refined, and obtains target dyestuff；Wherein, reaction equation is as follows：
The preparation method of described symmetrical anti-halo dye, in course of reaction, pentadienal contracting diphenylamine hydrochloride
It is 1 with 1- (4'- sulphenyls) -3- carboxyl -5- pyrazolones mol ratio:1.5~1:2.5.
The preparation method of described symmetrical anti-halo dye, in course of reaction, pentadienal contracting diphenylamine hydrochloride
It is 1 with the mol ratio of triethylamine:4~1:8.
The preparation method of described symmetrical anti-halo dye, in course of reaction, solvent for use is methyl alcohol, DMF
Or acetone.
The preparation method of described symmetrical anti-halo dye, in course of reaction, the reaction temperature after triethylamine addition
It it is 45 DEG C~60 DEG C, soaking time is 1~3 hour.
The preparation method of described symmetrical anti-halo dye, in course of reaction, sylvite is added with its saturated aqueous solution,
Sylvite is potassium chloride, potassium acetate, KI or potassium carbonate.
Advantages of the present invention and beneficial effect are：
1st, the present invention puies forward the synthetic method of magenta water solubility anti-halo dye, and the method has process is simple, into
This is low, is easy to implement large-scale production.
2nd, can solve rare earth intensifying screen using anti-halo dye of the present invention in green X-ray is felt produces fluorescence to dissipate
Penetrate, diffusion produces halation, it is also possible to the reflection halation in emulsion layer is absorbed, so as to improve the sharp keen of image boundary
Degree and readability.
3rd, possess the characteristic of the stabilization in film using anti-halo dye of the present invention in green X-ray is felt, i.e., it is right
Silver emulsion is inert, good water solubility, without the pollution of residual color.
Specific embodiment
In specific implementation process, the preparation method of anti-halo dye of the present invention, with pentadienal contracting hexichol amine salt
Hydrochlorate (N- (5-Anilino-2,4-Pentadienylidene) AnilineHydrochloride) and 1- (4'- sulphenyls) -3-
Carboxyl -5- pyrazolones (1- (4'-sulfophenyl) -3-carboxy-5-pyrazolone) are initiation material, add three
Ethamine and sylvite, then it is refined by ethanol, obtain target dyestuff.
Below, by embodiment, the present invention is described in more detail.
Embodiment 1：
The preparation method of symmetrical anti-halo dye in the present embodiment, with pentadienal contracting diphenylamine hydrochloride and 1- (4'-
Sulphenyl) -3- carboxyl -5- pyrazolones be initiation material, methyl alcohol is solvent, add triethylamine and saturation chlorination
Aqueous solutions of potassium, then it is refined by ethanol, target dyestuff is obtained, its reaction equation is as follows：
In the present embodiment, sylvite KX is KCl, is comprised the following steps that：
(1) by 2.84g (0.01mol) pentadienal contracting diphenylamine hydrochloride, 5.68g (0.02mol) 1- (4'-
Sulphenyl) -3- carboxyl -5- pyrazolones, 100ml methyl alcohol is added in 250ml reactors, is warming up to backflow,
Stirring 1 hour, is cooled to 45 DEG C, adds triethylamine 4.04g (0.04mol), and 45 DEG C are incubated 1 hour, add
Potassium chloride saturated aqueous solution (4.44gKCl), is down to room temperature and separates out 1 hour, filtering.
(2) by filter cake addition 100ml reactors, add 70ml ethanol and stir 30 minutes, filtering,
With ethanol rinse to colourless.35~42 DEG C of dryings 8~12 hours, obtain final product 4- [5- [3- carboxyl -5- hydroxyls
Base -1- (4- sulfophenyls) -1H- pyrazoles -4- bases] -2,4- Asias pentadienyl] -4,5- dihydro -5- oxos -1- (4- sulfophenyls) -1H-
Pyrazoles -3- carboxylic acid di-potassiums, outward appearance is dark green solid, the content more than 92% that liquid chromatogram is surveyed, UV absorption
More than 1.40 [0.01mg/ml water], yield 81%.
Anti-halo dye 4- [5- [3- carboxyl -5- hydroxyls -1- (4- sulfophenyls) -1H- pyrazoles -4- are obtained in the present embodiment
Base] -2,4- Asias pentadienyl] -4,5- dihydro -5- oxos -1- (4- sulfophenyls) -1H- pyrazoles -3- carboxylic acid di-potassiums, its nuclear-magnetism
The pedigree of resonance is as follows：1H NMR (400MHz, DMSO)：11.0(s,1H),8.0-7.0(s,6H),
6.9-6.0 (s, 5H), 5.0 (s, 1H), these data illustrate that symmetrical anti-halo dye structure is just obtained in the present embodiment
True.
Embodiment 2：
Difference from Example 1 is that sylvite KX is potassium acetate, is comprised the following steps that：
(1) by 5.68g (0.02mol) pentadienal contracting diphenylamine hydrochloride, 8.52g (0.03mol) 1- (4'-
Sulphenyl) -3- carboxyl -5- pyrazolones, 200ml acetone is added in 500ml reactors, is warming up to backflow,
Stirring 1 hour, is cooled to 45 DEG C, adds triethylamine 8.08g (0.08mol), and 55 DEG C are incubated 2 hours, add
Potassium acetate saturated aqueous solution (10.2g potassium acetates), is down to room temperature and separates out 2 hours, filtering.
(2) by filter cake addition 250ml reactors, add 150ml ethanol and stir 50 minutes, filtering,
With ethanol rinse to colourless.35~42 DEG C of dryings 8~12 hours, obtain final product 4- [5- [3- carboxyl -5- hydroxyls
Base -1- (4- sulfophenyls) -1H- pyrazoles -4- bases] -2,4- Asias pentadienyl] -4,5- dihydro -5- oxos -1- (4- sulfophenyls) -1H-
Pyrazoles -3- carboxylic acid di-potassiums, outward appearance is dark green solid, the content more than 92% that liquid chromatogram is surveyed, UV absorption
More than 1.40 [0.01mg/ml water], yield 79%.
Anti-halo dye 4- [5- [3- carboxyl -5- hydroxyls -1- (4- sulfophenyls) -1H- pyrazoles -4- are obtained in the present embodiment
Base] -2,4- Asias pentadienyl] -4,5- dihydro -5- oxos -1- (4- sulfophenyls) -1H- pyrazoles -3- carboxylic acid di-potassiums, its nuclear-magnetism
The pedigree of resonance is as follows：1H NMR (400MHz, DMSO)：11.0(s,1H),8.0-7.0(s,6H),
6.9-6.0 (s, 5H), 5.0 (s, 1H), these data illustrate that symmetrical anti-halo dye structure is just obtained in the present embodiment
True.
Embodiment 3：
Difference from Example 1 is that sylvite KX is potassium carbonate, is comprised the following steps that：
(1) by 5.68g (0.02mol) pentadienal contracting diphenylamine hydrochloride, 14.2g (0.05mol) 1- (4'-
Sulphenyl) -3- carboxyl -5- pyrazolones, 250ml DMF be added in 500ml reactors, is warming up to backflow,
Stirring 1 hour, is cooled to 45 DEG C, adds triethylamine 16.16g (0.16mol), and 60 DEG C are incubated 3 hours, add
Potassium carbonate saturated aqueous solution (15.8g potassium carbonate), is down to room temperature and separates out 1.5 hours, filtering.
(2) by filter cake addition 250ml reactors, add 200ml acetone and stir 60 minutes, filtering,
With acetone drip washing to colourless.35~42 DEG C of dryings 8~12 hours, obtain final product 4- [5- [3- carboxyl -5- hydroxyls
Base -1- (4- sulfophenyls) -1H- pyrazoles -4- bases] -2,4- Asias pentadienyl] -4,5- dihydro -5- oxos -1- (4- sulfophenyls) -1H-
Pyrazoles -3- carboxylic acid di-potassiums, outward appearance is dark green solid, the content more than 92% that liquid chromatogram is surveyed, UV absorption
More than 1.40 [0.01mg/ml water], yield 84%.
Anti-halo dye 4- [5- [3- carboxyl -5- hydroxyls -1- (4- sulfophenyls) -1H- pyrazoles -4- are obtained in the present embodiment
Base] -2,4- Asias pentadienyl] -4,5- dihydro -5- oxos -1- (4- sulfophenyls) -1H- pyrazoles -3- carboxylic acid di-potassiums, its nuclear-magnetism
The pedigree of resonance is as follows：1H NMR (400MHz, DMSO)：11.0(s,1H),8.0-7.0(s,6H),
6.9-6.0 (s, 5H), 5.0 (s, 1H), these data illustrate that symmetrical anti-halo dye structure is just obtained in the present embodiment
True.
Embodiment result shows that the method is easy to operate, high conversion rate, low cost, is easy to implement extensive work
Industry metaplasia is produced.
Claims (6)
1. a kind of preparation method of symmetrical anti-halo dye, it is characterised in that with pentadienal contracting diphenylamines hydrochloric acid
Salt and 1- (4'- sulphenyls) -3- carboxyl -5- pyrazolones are initiation material, triethylamine and sylvite are added, after reaction
Again by ethanol or acetone refining, target dyestuff is obtained；Wherein, reaction equation is as follows：
2. according to the preparation method of the symmetrical anti-halo dye described in claim 1, it is characterised in that reacted
Cheng Zhong, pentadienal contracting diphenylamine hydrochloride and 1- (4'- sulphenyls) -3- carboxyl -5- pyrazolone mol ratios are
1:1.5~1:2.5.
3. according to the preparation method of the symmetrical anti-halo dye described in claim 1, it is characterised in that reacted
Cheng Zhong, pentadienal contracting diphenylamine hydrochloride is 1 with the mol ratio of triethylamine:4~1:8.
4. according to the preparation method of the symmetrical anti-halo dye described in claim 1, it is characterised in that reacted
Cheng Zhong, solvent for use is methyl alcohol, DMF or acetone.
5. according to the preparation method of the symmetrical anti-halo dye described in claim 1, it is characterised in that reacted
Cheng Zhong, the reaction temperature after triethylamine is added is 45 DEG C~60 DEG C, and soaking time is 1~3 hour.
6. according to the preparation method of the symmetrical anti-halo dye described in claim 1, it is characterised in that reacted
Cheng Zhong, sylvite is added with its saturated aqueous solution, and sylvite is potassium chloride, potassium acetate, KI or potassium carbonate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001261664A (en) * | 2000-03-15 | 2001-09-26 | Konica Corp | Silver halide photosensitive material, method for forming image, compound and method for synthesizing the same compound |
| US6361571B1 (en) * | 1998-05-16 | 2002-03-26 | Wella Aktiengesellschaft | Agents and method for producing semi-permanent colorations of keratin fibers |
| US20020160299A1 (en) * | 2000-12-29 | 2002-10-31 | Kodak Polychrome Graphics, L.L.C. | Two-layer imageable element comprising thermally reversible polymers |
| JP2013159765A (en) * | 2012-02-08 | 2013-08-19 | Fujifilm Corp | Coloring composition, ink composition and ink for inkjet recording |
-
2015
- 2015-12-24 CN CN201510981151.4A patent/CN106916470A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6361571B1 (en) * | 1998-05-16 | 2002-03-26 | Wella Aktiengesellschaft | Agents and method for producing semi-permanent colorations of keratin fibers |
| JP2001261664A (en) * | 2000-03-15 | 2001-09-26 | Konica Corp | Silver halide photosensitive material, method for forming image, compound and method for synthesizing the same compound |
| US20020160299A1 (en) * | 2000-12-29 | 2002-10-31 | Kodak Polychrome Graphics, L.L.C. | Two-layer imageable element comprising thermally reversible polymers |
| JP2013159765A (en) * | 2012-02-08 | 2013-08-19 | Fujifilm Corp | Coloring composition, ink composition and ink for inkjet recording |
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