CN106366043A - Intermediate of magenta coupler for colored photosensitive material and preparation method thereof - Google Patents

Abstract

The invention discloses an intermediate of a magenta coupler for a colored photosensitive material. The intermediate has a structure as shown in a formula (I). A preparation method for the intermediate comprises the steps of, with 2-[3-(4-tert-butyl-phenyl)-1H-1,2,4-triazol-5-yl]acetic acid and 2,6-di-tert-butyl-4-methylcyclohexanol as raw materials, carrying out a reaction at 35 to 60 DEG C in a system composed of organic solvents like toluene, xylene, ethyl acetate, cyclohexane and n-heptane under the catalysis of acetic anhydride for 1 to 4 h so as to prepare 4-methyl-2,6-di-tert-butyl-cyclohexanol{1-acetyl-3-[4-tert-butylphenyl]-1H-1,2,4-triazol-5-yl]acetate. The preparation method provided by the invention is simple in process, mild in reaction condition, few in synthesis steps, short in preparation time, low in energy consumption and simple in after-treatment; the prepared final intermediate has high purity and yield; and the method is suitable for industrial large-scale production.

Description

A kind of color sensitive material magenta colour coupler intermediate and preparation method thereof

Technical field

The present invention relates to color sensitive material with colour coupler technical field and in particular in the middle of a kind of new magenta colour coupler Body and medicine intermediate 4- methyl -2,6- di-t-butyl Hexalin 1- acetyl group -3- [4- tert-butyl-phenyl] -1h-1,2,4- tri- Azoles -5- base } acetass and preparation method thereof.

Background technology

Colour coupler is that color sensitive material obtains the indispensable Organic substance of color institute, and wherein, magenta colour coupler is to expose In the presence of crossing the silver halide of light, react, with color developer oxidation product, the colour coupler generating magenta dye, be that ring-type is lived Bold and vigorous methylene methanone compounds, methylene and carbonyl are directly connected, and are most commonly used that there is the mother that 1,3- replaces -5- pyrazolone Body structure, can generate magenta azomethine dyes with color developer oxidation product.Its physical and chemical performance of magenta colour coupler The vividness and verity of colour picture is had a direct impact, therefore the research to new magenta colour coupler kind and its intermediate Exploitation is always the focal point of film industry, such as:

Chinese patent cn1199757 discloses a kind of polyermagenta colour coupler for color sensitive material, and its general structure is such as Under:

Wherein, r₃For-ch₃,-c₄h₉,-c₂h₄och₃,-c₂h₄oc₂h₅, this magenta colour coupler employs two chromophoric groups, Scalable resolution and root-mean-square granularity.

Chinese document (Xu Xu, Huang Deyin. the synthesis [j] of Latex Magenta Couplers. organic chemistry, 2003,23 (12) three kinds of New Emulsion aggretion type magenta colour couplers (l- magenta colour coupler 7～9): 1375-1379) are disclosed, its chemistry knot Structure formula is as follows:

But existing moral training agent at present and its middle preparation process generally existing synthetic route are long, and reactions steps are many, Condition is harsher, high energy consumption, and post processing is difficult, the problems such as product yield is relatively low.

Content of the invention

The drawbacks described above existing for existing magenta colour coupler synthesis technique, an object of the present invention is to provide one kind New type colorful sensitive material magenta colour coupler intermediate, it has a structure as shown in formula (i):

A further object of the present invention is to provide a kind of color sensitive material fuchsin quality of chemical constitution shown in formula (i) The preparation method of agent intermediate, specifically includes following steps: by 2- [3- (4- tert-butyl-phenyl) -1h-1,2,4- triazole -5- bases] Acetic acid, 2,6- di-t-butyls -4 methyl cyclohexanol, organic solvent adds reactor, and Deca acetic anhydride after cooling, in 35～60 DEG C Reaction, after reaction terminates, recrystallization acquisition target product 4- methyl -2 in a solvent, 6- di-t-butyl Hexalin 1- acetyl group - 3- [4- tert-butyl-phenyl] -1h-1,2,4- triazole -5- bases } acetass.

Preferably, described organic solvent is selected from toluene, dimethylbenzene, ethyl acetate, hexamethylene, at least in normal heptane Kind.

Preferably, described 2- [3- (4- tert-butyl-phenyl) -1h-1,2,4- triazole -5- bases] acetic acid, the tertiary fourth of described 2,6- bis- Base -4 methyl cyclohexanol is 1: 1～3: 2～5 with the mol ratio of described acetic anhydride.

Preferably, described 2- [3- (4- tert-butyl-phenyl) -1h-1,2,4- triazole -5- bases] acetic acid, the tertiary fourth of described 2,6- bis- Base -4 methyl cyclohexanol is 1: 1～2: 2～3 with the mol ratio of described acetic anhydride.

Preferably, the described response time is 1～4h, it is highly preferred that the described response time is 1～2.5h.

Preferably, described reaction temperature is 35～50 DEG C.

Preferably, described recrystallization solvent quality is 4- methyl -2,6- di-t-butyl Hexalin { 1- acetyl group -3- [uncle 4- Butyl phenyl] -1h-1,2,4- triazole -5- bases } 1～3 times of acetass.

The defect existing for current magenta colour coupler and middle preparation process, present invention applicant tests through continuous Grope, there is provided one kind has the new magenta colour coupler intermediate as (i) chemical structural formula, it also can be by introducing electrophilic Group prepares cyan colour coupler, separately can be used as a kind of medicine intermediate.Meanwhile, the invention provides in above-mentioned magenta colour coupler The preparation method of mesosome, this method puts in place for continuous one-step synthesis, and reaction condition is gentle, and synthesis step is few, and the time is short, and energy consumption is low, Post processing is simple, and finished product has high-purity and high yield, and preparation cost is low, is very suitable for industrialization large-scale production.

Brief description

Fig. 1 is embodiment 1 product 4- methyl -2,6- di-t-butyl Hexalin 1- acetyl group -3- [4- tert-butyl-phenyl] - 1h-1,2,4- triazole -5- bases } acetass¹Hnmr spectrogram.

Fig. 2 is embodiment 1 product 4- methyl -2,6- di-t-butyl Hexalin 1- acetyl group -3- [4- tert-butyl-phenyl] - 1h-1,2,4- triazole -5- bases } acetass ir spectrogram.

Specific embodiment

Below in conjunction with the accompanying drawings, embodiments of the present invention are described further, but the claim of the present invention are not done Any restriction.

Preparation embodiment

Embodiment 1

At 10～20 DEG C, respectively by 60ml ethyl acetate, 46.1 grams of 2,6- di-t-butyl -4 methyl cyclohexanols, 44 grams 2- [3- (4- tert-butyl-phenyl) -1h-1,2,4- triazole -5- bases] acetic acid puts in dry four-hole boiling flask, is cooled to 0～20 DEG C, 38.1 grams of anhydrous acetic acid acid anhydrides of Deca at 0～20 DEG C, after completion of dropping, it is warming up to 35～50 DEG C of stirring 1.5h, reaction terminates Afterwards, crystallisation by cooling, solid deionized water is cleaned twice, obtains white solid powder, by white solid powder wet feed 40～ 50 DEG C of drying under reduced pressure 10h, obtain 80.03 grams of white solid product, and yield is 96%, purity 99.7%.

It is illustrated in figure 1 product¹Hnmr spectrogram (cdcl₃): δ: 0.8～1.2 (m, 26h, rh), 1.35 (s, 9h, ch₃), 1.5～1.6 (t, 2h, ch), 2.8 (s, 3h, ch₃), 4.3 (s, 2h, ch₂), 5.7 (s, 1h, ch), 7.4～7.5 (d, 2h, arh), 8.0 (d, 2h, ar).

Product ir (Fig. 2) v:2963,2866 (c-h), 1757,1734 (c=0 stretching vibration), 1479 (c-n stretch shakes Dynamic), 1326,1250 (c-h), 958 (vibrations of c-h annular strain), 849 (phenyl ring is disubstituted) cm^-1.

Product is verified as 4- methyl -2 through above-mentioned, 6- di-t-butyl Hexalin 1- acetyl group -3- [4- tert-butyl-phenyl] - 1h-1,2,4- triazole -5- bases } acetass.

Embodiment 2

At 5～10 DEG C, respectively by 115.25 grams of 2,6- di-t-butyl -4 methyl cyclohexanols, 125ml toluene, 88 grams of 2- [3- (4- tert-butyl-phenyl) -1h-1,2,4- triazole -5- bases] acetic acid is added in dry four-hole boiling flask, is cooled to 0～20 DEG C, drips Plus 97 grams of anhydrous acetic acid acid anhydrides, after completion of dropwise addition, it is warming up to 45 DEG C, react 2h at 45～50 DEG C, after reaction terminates, cooling knot Crystalline substance, filters, filter cake ionized water cleans twice, obtains white solid powder, and white solid powder wet feed is subtracted at 40～50 DEG C Press dry dry 10h, obtain 167.79 grams of white solid product, yield is 97%, purity 99.65%.

With embodiment 1, empirical tests product is 4- methyl -2,6- di-t-butyl Hexalin { 1- acetyl group -3- for product checking [4- tert-butyl-phenyl] -1h-1,2,4- triazole -5- bases } acetass.

Embodiment 3

At 15～20 DEG C, respectively by 31.69 grams of 2,6- di-t-butyl -4 methyl cyclohexanols, 30ml toluene and 30ml acetic acid Ethyl ester, 25.93 grams of 2- [3- (4- tert-butyl-phenyl) -1h-1,2,4- triazole -5- bases] acetic acid are added to dry four-hole boiling flask In, it is cooled to 0～15 DEG C, 26.54 grams of anhydrous acetic acid acid anhydrides of Deca, after completion of dropwise addition, it is warming up to 40 DEG C, react at 40～50 DEG C 2h, after reaction terminates, crystallisation by cooling, filters, filter cake ionized water cleans twice, obtains white solid powder, by white solid Powder wet feed, in 40～50 DEG C of drying under reduced pressure 10h, obtains 49.08 grams of white solid product, and yield is 96.3%, purity 99.8%.

With embodiment 1, empirical tests product is 4- methyl -2,6- di-t-butyl Hexalin { 1- acetyl group -3- for product checking [4- tert-butyl-phenyl] -1h-1,2,4- triazole -5- bases } acetass.

If no special instructions, raw material involved by the present embodiment and reagent are commercially available prod, and institute is using production equipment This area conventional equipment.

It is understood that above with respect to the specific descriptions of the present invention, being merely to illustrate the present invention and be not limited to this Technical scheme described by inventive embodiments.It will be understood by those within the art that, still the present invention can be carried out Modification or equivalent, to reach identical technique effect；As long as meet use needs, all protection scope of the present invention it Interior.

Claims (8)

1. a kind of color sensitive material magenta colour coupler intermediate is it is characterised in that have the structure as shown in formula (i):

2. the color sensitive material described in claim 1 with the preparation method of magenta colour coupler intermediate it is characterised in that concrete Comprise the following steps: by 2- [3- (4- tert-butyl-phenyl) -1h-1,2,4- triazole -5- bases] acetic acid, 2,6- di-t-butyl -4- first Cyclohexanol, organic solvent adds reactor, Deca acetic anhydride after cooling, reacts in 35～60 DEG C, after reaction terminates, cooling knot Brilliant acquisition target product 4- methyl -2,6- di-t-butyl Hexalin 1- acetyl group -3- [4- tert-butyl-phenyl] -1h-1,2,4- tri- Azoles -5- base } acetass.

3. color sensitive material according to claim 2 with the preparation method of magenta colour coupler intermediate it is characterised in that: Described organic solvent is selected from toluene, dimethylbenzene, ethyl acetate, hexamethylene, at least one in normal heptane.

4. color sensitive material according to claim 2 with the preparation method of magenta colour coupler intermediate it is characterised in that: Described 2- [3- (4- tert-butyl-phenyl) -1h-1,2,4- triazole -5- bases] acetic acid, described 2,6- di-t-butyl -4 methyl cyclohexanol Mol ratio with described acetic anhydride is 1: 1～3: 1～3.

5. color sensitive material according to claim 2 with the preparation method of magenta colour coupler intermediate it is characterised in that: Described 2- [3- (4- tert-butyl-phenyl) -1h-1,2,4- triazole -5- bases] acetic acid, described 2,6- di-t-butyl -4 methyl cyclohexanol Mol ratio with described acetic anhydride is 1: 1～2: 1～2.5.

6. color sensitive material according to claim 2 with the preparation method of magenta colour coupler intermediate it is characterised in that: The described response time is 1～4h.

7. color sensitive material according to claim 2 with the preparation method of magenta colour coupler intermediate it is characterised in that: The described response time is 1～2.5h.

8. color sensitive material according to claim 2 with the preparation method of magenta colour coupler intermediate it is characterised in that: Described reaction temperature is 35～50 DEG C.