JPS6290657A - Production of two equivalent coupler monomer - Google Patents

Abstract

PURPOSE:To produce the titled monomer without generating any side reaction by introducing an amino group to a derivative of propionic acid, and then by halogenating a coupled position followed by substituting the halogen atom with a releasable group and then by changing a propyl reside of propionic acid to a double bond. CONSTITUTION:The compd. shown by formula II is obtd. by reacting the derivative of propionic acid with a 4 equivalent coupler amine shown by formula I followed by halogenating the coupling position. And then, the halogen atom is substituted with the releasable group followed by introducing the double bond to the propyl residue of propionic acid to produce the 2 equivalent coupler monomer shown by formula III. Thus, Q is a coupler residue, Y is an alkylene or a phenylene group, A is a binding group of Q and Y, X is a chlorine or a bromine atom, L is a halogen atom, a hydroxy or a carbonyloxy group, etc., R1 and R2 are each a hydrogen atom or an alkyl group, Z is a releasable group, (m) and (n) are each 0 or 1. Thus, as the prescribed reaction is effected using a starting material which is easy to obtain, controlling the side reaction, the 2 equivalent coupler monomer may be obtd. with a high yield.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is directed to the production of color image-forming 2-equivalent couplers useful as synthetic raw materials for polyester couplers or latex couplers used in silver halide color photographic light-sensitive materials. This invention relates to a method for producing a polymer.

(Prior Art) Photographic couplers are broadly classified according to the hue of their coloring dyes, and are also broadly classified into two types based on stoichiometry: 4-equivalent couplers and 2-equivalent couplers. A 4-equivalent coupler produces 1 mole of dye by consuming 4 moles of silver halide atoms, whereas a 2-equivalent coupler has a leaving group at the coupling position of the coupler and produces 1 mole of dye from 2 moles of silver halide. It is known to be a right-handed coupler from a silver-saving point of view because it generates moles. Furthermore, the 2-equivalent coupler is
Since the color development speed is high, photographic sensitivity can be improved. Furthermore, it has properties such as less generation of heat stain and less reaction with formalin gas. Therefore, 2-equivalent couplers are becoming increasingly important in the current era of increasing sensitivity of silver halide color photographic materials.

One such color image-forming 2-equivalent coupler is a 2-equivalent polymer coupler or latex coupler (hereinafter simply 2-equivalent coupler).
This 2-equivalent polymer coupler has high coupling reactivity, for example,
Stability during storage (formalin resistance, heat resistance, moisture resistance, etc.)
Excellent for.

In addition, it has many advantages, such as good light fastness of color images and the ability to reduce the amount of organic solvent used during coating, making it possible to form a PJ layer. Examples of such 2-equivalent polymer couplers include JP-A-57-94752 and JP-A-57-94752;
224352, No. 58-211756, No. 59-40
No. 643, 59-42543 Gin, 59-22825
Compounds described in publications such as No. 2 are known.

As mentioned above, 2-equivalent polymer couplers have excellent performance, but when producing them, it is important to prepare the raw material monomeric 2-equivalent couplers efficiently and inexpensively and with high purity. This will become an important issue.

Typical methods for preparing conventional two-equivalent coupler monomers are described in the aforementioned patent publications. This is represented by Scheme 1 and Scheme 2 below.

7-' [Scheme 1] (2-equivalent force puller monomer) [Scheme 2] (2-equivalent force puller monomer) (-) In schemes 1 and 2, Q is coupled with the oxidized developing agent. Z represents a group that can be separated from Q by a bipedal coupling reaction, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y represents an unsubstituted or represents a substituted alkylene group, aralkylene group or phenylene group, and A
(represents a linking group between Q and Y, X represents a chlorine or bromine atom, 0m and n represents 0 or 1) (Problems to be solved by the invention) In other words, in the conventional production method, for example, (1) After protecting the amino group with an acetyl group and introducing the leaving group Z as in Scheme 1, deprotecting the amine 7 group by acid hydrolysis,
Next, a polymerizable unsaturated group (acryloyl group) is introduced, or (2) as shown in Scheme 2, a reduction reaction of the nitro group is performed after the introduction of the leaving group Z.

Therefore, Scheme I requires protection and deprotection steps of the amino group, and if the coupler residue is a group that is unstable under acidic conditions, side reactants may be mixed into the product, making purification difficult. There is. In particular, in the case of 5-pyrazolone derivatives, which are magenta coupler residues 2 (2), they have drawbacks such as producing by-product compounds that have an adverse effect on silver halide emulsions. For example, phenylhydrazine derivatives, etc.In the case of Scheme 2, ``the problems associated with the protection and deprotection of amine groups as described above were avoided.However, the reduction of the nitro group of the intermediate is generally Because of its poor solubility, a large amount of acetic acid is used as a solvent for chemical reduction with iron powder, and the acetic acid acetylates the amino groups of the product, requiring complicated treatments for removal and separation, resulting in a significant drop in productivity. Furthermore, if the leaving group 2 is expensive, there are various problems such as being disadvantageous in terms of economy.

On the other hand, in order to eliminate the above-mentioned drawbacks, there have been disclosed in, for example, JP-A-58-43955, JP-A-58-211756, JP-A-59-40643, and JP-A-59-42543. A possible method is to introduce a leaving group Z (same meaning as above) after /\ rogogenation of the coupling position of the 4 m amount rn & body coupler (Scheme 3ij
(where R5Y, A, Q, B, X, m, and n have the same meanings as above).

[Scheme 3] However, the introduction of the leaving group 2 into a halogen-substituted product having a polymerizable unsaturated group as shown in Kitagi causes polymerization and other side reactions of the starting materials or products, and the purpose of high purity is not achieved. It made it extremely difficult to get things.

(Means for Solving the Problems) In order to overcome the drawbacks of these conventional methods, the present inventors have
As a result of various studies, it was found that a certain propionic acid derivative was introduced into the 7-mino group, the coupling position was subsequently halogenated, this /\ halogen atom was replaced with a leaving group, and then the desorption at the propionic acid site was performed. It has been found that by introducing a double bond through a dissociation reaction, the desired diagonal monomer coupler can be produced without side reactions, and the drawbacks of the conventional method described in L can be significantly improved.

The present invention has been made based on this knowledge.

That is, the present invention is based on the following general formula (wherein Q represents a coupler residue capable of forming a color image by coupling with an oxidized form of a developing agent, A represents a linking group that connects Q and Y, and Y represents Represents an unsubstituted or substituted alkylene group or substituted phenylene group. The alkylene group may be a straight chain or a branched button. X represents a chlorine or bromine atom, and L represents a halogen atom, hydroxyl group, carbonyloxy group, or alkylsulfonic acid ester or represents an arylsulfonic acid ester group, R1 and R2 each represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and m and n represent O or l) through a nucleophilic reaction. introducing a leaving group into the active position to which the halogen atom represented by X is bonded,
Then, by deLH reaction, the general formula (wherein Q, A, Y,
R, R2, m and n have the same meanings as above, and Z represents a leaving group. .

In the method of the present invention, the compound represented by the general formula (I) as a starting material has the general formula H2N-(Y)m-('A)mlpeQHH...[■]
(In the formula, Q, A, Y, m, and n have the same meanings as above.) It can be prepared by reacting the amino group of a 4-equivalent coupler with a propionic acid derivative and then halogenating it. .

Next, in the method of the present invention, by a substitution reaction between the active halide derivative represented by the general formula (I) derived from the amine derivative represented by the general formula (III) and the leaving group Z,
It is preferable to obtain a substituted product of Z, and then form a double bond under J1!2& conditions to obtain a compound represented by the general formula (II).

The compound represented by the general formula (CI) is converted into a compound represented by the general formula (I).
It is preferable to synthesize it in one step from the compound represented by II).

In the method of the present invention, general formulas (I), (H) and (I
Examples of the compound represented by II) include those having the following structure.

That is, the color coupler residue represented by Q includes yellow coupler residue, magenta coupler residue and cyan coupler residue, and yellow or magenta coupler residue is more preferable.

Yellow coupler residues include pivaloylacetonilide type [■], benzoylacetanilide type (V), (VT
), where R3, R4, R5 and R6 are each a hydrogen atom or a known substituent of the yellow coupler residue, such as an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, or an alkoxycarbamoyl group. ,
Aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcaroctamoyl group, arylamido group, arylsulfamoyl group, aryl Sulfonamide group, arylureido group, carboxy group, sulfo group,
It represents a nitro group, cyan group, thiocyano group, etc., and these substituents may be the same or different. xl represents a hydrogen atom, a /\rogen atom, or a bond r2 of a leaving group Z (having the same meaning as above).

The magenta color-forming coupler residue is preferably of the 5-vilasolone type [■] or the bilanlotriazole type [■].

In the formula, R7 has the same meaning as the substituents listed above for R3, R9, R5 and R6, and a particularly preferred example among them is a phenyl group substituted with two or three chlorine atoms. . XI represents the same meaning as above,
Or one force of x3 represents the bond with A, and the other is,
hydrogen atom.

Hydroxyl group, each unsubstituted or substituted alkyl group, aryl group, 5 to 6 atoms composed of 5 to 6 atoms, alkylamine 7 groups, anrulamino group, anilino group, alkoxy group, aryl carbonyl group, alkylthion group represents an arylthio group, carbamoyl group, sulfamoyl group, or sulfo/amide group, and X2 and X3
do not express the same thing at the same time.

In the compounds represented by general formulas CI), (n) and ([1), the linking group represented by A is 1, for example -
CONH-, -NHCONH-, -N)ICOO-1-
NHCO-, -0CONH-, -NH-5-COO-
, -GO-1-〇-1-S-, -502-, -NHSO
2- or -502N)I-. Y is an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms,
It represents an aralkylene group or an unsubstituted or substituted arylene group, and examples of these substituents include the same substituents as R3-R6 above, and an alkylene group! It can be a straight chain or a branched button.

In the general formula (I), examples of X include a chlorine atom or a bromine atom, and examples of L include a chlorine atom, a bromine atom, a wood group, an alkylsulfone ugly ester (such as methanesulfonic acid ester), or an arylsulfone Examples include acid esters (for example, p-toluenesulfonic acid ester), and chlorine atom, methanesulfonic acid ester, or p-toluenesulfonic acid ester are preferred.

In the general formula (II), Z is preferably a leaving group bonded to the coupling position at an oxygen atom, nitrogen atom, or sulfur atom. , an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group, or a heterocyclic group (here, the furkyl group, aryl group, and heterocyclic group are the substituents of R3 to R6 above, or a hydroxycarbonyl group, a hydroxyl group, etc.). In the case of a nitrogen atom, it means a group containing the nitrogen atom that can form a 5- or 6-membered ring and serve as a leaving group. Particularly preferred as the leaving group Z is the case where Z is a heterocyclic group containing a nitrogen atom and forming 5 negative or 6 (1 ring); specific examples include a pyrazolyl group, an imidazolyl group, a doriagril group, a tetrazolyl group, Examples include hytantoyl groups, which may have substituents listed in R3 to R6 above at substitutable positions.

In general formulas (II) and (III), R1 and R2 are hydrogen atom, methyl group, ethyl group, propyl group (straight chain or branched), butyl group (straight chain or branched)
Among them, a hydrogen atom or a methyl group is particularly preferred.

The entire process of synthesizing a two-equivalent monomer coupler using the method of the present invention can be represented by the following reaction scheme (
In the case of R,=H in the general formula (1)).

[Reaction process formula]

H2N-(Y tighten-(A layer Q side H (III) two The above reaction I equation will be explained in detail.

[of the process]

Synthesis of the compound represented by the general formula (IX) from the --- class amine derivative represented by the general formula (m) is as follows.

In the presence of an a base or a solvent that can act as a deoxidizing agent (-
In general, L-CH2C:)I(R) in a solvent 1 containing a nitrogen atom such as an amide bond (e.g., dimethylacetamide, acetonitrile, tetramethylurea, dimethylformamide, etc.) or in the coexistence of the above solvents.
This is achieved by reacting COC:u. Examples of organic bases include triethylamine, diazabicyclononene (DBN), diazabicycloundecene (DBtJ),
Examples include 4-(N,N-dimethyl)pyridine and pyridine.

The reaction solvent can be used without any particular restriction as long as it does not have active protons, but solvents with high solubility are preferred from the viewpoint of productivity. DMAc), N
, N-dimethylimidacylin-2-one (DMI),
Examples include acetonitrile, tetrahydrofuran (THF), chloroform, and methylene chloride. Moreover, the reaction temperature is preferably in the range of 0°C to 80°C.

[Process (shi)]

For the halogenation reaction of the compound represented by the general formula (IX), conditions and methods commonly used for the halogenation of conventional 4-equivalent couplers can be applied. That is, the halogenating agents include bromine (Br2), N-bromosuccinimide (NBS), and sulfuryl chloride (S02CL; L2).
, N-chlorosuccinimide (NCS).

As the reaction solvent, it can be used without any particular restrictions, except for those that do not have active methylene or active methine protons (for example, acetone, methyl isobutyl ketone, etc.).
Preferred solvents that are inert during the halogenation reaction include chloroform, methylene chloride, and carbon tetrachloride. Furthermore, if the solubility of the E-grade melt is low, the above-mentioned solvents and the following solvents may be mixed and used. DMF, DMAc, THF, acetonitrile, etc. are preferable as the solvents to be mixed.

The reaction temperature is in the range of -20°C to 60°C, more preferably in the range of -5°C to 25°C to achieve high purity...General formula (I)
It is suitable for obtaining a compound represented by

Here, in step 1 and step 2, J! ! It may be carried out continuously (in mass production, it is preferable from the viewpoint of productivity. As for the solvent, it is preferable to use the same process in Step 1 and Step 2. For example, a mixed solvent of a halogen solvent and an amide solvent is preferable. Particularly preferred (e.g. chloroform and DMF, chloroform and D
MAc, methylene chloride and DMAc, etc.).

[Process ■]

The nucleophilic substitution reaction between the compound represented by the general formula (1) and the leaving group Z can be roughly divided into the following two methods (1) and (2) depending on the type of the leaving group Z.

■: ls Degrouping Z is substituted with oxygen or sulfur atom In such a case, the base is triethylamine, DB
N, DBU, 4-(N,N-dimethyl)pyridine, pyridine, sodium carbonate (anhydrous), potassium carbonate (anhydrous)
Examples include.

In addition, a salt of the leaving group Z (for example, sodium salt, potassium salt, etc.) may be used. In this case, the salt of the leaving group Z is 1.2
Aromatic solvents (e.g. benzene, tornidi,
chlorobenzene, dichlorobenzene, etc.), ether solvents (e.g., ether, THF, dicrime, dimethoxyethane, etc.), and in addition, DMF, DMAc, acetonitrile, etc. are preferred.The reaction temperature is 0°C to 120°C.
℃ range, more preferably 10℃ to 80℃ range.

-'d: @Degroup When Z is substituted with a nitrogen atom In such a case, Z is a nitrogen-containing heterocycle and can act as a deoxidizing agent. Therefore, the nitrogen-containing heterocycle is preferably added in excess of 2
By using ~4 equivalents, the substitution reaction in step (2) can be achieved. Therefore, it is not necessary to use a base in particular, but the bases listed in item (2) above may be used. The above reaction is carried out at 0°C to 200°C.
It can be carried out in various solvents or by a solvent-free melting method within a temperature range of . The preferred temperature range is 20°C to 12°C.
In the solvent-free melting method at 0°C, there is no need to raise the temperature above the melting temperature as long as both are dissolved.

Preferred solvents include aromatic solvents (benzene, toluene, xylene, chlorobenzene, etc.), aprotic, polar solvents (DMF, DM Ac, N-methylpyrrolidone, sulfolane, hexamethylphosphotriamide, etc.) Examples include.

In this step (2), the leaving group Z does not undergo a substitution reaction with the chlorine atom of general formula CI), methanesulfonic acid ester, p-toluenesulfonic acid ester, etc., but is selected with the chlorogen atom at the coupling position of the coupler. This reaction is completely unpredictable.

[Process ■]

From the compound represented by general formula CX), general formula (II
) The synthesis of the compound represented by is as follows.

In general formula (X), when L is a hydroxyl group, reaction conditions other than those requiring acidic conditions or high temperatures can be applied without particular restriction. Preferably, reagents such as N,N'-dicyclohexylcarposiimide (DCC) and cupric tl chloride, thionyl chloride and pyridine, methanesulfonyl chloride and triethylamine are used. The reaction temperature is preferably in the range of 0°C to 60°C, and the reaction solvent is not particularly limited as long as it has good idiolysis, but preferably ether, THF, methylene chloride, chloroform, benzene, toluene, acetonitrile. , DMF, DMAc, etc.

--111 in formula (X), when L is a halogen atom, methanesulfonic acid ester, P-toluenesulfonic acid ester, etc., it is possible to obtain a compound represented by general formula (11) in the presence of a base. can. Examples of the base include tertiary amine bases such as triethylamine, pyridine, DBN, and DBU, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
As a solvent, alcoholic solvents (methanol, ethanol/
aprotic polar solvents (DMF, DMAc, etc.), ether solvents (THF, dioxane, etc.)
Examples include solvents that mix well with water.

In step (4) above, a reaction solvent that mixes well with water is used as a reaction solvent, and by-products derived from L are water-soluble salts (e.g., sodium chloride, triethylammonium chloride, methanesulfone This is because the desired product can be easily obtained by pouring the reaction mixture into water. This eliminates the need for extraction operations, which is a great manufacturing advantage.

Furthermore, the reaction conditions for HL removal in step (4) are relatively mild conditions, and there are almost no side reactions such as decomposition of the coupler core, and the purification of the target product is extremely easy, which is another advantage of the present invention. It will be done.

(Specific examples of compounds) As specific examples of compounds to which the method of the present invention is applied, compounds included in general formulas (I) and (: II) are shown below, but are not limited to these (invention Effects of the present invention) The effects of the present invention are listed as follows.

(1) A 2-equivalent monomer coupler suitable for producing a 2-equivalent polymer coupler having various leaving groups introduced into the active position can be produced in high yield using readily available raw materials.

(2) In a short process starting from an amine, and in addition, a polymer,
By suppressing the production of by-products, the desired 28-mer monomer coupler can be obtained with high purity.

(3) A two-equivalent monomer coupler having an appropriate leaving group introduced into the active position can be obtained at low cost.

(Example) Next, the present invention will be explained in detail based on examples.

Example 1 Synthesis of exemplified compound (n) - (1) ■4-chloro-3-(α-pivaloylacetylamino)aniline 53
．． 7g, pyridine 16g and acetonitrile 100mJ
The mixture was dissolved in 40 mJl of dimethylacetamide (DMAc) and heated to 50 to 60°C with stirring. 31 g of 2-chloro-1-methylpropionyl chloride was added dropwise to this over 30 minutes. After 5 hours, the mixture was cooled with ice water, 300 mM of methylene chloride was added to the mixture, and the mixture was cooled to 0°C to 5°C. A solution of 27 g of sulfuryl chloride (SO2C) and 30 mQ of methylene chloride was added to this over 20 minutes, and after stirring for 15 minutes, 200 m4 of water was added to the reaction mixture, and sodium carbonate (powder) was added little by little to neutralize it. 'The mixture is Na
After saturation with CfL, 200 mL of methylene chloride was added and the methylene chloride layer was separated, dried over Na2SO4, concentrated on a rotary evaporator, and the residue was crystallized from an ethyl acetate-hexane solvent system. The white crystals were collected by filtration to obtain 69.4 g (yield: 85%) of exemplified compound CI)-(1). The structure of CI)-(1) is determined by mass spectrometry, IR,
Confirmed by NMR spectrum.

■40.8 g of CI)-(1) synthesized above and 51.5 g of 1-benzyl-5-ethoxyhydantoin were added to 150 mJ1 of acetonitrile, and the mixture was added at 45° to 55°C under a nitrogen atmosphere.
The mixture was heated and stirred. After 4 hours, cool to room temperature and pour approximately 100 m of water.
Added sentences and crystallized. The crystals were filtered and dissolved in water-MeOH (
After washing with a mixed solution (2:1) and air drying, 52.2g (yield: 8
6%) of the substituted product was obtained.

■Next, 42.5 g of the above substitution product was added to 100 g of methanol.
The mixture was dissolved in mJ1, 0.2 mM of nitrobenzene was added, and the mixture was cooled to 5° C. or lower with ice water. To this, potassium hydroxide l
A solution of 2 g of methanol in 120 ml was added. Add water drain for 1 hour, add 0.5N hydrochloric acid solution and adjust the pH.
I gave it a 3-4.

The mixture was extracted with ethyl acetate and Na2SO4
After drying with am+,... The residue was crystallized using a mixed solvent of ethyl acetate and hexane, and the precipitated crystals were collected by filtration to obtain 35.4 g (yield: 89%) of the target product (II)-(1).
The total yield was 65% of the aniline compound as the starting material.

(II) - The structure of (1) is shown in mass spectra, IR
, confirmed by NMR spectrum.

Comparative Example 1 Synthesis of Exemplified Compound (II)-(1) by Conventional Method ■ 45 g of 4-chloro-3-(α-h/heroylacetylamino)nitrobenzene was dissolved in 300 mM of methylene chloride.
The solution was dissolved in water and kept at 5°C or lower with ice water. In this, 5O2C
1222, 3g methylene chloride solution 50m sentence 45
Added in minutes. Add 200 m of water for 1 hour, Na2C
After neutralization by adding o3, the methylene chloride 91 layer was separated.

The organic layer was concentrated under reduced pressure using a dry aspirator using Na 2 SO 3 , and the residue was crystallized from a mixed solvent of ethyl acetate and n-hexane. The crystals were collected by filtration and 4-chloro-3-
41.2 g (yield: 82%) of (α-chloro-α-pivaloylacetylamino)nitrobenzene was obtained.

■Next, 40 g of the above active chloroform and 1-benzene 5
-62g of ethoxyhydantoin in 200ml of acetonitrile
Dissolved in mM. To this, 12.2 g of triethylamine was added and reacted for 5 hours at 50°C to 55°C under a nitrogen atmosphere. The reaction mixture was poured into a 300m wooden container. 1. The pH was adjusted to 3 by adding an aqueous N-HC solution, extracted twice with 300 mM ethyl acetate, and the ethyl acetate layer was washed twice with water and dried over Na25O. It was concentrated under reduced pressure, the residue was crystallized from a mixed solvent of ethyl acetate and hexane, and the white crystals were collected by filtration to give the desired 2-chloro-5-nitro-α-pivaloyl-α-(1-benzyl-
48.4 g (yield 76%) of 5-ethoxy-3-hydantoinl)acetanilide was obtained.

(2) Next, the nitro groups of the hydantoin synthesized above and the sample were reduced as follows. Iron powder 23g, acetic acid 1.8
1.8 g of ammonium chloride is mixed with 50 m of isopropyl alcohol! ;1. and 15 ml of water were refluxed and stirred vigorously. After 15 minutes, a solution of 26.5 g of the nitro compound described above dissolved in isopropyl alcohol roomjl was added to 3
It was dropped in 0 minutes. After refluxing for 30 minutes, add tetrahydrofuran 1
00m! ;L was added, iron powder was removed through Celite, and the mixture was thoroughly washed with ethyl acetate. The filtrate was concentrated under reduced pressure, and the residue was crystallized from ethyl acetate-hexane solvent to give 2-chloro-5-
7 minnow α-hibaloyl-α-(1-benzyl-5-ethoxy-3-hydantoinl)acetanilide in 17.
5g (yield 70%) was obtained.

(2) Next, a polymerizable unsaturated group was introduced. Dissolve 15 g of the amino compound prepared above in 120 ml of acetonitrile,
9.5 g of pyridine and 0.1 mM of nitrobenzene were added to this, and the temperature was maintained at 35°C to 40°C. 4.1 g of methacryloyl chloride was added to this mixture and reacted for 3 hours. After cooling, 400 mJJ of water was added, and the mixture was extracted three times with 300 ml of ethyl acetate, washed with water, and dried over Na25O4. It was concentrated under reduced pressure, and the residue was crystallized from a mixed solvent of ethyl acetate and hexane. Filter the crystals and obtain 12.8g of the target product [■]-(1).
(yield 75%).

The total yield of CI-(1) by the above conventional method is 33
%Met.

Example 2 Synthesis of Exemplified Compound (n)-(9)>■3-Amino-1-(2,4,6-dolichlorophenyl)-5-1:' 139.3 g of lazolone was added to DMAclOO
The mixture was added to 200 mM of methylene chloride and stirred under reflux. To this, 3-chloropropionyl chloride 66.7
g was added dropwise over 20 minutes. After 4 hours, the mixture was cooled to 20° C. and 84 g of sodium hydrogen carbonate was added. After 30 minutes, 300 mM of methylene chloride was added and the mixture was cooled to below 10°C.

Thirty minutes after the completion of dropping a solution of 176 g of odor in methylene chloride (50 mfL), 400 mft of water was slowly added. The methylene chloride layer was separated, washed with water, and Na2
After drying with SO4, it was concentrated under reduced pressure. The residue was crystallized from acetonitrile to give 4-bromo-1-(2,4,6-dolichlorophenyl)-3-(3-chloropropionylamino)-5-pyrazolone (exemplified compound CI)-(7) for 16
9 g (yield 76%) was obtained.

■Next, 54 g of the above bromo compound (1)-(7), 24.6 g of pyrazole, 2.6-di-tert-butyl-4
- 8 g of methylphenol was added to 120 mJl of sulborane and reacted at 60°C for 9 hours. After cooling, ethyl acetate 40
0mJl! , 300mM of water was added for extraction, and the ethyl acetate layer was washed with water, dried over Na25O4, and concentrated under reduced pressure. The residue was crystallized from acetonitrile to obtain the target product 1-(2,4
,6-)lichlorophenyl)-3-(3-10loprobionylamino)-4-pyrazolyl-5-pyrazolone to 3
5.2 g (yield 67%) was obtained.

(2) Next, the formation of polymerizable unsaturated groups by removing HCu was carried out in the same manner as in Example 1. That is, 30.5 g of the pyrazole adduct synthesized above was dissolved in methanol LOOmjL, 0.2 mM of nitrobenzene was added, and the mixture was cooled to 5° C. or lower. To this, add 12g of potassium hydroxide and 11g of methanol.
20 ml of solution was added and reacted for 1 hour. 0.5N-HC
! Adjusted to pH 4 with L water and poured into cold water with stirring, 30
After a few minutes, the precipitated crystals were collected by filtration, and the resulting crude crystals were suspended in acetonitrile, stirred for 30 minutes, and then filtered. The obtained crystals were dried, and the target product (II)-(9) was obtained as 25,7
g [yield 92%] was obtained. Each synthetic intermediate and (II)
-(9), each structure was confirmed from various spectral data. Also.

The total yield of (II)-(9) was 47%.

Comparative Example 2 Synthesis of Exemplified Compound [n]-(9) by Conventional Method ■ 50.1 g of 3-amino-1-(2,4,6-drichlorophenyl)-5-pyrazolone and 125 mM of acetic acid were
The mixture was stirred at 0°C to 40°C, 21 ml of acetic anhydride was added thereto, reacted for 4 hours, and then cooled to 10°C or lower.

Next, add 27.4 g of bromine to 20 mf of acetic acid to the above reaction mixture.
A solution of L was added dropwise. After 30 minutes, add 700ml of water to the reaction mixture.
The precipitated crystals were collected by filtration, suspended in acetonitrile, and filtered to obtain crystals. 4-bromo-3-acetylamino-1-(2,4,
The yield of 6-dolychlorophenyl)-5-pyrazolone is 5
3 g (yield 74%).

■Next, 40g of the upper body of the above professional, 27.2g of pyrazole,
6 g of 2,6-tert-butyl-4-methylphenol was added to 100 mJl of sulfolane and reacted at 65°C for 7 hours. After cooling, ethyl acetate 400mA and water 300mj
Add L and extract.

After washing with water and drying with Na and SO2, it was contracted under reduced pressure.

25. The desired 1-(2,4,6-dolichlorophenyl)-3-7cetylamino-4-pyrazolyl-5-pyrazolone was obtained by crystallizing the residual liquid from acetonitrile.
2g (yield 65%) was obtained.

■21g of the pirabul substitute synthesized above was added to 30ml of concentrated hydrochloric acid.
The mixture was added to a solution of 200 ml of methanol and 200 ml of methanol, and the mixture was stirred and refluxed. After 4 hours, the mixture was cooled, neutralized with a 2N NaOH aqueous solution, and poured into water. The resulting crystals were collected, suspended in acetonitrile, and then filtered. After drying, 14.6 g (yield 75%) of 1-(2,4,6-)lichlorophenyl)-3-amino-4-pyrazolyl-5-pyrazolone was obtained.

In addition, in this reaction step, a by-product of a compound considered to have been ring-cleaved between the 1st and 5th positions of the pyrazolone ring was observed.

■Next, 14 g of the 3-amino-4-pyrazolyl compound obtained above,
Add 12.3 g of pyridine and 0.3 mQ of nitrobenzene to 100 m of acetonitrile and 50 ml of DMAc.
℃ to 40℃, and add acryloyl chloride 14 to this.
g was added. After 3 hours, 250 mfL of water was added, and the mixture was extracted twice with 400 mM ethyl acetate, washed with water, dried, and concentrated under reduced pressure. Furthermore, dissolve the residue in 100ml of methanol.
Then, add nitrobenzene at 0.3℃ and cool on ice.
Potassium hydroxide/rum 6.5g and methanol 60m! A solution of Q was added. After stirring for 1 hour, 200 ml of saturated brine was added to the reaction mixture, which had been neutralized with acetic acid, extracted twice with 300 ml of ethyl acetate, washed with water, dried, and concentrated under reduced pressure. The residue was crystallized from acetonitrile, filtered, and dried to obtain 11 g of (II)-(9) (yield: 68%).

The total yield of (IT)-(9) by the conventional method shown above was 28%.

Example 3 Synthesis of exemplified compound CI-(12)>■1-(2,
4,6-1lichlorophenyl)-3-(2-chloro-5
-aminobenzoylamino)-5-pyrazolone 86.
4g of DMA c70mM and methylene chloride 140mM
1 and stirred and refluxed. To this, 26.8 g of 3-chloropropionyl chloride was added, and after reacting for 5 hours,
The mixture was cooled to 5° C. with ice water, 500 ml of methylene chloride was added, and 33 g of sodium hydrogen carbonate was added. 30
After a few minutes, a solution of 30.4 g of bromine in 30 mλ of methylene chloride was added dropwise. After 40 minutes, slowly add 400mM of water.
The methylene chloride layer was separated, washed with water, dried, and evaporated under reduced pressure. The residue was crystallized from acetonitrile, yielding 82.2 g.
(yield 79%) of 4-bromo-1-(2,4°6-dolichlorophenyl)-3-(2-chloro-5-(3-chloropropionylamino)benzoylcy-5-pyrazolone was obtained.

■Next, the above 4-Pro upper body 52.3g, Virasole 2
Add 0.4 g and 4.5 g of 2.6-tert-butyl-4-methylphenol to a 7100m bottle of sulfola,
The reaction was carried out at 0°C for 8.5 hours. After cooling, ethyl acetate 300
The mixture was extracted with 250 m of water, washed with water, dried, and concentrated under reduced pressure. The residue was crystallized from acetonitrile to give the pyrazole-substituted 4-pyrazolyl-1-(2,4,6-dolichlorophenyl)-3-(2-chloro-5-(3-trit17tffnia'ropionylamino)benzoyl- 5
-35.2g (yield 69%) of pyrazolone was obtained.

(■Additionally, 32g of pyrazole adduct and 0.2mM of nitrobenzene were added to 100ml of methanol and heated to 10'C.
Cooled below. To this was added a solution of 111i of potassium hydroxide in 120ml of methanol.

After 1 hour, adjust the pH to 4i with 0.5N-HCl water,
Pour into cold water with stirring, collect the precipitated crystals, put in acetonitrile, stir for 10 minutes, filter and dry, 25.
8g (yield 87%) of the target product (n)-(t2)
I got it. (II) - (12) and each intermediate is
Each structure was confirmed using various spectral data. Moreover, the total yield of (IT)-(12) was 47.4%.

Comparative Example 3 Synthesis of exemplified compound (It)-(12) by conventional method> ■1-(2,4,6-)lichlorophenyl)=3-(2
-Chloro-5-nitrobenzoylamino)-5-pyrazolone 46.2g was placed in chloroform 300mJ1,
A solution of 17.5 g of bromine in 30 mM chloroform was added dropwise while maintaining the temperature at 10° C. or lower. Drain water for 1 hour, add 200mM, and add 1,5-NNa HCO3 aqueous solution tep.
H5 and filtered. The crystals were collected and washed with acetonitrile, and after drying, 4'4.8g (yield 81%) of 4-bromo-1-(2,4,6-)lichlorophenyl)-3-(2
-chloro-5-nitrobenzoylamino)-5-pyrazolone was obtained.

■Next, 40g of the above professional upper body, 17g of pyrazole, 2
．． 6-tert-butyl-4-methylphenol 3
．． 5 g was added to 63 ml of sulfolane and reacted at 65°C for 6 hours. After cooling, 300mM of ethyl acetate and 200mM of water were added for extraction, washed with water, dried, and concentrated under reduced pressure. The residue was crystallized from 7cetonitrile to obtain 4, which is a pyrazole substituted product.
-pyrazolyl-1-(2,4,6-dolichlorophenyl)-3-(2-chloro-5-nitrobenzoylamino)
28.1 g (yield 72%) of -5-pyrazolone was obtained.

[Phase] Next, 28 g of the pyrazole substituted product obtained above was mixed with 3 iron powder.
0 g, ammonium chloride 1.9 g, acetic acid 1.9 mM,
15mM water and 150mM isopropyl alcohol! ;L
was added in small portions to the refluxed liquid in 6 portions. After 40 minutes, 150+nJJ of tetrahydrofuran was added and the mixture was filtered through Celite, and the filtrate was evaporated. The residue was crystallized from acetonitrile to give 4-pyrazolyl-1-(2,4,6-
20.6 g (yield: 78%) of (dolichlorophenyl)-3-<2-chloro-5-7minobennylamino)-5-pyrazolone was obtained.

■Continuing, 20g of the above amine and 12.8g of pyridine
g was added to 100 mJ of acetonitrile and 50 mJl of DMAc and kept at 40°C to 45°C. Nitrobenzene 0.3
mJl and 4.2 g of acryloyl chloride were added.

The extract was extracted using 300 ml of water after 3 hours and 500 ml of ethyl acetate, washed with water, dried, and concentrated under reduced pressure. The residue was crystallized from acetonitrile to obtain the desired product [■]-(12)
13.9g (yield 73%) was obtained.

The total yield of (II)-(12) by the conventional method was 33.
It was 2%.

The total yield, number of steps, and purity of the final products obtained in Examples 1 to 3 and Comparative Examples 1 to 3 are shown in the table below. Note that the purity is the result of quantitative determination by high performance liquid chromatography.

From the above table, it is clear that the method of the present invention has a short number of steps (1). I understand.

Procedural City Paper (self-motivated) May 16, 1985 1. Indication of the incident [■ 1985 Patent Application No. 231968 2. Name of month of publication 2. Manufacturing method of equivalent force puller monomer 3. Person making the amendment: Relationship with 19 cases Patent applicant address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52
0) Fuji Photo Film Co., Ltd. Representative Minoru Ohnishi 4, Agent address 7th floor, Midoriya 2nd Building, 3-7-3 Shintachibana, Minato-ku, Tokyo 105 Phone (03) 591-7387 Name (7643) Patent attorney Shihan) Bk! L 3i゛, 7 1] 5. Date of amendment order Voluntary 6. Subject of amendment ``Detailed description of the invention'' column 7 of the specification
, Contents of the amendment (1) "Pyrazolotriazole type [VI]
Correct to -al or [w-b]J.

(2) General formula on the same page of the same book will be corrected.

(3) "Table 3" in the first line of page 31 of the same document is corrected to "Table 3-1."

(4) The following Table 3-2 is inserted below Table 3 (amended Table 3-1) on the same page of the same book.

(5) "Table 6" in the first line of page 36 of the same document is corrected to "Table 6-1."

(6) The following Table 6-2 is inserted below Table 6 (Amended Table 6-1) on the same page of the same book.

Claims (1)

[Claims] 1. The following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ represents a linking group connecting Q and Y, Y represents an unsubstituted or substituted alkylene group or a substituted phenylene group, and the alkylene group may be a straight chain or a branched chain. X represents a chlorine or bromine atom, and L represents a halogen atom, a hydroxyl group, a carbonyloxy group, or an alkylsulfonic acid ester or an arylsulfonic acid ester group, R_1 and R_2 each represent a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and m and n are 0. or 1) is subjected to a nucleophilic reaction to replace the halogen atom represented by (wherein Q, A, Y, R_1, R_2, m and n have the same meanings as above, and Z represents a leaving group) A 2-equivalent coupler monomer characterized by obtaining a compound represented by the following: manufacturing method. 2. A 4-equivalent coupler represented by the general formula H_2N-(Y)_m-(A)_n-(Q)-H (wherein Q, A, Y, m and n have the same meanings as above). After reacting the amino group with a propionic acid derivative, it is halogenated and the general formula ▲ has a mathematical formula, a chemical formula, a table, etc. ▼ (wherein, Q, A, Y, X, L, R_1, R_2, m and n are the above (has the same meaning as ) Claim 1 to obtain the starting compound represented by
A method for producing a 2-equivalent coupler monomer as described in . 3. The method for producing a 2-equivalent coupler monomer according to claim 1, wherein the LH removal reaction is carried out under basic conditions.