阅读说明：本技术 一种双（1-芳基-4h-吡唑）结构有机颜料及其制备方法 (Organic pigment with bis (1-aryl-4H-pyrazole) structure and preparation method thereof ) 是由 张晓明 于 2021-07-23 设计创作，主要内容包括：本发明提供一种双(1-芳基-4H-吡唑)结构有机颜料,其合成所用原料包括：对二卤代苯、丙二腈、苯肼和取代苯肼。合成路线是：对二卤代苯与丙二腈发生偶联反应,生成1,4-二丙二氰基苯(苯连二丙二腈),然后再与苯肼或取代苯肼关环。本发明制备的双(1-芳基-4H-吡唑)结构有机颜料结构由苯环联接,耐热和耐迁移性能好,颜色鲜艳(为嫩黄和金黄色),耐候性能好。合成过程简单,合成产物收率高(＞80％)。(The invention provides a bis (1-aryl-4H-pyrazole) structure organic pigment, which is synthesized by using the following raw materials: p-dihalobenzenes, malononitriles, phenylhydrazines and substituted phenylhydrazines. The synthetic route is as follows: p-dihalobenzene and malononitrile are subjected to coupling reaction to generate 1, 4-dipropylenedicyanobenzene (benzene-dipropylenedinitrile), and then the ring is closed with phenylhydrazine or substituted phenylhydrazine. The organic pigment with the bis (1-aryl-4H-pyrazole) structure prepared by the invention has the advantages of good heat resistance and migration resistance, bright color (light yellow and golden yellow) and good weather resistance because the structure is connected by benzene rings. The synthesis process is simple, and the yield of the synthesized product is high (more than 80%).)

1. The organic pigment with the bis (1-aryl-4H-pyrazole) structure is characterized in that the organic pigment is synthesized by using the following raw materials: p-dihalobenzenes, malononitriles, phenylhydrazines and substituted phenylhydrazines.

2. The organic pigment of bis (1-aryl-4H-pyrazole) structure according to claim 1, which has the formula V:

in the formula V, R is H, Cl, Br, NO₂and-CH₃One kind of (1).

3. The bis (1-aryl-4H-pyrazole) structured organic pigment according to claim 1, wherein the p-dihalobenzene is one of p-dichlorobenzene, p-dibromobenzene and p-diiodobenzene.

4. The bis (1-aryl-4H-pyrazole) structured organic pigment according to claim 1, wherein the substituted phenylhydrazine is one of 4-chlorophenylhydrazine, 4-nitrophenylhydrazine, 4-bromophenylhydrazine and 4-methylphenylhydrazine.

5. A process for producing an organic pigment of bis (1-aryl-4H-pyrazole) structure according to any one of claims 1 to 4, which comprises the steps of:

s1, adding dihalogenated benzene and malononitrile into a reactor filled with a reaction solvent, adding a catalyst, stirring at room temperature for 0.5-3 hours, heating to 80-140 ℃, continuing to react for 2-3 hours, concentrating a reaction system, cooling to room temperature, and filtering to obtain 1, 4-dipropylenedicyanobenzene (benzene-adiponitrile); the reaction formula is as shown in formula VI:

s2, adding the 1, 4-dipropylenedicyanobenzene (benzene-linked-dipropylenedinitrile) obtained in the step S1 into a reactor filled with ethanol, adding phenylhydrazine or substituted phenylhydrazine while stirring, refluxing for 2-5 hours, cooling, filtering, and recrystallizing to obtain the organic pigment with the bis (1-aryl-4H-pyrazole) structure; the reaction formula is as shown in formula VII:

6. the method for producing an organic pigment of bis (1-aryl-4H-pyrazole) structure according to claim 5, wherein the catalyst used in step S1 is one or more selected from the group consisting of sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, sodium butoxide, palladium dichloride, triphenylphosphine, tricyclohexylphosphine, and bisdiphenylphosphinobutane.

7. The method for producing an organic pigment of bis (1-aryl-4H-pyrazole) structure according to claim 5, wherein the reaction solvent used in step S1 is one or more selected from the group consisting of xylene, tetrahydrofuran, N-methylpyrrolidone, and pyridine.

Technical Field

The invention belongs to the field of organic chemical industry, and particularly relates to a bis (1-aryl-4H-pyrazole) structure organic pigment and a preparation method thereof.

Background

Pyrrole and pyrazole structural compounds are one of important organic pigments and dyes, and both azo structural organic pigments and dyes and heterocyclic structural organic pigments and dyes have pyrazole and pyrrole structures.

Pigment red 254 and pigment red 264 are compounds having a pyrrolopyrroledione structure. Yuh Wen Ho describes azo organic Dyes containing pyrazole-containing structures (e.g.formula I) (Dyes and Pigments,2005, 64: 223-.

FikretAnd AykutA process for preparing azo organic Dyes containing 4-arylazo-1H-pyrazole structures is also described (Dyes and Pigments,2007,74: 288-. The synthetic route is shown as the following formula II and formula III:

besides dyes and pigments, there are also many pyrrole structure compounds in the drugs, and patent US20030060453 discloses a synthesis method of a proliferation active drug containing pyrazole azo structure (formula IV):

although the pyrrole structure compound has been used in the preparation of dyes and pigments, the synthesized pigments have poor weather resistance, relatively complex synthesis process and low yield of the synthesized products.

Disclosure of Invention

The invention aims to solve the technical problem of providing the bis (1-aryl-4H-pyrazole) structure organic pigment and the preparation method thereof, wherein the organic pigment is connected by benzene rings, has good heat resistance and migration resistance, bright color (light yellow to golden yellow), good weather resistance, simple synthesis process and high yield of synthesized products.

In order to solve the above technical problems, an embodiment of the present invention provides a bis (1-aryl-4H-pyrazole) structured organic pigment, which is synthesized from the following raw materials: p-dihalobenzene, malononitrile, phenylhydrazine and substituted phenylhydrazine. Wherein the structural formula of the organic pigment with the bis (1-aryl-4H-pyrazole) structure is shown as a formula V:

in the formula V, R is H, Cl, Br, NO₂and-CH₃One kind of (1).

Preferably, the p-dihalobenzene is selected from one of p-dichlorobenzene, p-dibromobenzene and p-diiodobenzene.

Preferably, the substituted phenylhydrazine is one of 4-chlorophenylhydrazine, 4-nitrophenylhydrazine, 4-bromophenylhydrazine and 4-methylphenylhydrazine.

The invention also provides a preparation method of the organic pigment with the bis (1-aryl-4H-pyrazole) structure, which comprises the following steps:

s1, adding dihalogenated benzene and malononitrile into a reactor filled with a reaction solvent, adding a catalyst, stirring at room temperature for 0.5-3 hours, heating to 80-140 ℃, continuing to react for 2-3 hours, concentrating the reaction system, cooling to room temperature, and filtering to obtain 1, 4-dipropylenedicyanobenzene (benzene-associated-malononitrile); the reaction formula is as shown in formula VI:

s2, adding the 1, 4-dipropylenedicyanobenzene (benzene-linked-dipropylenedinitrile) obtained in the step S1 into a reactor filled with ethanol, adding phenylhydrazine or substituted phenylhydrazine while stirring, refluxing for 2-5 hours, cooling, filtering, and recrystallizing to obtain the organic pigment with the bis (1-aryl-4H-pyrazole) structure; the reaction formula is as shown in formula VII:

wherein, the catalyst used in step S1 is one or more of sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, sodium butoxide, palladium dichloride, triphenylphosphine, tricyclohexylphosphine and bisdiphenylphosphinobutane.

Wherein, the reaction solvent used in step S1 is one or more of xylene, tetrahydrofuran, N-methyl pyrrolidone and pyridine.

The technical scheme of the invention has the following beneficial effects:

the invention provides an organic pigment containing a bis (1-aryl-4H-pyrazole) structure and a preparation method thereof, wherein the prepared bis (1-aryl-4H-pyrazole) structure organic pigment is connected by benzene rings, and has good heat resistance and migration resistance, bright color (bright yellow and golden yellow) and good weather resistance. The synthesis process is simple, and the yield of the synthesized product is high (more than 80%).

Drawings

FIG. 1 is the magnetic resonance hydrogen spectrum of 1, 4-bis (5-imino-3-amino-1-phenyl-1H-pyrazol-4-yl) benzene in the first embodiment of the invention.

Detailed Description

In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.

The invention provides a bis (1-aryl-4H-pyrazole) structure organic pigment, which is synthesized by using the following raw materials: p-dihalobenzenes, malononitriles, phenylhydrazines and substituted phenylhydrazines.

The synthetic route of the organic pigment with the bis (1-aryl-4H-pyrazole) structure is as follows:

the structural formula of the organic pigment with the bis (1-aryl-4H-pyrazole) structure is shown as a formula V:

in the formula V, R is H, Cl, Br, NO₂and-CH₃One kind of (1).

Preferably, the p-dihalobenzene is selected from one of p-dichlorobenzene, p-dibromobenzene and p-diiodobenzene. The substituted phenylhydrazine is one of 4-chlorophenylhydrazine, 4-nitrophenylhydrazine, 4-bromophenylhydrazine and 4-methylphenylhydrazine.

The invention also provides a preparation method of the organic pigment with the bis (1-aryl-4H-pyrazole) structure, which comprises the following steps:

s1, adding dihalogenated benzene and malononitrile into a reactor filled with a reaction solvent, adding a catalyst, stirring at room temperature for 0.5-3 hours, heating to 80-140 ℃, continuing to react for 2-3 hours, concentrating the reaction system, cooling to room temperature, and filtering to obtain 1, 4-dipropylenedicyanobenzene (benzene-associated-malononitrile); the reaction formula is as shown in formula VI:

s2, adding the 1, 4-dipropylenedicyanobenzene (benzene-linked-dipropylenedinitrile) obtained in the step S1 into a reactor filled with ethanol, adding phenylhydrazine or substituted phenylhydrazine while stirring, refluxing for 2-5 hours, cooling, filtering, and recrystallizing to obtain the organic pigment with the bis (1-aryl-4H-pyrazole) structure; the reaction formula is as shown in formula VII:

preferably, the catalyst used in step S1 is one or more of sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride, sodium butoxide, palladium dichloride, triphenylphosphine, tricyclohexylphosphine, and bisdiphenylphosphinobutane. The reaction solvent used in step S1 is one or more of xylene, tetrahydrofuran, N-methylpyrrolidone, and pyridine.

The technical solution of the present invention is further illustrated below with reference to several specific examples.

Example 1:

(1-1) into a 500ml four-necked flask, 2.36g (0.01mol) of 1, 4-dibromobenzene (produced by Kagaku corporation), 1.45g (0.022mol) of malononitrile and 100ml of a xylene solution were placed, and while stirring, 0.5g of sodium butoxide was added, and after stirring at room temperature for 2 hours, palladium dichloride (PdCl) was added₂) 0.02g and 0.02g of tricyclohexylphosphine, heating to 140 ℃, refluxing and stirring for 20 hours, decompressing, collecting dimethylbenzene, cooling, filtering and recrystallizing to obtain 1.95g of intermediate product 1, 4-dipropylenedicyanobenzene (benzenedicarboxonitrile), wherein the yield is 95 percent and the melting point is 98 ℃.

(1-2) 1.92.00g of 1, 4-dipropylenedicyanobenzene was put into a four-necked flask containing 50ml of ethanol, 4.6g of phenylhydrazine was added under stirring, the mixture was refluxed for 3 hours, concentrated to about 20ml of ethanol in the reaction system, cooled to room temperature and filtered to obtain 4.02g of a bright yellow product, 1, 4-bis (5-imino-3-amino-1-phenyl-1H-pyrazol-4-yl) benzene, with a yield of 95% and a melting point of 156 ℃. The results of the magnetic resonance hydrogen spectroscopy are shown in FIG. 1.

¹HNMR(DMSO-d₆)：δ9.38(s,1H,-NH₂)；δ9.24(s,1H,＝NH)； δ7.86(s,2H,ArH)；δ7.69(s,2H,ArH)；δ7.23(s,2H,ArH)；δ6.86(s,1H, ArH)；δ2.00(s,1H,-CH)。

Example 2:

(2-1) adding 146g (1mol) of 1, 4-dichlorobenzene (the science and technology limit of Jiangsu Huaihe river) and 72.6(1.1mol) of malononitrile and 600ml of N-methylpyrrolidone solution into a 1L four-neck flask, stirring while adding 10g of cesium carbonate, stirring at room temperature for 4 hours, adding 5g of palladium dichloride and 5g of triphenylphosphine, heating to 125 ℃, refluxing and stirring for 20 hours, concentrating under reduced pressure to collect N-methylpyrrolidine, cooling, filtering, washing with water, recrystallizing to obtain 181.6g of intermediate product 1, 4-dipropylenedicyanobenzene (benzene-dipropylenedinitrile), wherein the yield is 90%;

(2-2) 180g of 1, 4-dipropylenedicyanobenzene was put into a 1L four-neck flask containing 700ml of ethanol, 358g of 4-chlorophenylhydrazine was added under stirring, and the mixture was refluxed for 3 hours, concentrated to about 400ml of ethanol in the reaction system, cooled to room temperature and filtered to obtain 354.23g of a yellow product, 1, 4-bis [ (5-imino-3-amino-1- (4-chlorophenyl) -1H-pyrazol-4-yl ] benzene, the yield was 96% and the melting point was 143 ℃.

Example 3:

(3-1) in a 1L four-necked flask, 118g (0.5mol) of 1, 4-dibromobenzene (limited science and technology, Jiangsu Huaihe river), 39.6(0.6mol) of malononitrile and 200ml of pyridine solution were added, 2g of sodium hydride was added while stirring, and after stirring at room temperature for 4 hours, palladium dichloride (PdCl) was added₂)3g and 2g of bis (diphenylphosphinobutane) are heated to 85 ℃, and after 24 hours of reflux stirring, pyridine is collected by decompression concentration, cooled, filtered, washed with water and recrystallized to obtain 96.8g of intermediate product 1, 4-dipropylenedicyanobenzene (benzene-dipropylenedinitrile), wherein the yield is 94%;

(3-2) 96.8g of 1, 4-dipropylenedicyanobenzene was put into a 1L four-necked flask containing 500ml of ethanol, 150g of 4-nitrophenylhydrazine (TCI Co.) was added thereto with stirring, and the mixture was refluxed for 3 hours, concentrated to about 200ml of ethanol in the reaction system, cooled to room temperature and filtered to obtain 229.6g of 1, 4-bis [ (5-imino-3-amino-1- (4-nitro-phenyl) -1H-pyrazol-4-yl ] benzene as a yellow product, the yield of which was 96% and the melting point of which was 167 ℃.

Example 4:

(4-1) A500 ml four-necked flask was charged with 32.98g (0.1mol) of 1, 4-diiodobenzene (Michelin Co.), 6.7g (0.101mol) of malononitrile and 200ml of a tetrahydrofuran solution, and 3g of sodium hydride was added thereto with stirring, and after stirring at room temperature for 1 hour, palladium dichloride (PdCl) was added thereto₂)3g and 2g of bis (diphenylphosphinobutane) are heated to 85 ℃, and after reflux stirring is carried out for 24 hours, pyridine is collected by decompression concentration, cooled, filtered, washed with water and recrystallized to obtain 20.2g of intermediate product 1, 4-dipropyldicyanobenzene (benzene-dipropylenedinitrile), wherein the yield is 98%;

(4-2) 20.2g of 1, 4-dipropylenedicyanobenzene was put into a 1L four-necked flask containing 300ml of ethanol, 23.9g of 4-methylphenylhydrazine (TCI Co.) was added thereto with stirring, and the mixture was refluxed for 3 hours, concentrated to about 200ml of ethanol in the reaction system, cooled to room temperature and filtered to obtain 41.9g of a yellow product, 1, 4-bis [ (5-imino-3-amino-1- (4-methyl-phenyl) -1H-pyrazol-4-yl ] benzene, with a yield of 95%.

Example 5:

(5-1) adding 11.8g (0.05mol) of 1, 4-dibromobenzene (Jiangsu Huaihe river science and technology Limited company), 77.26(0.11mol) of malononitrile and 300ml of N-methylpyrrolidone solution into a 500ml four-neck flask, stirring while adding 2g of potassium carbonate, stirring at room temperature for 2 hours, adding 1g of palladium dichloride and 2g of triphenylphosphine, heating to 125 ℃, refluxing and stirring for 10 hours, concentrating under reduced pressure, collecting N-methylpyrrolidine, cooling, filtering, washing with water, and recrystallizing to obtain 9.785g of intermediate product 1, 4-dipropylenedicyanobenzene (benzene-linked-dipropylenedinitrile), wherein the yield is 95%;

(5-2) 9.78g of 1, 4-dipropylenedicyanobenzene was put into a 500ml four-neck flask containing 100ml of ethanol, 11g of phenylhydrazine was added with stirring, the mixture was refluxed for 3 hours, concentrated to about 50ml of ethanol in the reaction system, cooled to room temperature and filtered to obtain 19.2g of 1, 4-bis [ (5-imino-3-amino-1-phenyl-1H-pyrazol-4-yl ] benzene, which is a yellow product, with a yield of 96%, a melting point of 230 ℃ C.