CN113061349B - Perylene pigment and preparation method thereof - Google Patents

Perylene pigment and preparation method thereof Download PDF

Info

Publication number
CN113061349B
CN113061349B CN202110315471.1A CN202110315471A CN113061349B CN 113061349 B CN113061349 B CN 113061349B CN 202110315471 A CN202110315471 A CN 202110315471A CN 113061349 B CN113061349 B CN 113061349B
Authority
CN
China
Prior art keywords
compound
structural formula
pigment
perylene
pigment blue
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110315471.1A
Other languages
Chinese (zh)
Other versions
CN113061349A (en
Inventor
李辰
尤利安·扎格拉尼亚尔斯基
段若蒙
赵雁飞
克劳斯·缪伦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan University of Technology
Original Assignee
Dongguan University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan University of Technology filed Critical Dongguan University of Technology
Priority to CN202110315471.1A priority Critical patent/CN113061349B/en
Priority to PCT/CN2021/086808 priority patent/WO2022198725A1/en
Publication of CN113061349A publication Critical patent/CN113061349A/en
Application granted granted Critical
Publication of CN113061349B publication Critical patent/CN113061349B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • 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
    • C09B57/00—Other synthetic dyes of known constitution

Abstract

The invention relates to the field of organic pigments, in particular toThe perylene pigment of the invention has a general formula as follows:
Figure DDA0002991000980000011
wherein Y is H or Cl; x is C ═ O, C ═ S, C ═ NH, BX, CR 'R', through introducing hydrogen bond, new chromophoric group, and electron withdrawing and electron pushing group combination, not only get blue compound, but also improve color stability and weatherability, the anti-flocculation property is good, can be used for heat sublimation, suitable for indoor and outdoor, the application prospect is extensive; the preparation method has the advantages of simple process, easy preparation and high yield, and meets the requirements of industrialized production and manufacturing.

Description

Perylene pigment and preparation method thereof
Technical Field
The invention relates to the technical field of organic pigments, in particular to a perylene pigment and a preparation method thereof.
Background
Perylene (perylene) based pigments, belonging to a class of high-grade organic pigments with excellent application properties, are a class of fused ring ketone pigments, which have been discovered as early as 1913. The perylene pigment has excellent weather fastness, light fastness and heat-resistant stability, and can be used as a functional organic pigment to be applied to the aspects of automobiles, metals, buildings, cosmetics, synthetic fibers, plastics and the like as a high-grade colorant; and can also be used as an organic semiconductor material in some high-tech applications.
Common perylene pigments are perylene diimides such as pigment red 123, pigment red 149, pigment red 178, pigment red 179, pigment red 190, pigment black 31, and pigment black 32. These pigments are synthesized from pigment red 224, i.e., perylenetetracarboxylic dianhydride, as the starting material. And pigment red 224 is obtained from pigment violet 29 by heating with concentrated sulfuric acid. It follows that the colour gamut of perylene pigments is mainly concentrated in red and black. To date, no perylene pigments of the blue series have been reported. The high-performance organic pigments of the blue series are few, and are mainly phthalocyanine blue, such as pigment blue 15 series, pigment blue 36, pigment blue 75, pigment blue 79 and other metal-containing complexes; and anthrone-based compounds such as pigment blue 60, pigment blue 22, pigment blue 64, and pigment blue 65. This is the largest market share of the pigment blue 15 series and pigment blue 60, which are the major pigments for the blue color of automobiles due to their excellent lightfastness, and are the major source of blue color required in color filters for LCD display devices. Compared with the pigment blue 15 series, the pigment blue 60 has darker color, is not as bright as the pigment blue 15, and has high production cost, so the application of the pigment blue is limited.
In addition, phthalocyanine blue and anthrone blue are large planar molecules with multiple aromatic rings, the intermolecular force is strong, aggregation and crystallization are easy, and the color difference of pigments can be caused by different molecular crystal structures, for example, pigment blue 15 series pigments are based on copper phthalocyanine, and the blue pigments can be modified in 11 ways to obtain 3 types of blue with different crystal forms, including: red pigment blue 15:0,15:1, and 15:2 of the alpha form, which is less thermally stable; thermally stable beta type green pigment blue 15:3 and 15: 4; and thermally stable gamma-type red pigment blue 15: 6. Therefore, most of phthalocyanine blue has poor flocculation resistance, and in outdoor application, the service life of the phthalocyanine blue is greatly shortened due to flocculation discoloration. The pigment blue 60 molecule contains hydrogen bonds, and the deflocculation performance is very outstanding.
On the other hand, phthalocyanine blue and anthrone blue are difficult to sublimate due to large molecular weight, and the pigment with ultrahigh purity needs to be sublimated and purified under ultrahigh vacuum and high temperature, so that the purification cost is high, and the pigment is not suitable for the application of sublimation pigment, such as thermal sublimation printing. While pigments suitable for sublimation printing are primarily disperse dyes, wherein the blue color is primarily anthraquinone-based, such as disperse blue 12, 28, 56, 60, 72, 73, 77, 334, 359, and 366. Most of the disperse dyes have molecular weight less than 400g/mol, but the light resistance, heat resistance and solvent resistance stability of the disperse dyes are poor, so that the application range of the disperse dyes is greatly limited.
Disclosure of Invention
In order to solve the problems, the invention provides a perylene pigment and a preparation method thereof, and the perylene pigment has small molecular weight, good flocculation resistance and stability, is blue, and can fill the vacancy of the prior high-performance organic blue pigment; the preparation method of the invention has simple process and easy preparation, and can meet the requirements of industrialized production and manufacturing.
The technical scheme adopted by the invention is as follows:
a perylene pigment having the formula:
Figure GDA0003219186290000021
wherein Y is H or Cl; x is C ═ O, C ═ S, C ═ NH, BX, CR' R "; x in BX is halogen, aryl, alkyl, alkoxy or hydroxyl, and R ' in CR ' R ' are each independently aryl or alkyl.
Specifically, perylene 3, 4-substituted imide groups are electron-withdrawing groups, and 9, 10-substituted diamine groups are electron-withdrawing groups, so that perylene with a push-pull structure is formed.
The preparation method of the perylene pigment comprises the following synthetic steps:
Figure GDA0003219186290000031
wherein R is1Is benzyl, aryl or alkyl, R2Is R', R3Is R', R4Namely X.
Specifically, the compound 1, aromatic primary amine or alkyl primary amine are added into N-methyl pyrrolidone, and the mixture is heated, reacted and purified under the nitrogen environment to obtain the dark blue compound 2.
Specifically, compound 2 is reacted with phosgene or triphosgene to give compound 3.
Specifically, compound 3 is heat treated with a base in a polar solvent to give compound 4.
Specifically, when R is1For benzyl, AlCl is added to a solution of compound 3 in dichloromethane3Stirring at room temperature, after reactionCompound 5 is obtained.
Specifically, when R is1In the case of benzyl, the toluene solution of 4 is heated and stirred to reflux, and then methyl sulfuric acid is slowly added to react to obtain a compound 6.
Specifically, compound 2 is reacted with a ketone or aldehyde to give compound 7, which is then heat-treated with a base in a polar solvent to give compound 8.
And reacting the compound 2 with boric acid or boron fluoride to obtain a compound 9.
The invention has the following beneficial effects:
1. the perylene pigment provided by the invention not only can obtain a blue compound, but also improves the stability and weather resistance of color by introducing hydrogen bonds, new chromophoric groups and combination of electron withdrawing groups and electron pushing groups, has good flocculation resistance, can be used for thermal sublimation, is suitable for indoor and outdoor, and has wide application prospect.
2. The preparation method of the invention has simple process and easy preparation, and meets the requirement of industrialized production and manufacturing.
Drawings
FIG. 1 shows absorption spectra of compounds 6, 4b and 5 synthesized in examples 1 to 3 in concentrated sulfuric acid;
FIG. 2 shows absorption spectra of vapor deposited films of compounds 6, 4b and 5 synthesized in examples 1 to 3.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The perylene pigment of the invention has a general formula:
Figure GDA0003219186290000041
wherein Y is H or Cl; x is C ═ O, C ═ S, C ═ NH, BX, CR' R ".
Specifically, perylene 3, 4-substituted imide groups are electron-withdrawing groups, and 9, 10-substituted diamine groups are electron-withdrawing groups, so that perylene with a push-pull structure is formed.
The perylene pigment improves the color stability and weather resistance by introducing hydrogen bonds and new chromophoric groups, has good metallic luster, is blue, has the molecular weight of less than 400, has good film forming property, is convenient for sublimation printing, can be applied to the aspects of automobile exterior paint, building exterior paint and the like, and has wide application prospect.
The invention will now be illustrated by means of specific preparation examples.
Example 1
Synthesis of pigment blue Compound 6, the structural formula is as follows:
Figure GDA0003219186290000051
the method comprises the following steps: synthesis of compound 2a, the structural formula of which is as follows:
Figure GDA0003219186290000052
adding the compound 1(10.0mmol,6.17g), 2, 4-dimethoxybenzylamine (50.0mmol,8.35g) and 4.0ml triethylamine into 100ml N-methylpyrrolidone, introducing nitrogen for protection, stirring at 90 ℃ for 30 minutes, adding the reaction solution obtained by stirring into a hydrochloric acid solution, filtering, washing with water, washing with methanol, and drying to obtain a dark blue crude product 2a, and purifying with a silica gel column to obtain a pure product 8g, wherein the yield is 85%.
2a Hydrogen spectra data as follows:
1H-NMR(δ(ppm),C2D2Cl4):3.56(s,6H,OCH3)；3.79(s,3H,OCH3)；3.86(s,6H,OCH3)；3.89(s,3H,OCH3)；4.31(s,4H,CH2)；5.34(s,2H,CH2)；6.33-6.52(m,8H)；6.89(d,1H,J＝8.4Hz)；6.96(s,2H)；7.12(d,2H,J＝8.2Hz)；8.52(s,2H).
step two: synthesis of compound 3a, the structural formula of which is as follows:
Figure GDA0003219186290000061
100ml of tetrahydrofuran suspension and triphosgene (6.0mmol,1.78g) were added to compound 2a (5.0mmol,4.70g), the reaction was refluxed for 1.5 hours under a nitrogen atmosphere, then the reaction solution was added to n-hexane (300ml), the precipitate was filtered to obtain a blue crude product, the obtained blue crude product was dissolved with a small amount of dichloromethane, slowly added to n-hexane (400ml), the obtained precipitate was filtered, and washed with n-hexane and methanol to obtain a violet product 4.54g, 3a, in 94% yield.
The hydrogen spectrum data of 3a are as follows:
1H-NMR(δ(ppm),DMSO-d6):3.69(s,3H,OCH3)；3.73(s,6H,OCH3)；3.84(s,3H,OCH3)；3.93(s,6H,OCH3)；5.10(s,2H,CH2)；5.15(d,2H,CH2,J＝16.9Hz)；5.38(d,2H,CH2,J＝16.5Hz)；6.31(dd,1H,J＝8.4Hz,J＝2.4Hz)；6.46(dd,2H,J＝8.5Hz,J＝2.3Hz)；6.58(d,1H,J＝2.4Hz)；6.67(d,2H,J＝2.4Hz)；6.85(d,1H,J＝8.4Hz)；7.13(s,2H)；7.17(d,2H,J＝8.5Hz)；8.35(s,2H).
step three: synthesis of compounds 4a and 4 a', the structural formulae of which are as follows:
Figure GDA0003219186290000062
to compound 3a (4.15mmol,4.0g) was added 10g of sodium hydroxide and 100ml of ethylene glycol, and after stirring at 170 ℃ for 24 hours, the reaction solution was neutralized with hydrochloric acid after cooling to room temperature, and the precipitate was filtered and washed with water to give black crude products 4a and 4 a', and 2.50 g of the product was obtained by passing through a silica gel column.
Step four: synthesis of compound 6, the structural formula of which is as follows:
Figure GDA0003219186290000071
heating a mixture of 2.5 g of the compounds 4a and 4 a' in a suspension of 100ml of toluene, stirring and refluxing vigorously, then slowly adding 4ml of methyl sulfuric acid, keeping refluxing for 6 hours, then cooling to room temperature, distilling under reduced pressure to remove the solvent, washing with a mixed solution of methanol and water in a ratio of 1: 1, then washing with any one solvent of methanol, tetrahydrofuran or dichloromethane until the eluent is clear to obtain a crude product, heating and dissolving the crude product in concentrated sulfuric acid, slowly heating water until precipitation appears, and filtering to obtain 1g of the compound 6 with a yield of 85%.
The hydrogen spectrum data for compound 6 are as follows:
1H-NMR(δ(ppm),D2SO4):7.80(d,2H,J＝8.6Hz)；8.67(d,2H,J＝9.0Hz)；8.86(d,2H,J＝9.6Hz)；9.51(d,2H,J＝9.2Hz).
example 2: synthesis of pigment blue compound 5, having the following structural formula:
Figure GDA0003219186290000072
compound 5 was prepared from 3a prepared in the above example using the following procedure, as follows:
to compound 3a (4.0mmol,3.86g) was added 200ml of dichloromethane solution and AlCl3(40.0mmol,5.33g), stirring at room temperature for 4 hours, distilling under reduced pressure to remove dichloromethane, washing with a mixed solution of methanol and water at a ratio of 1: 1, washing with methanol, drying to obtain a crude product, dissolving the crude product in tetrahydrofuran, filtering to remove insoluble substances,the solution was then poured into n-hexane, the precipitate was filtered and washed with methanol to give 1.9 g of compound 5 as a purple solid in 92% yield.
The hydrogen spectrum data for compound 5 are as follows:
1H-NMR(δ(ppm),DMSO-d6):7.02(s,2H)；8.34(s,2H)；11.54(s,2H,NH)；11.94(s,1H,NH).
example 3: synthesis of pigment blue Compound 4b, the structural formula is as follows:
Figure GDA0003219186290000081
the method comprises the following steps: synthesis of compound 2b, the structural formula of which is as follows:
Figure GDA0003219186290000082
to compound 1(5.0mmol,3.10g) was added 40% aqueous ethylamine (30.0mmol,3.5ml), 2ml triethylamine and 60ml N-methylpyrrolidone, stirred at 90 ℃ for 40 minutes under nitrogen protection, then the reaction was added to a mixture of water and concentrated hydrochloric acid in a ratio of 10 to 1, the precipitate was filtered, washed with water, then with methanol and dried, and purified with silica gel column to give 2.09 g of black compound 2b in 73% yield.
Compound 2b hydrogen spectra data are as follows:
1H-NMR(δ(ppm),C2D2Cl4):1.34(t,3H,CH3,J＝7.0Hz)；1.44(t,6H,CH3,J＝7.0Hz)；3.32(q,4H,CH2,J＝7.0Hz)；4.24(q,2H,CH2,J＝6.9Hz)；5.85(bs,2H,NH)；6.86(s,2H)；8.51(s,2H).
step two: synthesis of compound 3b, the structural formula of which is as follows:
Figure GDA0003219186290000083
compound 2b (3.0mmol,1.72g) was added to 60ml of anhydrous tetrahydrofuran and stirred under reflux, followed by the slow addition of triphosgene (3.3mmol,0.98g) and the reflux reaction was maintained under nitrogen for 1.5 hours, the reaction mixture was poured into 150ml of n-hexane, and the precipitate was filtered and purified by silica gel column to give 1.55 g of black compound 3b in 86% yield.
The hydrogen spectrum data for compound 3b are as follows:
1H-NMR(δ(ppm),C2D2Cl4):1.35(t,3H,CH3,J＝6.9Hz)；1.45(t,6H,CH3,J＝7.0Hz)；4.07-4.35(m,6H,CH2)；7.03(s,2H)；8.57(s,2H).
step three: synthesis of compound 4b, the structural formula of which is as follows:
Figure GDA0003219186290000091
compound 3b (2.0mmol,1.20g) was added to 4g of sodium hydroxide and 30ml of ethylene glycol solution, stirred at 170 ℃ for 2 hours, after cooling, the reaction solution was neutralized with hydrochloric acid, the precipitate was filtered and washed with water and methanol, 50ml of dichloromethane was added to the solid obtained and stirred for 1 hour, and 0.8 g of compound 4b as a black solid was obtained after filtration in 86% yield.
The hydrogen spectrum data for compound 4b are as follows:
1H-NMR(δ(ppm),D2SO4):1.43-1.50(m,9H,CH3)；4.60-4.79(m,6H,CH2)；8.17(d,2H,J＝9.0Hz)；8.83(d,2H,J＝8.3Hz)；9.18(d,2H,J＝10.6Hz)；9.84(d,2H,J＝9.5Hz)；.
example 4: synthesis of pigment blue compound 8, having the following structural formula:
Figure GDA0003219186290000092
the method comprises the following steps: synthesis of compound 2', the structural formula of which is as follows:
Figure GDA0003219186290000093
n- (2, 6-diisopropylphenyl) -1, 6, 7, 12-tetrachloro-9, 10-dibromo-3, 4-perylene imide (see WO2014147525, WO2014033622, and Organic Letters 2012,14, 5444-perylene 5447) (5.0mmol,3.89g), benzylamine (20.0mmol,2.14g) and triethylamine (1.21g) was added to 60ml of N-methylpyrrolidone and reacted at 90 ℃ for 30 minutes under nitrogen protection, and the reaction mixture was poured into water and hydrochloric acid 10: 1, the precipitate was filtered and purified by a silica gel column to obtain 3.53 g of a blue compound 2', and the yield was 85%.
The hydrogen spectrum data for compound 2' are as follows:
1H-NMR(δ(ppm),CD2Cl2):1.14(d,6H,CH3,3JHH＝6.8Hz)；1.15(d,6H,CH3,3JHH＝7.0Hz)；2.71-2.80(m,2H,CH)；4.42(d,4H,CH2,3JHH＝4.9Hz)；6.18(t,2H,NH,3JHH＝5.2Hz)；7.00(s,2H,CH)；7.26-7.37(m,12H)；7.51(dd,1H,CH,3JHH＝8.3Hz,3JHH＝7.1Hz)；8.57(s,2H,CH).
step two: synthesis of compound 7, the structural formula of which is as follows:
Figure GDA0003219186290000101
2' (1.69mmol,1.40g) was added to 60ml of anhydrous acetone, and trifluoroacetic acid was slowly added under stirring and maintained at reflux for 24 hours. After the solvent was distilled off under reduced pressure, the crude product was purified by a silica gel column to obtain 1.39 g of blue compound 7 in a yield of 95%.
The hydrogen spectrum data for compound 7 are as follows:
1H-NMR(δ(ppm),CD2Cl2):1.04(d,6H,CH3,3JHH＝6.8Hz)；1.05(d,6H,CH3,3JHH＝6.8Hz)；1.64(s,6H,CH3)；2.65(hept,2H,CH,3JHH＝6.8Hz)；4.78(m,4H,CH2Ph)；7.70(s,2H,CH)；7.22-7.43(m,13H)；8.45(s,2H,CH).
step three: synthesis of compound 8, the structural formula of which is as follows:
Figure GDA0003219186290000102
compound 7(1.5mmol,1.30g) was added to 5g of sodium hydroxide and 50ml of ethylene glycol solution, stirred at 170 ℃ for 24 hours, after cooling, the reaction solution was neutralized with hydrochloric acid, filtered to obtain a precipitate, washed with water and methanol, added to the obtained solid 50ml of dichloromethane and stirred for 1 hour, filtered to obtain 0.60 g of compound 8 as a black solid, with a yield of 55%.
The hydrogen spectra data for compound 8 are as follows:
1H-NMR(δ(ppm),CD2Cl4,393K):1.23(d,12H,CH3,3JHH＝6.8Hz)；1.73(s,6H,CH3)；2.83(hept,2H,CH,3JHH＝6.8Hz)；4.88(s,4H,CH2Ph)；6.82(bs,2H,CH)；7.32-7.46(m,13H,CH)；8.13(bs,2H,CH)；8.36(d,2H,CH,3JHH＝8.7Hz)；8.53(d,2H,CH,3JHH＝8.3Hz).
example 5: synthesis of pigment blue Compound 9, the structural formula is as follows:
Figure GDA0003219186290000111
the method comprises the following steps: synthesis of compound 2' a, having the following structural formula:
Figure GDA0003219186290000112
2' (2.0mmol,1.66g) was dissolved in 100ml of anhydrous dichloromethane and AlCl was added3(6.0mmol,0.80g), the reaction mixture was stirred at room temperature for 48 hours, the dichloromethane was removed by distillation under reduced pressure, and then the mixture was treated with methanol and water in a ratio of 1The crude product was dissolved in tetrahydrofuran, filtered to remove insoluble matter, the solution was poured into n-hexane, the precipitate was filtered, and washed with methanol to give 1.2 g of dark blue solid compound 2' a in 92% yield.
The hydrogen spectrum data for compound 2' a are as follows:
1H-NMR(δ(ppm),DMSO-d6):1.05(d,6H,CH3,3JHH＝6.7Hz)；1.06(d,6H,CH3,3JHH＝6.9Hz)；2.64-2.73(m,2H,CH)；7.06(s,2H,CH)；7.21(bs,4H,NH,3JHH＝5.2Hz)；7.32(d,2H,CH,3JHH＝7.7Hz)；7.45(dd,1H,CH,3JHH＝8.4Hz,3JHH＝6.9Hz)；8.35(s,2H,CH).
step two: synthesis of compound 9, the structural formula of which is as follows:
2' a (1.0mmol,0.65g) was added to 100ml of anhydrous dichloromethane to dissolve and BF3.OEt2(0.5ml) was added, the reaction mixture was stirred at room temperature for 30 minutes and then 1ml of triethylamine was added, after one hour the solvent was distilled off under reduced pressure, and after the crude product was purified by silica gel column to obtain 0.60 g of blue compound 9 in 89% yield.
The hydrogen spectrum data for compound 9 are as follows:
1H-NMR(δ(ppm),DMSO-d6):1.05(d,6H,CH3,3JHH＝6.9Hz)；1.07(d,6H,CH3,3JHH＝6.8Hz)；2.69(hept,2H,CH,3JHH＝6.4Hz)；7.26(s,2H,CH)；7.33(d,2H,CH,3JHH＝7.6Hz)；7.45(dd,1H,CH,3JHH＝8.4Hz,3JHH＝6.8Hz)；8.40(s,2H,CH)；8.96(bs,2H,NH).
referring to examples 1-5, the preparation method of the present invention has the advantages of simple process and easy preparation, and compared with the prior art in which the yield of the alkali fusion process is about 50%, the preparation method of the present invention has high yield and can meet the industrial production and preparation requirements.
As shown in the attached drawings 1-2, the perylene pigment prepared by the invention is blue, the light absorbed by the perylene pigment is moved to long wave, the color is more bright and beautiful, meanwhile, the organic blue pigment in the prior art only contains blue 15 and blue 60, the blue perylene pigment can greatly enrich the selection of the organic blue pigment, and the practicability is strong.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A perylene pigment comprising any of the following compounds:
a pigment blue compound 4b having the structural formula
Figure FDA0003629845560000011
A pigment blue compound 5 having the structural formula
Figure FDA0003629845560000012
Pigment blue compound 6 of the formula
Figure FDA0003629845560000013
A pigment blue compound 8 of the formula
Figure FDA0003629845560000014
And a pigment blue compound 9 having the structural formula
Figure FDA0003629845560000015
2. The perylene pigment of claim 1, wherein the perylene imide groups substituted at the 3, 4-positions are electron-withdrawing groups, and the diamine groups substituted at the 9, 10-positions are electron-withdrawing groups, thereby forming a perylene with a push-pull structure.
3. A process for preparing perylene pigments according to claim 1 or 2, wherein the pigment blue compounds 4b, 5 and 6 are synthesized by the following steps,
Figure FDA0003629845560000021
the structural formula of the compound 1 is
Figure FDA0003629845560000022
The structural formula of the compound 2a is
Figure FDA0003629845560000023
The structural formula of the compound 2b is
Figure FDA0003629845560000024
The structural formula of the compound 3a is
Figure FDA0003629845560000031
The structural formula of the compound 3b is
Figure FDA0003629845560000032
The structural formulas of the compounds 4a and 4 a' are shown in the specification
Figure FDA0003629845560000033
Wherein the pigment blue compounds 8 and 9 are synthesized by the following steps,
adding N- (2, 6-diisopropylphenyl) -1, 6, 7, 12-tetrachloro-9, 10-dibromo-3, 4-perylene bisimide, benzylamine and triethylamine into N-methylpyrrolidone, reacting under the protection of nitrogen, pouring the reaction mixture into a mixed solution of water and hydrochloric acid, precipitating, filtering, and purifying by using a silica gel column to obtain a blue compound 2', wherein the structural formula is shown in the specification
Figure FDA0003629845560000041
Adding 2' into anhydrous acetone, adding trifluoroacetic acid under stirring, refluxing for 24 hr, distilling under reduced pressure to remove solvent, and purifying the crude product with silica gel column to obtain compound 7 with structural formula
Figure FDA0003629845560000042
Adding a compound 7 into a sodium hydroxide and ethylene glycol solution, stirring for 24 hours at 170 ℃, cooling, neutralizing a reaction solution with hydrochloric acid, filtering to obtain a precipitate, washing with water and methanol, adding 50ml of dichloromethane into the obtained solid, stirring for 1 hour, and filtering to obtain a compound 8;
adding 2' into anhydrous dichloromethane for dissolving, and adding AlCl3The reaction mixture was stirred at room temperature for 48 hours, and after removing methylene chloride by distillation under reduced pressure, the reaction mixture was washed with a mixture of methanol and water, and then with waterWashing with methanol, drying to obtain crude product, dissolving in tetrahydrofuran, filtering to remove insoluble substances, pouring the solution into n-hexane, precipitating, filtering, and washing with methanol to obtain compound 2' a with structural formula
Figure FDA0003629845560000043
Adding 2' a into anhydrous dichloromethane for dissolving, and adding BF3.OEt2The reaction mixture was stirred at room temperature for 30 minutes, triethylamine was added, after one hour, the solvent was removed by distillation under reduced pressure, and the crude product was purified by a silica gel column to obtain compound 9.
4. The method of claim 3, wherein the compound 1 and the aromatic amine or alkylamine are added into N-methylpyrrolidone, and the mixture is stirred with nitrogen gas, heated, reacted and purified to obtain the compound 2a or 2 b.
5. The method of claim 3, wherein the compound 2a is reacted with phosgene or triphosgene to obtain a compound 3 a; reacting compound 2b with phosgene or triphosgene to give compound 3 b.
6. The process of claim 3 wherein the compound 3a is heat treated with a base in a polar solvent to provide compounds 4a and 4 a'; and (3) heating the compound 3b by using alkali in a polar solvent to obtain a pigment blue compound 4 b.
7. A process for preparing perylene pigments according to claim 3, wherein a solution of compound 3a in methylene chloride is added to AlCl3Then, the mixture was stirred at room temperature to react, thereby obtaining a pigment blue compound 5.
8. The preparation method of perylene pigment according to claim 3, wherein the toluene solution of the compounds 4a and 4 a' is heated and stirred to reflux, and then methyl sulfuric acid is slowly added to react to obtain the pigment blue compound 6.
CN202110315471.1A 2021-03-24 2021-03-24 Perylene pigment and preparation method thereof Active CN113061349B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202110315471.1A CN113061349B (en) 2021-03-24 2021-03-24 Perylene pigment and preparation method thereof
PCT/CN2021/086808 WO2022198725A1 (en) 2021-03-24 2021-04-13 Perylene pigment and preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110315471.1A CN113061349B (en) 2021-03-24 2021-03-24 Perylene pigment and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113061349A CN113061349A (en) 2021-07-02
CN113061349B true CN113061349B (en) 2022-06-17

Family

ID=76561972

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110315471.1A Active CN113061349B (en) 2021-03-24 2021-03-24 Perylene pigment and preparation method thereof

Country Status (2)

Country Link
CN (1) CN113061349B (en)
WO (1) WO2022198725A1 (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6403797B1 (en) * 2000-12-22 2002-06-11 Bayer Corporation Process for the preparation of perylene pigments
DE102008061452A1 (en) * 2007-12-12 2010-07-08 Langhals, Heinz, Prof. Dr. Imidazoloperylenbisimide
US9630973B2 (en) * 2012-08-30 2017-04-25 Basf Se Double donor functionalisation of the peri-positions of perylene and naphthalene monoimide via versatile building blocks
TWI670331B (en) * 2014-05-09 2019-09-01 德商巴地斯顏料化工廠 Cyanated perylene compounds

Also Published As

Publication number Publication date
CN113061349A (en) 2021-07-02
WO2022198725A1 (en) 2022-09-29

Similar Documents

Publication Publication Date Title
Keller et al. Hydrogen‐bonding and phase‐forming behavior of a soluble quinacridone
CN113061349B (en) Perylene pigment and preparation method thereof
FR2713234A1 (en) New derivatives of triphenodioxazine, their preparation and their use as pigments.
KR20130104551A (en) Water-soluble perylene compounds having light interception and shift wavelength and process for producing the same
JP4962812B2 (en) Phthalocyanine compound and method for producing the same, and coloring composition containing the phthalocyanine compound
EP3008133A2 (en) Carbazole dioxazine pigment and a method for its preparation
CA1094060A (en) Method for the preparation of 2-hydroxybenzathrone and of the substitution derivatives thereof
CN114516817B (en) Chemical intermediate and preparation method thereof
JPWO2020045200A1 (en) Alkylene compound, quinophthalone compound and quinophthalone mixture
US3821195A (en) Synthesis of cyanoazo dyes
US2043985A (en) 1-nitro-anthraquinonyl-6-amino compounds and their production
US3936477A (en) Blue anthraquinoid disperse dyes, their production and use
CN106946918A (en) Asymmetric pyrroles's fluorescent dye of naphthalene nucleus fusion fluorine boron two and preparation method thereof
EP2989102B1 (en) Carbazole dioxazine pigments
CN1597788A (en) Red anthraquinone dispersion dye
CN109096790B (en) Synthetic method of perylene red dye perylene red 620
CN114605409B (en) Production and preparation method of 4-hydroxy-1, 5-naphthyridine ligand
CN113861180A (en) Saccharin derivative organic pigment and preparation method thereof
CN110791117A (en) Aromatic imino-substituted DPP (dipeptidyl peptidase) organic pigment and synthesis method and application thereof
US2353010A (en) Compounds of the anthraquinone series
CN115260197A (en) Fused ring compound and preparation method and application thereof
TW202030266A (en) Xanthene dye, coloring composition containing the dye, colorant for color filter, and color filter
KR20220113687A (en) Quinophthalone compound, pigment composition and color filter
US1819014A (en) New vat dyestuffs of the dianthraquinonylamine-carbazole series
US2080106A (en) Process for the preparation of anthraquinone compounds and a product produced thereby

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant