CN102167701B - Fluorine-containing diphenyl-pyrrolo-pyrrolidinedione (DPP) pigments and preparation method thereof - Google Patents
Fluorine-containing diphenyl-pyrrolo-pyrrolidinedione (DPP) pigments and preparation method thereof Download PDFInfo
- Publication number
- CN102167701B CN102167701B CN2011100472244A CN201110047224A CN102167701B CN 102167701 B CN102167701 B CN 102167701B CN 2011100472244 A CN2011100472244 A CN 2011100472244A CN 201110047224 A CN201110047224 A CN 201110047224A CN 102167701 B CN102167701 B CN 102167701B
- Authority
- CN
- China
- Prior art keywords
- formula
- fluorine
- compound shown
- hours
- group
- 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
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 26
- 239000011737 fluorine Substances 0.000 title claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000000049 pigment Substances 0.000 title abstract description 10
- 238000002360 preparation method Methods 0.000 title description 2
- AQDXOENJKIIKFC-UHFFFAOYSA-N 2,3-diphenyl-1,4-dihydropyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound O=C1C(=O)NC2=C1NC(C=1C=CC=CC=1)=C2C1=CC=CC=C1 AQDXOENJKIIKFC-UHFFFAOYSA-N 0.000 title 1
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 11
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 4
- 238000001035 drying Methods 0.000 claims 3
- 238000002386 leaching Methods 0.000 claims 3
- 238000000605 extraction Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000001953 recrystallisation Methods 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 16
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 12
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 5
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000005457 ice water Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 5
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- -1 lactam compound Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YXWJGZQOGXGSSC-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzonitrile Chemical compound FC1=C(F)C(F)=C(C#N)C(F)=C1F YXWJGZQOGXGSSC-UHFFFAOYSA-N 0.000 description 1
- UIIJZQVROQHLAP-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-yloxy)butane;sodium Chemical compound [Na].CCC(C)(C)OC(C)(C)CC UIIJZQVROQHLAP-UHFFFAOYSA-N 0.000 description 1
- YRUNCQNKZIQTEO-UHFFFAOYSA-N 3,4,5-trifluorobenzoyl chloride Chemical compound FC1=CC(C(Cl)=O)=CC(F)=C1F YRUNCQNKZIQTEO-UHFFFAOYSA-N 0.000 description 1
- CQXZSEXZQVKCHW-UHFFFAOYSA-N 3,5-difluorobenzonitrile Chemical compound FC1=CC(F)=CC(C#N)=C1 CQXZSEXZQVKCHW-UHFFFAOYSA-N 0.000 description 1
- CZKLEJHVLCMVQR-UHFFFAOYSA-N 4-fluorobenzoyl chloride Chemical compound FC1=CC=C(C(Cl)=O)C=C1 CZKLEJHVLCMVQR-UHFFFAOYSA-N 0.000 description 1
- BPMBNLJJRKCCRT-UHFFFAOYSA-N 4-phenylbenzonitrile Chemical compound C1=CC(C#N)=CC=C1C1=CC=CC=C1 BPMBNLJJRKCCRT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical class C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- QKWILNTYPDJSME-UHFFFAOYSA-N pyrrolo[3,4-c]pyrrole-3,6-dione Chemical class C1=NC(=O)C2=C1C(=O)N=C2 QKWILNTYPDJSME-UHFFFAOYSA-N 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/004—Diketopyrrolopyrrole dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
本发明涉及一种含氟1，4-二酮吡咯[3，4-C]并吡咯衍生物，其结构如式I所示。本发明所揭示的含氟1，4-二酮吡咯[3，4-C]并吡咯衍生物可用作颜料，其丰富了现有DPP类颜料的色谱。
Description
技术领域 technical field
本发明涉及一种含氟吡咯并吡咯衍生物，具体地说，涉及一种含氟1，4-二酮吡咯[3，4-C]并吡咯衍生物。The present invention relates to a fluorine-containing pyrrolopyrrole derivative, in particular to a fluorine-containing 1,4-diketopyrrolo[3,4-C]pyrrole derivative.
背景技术 Background technique
1，4-二酮吡咯[3，4-C]并吡咯类化合物为一种高性能颜料(简称DPP类颜料)。DPP类颜料具有高的着色强度、良好的流动性、分散性和耐酸/碱性和耐溶剂性，非常适用于汽车漆、塑料和高档工业涂料。1,4-diketopyrrole[3,4-C]pyrrole compounds are high-performance pigments (DPP pigments for short). DPP pigments have high tinting strength, good fluidity, dispersibility and acid/alkali and solvent resistance, and are very suitable for automotive paint, plastics and high-grade industrial coatings.
然而，现有DPP类颜料的色谱基本上为红光，色谱较窄，尚不令人满意。However, the chromatogram of the existing DPP pigments is basically red, and the chromatogram is relatively narrow, which is not satisfactory yet.
发明内容 Contents of the invention
本发明的发明人在现有1，4-二酮吡咯[3，4-C]并吡咯类化合物中引入氟原子，获得一种新颖的含氟1，4-二酮吡咯[3，4-C]并吡咯衍生物，发现其色光为黄光红色，丰富了现有DPP类颜料的色谱。The inventors of the present invention introduced fluorine atoms into existing 1,4-diketopyrrole[3,4-C]pyrrole compounds to obtain a novel fluorine-containing 1,4-diketopyrrole[3,4- C] pyrrole derivatives, found that its shade is yellowish red, which enriches the chromatogram of existing DPP pigments.
本发明所述的含氟1，4-二酮吡咯[3，4-C]并吡咯衍生物，其结构如式I所示：The structure of the fluorine-containing 1,4-diketopyrrole [3,4-C] pyrrole derivative described in the present invention is shown in formula I:
式I中，A和B分别独立选自：芳环基、杂环基、含氟芳环基或含氟杂环基杂环基中一种，且A和B中至少有一个为含氟芳环基或含氟杂环基杂环基；In formula I, A and B are independently selected from one of: aromatic ring group, heterocyclic group, fluorine-containing aromatic ring group or fluorine-containing heterocyclic group heterocyclic group, and at least one of A and B is a fluorine-containing aromatic ring group. Cyclic group or fluorine-containing heterocyclic heterocyclic group;
其中，所说的杂环基或含氟芳环基的杂原子选自：N、O或S中一种或二种以上(含二种)，杂原子的个数为1～3的整数。Wherein, the heteroatoms of the heterocyclic group or fluorine-containing aromatic ring group are selected from one or more than two (including two types) of N, O or S, and the number of heteroatoms is an integer of 1-3.
本发明还提供一种制备式I所示化合物的方法，其主要步骤是：由内酰胺类化合物(其结构如式II所示)与相应的腈(BCN)反应，制得目标物(式I所示化合物)。The present invention also provides a method for preparing the compound shown in formula I, the main steps of which are: reacting the lactam compound (its structure as shown in formula II) with the corresponding nitrile (BCN) to obtain the target compound (formula I indicated compounds).
式II中，R为烷基或芳(香)基(优选的R是C1～C6直链或支链烷基，更优选的R是C1～C3直链或支链烷基)；A的定义与前文所述相同。In formula II, R is an alkyl group or an aromatic (aromatic) group (preferably R is a C 1 to C 6 straight chain or branched chain alkyl, more preferably R is a C 1 to C 3 straight chain or branched chain alkyl) ; The definition of A is the same as described above.
具体实施方式 Detailed ways
在本发明一个优选的技术方案中，A和B分别独立选自：C6～C20芳环基或含氟的C6～C20芳环基一种，且A和B中至少有一个为含氟的C6～C20芳环基；In a preferred technical solution of the present invention, A and B are independently selected from one of C 6 -C 20 aromatic ring groups or fluorine-containing C 6 -C 20 aromatic ring groups, and at least one of A and B is Fluorine-containing C 6 -C 20 aromatic ring group;
更优选的技术方案是，A和B分别独立选自：C6～C12芳环基或含氟的C6～C12芳环基一种，且A和B中至少有一个为含氟的C6～C12芳环基；A more preferred technical solution is that A and B are independently selected from: C 6 -C 12 aromatic ring groups or C 6 -C 12 aromatic ring groups containing fluorine, and at least one of A and B is fluorine-containing C 6 ~C 12 aromatic ring group;
最佳的技术方案是，A和B分别独立选自：苯基、联苯基、萘基、式III所示基团、式IV所示基团、式V所示基团或式VI所示基团中一种，且A和B中至少有一个为式III、IV、V或VI所示基团：The best technical solution is that A and B are independently selected from: phenyl, biphenyl, naphthyl, the group shown in formula III, the group shown in formula IV, the group shown in formula V or the group shown in formula VI One of the groups, and at least one of A and B is the group shown in formula III, IV, V or VI:
其中：m为1～7的整数；n为1～5的整数；p为0～5的整数、q为0～4的整数，且p和q不同时为零；曲线所标处为取代位置。Among them: m is an integer from 1 to 7; n is an integer from 1 to 5; p is an integer from 0 to 5, q is an integer from 0 to 4, and p and q are not zero at the same time; the position marked by the curve is the substitution position .
本发明所提供的制备式I所示化合物(目标化合物)的方法，其合成路线如下所示：The method for the compound (target compound) shown in the preparation formula I provided by the present invention, its synthetic route is as follows:
具体包括如下步骤：Specifically include the following steps:
(1)在0℃下，向式VIII所示化合物(具体如乙酰乙酸乙酯等)的NaOH溶液中(质量浓度为10％～20％，)滴加式VII所示化合物，滴加完毕，在室温(20℃～30℃)状态保持至少1小时，再加入氯化铵，搅拌至少0.5小时后，依次经萃取、干燥及减压蒸馏得到式IX所示化合物；(1) At 0°C, add the compound shown in the formula VII dropwise in the NaOH solution (mass concentration is 10% to 20%) of the compound shown in the formula VIII (specifically, such as ethyl acetoacetate, etc.), and the dropwise addition is completed, Keep it at room temperature (20°C-30°C) for at least 1 hour, then add ammonium chloride, stir for at least 0.5 hours, then extract, dry and distill under reduced pressure to obtain the compound shown in formula IX;
(2)在碱性条件下，向式IX所示化合物的乙醇溶液中滴加溴乙酸乙酯，回流至少24小时后，过滤掉固体无机碱或盐，并用乙醇洗涤无机盐盐，滤液蒸除溶剂，减压蒸馏得到式X所示化合物；(2) Under alkaline conditions, add ethyl bromoacetate dropwise to the ethanol solution of the compound shown in formula IX, after refluxing for at least 24 hours, filter off the solid inorganic base or salt, and wash the inorganic salt with ethanol, and the filtrate is evaporated Solvent, distillation under reduced pressure obtains the compound shown in formula X;
(3)将式X所示化合物与乙酸铵在乙酸中回流至少20小时，反应液倒入冰水中，过滤，洗涤滤饼，滤饼用二氯甲烷重结晶后得到式II所示化合物；(3) Reflux the compound shown in formula X and ammonium acetate in acetic acid for at least 20 hours, pour the reaction solution into ice water, filter, wash the filter cake, and recrystallize the filter cake with dichloromethane to obtain the compound shown in formula II;
(4)在有惰性气体(如氮气等)存在条件下，将式II所示化合物与腈类化合物(BCN，其中B的定义与前文所述相同)于叔戊醇钠的叔戊醇溶液中回流至少6小时，然后将所得反应液加入到由甲醇、水和乙酸组成的混合溶液中(质子化)，过滤并洗涤滤饼，干燥后得到目标化合物(式I所示化合物)。(4) In the presence of an inert gas (such as nitrogen, etc.), the compound shown in the formula II and the nitrile compound (BCN, wherein the definition of B is the same as described above) in a tert-amyl alcohol solution of sodium tert-amyloxide Reflux for at least 6 hours, then add the resulting reaction solution into a mixed solution consisting of methanol, water and acetic acid (protonation), filter and wash the filter cake, and dry to obtain the target compound (compound shown in formula I).
本发明所揭示的含氟1，4-二酮吡咯[3，4-C]并吡咯衍生物可用作颜料，其丰富了现有DPP类颜料的色谱。The fluorine-containing 1,4-diketopyrrole[3,4-C]pyrrole derivative disclosed in the present invention can be used as a pigment, which enriches the color spectrum of existing DPP pigments.
下面通过实施例对本发明作进一步阐述，所列实施例并不限制本发明的保护范围。The present invention is described further below by embodiment, listed embodiment does not limit protection scope of the present invention.
在下列实施例中。所说的室温是20℃～30℃in the following examples. Said room temperature is 20℃～30℃
实施例1Example 1
(1)质量浓度为15％的氢氧化钠水溶液150ml在冰浴下降温至0℃，然后加入乙酰乙酸乙酯(13.00g，0.1mol)，机械搅拌下，慢慢滴加苯甲酰氯(15.47g，0.11mol)到以上混合液中，滴完毕后，升温至室温，TLC跟踪反应至终点(反应时间约为1小时，硅胶板，展开剂乙酸乙酯∶石油醚＝1∶1(v/v))，加入氯化铵(5.30g，0.1mol)，搅拌0.5h后，石油醚萃取(30ml×3)水相，合并有机相，无水硫酸镁干燥后，减压蒸馏，得到无色油状物15.99g，结构如式IX-1所示，产率83.2％；(1) 150ml of aqueous sodium hydroxide solution with a mass concentration of 15% was cooled to 0°C in an ice bath, then ethyl acetoacetate (13.00g, 0.1mol) was added, and under mechanical stirring, benzoyl chloride (15.47 g, 0.11mol) into the above mixed solution, after the drop is complete, warm up to room temperature, TLC tracking reaction to the end point (reaction time is about 1 hour, silica gel plate, developer ethyl acetate: petroleum ether=1: 1 (v/ v)), add ammonium chloride (5.30g, 0.1mol), stir for 0.5h, extract the aqueous phase with petroleum ether (30ml×3), combine the organic phases, dry over anhydrous magnesium sulfate, and distill under reduced pressure to obtain colorless 15.99 g of oil, the structure is shown in formula IX-1, and the yield is 83.2%;
1H-NMR(400Hz，CDCl3)：δ＝1.23-1.27(t，3H)，3.99(s，2H)，4.19-4.28(m，2H)，7.46-7.50(t，2H，)，7.56-7.61(t，1H)，7.93-7.97(t，2H，)；13C-NMR：δ＝14.1，48.2，61.5，128.4，128.7，133.5，133.9，170.1，190.5；MS：M+＝192.1。 1 H-NMR (400Hz, CDCl 3 ): δ=1.23-1.27(t, 3H), 3.99(s, 2H), 4.19-4.28(m, 2H), 7.46-7.50(t, 2H,), 7.56- 7.61 (t, 1H), 7.93-7.97 (t, 2H,); 13 C-NMR: δ = 14.1, 48.2, 61.5, 128.4, 128.7, 133.5, 133.9, 170.1, 190.5; MS: M + = 192.1.
(2)式IX-1所示化合物(10.19g，0.053mol)、K2CO3(7.62g，0.055mol)与溴乙酸乙酯(9.02g，0.054mol)悬浮于100ml乙醇溶液中，加热回流24h。然后冷却到室温，过滤掉固体物质，并用乙醇洗涤固体，合并乙醇溶液，减压蒸馏，得到无色油状物11.73g，结构如式X-1所示，产率79.5％。(2) Suspend the compound shown in formula IX-1 (10.19g, 0.053mol), K 2 CO 3 (7.62g, 0.055mol) and ethyl bromoacetate (9.02g, 0.054mol) in 100ml ethanol solution, heat to reflux 24h. Then cool to room temperature, filter off the solid matter, wash the solid with ethanol, combine the ethanol solutions, and distill under reduced pressure to obtain 11.73 g of a colorless oily substance, the structure of which is shown in Formula X-1, and the yield is 79.5%.
1H-NMR(400Hz，CDCl3)：δ＝1.15-1.19(t，3H)，1.22-1.26(t，3H)，3.00-3.14(m，2H)，4.12-4.18(m4H)，4.86-4.90(t，1H)，7.49-7.53(t，2H)，7.60-7.63(t，1H)，8.04-8.06(t，2H)；13C-NMR：14.1，35.2，49.1，61.3，128.6，128.8，133.5，135.5，169.9，173.3，195.1；MS：M+＝278.3。 1 H-NMR (400Hz, CDCl 3 ): δ=1.15-1.19(t, 3H), 1.22-1.26(t, 3H), 3.00-3.14(m, 2H), 4.12-4.18(m4H), 4.86-4.90 (t, 1H), 7.49-7.53(t, 2H), 7.60-7.63(t, 1H), 8.04-8.06(t, 2H); 13 C-NMR: 14.1, 35.2, 49.1, 61.3, 128.6, 128.8, 133.5, 135.5, 169.9, 173.3, 195.1; MS: M + = 278.3.
(3)式X-1所示化合物(11.13g，0.04mol)和醋酸铵(12.31g，0.16mol)在50ml乙酸中回流20h，TLC控制反应终点。然后反应物倒入200ml冰水中，立刻有大量浅黄色固体析出，过滤，用冰水洗涤滤饼，干燥后，用二氯甲烷重结晶，得到7.56白色固体，结构如式II-1所示，产率81.7％；(3) The compound represented by formula X-1 (11.13 g, 0.04 mol) and ammonium acetate (12.31 g, 0.16 mol) were refluxed in 50 ml of acetic acid for 20 h, and the end point of the reaction was controlled by TLC. Then the reactant was poured into 200ml of ice water, and a large amount of light yellow solid was precipitated immediately, filtered, and the filter cake was washed with ice water, dried, and recrystallized with dichloromethane to obtain 7.56 g of white solid, the structure of which was shown in formula II-1, Yield 81.7%;
1H-NMR(400Hz，CDCl3)：δ＝1.03-1.07(t，3H)，3.33-3.35(d，2H)，3.92-3.98(m，2H)，7.40-7.47(m，3H)，7.54-7.58(m，2H)，10.64(br s，1H)；13C-NMR：δ＝14.4，48.2，61.1，127.8，128.5，132.3，133.9，168.8，192.7；MS：M+＝231.1；mp：180-182℃。 1 H-NMR (400Hz, CDCl 3 ): δ=1.03-1.07(t, 3H), 3.33-3.35(d, 2H), 3.92-3.98(m, 2H), 7.40-7.47(m, 3H), 7.54 -7.58 (m, 2H), 10.64 (br s, 1H); 13 C-NMR: δ = 14.4, 48.2, 61.1, 127.8, 128.5, 132.3, 133.9, 168.8, 192.7; MS: M + = 231.1; mp: 180-182°C.
(4)在氮气保护下，将金属钠(0.92g，0.04mol)加入到30ml叔戊醇中，然后加入催化量的FeCl3，加热回流，2h后钠反应完毕，加入苯腈(2.06g，0.02mol)，式II-1所示化合物(4.62g，0.02mol)溶解到20ml叔戊醇中，慢慢滴加到上述溶液中，2h滴加完毕。然后在回流状态下保持5h。反应液冷却到60℃，加入由甲醇、水和乙酸组成的混合溶液50ml，室温搅拌2h后，回流2h，过滤，用热的甲醇和水洗涤滤饼，得到黄光红色固体4.58g，结构如式I-1所示，产率79.9％。(4) Under the protection of nitrogen, metal sodium (0.92g, 0.04mol) was added to 30ml of tert-amyl alcohol, then a catalytic amount of FeCl 3 was added, and heated to reflux. After 2h, the sodium reaction was completed, and benzonitrile (2.06g, 0.02mol), the compound represented by formula II-1 (4.62g, 0.02mol) was dissolved in 20ml of tert-amyl alcohol, and slowly added dropwise to the above solution, and the dropwise addition was completed within 2 hours. Then keep it under reflux for 5h. The reaction solution was cooled to 60°C, 50ml of a mixed solution consisting of methanol, water and acetic acid was added, stirred at room temperature for 2 hours, refluxed for 2 hours, filtered, and the filter cake was washed with hot methanol and water to obtain 4.58g of a yellowish red solid with the structure as As shown in formula I-1, the yield is 79.9%.
实施例2Example 2
在氮气保护下，将金属钠(0.92g，0.04mol)加入到30ml叔戊醇中，然后加入催化量的FeCl3，加热回流，2h后钠反应完毕，加入对苯基苯腈(3.58g，0.02mol)，式II-1所示化合物(4.62g，0.02mol)溶解到20ml叔戊醇中，慢慢滴加到上述溶液中，2h滴加完毕。然后在回流状态下继续反应5h。反应液冷却到60℃，加入甲醇、水和乙酸的混合溶液50ml，室温搅拌2h后，回流2h，过滤，用热的甲醇和水洗涤滤饼，得到紫光红色固体5.88g，结构如式I-2所示，产率80.7％；Under the protection of nitrogen, metal sodium (0.92g, 0.04mol) was added to 30ml of tert-amyl alcohol, then a catalytic amount of FeCl 3 was added, and heated to reflux. After 2h, the sodium reaction was completed, and p-phenylbenzonitrile (3.58g, 0.02mol), the compound represented by formula II-1 (4.62g, 0.02mol) was dissolved in 20ml of tert-amyl alcohol, and slowly added dropwise to the above solution, and the dropwise addition was completed within 2 hours. Then the reaction was continued for 5h under reflux. The reaction solution was cooled to 60°C, 50ml of a mixed solution of methanol, water and acetic acid was added, stirred at room temperature for 2h, refluxed for 2h, filtered, and the filter cake was washed with hot methanol and water to obtain 5.88g of a purple-red solid, the structure of which was shown in formula I- 2, yield 80.7%;
实施例3Example 3
在氮气保护下，将金属钠(0.92g，0.04mol)加入到30ml叔戊醇中，然后加入催化量的FeCl3，加热回流，2h后钠反应完毕，加入噻吩腈(2.18g，0.02mol)，式II-1所示化合物(4.62g，0.02mol)溶解到20ml叔戊醇中，慢慢滴加到上述溶液中，2h滴加完毕。然后在回流状态下继续反应5h。反应液冷却到60℃，加入甲醇、水和乙酸的混合溶液50ml，室温搅拌2h后，回流2h，过滤，用热的甲醇和水洗涤滤饼，得到红色固体4.54g，结构如式I-3所示，产率77.2％。Under the protection of nitrogen, metal sodium (0.92g, 0.04mol) was added to 30ml of tert-amyl alcohol, then a catalytic amount of FeCl 3 was added, and heated to reflux. After 2h, the sodium reaction was completed, and thiophenonitrile (2.18g, 0.02mol) was added , the compound represented by formula II-1 (4.62 g, 0.02 mol) was dissolved in 20 ml of tert-amyl alcohol, and slowly added dropwise to the above solution, and the dropwise addition was completed within 2 hours. Then the reaction was continued for 5h under reflux. The reaction solution was cooled to 60°C, 50ml of a mixed solution of methanol, water and acetic acid was added, stirred at room temperature for 2 hours, refluxed for 2 hours, filtered, and the filter cake was washed with hot methanol and water to obtain 4.54g of a red solid, the structure of which was shown in formula I-3 As shown, the yield is 77.2%.
实施例4Example 4
(1)质量浓度15％的氢氧化钠水溶液150ml在冰浴下降温至0℃，然后加入乙酰乙酸乙酯(13.00g，0.1mol)，机械搅拌下，慢慢滴加对氟苯甲酰氯(15.90g，0.11mol)到以上混合液中，滴加完毕后，升温至室温，TLC跟踪反应至终点(反应时间约为1小时，硅胶板，乙酸乙酯∶石油醚＝1∶1(v/v))，加入氯化铵(5.30g，0.1mol)，搅拌0.5h后，石油醚萃取(30ml×3)水相，合并有机相，无水硫酸镁干燥后，减压蒸馏，得到浅黄色油状物17.02g，结构式IX-2所示，产率81.0％；(1) 150ml of aqueous sodium hydroxide solution with a mass concentration of 15% was cooled to 0°C in an ice bath, then ethyl acetoacetate (13.00g, 0.1mol) was added, and under mechanical stirring, p-fluorobenzoyl chloride was slowly added dropwise ( 15.90g, 0.11mol) into the above mixed solution, after the dropwise addition, the temperature was raised to room temperature, and TLC tracked the reaction to the end point (the reaction time was about 1 hour, silica gel plate, ethyl acetate: petroleum ether=1: 1 (v/ v)), add ammonium chloride (5.30g, 0.1mol), stir for 0.5h, extract the aqueous phase with petroleum ether (30ml×3), combine the organic phases, dry over anhydrous magnesium sulfate, and distill under reduced pressure to obtain light yellow 17.02 g of oil, represented by structural formula IX-2, with a yield of 81.0%;
1H-NMR(400Hz，CDCl3)：δ＝1.21-1.25(t，3H)，3.97(s，2H)，4.15-4.21(m，2H)，7.10-7.14(t，2H，)，7.96-7.98(d，2H)；13C-NMR：δ＝14.09，45.96，61.55，115.86.131.39，167.39，164.44，167.38，191.03，191.07；MS：M+＝210.1。 1 H-NMR (400Hz, CDCl 3 ): δ=1.21-1.25(t, 3H), 3.97(s, 2H), 4.15-4.21(m, 2H), 7.10-7.14(t, 2H,), 7.96- 7.98 (d, 2H); 13 C-NMR: δ = 14.09, 45.96, 61.55, 115.86.131.39, 167.39, 164.44, 167.38, 191.03, 191.07; MS: M + = 210.1.
(2)式IX-2所示化合物(11.11g，0.053mol)、K2CO3(7.62g，0.055mol)与溴乙酸乙酯(9.02g，0.054mol)悬浮于100ml乙醇溶液中，加热回流24h，TLC控制反应终点。然后冷却到室温，过滤掉固体物质，并用乙醇洗涤固体，合并乙醇溶液，减压蒸馏，得到无色油状物12.02g，结构如式X-2所示，产率76.4％；(2) The compound shown in formula IX-2 (11.11g, 0.053mol), K 2 CO 3 (7.62g, 0.055mol) and ethyl bromoacetate (9.02g, 0.054mol) were suspended in 100ml ethanol solution, heated to reflux 24h, TLC control reaction end point. Then cool to room temperature, filter off the solid matter, wash the solid with ethanol, combine the ethanol solution, and distill under reduced pressure to obtain 12.02 g of a colorless oily substance, the structure of which is shown in Formula X-2, and the yield is 76.4%;
1H-NMR(400Hz，CDCl3)：δ＝1.19-1.25(m，6H)，3.10-3.15(m，2H)，4.11-4.17(m，4H)，4.83-4.87(t，1H)，7.56-7.62(m，2H)，8.59-8.65(m，2H)；13C-NMR：δ＝13.7，13.9，33.1，49.4，60.8，61.6，128.5，128.7，133.5，135.8，168.5，171.0；MS：M+＝296.1。 1 H-NMR (400Hz, CDCl 3 ): δ=1.19-1.25 (m, 6H), 3.10-3.15 (m, 2H), 4.11-4.17 (m, 4H), 4.83-4.87 (t, 1H), 7.56 -7.62 (m, 2H), 8.59-8.65 (m, 2H); 13 C-NMR: δ=13.7, 13.9, 33.1, 49.4, 60.8, 61.6, 128.5, 128.7, 133.5, 135.8, 168.5, 171.0; MS: M + = 296.1.
(3)式X-2所示化合物(11.92g，0.04mol)和醋酸铵(12.31g，0.16mol)在50ml乙酸中回流20h，然后反应物倒入200ml冰水中，立刻有大量浅黄色固体析出，过滤，用冰水洗涤滤饼，干燥后，用二氯甲烷重结晶，得到7.92g白色固体，结构如式II-2所示，产率80.2％。(3) The compound shown in formula X-2 (11.92g, 0.04mol) and ammonium acetate (12.31g, 0.16mol) were refluxed in 50ml of acetic acid for 20h, then the reactant was poured into 200ml of ice water, and a large amount of light yellow solid was precipitated immediately , filtered, washed the filter cake with ice water, dried, and recrystallized with dichloromethane to obtain 7.92 g of a white solid with the structure shown in Formula II-2, and the yield was 80.2%.
1H-NMR(400Hz，CDCl3)：δ＝1.17-1.21(t，3H)，3.49(s，2H)，4.10-4.14(m，2H)，7.41-7.49(m，2H)，7.58-7.62(m，2H)，9.12(br s，1H)；13C-NMR：δ＝14.5，39.1，60.4，105.0，128.6，129.1，130.0，130.9，151.6，163.6，177.5；MS：M+＝249.1；mp：190-192℃； 1 H-NMR (400Hz, CDCl 3 ): δ=1.17-1.21(t, 3H), 3.49(s, 2H), 4.10-4.14(m, 2H), 7.41-7.49(m, 2H), 7.58-7.62 (m, 2H), 9.12 (br s, 1H); 13 C-NMR: δ = 14.5, 39.1, 60.4, 105.0, 128.6, 129.1, 130.0, 130.9, 151.6, 163.6, 177.5; MS: M + = 249.1; mp: 190-192°C;
(4)在氮气保护下，将金属钠(0.92g，0.04mol)加入到30ml叔戊醇中，然后加入催化量的FeCl3，加热回流，2h后钠反应完毕，加入3，5-二氟苯腈(2.78g，0.02mol)，式II-2所示化合物(5.00g，0.02mol)溶解到20ml叔戊醇中，慢慢滴加到上述溶液中，2h滴加完毕。然后在回流状态下保持5h。反应液冷却到60℃，加入由甲醇、水和乙酸组成的混合溶液50ml，室温搅拌2h后，回流2h，过滤，用热的甲醇和水洗涤滤饼，得到黄光红色固体5.11g，结构如式I-4所示，产率75.0％。(4) Under the protection of nitrogen, metal sodium (0.92g, 0.04mol) was added to 30ml of tert-amyl alcohol, then a catalytic amount of FeCl 3 was added, and heated to reflux. After 2 hours, the sodium reaction was completed, and 3,5-difluoro Benzonitrile (2.78g, 0.02mol) and the compound represented by formula II-2 (5.00g, 0.02mol) were dissolved in 20ml of tert-amyl alcohol, and slowly added dropwise to the above solution, and the dropwise addition was completed within 2 hours. Then keep it under reflux for 5h. The reaction solution was cooled to 60°C, 50ml of a mixed solution composed of methanol, water and acetic acid was added, stirred at room temperature for 2h, refluxed for 2h, filtered, and the filter cake was washed with hot methanol and water to obtain 5.11g of a yellowish red solid with the structure as As shown in formula I-4, the yield is 75.0%.
实施例5Example 5
(1)质量浓度为15％的氢氧化钠水溶液中150ml在冰浴下降温至0℃，然后加入乙酰乙酸乙酯(13.00g，0.1mol)，机械搅拌下，慢慢滴加3，4，5-三氟苯甲酰氯(21.40g，0.11mol)，滴加完毕后，升温至室温，TLC跟踪反应至终点(反应时间约为1小时，硅胶板，乙酸乙酯∶石油醚＝1∶1(v/v))，加入氯化铵(5.30g，0.1mol)，搅拌0.5h后，石油醚萃取(30ml×3)，合并有机相，无水硫酸镁干燥后，减压蒸馏，得到浅黄色油状物20.37g，结构如式IX-3所示，产率82.8％；(1) 150ml of sodium hydroxide aqueous solution with a mass concentration of 15% was cooled to 0°C in an ice bath, then ethyl acetoacetate (13.00g, 0.1mol) was added, and under mechanical stirring, slowly added 3, 4, 5-trifluorobenzoyl chloride (21.40g, 0.11mol), after the dropwise addition was completed, the temperature was raised to room temperature, and TLC tracked the reaction to the end point (reaction time was about 1 hour, silica gel plate, ethyl acetate:petroleum ether=1:1 (v/v)), add ammonium chloride (5.30g, 0.1mol), stir for 0.5h, extract with petroleum ether (30ml×3), combine the organic phases, dry over anhydrous magnesium sulfate, and distill under reduced pressure to obtain shallow 20.37 g of yellow oil, the structure of which is shown in formula IX-3, and the yield is 82.8%;
1H-NMR(400Hz，CDCl3)：δ＝1.25-1.29(t，3H)，3.51(s，2H)，4.07-4.13(m，2H)，7.25-7.27(d，2H)；13C-NMR：δ＝14.1，48.2，61.0，110.8，134.5，144.7，160.4，168.9，190.1；MS：M+＝246.2。 1 H-NMR (400Hz, CDCl 3 ): δ=1.25-1.29(t, 3H), 3.51(s, 2H), 4.07-4.13(m, 2H), 7.25-7.27(d, 2H); 13 C- NMR: δ = 14.1, 48.2, 61.0, 110.8, 134.5, 144.7, 160.4, 168.9, 190.1; MS: M + = 246.2.
(2)式IX-3所示化合物(13.00g，0.053mol)、K2CO3(7.61g，0.055mol)与溴乙酸乙酯(9.00g，0.054mol)悬浮在100ml乙醇溶液中，加热回流24h，然后冷却到室温，过滤掉固体物质，并用乙醇洗涤固体，合并乙醇溶液，减压蒸馏，得到无色油状物13.91g，结构如式X-3所示，产率79.5％。(2) Suspend the compound shown in formula IX-3 (13.00g, 0.053mol), K 2 CO 3 (7.61g, 0.055mol) and ethyl bromoacetate (9.00g, 0.054mol) in 100ml ethanol solution, heat to reflux 24h, then cooled to room temperature, filtered off the solid matter, washed the solid with ethanol, combined the ethanol solutions, and distilled under reduced pressure to obtain 13.91 g of a colorless oily substance, the structure of which was shown in Formula X-3, and the yield was 79.5%.
1H-NMR(400Hz，CDCl3)：δ＝1.21-1.27(m，6H)，3.11-3.17(m，2H)，4.08-4.14(m，4H)，4.43-4.47(t，1H)，7.28-7.34(m，2H)；13C-NMR：δ＝14.1.35.2，49.1，61.3，110.8，135.5，144.5，159.5，169.9，173.1，195.2；MS：M+＝332.1。 1 H-NMR (400Hz, CDCl 3 ): δ=1.21-1.27 (m, 6H), 3.11-3.17 (m, 2H), 4.08-4.14 (m, 4H), 4.43-4.47 (t, 1H), 7.28 -7.34 (m, 2H); 13 C-NMR: δ = 14.1.35.2, 49.1, 61.3, 110.8, 135.5, 144.5, 159.5, 169.9, 173.1, 195.2; MS: M + = 332.1.
(3)式X-3所示化合物(13.31g，0.04mol)和醋酸铵(12.32g，0.16mol)在50ml乙酸中回流20h，然后反应物倒入200ml冰水中，立刻又大量固体析出，过滤，用冰水洗涤滤饼，干燥后，用二氯甲烷重结晶，得到9.12g固体，结构如式II-3所示，产率80.5％。(3) compound shown in formula X-3 (13.31g, 0.04mol) and ammonium acetate (12.32g, 0.16mol) are refluxed 20h in 50ml acetic acid, then reactant is poured into 200ml ice water, and a large amount of solids precipitate out again immediately, filter , washed the filter cake with ice water, dried, and recrystallized with dichloromethane to obtain 9.12 g of solid, the structure of which was shown in formula II-3, and the yield was 80.5%.
1H-NMR(400Hz，CDCl3)：δ＝1.22-1.26(t，3H)，2.87(s，2H)，4.11-4.17(m，2H)，7.17-7.23(m，2H)，9.21(br s，1H)；13C-NMR：δ＝14.7，61.7，42.7，101.2，108.4，133.8，139.4，144.8，167.7，180.1；MS：M+＝285.1；mp：216-218℃。 1 H-NMR (400Hz, CDCl 3 ): δ=1.22-1.26(t, 3H), 2.87(s, 2H), 4.11-4.17(m, 2H), 7.17-7.23(m, 2H), 9.21(br s, 1H); 13 C-NMR: δ = 14.7, 61.7, 42.7, 101.2, 108.4, 133.8, 139.4, 144.8, 167.7, 180.1; MS: M + = 285.1; mp: 216-218°C.
(4)在氮气保护下，将金属钠(0.92g，0.04mol)加入到30ml叔戊醇中，然后加入催化量的FeCl3，加热回流，2h后钠反应完毕，加入五氟苯腈(3.86g，0.02mol)，式II-3所示化合物(5.71g，0.02mol)溶解到20ml叔戊醇中，慢慢滴加到上述溶液中，2h滴加完毕。然后在回流状态下保持5h。反应液冷却到60℃，加入由甲醇、水和乙酸组成的混合溶液50ml，室温搅拌2h后，回流2h，过滤，用热的甲醇和水洗涤滤饼，得到黄光红色固体6.40g，结构如式I-5所示，产率73.9％。(4) Under the protection of nitrogen, metal sodium (0.92g, 0.04mol) was added to 30ml of tert-amyl alcohol, then a catalytic amount of FeCl 3 was added, and heated to reflux. After 2h, the sodium reaction was completed, and pentafluorobenzonitrile (3.86 g, 0.02mol), the compound represented by formula II-3 (5.71g, 0.02mol) was dissolved in 20ml of tert-amyl alcohol, and slowly added dropwise to the above solution, and the dropwise addition was completed after 2h. Then keep it under reflux for 5h. Cool the reaction solution to 60°C, add 50ml of a mixed solution consisting of methanol, water and acetic acid, stir at room temperature for 2h, reflux for 2h, filter, wash the filter cake with hot methanol and water, and obtain 6.40g of a yellowish red solid with the structure as As shown in formula I-5, the yield is 73.9%.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100472244A CN102167701B (en) | 2011-02-25 | 2011-02-25 | Fluorine-containing diphenyl-pyrrolo-pyrrolidinedione (DPP) pigments and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100472244A CN102167701B (en) | 2011-02-25 | 2011-02-25 | Fluorine-containing diphenyl-pyrrolo-pyrrolidinedione (DPP) pigments and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102167701A CN102167701A (en) | 2011-08-31 |
| CN102167701B true CN102167701B (en) | 2013-04-17 |
Family
ID=44489042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100472244A Active CN102167701B (en) | 2011-02-25 | 2011-02-25 | Fluorine-containing diphenyl-pyrrolo-pyrrolidinedione (DPP) pigments and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102167701B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6269176B2 (en) * | 2014-03-05 | 2018-01-31 | 東洋インキＳｃホールディングス株式会社 | Pigment additive, pigment composition using the same, coloring composition, and color filter |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1231167A (en) * | 1998-03-27 | 1999-10-13 | 莱雅公司 | Cosmitis compositions containing novel pigment |
| CN1297450A (en) * | 1998-04-22 | 2001-05-30 | 西巴特殊化学品控股有限公司 | Preparation of alkylthio- and/or arylthio-substd. diketo-diaryl-pyrrolopyrroles |
| WO2004007604A1 (en) * | 2002-07-17 | 2004-01-22 | Ciba Specialty Chemicals Holding Inc. | High-molecular-weight polymeric material comprising diketopyrrolopyrrole pigments |
| CN1749327A (en) * | 2005-09-28 | 2006-03-22 | 华东理工大学 | A kind of preparation method of DPP pigment |
-
2011
- 2011-02-25 CN CN2011100472244A patent/CN102167701B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1231167A (en) * | 1998-03-27 | 1999-10-13 | 莱雅公司 | Cosmitis compositions containing novel pigment |
| CN1297450A (en) * | 1998-04-22 | 2001-05-30 | 西巴特殊化学品控股有限公司 | Preparation of alkylthio- and/or arylthio-substd. diketo-diaryl-pyrrolopyrroles |
| WO2004007604A1 (en) * | 2002-07-17 | 2004-01-22 | Ciba Specialty Chemicals Holding Inc. | High-molecular-weight polymeric material comprising diketopyrrolopyrrole pigments |
| CN1749327A (en) * | 2005-09-28 | 2006-03-22 | 华东理工大学 | A kind of preparation method of DPP pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102167701A (en) | 2011-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2017141215A (en) | New oxocarbon compounds | |
| EP1362040B1 (en) | Process for the preparation of mesylates of piperazine derivatives | |
| CN114149431B (en) | A narrow emission quinacridone derivative and its preparation method and application | |
| AU2002250962A1 (en) | Process for the preparation of mesylates of piperazine derivatives | |
| CN110256493B (en) | A kind of C2-phosphono indole compound and preparation method thereof | |
| CN102167701B (en) | Fluorine-containing diphenyl-pyrrolo-pyrrolidinedione (DPP) pigments and preparation method thereof | |
| CN103937287B (en) | Fluorine boron fluorescence dye and its preparation method and application | |
| CN113121442B (en) | Synthesis method and application of spiro-substituted acridine compound | |
| EP3737678A1 (en) | Process for the preparation of disubstituted diaryloxybenzoheterodiazole compounds | |
| CN103554023B (en) | The synthetic method of acridine derivatives and the polycyclic acridine derivative of synthesis | |
| JP5130521B2 (en) | Heteropolycyclic phenazine compounds | |
| CN102712602B (en) | The preparation method of 2-methyl-4-amino-5-cyanopyrimidine | |
| JP6530807B2 (en) | Process for the preparation of indenoisoquinoline derivatives | |
| JP2524491B2 (en) | Novel aminocarboxylic acid ester and process for producing the same | |
| CN106479217B (en) | Near infrared fluorescent dye and its application | |
| KR20190043743A (en) | Dicyanstyryl benzene derivatives and fluorescent material comprising the same | |
| CN110357880B (en) | Chiral fluorescent compounds with circularly polarized luminescence properties based on folded bodies and their preparation methods and applications | |
| CN109503452B (en) | A kind of preparation method of 2,3,4-tri-substituted pyrrole derivatives | |
| CN102786532B (en) | Sulfur heterocyclic compound and preparation process thereof | |
| JP3804208B2 (en) | Method for producing azulene derivatives | |
| CN105968055B (en) | A kind of preparation method of Arylpyrimidines and its derivative | |
| CN120987842A (en) | A method for synthesizing a chiral 1-arylisoquinoline compound | |
| CN117510478A (en) | Design, synthesis and application of organic photocatalysts based on pyrazine and quinoxaline skeletons | |
| CN117964458A (en) | Preparation method of vicinal diol compound | |
| JP2009209138A (en) | Condensed polycyclic phenazine compound and its production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 200237 Meilong Road, Shanghai, No. 130, No. Patentee after: East China University of Science and Technology Patentee after: Lily Group Co., Ltd. Address before: 200237 Meilong Road, Shanghai, No. 130, No. Patentee before: East China University of Science and Technology Patentee before: Lily Group Co., Ltd. |