CN101368004A - A kind of synthetic method of coumarin fluorescent dye - Google Patents
A kind of synthetic method of coumarin fluorescent dye Download PDFInfo
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- CN101368004A CN101368004A CNA200810121332XA CN200810121332A CN101368004A CN 101368004 A CN101368004 A CN 101368004A CN A200810121332X A CNA200810121332X A CN A200810121332XA CN 200810121332 A CN200810121332 A CN 200810121332A CN 101368004 A CN101368004 A CN 101368004A
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- ethyl cyanoacetate
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- coumarin
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 19
- 229960000956 coumarin Drugs 0.000 title claims abstract description 18
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 17
- 238000010189 synthetic method Methods 0.000 title claims abstract description 5
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 24
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000012065 filter cake Substances 0.000 claims description 17
- 239000003586 protic polar solvent Substances 0.000 claims description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 10
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 7
- 150000004775 coumarins Chemical class 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 claims description 6
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 3
- 239000000126 substance Substances 0.000 claims 2
- 238000010992 reflux Methods 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000000975 dye Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002798 polar solvent Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- UJOQSHCJYVRZKJ-UHFFFAOYSA-N 3-(1,3-benzoxazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2OC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 UJOQSHCJYVRZKJ-UHFFFAOYSA-N 0.000 description 4
- -1 3-(5'-nitro-2-benzoxazolyl)-7-diethylamino-2H-1-benzopyran-2-one Chemical compound 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PCAXITAPTVOLGL-UHFFFAOYSA-N 2,3-diaminophenol Chemical compound NC1=CC=CC(O)=C1N PCAXITAPTVOLGL-UHFFFAOYSA-N 0.000 description 2
- VLZVIIYRNMWPSN-UHFFFAOYSA-N 2-Amino-4-nitrophenol Chemical compound NC1=CC([N+]([O-])=O)=CC=C1O VLZVIIYRNMWPSN-UHFFFAOYSA-N 0.000 description 2
- SWFNPENEBHAHEB-UHFFFAOYSA-N 2-amino-4-chlorophenol Chemical compound NC1=CC(Cl)=CC=C1O SWFNPENEBHAHEB-UHFFFAOYSA-N 0.000 description 2
- ZMXYNJXDULEQCK-UHFFFAOYSA-N 2-amino-p-cresol Chemical compound CC1=CC=C(O)C(N)=C1 ZMXYNJXDULEQCK-UHFFFAOYSA-N 0.000 description 2
- CBNSBRVOBGWOBM-UHFFFAOYSA-N 3-(5-chlorobenzoxazol-2-yl)-7-diethylaminocoumarin Chemical compound ClC1=CC=C2OC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 CBNSBRVOBGWOBM-UHFFFAOYSA-N 0.000 description 2
- PTAGJQADNFQMGR-UHFFFAOYSA-N 7-(diethylamino)-3-(5-methyl-1,3-benzoxazol-2-yl)chromen-2-one Chemical compound CC1=CC=C2OC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 PTAGJQADNFQMGR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000990 laser dye Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- ACMLKANOGIVEPB-UHFFFAOYSA-N 2-oxo-2H-chromene-3-carboxylic acid Chemical compound C1=CC=C2OC(=O)C(C(=O)O)=CC2=C1 ACMLKANOGIVEPB-UHFFFAOYSA-N 0.000 description 1
- WAVOOWVINKGEHS-UHFFFAOYSA-N 3-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=CC(O)=C1 WAVOOWVINKGEHS-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ABDMQSFNJPYOLA-UHFFFAOYSA-N NS(=O)(=O)[N+]([O-])=O Chemical compound NS(=O)(=O)[N+]([O-])=O ABDMQSFNJPYOLA-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- LTMHNWPUDSTBKD-UHFFFAOYSA-N diethyl 2-(ethoxymethylidene)propanedioate Chemical compound CCOC=C(C(=O)OCC)C(=O)OCC LTMHNWPUDSTBKD-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
(一)技术领域 (1) Technical field
本发明涉及一种香豆素类荧光染料的合成方法。The invention relates to a method for synthesizing coumarin fluorescent dyes.
(二)背景技术 (2) Background technology
香豆素类化合物是一类典型的含分子内电荷迁移系的大π共轭结构化合物，是目前荧光材料中研究最为广泛的一类。香豆素类荧光色素具有强烈的荧光、鲜艳的色泽、良好的应用性能，日本、德国和瑞士等染料工业发达国家都予以高度重视。香豆素类化合物荧光量子效率高、成膜性能优良，可掺杂到空穴传输材料聚乙烯咔唑(PVK)中，用作有机电致发光材料。此外，香豆素类化合物由于能输出较宽区域(420-570nm)的蓝绿色调谐激光，因而近年来在激光染料方面异军突起。到目前为止，在常用的30多种商品级激光染料中，已有近20种是香豆素类化合物。香豆素类荧光染料具有较好的湿牢度、升华牢度、耐洗坚牢度、光牢度及快速染色等性能，可用于塑料着色、彩色荧光涂料、太阳能聚集器的彩色荧光树脂，以及感光材料、光敏材料、光盘记录材料等高新技术领域，是一种具有广阔应用前景的荧光色素材料。Coumarin compounds are a typical class of compounds with large π-conjugated structures containing intramolecular charge transfer systems, and are the most widely studied class of fluorescent materials. Coumarin-based fluorescent pigments have strong fluorescence, bright color, and good application performance. Japan, Germany, Switzerland and other developed countries in the dye industry have attached great importance to them. Coumarin compounds have high fluorescence quantum efficiency and excellent film-forming properties, and can be doped into the hole transport material polyvinylcarbazole (PVK) to be used as organic electroluminescent materials. In addition, coumarin compounds have become prominent in laser dyes in recent years because they can output blue-green tuned laser light in a wider region (420-570nm). So far, among more than 30 kinds of commercial grade laser dyes commonly used, nearly 20 kinds are coumarin compounds. Coumarin-based fluorescent dyes have good wet fastness, sublimation fastness, washing fastness, light fastness and fast dyeing properties, and can be used for coloring plastics, colored fluorescent coatings, and colored fluorescent resins for solar concentrators. As well as high-tech fields such as photosensitive materials, photosensitive materials, and optical disc recording materials, it is a fluorescent pigment material with broad application prospects.
香豆素荧光染料的结构通式为：The general structural formula of coumarin fluorescent dye is:
其结构通式中：取代基X可以为氢、C1～C4的烷基、C1～C4的烷氧基、卤素、硝基、磺酰胺基等。该类化合物的合成方法可以归纳为两种：一是先构建香豆素环，如由4-N，N-二乙氨基水杨醛和丙二酸二乙酯缩合关环(参见美国专利US3933847)，或3-N，N-二乙氨基苯酚和乙氧基亚甲基丙二酸二乙酯在催化剂TiCl4的存在下关环，制备得到香豆素羧酸酯，再与取代的邻氨基酚缩合得到香豆素染料；另一种方法是先构建苯并噁唑环，再与4-N，N-二乙氨基水杨醛缩合生成香豆素染料，即由氰乙酸乙酯在3-甲氧基丙胺存在下首先与取代2-氨基苯酚形成噁唑环，再与4-N，N-二乙氨基水杨醛关环(参见德国专利1329043和美国专利4146712)。这些方法均需多步反应、反应条件苛刻(需要强酸催化剂)、操作复杂，且收率不高。中国专利CN1760194提出以氰乙酸乙酯、4-N，N-二乙氨基水杨醛和取代邻氨基苯酚为原料，一锅法合成香豆素荧光染料，大大简化了合成步骤，新方法仍需以苯甲酸为催化剂，且用量较大。In its general structural formula: the substituent X can be hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, nitro, sulfonamide, etc. The synthetic method of this class compound can be summarized into two kinds: the one, construct coumarin ring earlier, as by 4-N, N-diethylamino salicylaldehyde and diethyl malonate condensation ring closing (referring to U.S. Patent US3933847 ), or 3-N, N-diethylaminophenol and diethyl ethoxymethylenemalonate are ring-closed in the presence of catalyst TiCl 4 to prepare coumarin carboxylate, and then with substituted ortho Aminophenol is condensed to obtain coumarin dyes; another method is to construct a benzoxazole ring first, and then condense with 4-N, N-diethylaminosalicylaldehyde to generate coumarin dyes, that is, ethyl cyanoacetate in In the presence of 3-methoxypropylamine, first form an oxazole ring with substituted 2-aminophenol, and then close the ring with 4-N, N-diethylamino salicylaldehyde (see German Patent 1329043 and US Patent 4146712). These methods all need multi-step reaction, harsh reaction conditions (requiring strong acid catalyst), complicated operation, and low yield. Chinese patent CN1760194 proposes to use ethyl cyanoacetate, 4-N, N-diethylaminosalicylaldehyde and substituted o-aminophenol as raw materials to synthesize coumarin fluorescent dyes in one pot, which greatly simplifies the synthesis steps, and the new method still needs Benzoic acid is used as the catalyst, and the dosage is relatively large.
(三)发明内容 (3) Contents of the invention
本发明目的是提供一种无需催化剂催化、工艺简单、收率高的香豆素类荧光染料的合成方法。The purpose of the invention is to provide a method for synthesizing coumarin fluorescent dyes without catalyst catalysis, simple process and high yield.
本发明采用的技术方案是：The technical scheme adopted in the present invention is:
一种结构如式(I)所示的香豆素类荧光染料的合成方法，所述方法包括：将氰乙酸乙酯、4-N，N-二乙基氨基水杨醛和结构如式(II)所示的邻氨基苯酚衍生物于质子极性溶剂中回流反应7～9小时，反应结束后分离纯化得到所述的香豆素类荧光染料；A kind of synthetic method of the coumarin fluorescent dye shown in formula (I) of a kind of structure, described method comprises: ethyl cyanoacetate, 4-N, N-diethylaminosalicylaldehyde and structure such as formula ( II) The o-aminophenol derivative shown in the proton polar solvent is refluxed for 7 to 9 hours, and after the reaction is completed, the coumarin fluorescent dye is obtained by separation and purification;
式(I)、式(II)中：X为氢、C1～C4的烷基、C1～C4的烷氧基、卤素、硝基或磺酰氨基，为氢、氯、甲基、硝基或磺酰氨基；In formula (I) and formula (II): X is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, nitro or sulfonylamino, hydrogen, chlorine, methyl , nitro or sulfonylamino;
所述质子极性溶剂为下列之一：C1～C8的醇、C1～C8的酮或二甲基亚砜。The protic polar solvent is one of the following: C1-C8 alcohol, C1-C8 ketone or dimethyl sulfoxide.
本发明的关键在于在不用催化剂的条件下，直接使氰乙酸乙酯、4-N，N-二乙基氨基水杨醛、邻氨基苯酚衍生物进行一锅法反应，合成得到香豆素类荧光染料。氰乙酸乙酯、4-N，N-二乙基氨基水杨醛、邻氨基苯酚衍生物用量可使用常规用量，所述质子极性溶剂以足量为宜，过量亦可，并不会对反应本身有较大影响。The key of the present invention is to directly make ethyl cyanoacetate, 4-N, N-diethylaminosalicylaldehyde, and o-aminophenol derivatives carry out one-pot reaction without catalyst, and synthesize coumarins Fluorescent dyes. Ethyl cyanoacetate, 4-N, the amount of N-diethylaminosalicylaldehyde, ortho-aminophenol derivatives can be used in conventional amounts, and the protic polar solvent is advisable in a sufficient amount, and also in excess, and will not affect The reaction itself has a greater influence.
所述氰乙酸乙酯、4-N，N-二乙基氨基水杨醛和邻氨基苯酚衍生物的物质的量之比为1:1～2:1～2，优选为1:1～1.2:1～1.2，更优选为1:1:1。The ratio of the amount of ethyl cyanoacetate, 4-N, N-diethylamino salicylaldehyde and o-aminophenol derivatives is 1:1～2:1～2, preferably 1:1～1.2 :1 to 1.2, more preferably 1:1:1.
所述质子极性溶剂用量为1～10L/mol氰乙酸乙酯，优选为5～7L/mol氰乙酸乙酯，更优选为5L/mol氰乙酸乙酯。The dosage of the protic polar solvent is 1-10L/mol ethyl cyanoacetate, preferably 5-7L/mol ethyl cyanoacetate, more preferably 5L/mol ethyl cyanoacetate.
所述质子极性溶剂优选为下列之一：正丁醇、正戊醇、异戊醇、环己醇、丁酮、2-戊酮。The protic polar solvent is preferably one of the following: n-butanol, n-pentanol, isoamyl alcohol, cyclohexanol, butanone, 2-pentanone.
所述分离纯化可按常规方法进行，一般只需过滤，滤饼干燥即可得产物；也可在反应完毕后，冷却至室温，再加入适量强碱水溶液除去反应物中的杂质，再进行过滤，滤饼干燥得到产品。本发明中，所述分离纯化方法如下：反应结束后，冷却至室温，加入体积为溶剂体积1～3倍的1～5％NaOH水溶液搅拌0.5～2小时，过滤、滤饼烘干，得到所述香豆素类荧光染料。The separation and purification can be carried out according to conventional methods. Generally, it only needs to be filtered and the filter cake is dried to obtain the product; it can also be cooled to room temperature after the reaction is completed, and then an appropriate amount of strong alkali aqueous solution is added to remove impurities in the reactant, and then filtered , the filter cake is dried to obtain the product. In the present invention, the separation and purification method is as follows: after the reaction is completed, cool to room temperature, add 1-5% NaOH aqueous solution whose volume is 1-3 times the solvent volume, stir for 0.5-2 hours, filter, and dry the filter cake to obtain the obtained The coumarin-based fluorescent dyes.
优选的，所述方法如下：将物质的量之比为1:1～1.2:1～1.2的氰乙酸乙酯、4-N，N-二乙基氨基水杨醛和结构如式(II)所示的邻氨基苯酚衍生物于质子极性溶剂中回流反应7～9小时，反应结束后，冷却至室温，加入体积为剩余溶剂体积2倍的1％NaOH水溶液搅拌0.5小时，过滤、烘干，得到所述香豆素类荧光染料；所述质子极性溶剂为下列之一：正丁醇、正戊醇、异戊醇、环己醇、丁酮、2-戊酮，所述质子极性溶剂用量为5～7L/mol氰乙酸乙酯；式(I)、式(II)中，X为氢、氯、甲基、硝基或磺酰氨基。Preferably, the method is as follows: ethyl cyanoacetate, 4-N, N-diethylamino salicylaldehyde and a structure such as formula (II) The o-aminophenol derivative shown was refluxed in a protic polar solvent for 7 to 9 hours. After the reaction, cool to room temperature, add 1% NaOH aqueous solution whose volume is twice the volume of the remaining solvent, stir for 0.5 hours, filter and dry , to obtain the coumarin fluorescent dye; the proton polar solvent is one of the following: n-butanol, n-amyl alcohol, isoamyl alcohol, cyclohexanol, butanone, 2-pentanone, the proton polar The dosage of the neutral solvent is 5-7L/mol ethyl cyanoacetate; in formula (I) and formula (II), X is hydrogen, chlorine, methyl, nitro or sulfonylamino.
依照本发明所述合成方法，一般产物的收率可以达到60～80％。According to the synthesis method of the present invention, the yield of general products can reach 60-80%.
本发明的有益效果主要体现在：无需使用任何催化剂，可在一锅内进行，不仅减少了反应步骤，且合成工艺简单、反应条件温和、收率高、成本低，具有较大实施价值和社会经济效益。The beneficial effect of the present invention is mainly reflected in: no need to use any catalyst, it can be carried out in one pot, not only the reaction steps are reduced, but also the synthesis process is simple, the reaction conditions are mild, the yield is high, the cost is low, and it has great practical value and social economic benefits.
(四)具体实施方式 (4) Specific implementation methods
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此：The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:
实施例1：3-(5′-氯-2-苯并噁唑基)-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 1: Synthesis of 3-(5'-chloro-2-benzoxazolyl)-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.30g(2mmol)4-氯邻氨基苯酚，10mL正丁醇，加热回流，反应7小时，冷却至室温，加入1％的NaOH水溶液20mL搅拌半小时，过滤、滤饼烘干，得黄色粉末0.52g，收率68％，熔点为205～207℃。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylaldehyde, 0.30g (2mmol) 4-chloro-o- Aminophenol, 10mL of n-butanol, heated to reflux, reacted for 7 hours, cooled to room temperature, added 20mL of 1% NaOH aqueous solution and stirred for half an hour, filtered, and the filter cake was dried to obtain 0.52g of yellow powder with a yield of 68% and a melting point of 205～207℃.
1H NMR(CDCl3，500MHz)δ：8.60(s，1H，4-H)，7.74(s，1H，4’-H)，7.50-7.48(d，1H，7’-H)，7.42-7.40(d，1H，6’-H)，7.29-7.27(m，1H，5-H)，6.65-6.63(d，1H，6-H)，6.52-6.51(d，1H，8-H)，3.48-3.44(q，4H，NCH 2CH3)，1.26-1.23(t，6H，NCH2CH 3) 1 H NMR (CDCl 3 , 500MHz) δ: 8.60(s, 1H, 4-H), 7.74(s, 1H, 4'-H), 7.50-7.48(d, 1H, 7'-H), 7.42- 7.40(d, 1H, 6'-H), 7.29-7.27(m, 1H, 5-H), 6.65-6.63(d, 1H, 6-H), 6.52-6.51(d, 1H, 8-H) , 3.48-3.44 (q, 4H, NCH 2 CH 3 ), 1.26-1.23 (t, 6H, NCH 2 CH 3 )
实施例2：3-(5′-氯-2-苯并噁唑基)-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 2: Synthesis of 3-(5'-chloro-2-benzoxazolyl)-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.30g(2mmol)4-氯邻氨基苯酚，10mL正戊醇，加热回流，反应7小时，冷却至室温，加入2％的NaOH水溶液15mL搅拌半小时，过滤、滤饼烘干，得黄色粉末，收率54％。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylaldehyde, 0.30g (2mmol) 4-chloro-o- Aminophenol, 10mL of n-amyl alcohol, heated to reflux, reacted for 7 hours, cooled to room temperature, added 15mL of 2% NaOH aqueous solution and stirred for half an hour, filtered, and the filter cake was dried to obtain a yellow powder with a yield of 54%.
实施例3：3-(5′-甲基-2-苯并噁唑基)-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 3: Synthesis of 3-(5'-methyl-2-benzoxazolyl)-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.25g(2mmol)4-甲基邻氨基苯酚，10mL正丁醇，加热回流，反应9小时，冷却至室温，加入1％的NaOH水溶液20mL搅拌1小时，过滤、滤饼烘干，得黄色粉末0.44g，收率61％，熔点为205～208℃。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylaldehyde, 0.25g (2mmol) 4-methyl o-aminophenol, 10mL n-butanol, heated to reflux, reacted for 9 hours, cooled to room temperature, added 20mL of 1% NaOH aqueous solution and stirred for 1 hour, filtered, and the filter cake was dried to obtain 0.44g of yellow powder, yield 61%, melting point It is 205-208°C.
1H NMR(CDCl3，500MHz)δ：8.61(s，1H，4-H)，7.58(s，1H，7’-H)，7.46-7.41(m，2H，5-H，6’-H)，7.15-7.13(d，1H，4’-H)，6.65-6.64(d，1H，6-H)，6.54(s，1H，8-H)，3.48-3.44(q，4H，NCH 2CH3)，2.48(s，3H，Ar-CH 3)，1.26-1.23(t，6H，NCH2CH 3) 1 H NMR (CDCl 3 , 500MHz) δ: 8.61(s, 1H, 4-H), 7.58(s, 1H, 7'-H), 7.46-7.41(m, 2H, 5-H, 6'-H ), 7.15-7.13 (d, 1H, 4'-H), 6.65-6.64 (d, 1H, 6-H), 6.54 (s, 1H, 8-H), 3.48-3.44 (q, 4H, NCH 2 CH 3 ), 2.48 (s, 3H, Ar- CH 3 ), 1.26-1.23 (t, 6H, NCH 2 CH 3 )
实施例4：3-(5′-甲基-2-苯并噁唑基)-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 4: Synthesis of 3-(5'-methyl-2-benzoxazolyl)-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.25g(2mmol)4-甲基邻氨基苯酚，10mL环己醇，加热回流，反应9小时，冷却至室温，加入1％的NaOH水溶液30mL搅拌2小时，过滤、滤饼烘干，得黄色粉末，收率46％。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylaldehyde, 0.25g (2mmol) 4-methyl o-aminophenol, 10mL cyclohexanol, heated to reflux, reacted for 9 hours, cooled to room temperature, added 30mL of 1% NaOH aqueous solution, stirred for 2 hours, filtered, and the filter cake was dried to obtain a yellow powder with a yield of 46%.
实施例5：3-2-苯并噁唑基-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 5: Synthesis of 3-2-benzoxazolyl-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.23g(2mmol)邻氨基苯酚，10mL正丁醇，加热回流，反应9小时，冷却至室温，加入5％的NaOH水溶液10mL搅拌半小时，过滤、滤饼烘干，得黄色粉末0.53g，收率77％，熔点为185～187℃。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylaminosalicylaldehyde, 0.23g (2mmol) o-aminophenol in the 50mL four-neck flask that reflux device is housed, 10mL of n-butanol, heat to reflux, react for 9 hours, cool to room temperature, add 10mL of 5% NaOH aqueous solution and stir for half an hour, filter and dry the filter cake to obtain 0.53g of yellow powder with a yield of 77% and a melting point of 185-187 ℃.
1H NMR(CDCl3，500MHz)δ：8.60(s，1H，4-H)，7.81-7.79(m，1H，4’-H)，7.59-7.57(m，1H，7’-H)，7.42-7.40(d，1H，5-H)，7.34-7.32(m，2H，5’-H，6’-H)，6.65-6.63(d，1H，6-H)，6.53-6.52(d，1H，8-H)，3.47-3.43(q，4H，NCH 2CH3)，1.25-1.23(t，6H，NCH 2CH 3) 1 H NMR (CDCl 3 , 500MHz) δ: 8.60 (s, 1H, 4-H), 7.81-7.79 (m, 1H, 4'-H), 7.59-7.57 (m, 1H, 7'-H), 7.42-7.40(d, 1H, 5-H), 7.34-7.32(m, 2H, 5'-H, 6'-H), 6.65-6.63(d, 1H, 6-H), 6.53-6.52(d , 1H, 8-H), 3.47-3.43 ( q , 4H , NCH2CH3 ), 1.25-1.23 ( t, 6H, NCH2CH3 )
实施例6：3-2-苯并噁唑基-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 6: Synthesis of 3-2-benzoxazolyl-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.23g(2mmol)邻氨基苯酚，10mL丁酮，加热回流，反应9小时，冷却至室温，加入1％的NaOH水溶液20mL搅拌半小时，过滤、滤饼烘干，得黄色粉末，收率47％。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylaminosalicylaldehyde, 0.23g (2mmol) o-aminophenol in the 50mL four-neck flask that reflux device is housed, 10mL of butanone was heated to reflux, reacted for 9 hours, cooled to room temperature, added 20mL of 1% NaOH aqueous solution and stirred for half an hour, filtered, and the filter cake was dried to obtain a yellow powder with a yield of 47%.
实施例7：3-2-苯并噁唑基-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 7: Synthesis of 3-2-benzoxazolyl-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.23g(2mmol)邻氨基苯酚，10mL正辛醇，加热回流，反应9小时，冷却至室温，加入1％的NaOH水溶液20mL搅拌半小时，过滤、滤饼烘干，得黄色粉末，收率38％。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylaminosalicylaldehyde, 0.23g (2mmol) o-aminophenol in the 50mL four-neck flask that reflux device is housed, 10 mL of n-octanol was heated to reflux, reacted for 9 hours, cooled to room temperature, added 20 mL of 1% NaOH aqueous solution and stirred for half an hour, filtered, and the filter cake was dried to obtain a yellow powder with a yield of 38%.
实施例8：3-2-苯并噁唑基-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 8: Synthesis of 3-2-benzoxazolyl-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.23g(2mmol)邻氨基苯酚，10mL异丙醇，加热回流，反应9小时，冷却至室温，加入1％的NaOH水溶液20mL搅拌半小时，过滤、滤饼烘干，得黄色粉末，收率52％。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylaminosalicylaldehyde, 0.23g (2mmol) o-aminophenol in the 50mL four-neck flask that reflux device is housed, 10mL of isopropanol was heated to reflux, reacted for 9 hours, cooled to room temperature, added 20mL of 1% NaOH aqueous solution and stirred for half an hour, filtered, and the filter cake was dried to obtain a yellow powder with a yield of 52%.
实施例9：3-(5′-硝基-2-苯并噁唑基)-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 9: Synthesis of 3-(5'-nitro-2-benzoxazolyl)-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.32g(2mmol)4-硝基邻氨基苯酚，10mL正丁醇，加热至回流，反应9小时，冷却至室温，加入1％的NaOH水溶液20mL搅拌半小时，过滤、滤饼烘干，得黄色粉末4.70g，收率69％，熔点为263～265℃。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylaldehyde, 0.32g (2mmol) 4-nitro o-aminophenol, 10mL n-butanol, heated to reflux, reacted for 9 hours, cooled to room temperature, added 20mL of 1% NaOH aqueous solution and stirred for half an hour, filtered, and the filter cake was dried to obtain 4.70g of yellow powder with a yield of 69%. The melting point is 263-265°C.
1H NMR(CDCl3，500MHz)δ：8.62-8.61(m，2H，4’-H，6’-H)，8.28-8.26(d，1H，4-H)，7.67-7.65(d，1H，5-H)，7.43-7.42(d，1H，7’-H)，6.67-6.65(d，1H，6-H)，6.51(s，1H，8-H)，3.50-3.46(q，4H，NCH 2CH3)，1.28-1.25(t，6H，NCH2CH 3) 1 H NMR (CDCl 3 , 500MHz) δ: 8.62-8.61 (m, 2H, 4'-H, 6'-H), 8.28-8.26 (d, 1H, 4-H), 7.67-7.65 (d, 1H , 5-H), 7.43-7.42(d, 1H, 7'-H), 6.67-6.65(d, 1H, 6-H), 6.51(s, 1H, 8-H), 3.50-3.46(q, 4H, NCH 2 CH 3 ), 1.28-1.25 (t, 6H, NCH 2 CH 3 )
实施例10：3-(5′-硝基-2-苯并噁唑基)-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 10: Synthesis of 3-(5'-nitro-2-benzoxazolyl)-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.32g(2mmol)4-硝基邻氨基苯酚，10mL2-戊酮，加热至回流，反应9小时，冷却至室温，加入1％的NaOH水溶液20mL搅拌半小时，过滤、滤饼烘干，得黄色粉末，收率39％。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylamino salicylaldehyde, 0.32g (2mmol) 4-nitro o-aminophenol, 10mL 2-pentanone, heated to reflux, reacted for 9 hours, cooled to room temperature, added 20mL of 1% NaOH aqueous solution and stirred for half an hour, filtered, and the filter cake was dried to obtain a yellow powder with a yield of 39%.
实施例11：3-(5′-磺酰氨基-2-苯并噁唑基)-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 11: Synthesis of 3-(5'-sulfonylamino-2-benzoxazolyl)-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.39g(2mmol)4-磺酰氨基邻氨基苯酚，10mL正丁醇，加热回流，反应9小时，冷却至室温，加入1％的NaOH水溶液20mL搅拌半小时，过滤、滤饼烘干，得黄色粉末5.30g，收率73％，熔点为>300℃。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylaminosalicylaldehyde, 0.39g (2mmol) 4-sulfonyl in a 50mL four-necked flask equipped with a reflux device Amino-o-aminophenol, 10mL of n-butanol, heated to reflux, reacted for 9 hours, cooled to room temperature, added 20mL of 1% NaOH aqueous solution and stirred for half an hour, filtered, and the filter cake was dried to obtain 5.30g of yellow powder with a yield of 73%. The melting point is >300°C.
1H NMR(CDCl3，500MHz)δ：8.83(s，1H，4-H)，8.15(s，1H，4’-H)，7.94-7.92(d，1H，6’-H)，7.89-7.87(d，1H，7’-H)，7.71-7.70(d，1H，5-H)，7.48(s，2H，SO2NH 2)，6.82-6.79(d，1H，6-H)，6.60(s，1H，8-H)，3.51-3.47(q，4H，NCH 2CH3)，1.17-1.14(t，6H，NCH2CH 3) 1 H NMR (CDCl 3 , 500MHz) δ: 8.83(s, 1H, 4-H), 8.15(s, 1H, 4'-H), 7.94-7.92(d, 1H, 6'-H), 7.89- 7.87(d, 1H, 7'-H), 7.71-7.70(d, 1H, 5-H), 7.48(s, 2H, SO 2 N H 2 ), 6.82-6.79(d, 1H, 6-H) , 6.60 (s, 1H, 8-H), 3.51-3.47 (q, 4H, NCH 2 CH 3 ), 1.17-1.14 (t, 6H, NCH 2 CH 3 )
实施例12：3-(5′-磺酰氨基-2-苯并噁唑基)-7-二乙基氨基-2H-1-苯并吡喃-2-酮的合成Example 12: Synthesis of 3-(5'-sulfonylamino-2-benzoxazolyl)-7-diethylamino-2H-1-benzopyran-2-one
在装有回流装置的50mL四口烧瓶内加入0.23g(2mmol)氰乙酸乙酯，0.40g(2mmol)4-N，N-二乙基氨基水杨醛，0.39g(2mmol)4-磺酰氨基邻氨基苯酚，10mL DMSO，加热回流，反应9小时，冷却至室温，加入1％的NaOH水溶液20mL搅拌半小时，过滤、滤饼烘干，得黄色粉末收率53％。Add 0.23g (2mmol) ethyl cyanoacetate, 0.40g (2mmol) 4-N, N-diethylaminosalicylaldehyde, 0.39g (2mmol) 4-sulfonyl in a 50mL four-necked flask equipped with a reflux device Amino-o-aminophenol, 10mL DMSO, heated to reflux, reacted for 9 hours, cooled to room temperature, added 20mL of 1% NaOH aqueous solution, stirred for half an hour, filtered, and the filter cake was dried to obtain a yellow powder with a yield of 53%.
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| CN103194087A (en) * | 2013-03-29 | 2013-07-10 | 万隆化工有限公司 | Solvent-based yellow dye for environment-friendly fluorescent pigment |
| CN103365088A (en) * | 2012-04-04 | 2013-10-23 | 住友化学株式会社 | Colored curable resin composition |
| CN105777729A (en) * | 2016-05-31 | 2016-07-20 | 浙江工业大学 | Coumarin amides compound as well as preparation method and application of coumarin amides compound |
| CN114806213A (en) * | 2022-05-23 | 2022-07-29 | 万隆化工有限公司 | A solvent yellow 160:1 green synthesis process |
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| US4146712A (en) * | 1976-03-11 | 1979-03-27 | Ciba-Geigy Corporation | Process for the manufacture of coumarin dyes |
| CN1279121C (en) * | 2004-06-17 | 2006-10-11 | 上海交通大学 | Fluorescent coumarin dye |
| CN1304392C (en) * | 2005-08-16 | 2007-03-14 | 浙江工业大学 | Method for synthesizing 3-(5'-substitution-2-benzoxazole group)-7-diethyl amino group H-1-benzopyrans-2-ketone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103365088A (en) * | 2012-04-04 | 2013-10-23 | 住友化学株式会社 | Colored curable resin composition |
| CN103365088B (en) * | 2012-04-04 | 2019-01-11 | 住友化学株式会社 | Colored curable resin composition |
| CN103194087A (en) * | 2013-03-29 | 2013-07-10 | 万隆化工有限公司 | Solvent-based yellow dye for environment-friendly fluorescent pigment |
| CN103194087B (en) * | 2013-03-29 | 2015-12-23 | 万隆化工有限公司 | Environmental protection high-visibility pigment solvent-borne type yellow dye |
| CN105777729A (en) * | 2016-05-31 | 2016-07-20 | 浙江工业大学 | Coumarin amides compound as well as preparation method and application of coumarin amides compound |
| CN114806213A (en) * | 2022-05-23 | 2022-07-29 | 万隆化工有限公司 | A solvent yellow 160:1 green synthesis process |
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