CN1111190C - Fluorescent coumarin dye - Google Patents

Fluorescent coumarin dye Download PDF

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Publication number
CN1111190C
CN1111190C CN00101751A CN00101751A CN1111190C CN 1111190 C CN1111190 C CN 1111190C CN 00101751 A CN00101751 A CN 00101751A CN 00101751 A CN00101751 A CN 00101751A CN 1111190 C CN1111190 C CN 1111190C
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compound
alkyl
aryl
coumarin dye
fluorescent coumarin
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CN1258698A (en
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罗先金
程侣柏
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Dalian University of Technology
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Dalian University of Technology
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    • 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
    • C09B57/02—Coumarine dyes

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  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The present invention relates to serial fluorescent coumarin dye which has a structure general formula disclosed in the specification. A derivative of alpha-benzopyran precursor and chlorosulfonic acid have chlorosulfonation reaction, a reaction product and a compound with primary amino, secondary amino or hydroxy have nucleophilic reaction, and the present invention is prepared. Yellow and red dye prepared according to a general formula (I) disclosed in the specification can strengthen fluorescent light, increases the dissolvability of the dye, improves the application performance of the dye and widens the range of application of the fluorescent coumarin dye.

Description

Fluorescent coumarin dye
The present invention relates to-class fluorescent coumarin dye and method for making thereof.
Tonka bean camphor extensively is present in the plant, as orchid, beanpod, turnip, samphire.The English name of coumarin kind compound is: Coumarin, precursor structure called after α-benzene a pair of horses going side by side pyrans.The precursor structure formula of tonka bean camphor is:
Introducing the heteroaromatic substituting group on 3 can greatly improve the coloured light of dyestuff and strengthen fluorescence.Germany publication Ger.offen.2,058,877 has reported the preparation of time array structure dyestuff:
It is to use NCCH 2CO 2Et and MeO (CH 2) 3NH 260 ℃ of reactions 30 minutes, add 3 again, 4-H 2N (OH) C 6H 3Me 180 ℃ of reactions 6 hours, and then adds 2,4-OH (Et 2N) C 6H 3CHO and a spot of piperidines reflux in Virahol and made yellow dyes in 20 hours, R=Me wherein, R '=Et.Some patent Ger.offen.2 also, 030,507; 2,065,552; 2,065,076 has also reported the preparation of this compounds.And German publication Ger.offen.2,364,478 have reported the preparation of following dyestuff: It is to reflux 10 hours in 50% sulfuric acid with O-Phenylene Diamine and ethyl cyanoacetate, and then with 2,4-OH (Et 2N) C 6H 3CHO reaction can make yellow dyes, R=Et wherein, R '=H.U.S. Pat P.4,146,712 have reported and have used 4-N, N-diethylin-2-hydroxy benzaldehyde and the reaction of cyanoethyl benzene a pair of horses going side by side thiazole make down the compound of array structure:
The objective of the invention is with α-benzene a pair of horses going side by side pyrans precursor structure derivative, by introducing sulfuryl chlorio, again with the compound reaction that has amino, hydroxyl, the fluorescent coumarin dye that preparation series is new.
The general structure of the present invention's series fluorescent coumarin dye is:
Figure C0010175100053
In the formula: R represents H, CN, COOV, and wherein: V represents hydrogen, alkyl, particularly C 1～C 6Alkyl;
X represents O, S, NH; The Y representative
Figure C0010175100054
OR 1, NHCOR ' 1Or NHSO 2R ' 1, wherein: R 1, R 2Can represent hydrogen, alkyl respectively, have substituent or not have substituent cycloalkyl, aralkyl or aryl, and with A ring form thick and or 5 to 7 saturated rings, R ' 1: represent alkyl, have substituent or do not have substituent cycloalkyl, aralkyl and aryl; Z represents NR 6, NCOR 7, O, wherein R 6Represent hydrogen, alkyl, have substituent or do not have substituent aryl, R 7Representative has substituent or does not have substituent alkyl, aralkyl, aryl, vinyl, alkoxyl group, phenoxy group or amino;
The B representative has substituent or does not have substituent phenyl ring, naphthalene nucleus, two benzofuran ring;
M represent Cl,
Figure C0010175100061
OR 5, R wherein 3, R 4, R 5Represent hydrogen, alkyl, substituting group is arranged
Or do not have a substituent aryl.
The preparation method of fluorescent coumarin dye of the present invention, it is the chlorsulfonic acid that adopts compound (II) and 2～20 times (molecular ratios), under 10～180 ℃, react 1～3 hour preparation compound (III), then compound (III) is made with having the compound generation nucleophilic reaction of primary amino, secondary amino group, hydroxyl.Their reaction process formula can be expressed as follows:
Figure C0010175100062
The novel coumarin fluorescence dye that makes can be yellow or red, and compound (I) has stronger fluorescence than compound (II), and increases the solubleness of dyestuff.For example: In 50 ml methanol, only dissolve 0.05 gram, and the dyestuff after improving:
Figure C0010175100071
In 50 ml methanol, can dissolve 0.2 gram.Therefore, compound (I) has not only improved the application performance of fluorescent coumarin dye, and has widened range of application.
Embodiment 1
Take by weighing 5 gram 3-(benzene a pair of horses going side by side thiazolyl)-7-N, N dimethylamine base benzene a pair of horses going side by side pyrone-2 (0.0143 mole), structural formula is as follows:
Be added in the 13.3 gram chlorsulfonic acids (0.114 mole), be warmed up to 120 ℃, 120～130 ℃ of insulations 1 hour, cool to 10 ℃, be added in the 120 gram ice, filter, use the frozen water washing leaching cake, being washed till wash water is slightly acidic, filter cake is added in the there-necked flask, drips diethylamine 1.5 grams, kept 2 hours at 0～10 ℃, filtration washing, dry yellow fluorescent coumarin dye 6.7 grams (theoretical yield 96.7%) The dyestuff that makes is done mass spectroscopy: M +485 ultimate analyses: C%59.1 H%5.54 N%8.6 S%13.01
Embodiment 2～18
Press and example 1 similar method and condition, the compound (II) of using different substituents can make following compounds (as shown in table 1) as raw material:
Table 1
The example sequence number R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 X
2 C 2H 5 C 2H 5 H H H H H CH 3 H H S
3 C 2H 5 C 2H 5 H H H H H Cl H H S
4 C 2H 5 C 2H 5 H H H H H H H H O
5 C 2H 5 C 2H 5 H H H H H CH 3 H H O
6 C 2H 5 C 2H 5 H H H H H Cl H H O
7 C 2H 5 C 2H 5 H H H H H H H H NH
8 C 2H 5 C 2H 5 H H H H H CH 3 H H NH
9 C 2H 5 C 2H 5 H H H H H Cl H H NH
10 C 2H 5 C 2H 5 H H H CN H H H H S
11 C 2H 5 C 2H 5 H H H CN H CH 3 H H S
12 C 2H 5 C 2H 5 H H H CN H Cl H H S
13 C 2H 5 C 2H 5 H H H CN H H H H O
14 C 2H 5 C 2H 5 H H H CN H CH 3 H H O
15 C 2H 5 C 2H 5 H H H CN H Cl H H O
16 C 2H 5 C 2H 5 H H H CN H H H H NH
17 C 2H 5 C 2H 5 H H H CN H CH 3 H H NH
18 C 2H 5 C 2H 5 H H H CN H Cl H H NH
Embodiment 19～27
Press and example 1 similar method and condition, can make following compounds (as shown in table 2):
Table 2
The example sequence number X R 18 R 19
19 S H C 2H 4OH
20 S H C 6H 4(CH 3) 2
21 S H CH 3O(CH 2) 3
22 O H C 2H 4OH
23 O H C 6H 4(CH 3) 2
24 O H CH 3O(CH 2) 3
25 NH H C 2H 4OH
26 NH H C 6H 4(CH 3) 2
27 NH H CH 3O(CH 2) 3
Embodiment 28
Take by weighing product 3 grams and the 30 gram dimethyl formamides that example 1 makes and be added to together in 100 milliliters of there-necked flasks, add 30% sodium cyanide solution, 3 grams,, drip 2.8 gram bromines down, filter and obtain 2.8 and restrain following products at 0～5 ℃ 40 ℃ of insulations 1 hour.
Embodiment 29～36
The product that use-case 2～9 makes can make example 11～18 corresponding products by example 28 similar method and conditions.
Embodiment 37～45
The product that use-case 19～27 makes can make following compounds (as shown in table 3) by example 28 similar method and conditions:
Figure C0010175100101
Table 3
The example sequence number X R 18 R 19
37 S H C 2H 4OH
38 S H C 6H 4(CH 3) 2
39 S H CH 3O(CH 2) 3
40 O H C 2H 4OH
41 O H C 6H 4(CH 3) 2
42 O H CH 3O(CH 2) 3
43 NH H C 2H 4OH
44 NH H C 6H 4(CH 3) 2
45 NH H CH 3O(CH 2) 3

Claims (2)

1, a class is characterized in that by the fluorescent coumarin dye compound that α-benzene a pair of horses going side by side pyrans precursor structure is made the general structure of this fluorescent coumarin dye compound (I) is:
In the formula: R represents H, CN, COOV, and wherein V represents hydrogen or C 1-C 6Alkyl;
X represents O, S, NH;
The Y representative OR 1, NHCOR 1', NHSO 2R 1', R wherein 1, R 2Can represent hydrogen, alkyl, cycloalkyl, aralkyl or aryl respectively, and with A ring form thick and or 5 to 7 yuan of saturated rings, R 1' represent alkyl, cycloalkyl, aralkyl or aryl;
Z represents O, NR 6, NCOR 7, R wherein 6Represent hydrogen, alkyl, aryl, R 7Represent alkyl, aralkyl, aryl, vinyl, alkoxyl group, phenoxy group or amino;
M represent Cl,
Figure C0010175100023
OR 5, R wherein 3, R 4, R 5Represent hydrogen, alkyl, aryl;
B represents phenyl ring, naphthalene nucleus, two benzofuran ring.
2 ,-and the preparation method of class fluorescent coumarin dye compound, it is characterized in that this fluorescent coumarin dye is by compound (II):
With the chlorsulfonic acid of 2～20 times (molecular ratios), at 10～180 ℃, reacted 1～3 hour, make sulfonyl chloride compound (III):
Then, compound (III) makes compound (I) with the compound generation nucleophilic reaction of band primary amino or secondary amino group or hydroxyl again, and its general structure is:
Wherein X, Y, Z, M, B, R have definition given in the claim 1.
CN00101751A 2000-01-21 2000-01-21 Fluorescent coumarin dye Expired - Fee Related CN1111190C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100355743C (en) * 2003-12-26 2007-12-19 中国科学院理化技术研究所 3- or 4- carbonyl substituted coumarin connected with naphthenones and its synthesis method and use
CN100469841C (en) * 2005-12-27 2009-03-18 中国科学院理化技术研究所 Coumarin dye connected by diphenyl ethylene and its synthesis method and use

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1411089A1 (en) * 2002-10-18 2004-04-21 Clariant International Ltd. Azo compounds
CN1328273C (en) * 2003-12-26 2007-07-25 中国科学院理化技术研究所 Coumarin dyestuff linked by naphthene ketones, method for synthesis and use thereof
KR102021024B1 (en) * 2011-12-26 2019-09-11 스미또모 가가꾸 가부시키가이샤 Compound for dye
CN104237194B (en) * 2014-10-22 2017-01-11 贵州大学 Fluorescent spectrometry for detecting micro-Mg2+, Zn2+ or F-
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
CN107793407B (en) * 2016-09-06 2022-07-08 住友化学株式会社 Compounds useful as colorants

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1138041A (en) * 1995-02-21 1996-12-18 拜尔公司 Coumarin derivatives, method of preparing them and their use as intermediates

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1138041A (en) * 1995-02-21 1996-12-18 拜尔公司 Coumarin derivatives, method of preparing them and their use as intermediates

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100355743C (en) * 2003-12-26 2007-12-19 中国科学院理化技术研究所 3- or 4- carbonyl substituted coumarin connected with naphthenones and its synthesis method and use
CN100469841C (en) * 2005-12-27 2009-03-18 中国科学院理化技术研究所 Coumarin dye connected by diphenyl ethylene and its synthesis method and use

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