CN1111190C - Fluorescent coumarin dye - Google Patents

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

Coumarin fluorescent dye

The invention relates to a coumarinoid fluorescent dye and a preparation method thereof.

Coumarin widely exists in plants, such as orchids, bean pods, turnips, and umbelliferous plants. The English name of the coumarin compound is: Coumarin, and the parent structure is named α-benzopyran. The parent structure of coumarin is:

The introduction of an aromatic heterocyclic substituent at the 3-position can greatly improve the color shade and enhance the fluorescence of the dye. German published patent Ger.offen.2,058,877 reports the preparation of the following structural dyes:

It was reacted with NCCH ₂ CO ₂ Et and MeO(CH ₂ ) ₃ NH ₂ at 60°C for 30 minutes, then added 3,4-H ₂ N(OH)C ₆ H ₃ Me, reacted at 180°C for 6 hours, and then Then add 2,4-OH(Et ₂ N)C ₆ H ₃ CHO and a small amount of piperidine to reflux in isopropanol for 20 hours to obtain a yellow dye, wherein R=Me, R'=Et. There are also some patents Ger.offen.2,030,507; 2,065,552; 2,065,076 also reported the preparation of such compounds. And German open patent Ger.offen.2,364,478 reports the preparation of following dyestuff: It is refluxed with o-phenylenediamine and ethyl cyanoacetate in 50% sulfuric acid for 10 hours, and then reacted with 2,4-OH(Et ₂ N)C ₆ H ₃ CHO to prepare a yellow dye, where R=Et , R'=H. U.S. Patent USP.4,146,712 reports to use 4-N, the compound of N-diethylamino-2-hydroxybenzaldehyde and cyanoethylbenzothiazole reaction is prepared following structure:

The object of the present invention is to prepare a series of new coumarin fluorescent dyes by introducing sulfonyl chloride group and reacting with compounds with amino and hydroxyl groups by using α-benzopyran parent structure derivatives.

式中：R代表H、CN、COOV，其中：V代表氢、烷基，特别是C₁～C₆烷基；The general structural formula of the series of coumarin fluorescent dyes of the present invention is:

In the formula: R represents H, CN, COOV, wherein: V represents hydrogen, alkyl, especially C ₁ ~ C ₆ alkyl;

OR₁、NHCOR′₁或NHSO₂R′₁，其中：R₁、R₂可以分别代表氢、烷基、有取代基的或没有取代基的环烷基、芳烷基或芳基，以及与A环形成稠和的或饱和的5至7环，R′₁：代表烷基、有取代基的或没有取代基的环烷基、芳烷基和芳基；Z代表NR₆、NCOR₇、O，其中R₆代表氢、烷基、有取代基的或没有取代基的芳基，R₇代表有取代基的或没有取代基的烷基、芳烷基、芳基、乙烯基、烷氧基、苯氧基或氨基；X stands for O, S, NH; Y stands for

OR ₁ , NHCOR' ₁ or NHSO ₂ R' ₁ , wherein: R ₁ and R ₂ can represent hydrogen, alkyl, substituted or unsubstituted cycloalkyl, aralkyl or aryl, and A ring forms a condensed or saturated 5 to 7 ring, R' ₁ : represents an alkyl group, a substituted or unsubstituted cycloalkyl group, an aralkyl group and an aryl group; Z represents NR ₆ , NCOR ₇ , O, wherein R ₆ represents hydrogen, alkyl, substituted or unsubstituted aryl, R ₇ represents substituted or unsubstituted alkyl, aralkyl, aryl, vinyl, alkoxy group, phenoxy group or amino group;

B represents a substituted or unsubstituted benzene ring, naphthalene ring, and bisbenzofuran ring;

OR₅，其中R₃、R₄、R₅代表氢、烷基、有取代基M stands for Cl,

OR ₅ , wherein R ₃ , R ₄ , R ₅ represent hydrogen, alkyl, substituent

aryl with or without substituents.

制得的新香豆素荧光染料可以是黄色或红色，化合物(I)比化合物(II)有更强的荧光，并增加染料的溶解度。例如：在50毫升甲醇中仅溶解0.05克，而改进后的染料：

The preparation method of coumarin fluorescent dye of the present invention is to adopt compound (II) and the chlorosulfonic acid of 2～20 times (molecular ratio), under 10～180 ℃, react 1～3 hour to prepare compound (III), then It can be prepared by nucleophilic reaction between compound (III) and compounds with primary amino group, secondary amino group and hydroxyl group. Their reaction process formula can be expressed as follows:

The prepared new coumarin fluorescent dye can be yellow or red, and the compound (I) has stronger fluorescence than the compound (II), and increases the solubility of the dye. For example: Only 0.05 g was dissolved in 50 ml of methanol, and the improved dye:

0.2 g can be dissolved in 50 ml of methanol. Therefore, the compound (I) not only improves the application performance of the coumarin fluorescent dye, but also broadens the application range.

Example 1

Weigh 5 grams of 3-(benzothiazolyl)-7-N, N-diethylaminobenzopyrone-2 (0.0143 moles), the structural formula is as follows:

Add it to 13.3 grams of chlorosulfonic acid (0.114 moles), raise the temperature to 120°C, keep it at 120-130°C for 1 hour, cool it down to 10°C, add it to 120 grams of ice, filter, wash the filter cake with ice water, and wash until The washing water is weakly acidic, and the filter cake is added to a three-necked flask, 1.5 grams of diethylamine is added dropwise, kept at 0-10° C. for 2 hours, filtered and washed, and dried to obtain 6.7 grams of yellow coumarin fluorescent dye (theoretical yield of 96.7%) Mass spectrometry analysis of the prepared dye: M ⁺ 485 Elemental analysis: C% 59.1 H% 5.54 N% 8.6 S% 13.01

Example 2-18

By the method and condition similar to example 1, with the compound (II) of different substituents as raw material, can obtain following compound (as shown in table 1):

Table 1 instance number R ₈ R ₉ R ₁₀ R ₁₁ R ₁₂ R ₁₃ R ₁₄ R ₁₅ R ₁₆ R ₁₇ x 2 C ₂ H ₅ C ₂ H ₅ h h h h h _CH3 h h S 3 C ₂ H ₅ C ₂ H ₅ h h h h h Cl h h S 4 C ₂ H ₅ C ₂ H ₅ h h h h h h h h o 5 C ₂ H ₅ C ₂ H ₅ h h h h h _CH3 h h o 6 C ₂ H ₅ C ₂ H ₅ h h h h h Cl h h o 7 C ₂ H ₅ C ₂ H ₅ h h h h h h h h NH 8 C ₂ H ₅ C ₂ H ₅ h h h h h _CH3 h h NH 9 C ₂ H ₅ C ₂ H ₅ h h h h h Cl h h NH 10 C ₂ H ₅ C ₂ H ₅ h h h CN h h h h S 11 C ₂ H ₅ C ₂ H ₅ h h h CN h _CH3 h h S 12 C ₂ H ₅ C ₂ H ₅ h h h CN h Cl h h S 13 C ₂ H ₅ C ₂ H ₅ h h h CN h h h h o 14 C ₂ H ₅ C ₂ H ₅ h h h CN h _CH3 h h o 15 C ₂ H ₅ C ₂ H ₅ h h h CN h Cl h h o 16 C ₂ H ₅ C ₂ H ₅ h h h CN h h h h NH 17 C ₂ H ₅ C ₂ H ₅ h h h CN h _CH3 h h NH 18 C ₂ H ₅ C ₂ H ₅ h h h CN h Cl h h NH

Example 19-27

By the method and condition similar to example 1, can make following compound (as shown in table 2):

Table 2 instance number x R ₁₈ R ₁₉ 19 S h C ₂ H ₄ OH 20 S h C ₆ H ₄ (CH ₃ ) ₂ twenty one S h CH ₃ O(CH ₂ ) ₃ twenty two o h C ₂ H ₄ OH twenty three o h C ₆ H ₄ (CH ₃ ) ₂ twenty four o h CH ₃ O(CH ₂ ) ₃ 25 NH h C ₂ H ₄ OH 26 NH h C ₆ H ₄ (CH ₃ ) ₂ 27 NH h CH ₃ O(CH ₂ ) ₃

Example 28

Weigh 3 grams of the product obtained in Example 1 and add 30 grams of dimethylformamide to a 100 ml three-necked flask together, add 3 grams of 30% sodium cyanide solution, and keep warm at 40°C for 1 hour. 2.8 g of bromine were added dropwise, and 2.8 g of the following product were obtained by filtration.

Example 29-36

The product that uses example 2～9 to make is by the similar method and condition of example 28, can make the corresponding product of example 11～18.

Example 37-45

The product that uses example 19～27 to make is by example 28 similar methods and conditions, can make following compound (as shown in table 3):

table 3 instance number x R ₁₈ R ₁₉ 37 S h C ₂ H ₄ OH 38 S h C ₆ H ₄ (CH ₃ ) ₂ 39 S h CH ₃ O(CH ₂ ) ₃ 40 o h C ₂ H ₄ OH 41 o h C ₆ H ₄ (CH ₃ ) ₂ 42 o h CH ₃ O(CH ₂ ) ₃ 43 NH h C ₂ H ₄ OH 44 NH h C ₆ H ₄ (CH ₃ ) ₂ 45 NH h CH ₃ O(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,

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.