CN1594441A - Fluorescent coumarin dye - Google Patents

Abstract

The invention relates to a method for refining 1-nitroanthraquinone by using mixed nitroanthraquinone which consists of, charging solubilizing agent and auxiliary agent simultaneously for primary recrystallization into mixed nitroanthraquinone wherein the content of 1-nitroanthraquinone is 70-90%, the dissolvent is one or more from dimethyl formamide, chlorobenzene, toluene or dimethylbenzene, and the adjuvant is one or more from sulphur, sodium nitrite, urea, whose content is 0.5-3.0 wt% of the mixed nitroanthraquinone.

Description

Fluorescent coumarin dye

Technical field:

The present invention relates to organic functions dye well its preparation method, particularly a class and in the tonka bean camphor precursor structure, introduce the substituting group of unsaturated double-bond, can be used to prepare the tonka bean camphor polymeric fluorescent dye.

Background technology:

Fluorescence dye is a kind of very important function dyestuff, is widely used in departments such as industry, agricultural, medical science, weaving, the energy and national defence.The coloring intensity height of fluorescence dye, lovely luster is firmly got liking of people.Fluorescent coumarin dye is one of kind very important in the fluorescence dye, can be used as fluorescence dye, pigment, laser dyes etc.Their coloring intensity height, fluorescence quantum yield height, the chromatogram coverage is wide, and fluorescent yellow, fluorescent red and Day-Glo blue can be arranged, and has very high using value.

Germany publication Ger.Offen.2,058,877 has reported the preparation of the fluorescent coumarin dye of time array structure.

U.S. Pat 4,146,712 have reported the preparation of the fluorescent coumarin dye of time array structure.

Our Chinese patent ZL00101751.9 has reported and introduced the sulfonamide substitutions base in the fluorescent coumarin dye molecule before this, the fluorescent effect and the solvability of dyestuff have been strengthened, improved the application performance of dyestuff, but these dyestuffs are when being applied to dye, the simple mixing that all is dyestuff is dyestuff and synthon mechanically mixing, aspect of performance such as intensity, solvent resistance, heat-resisting, anti-migration a little less than.

Summary of the invention: the objective of the invention is in coloring intensity height, lovely luster, the fluorescent coumarin dye molecule that is loved by the people, to introduce can polymerization reaction take place two keys, the monomer of preparation tonka bean camphor polymeric fluorescent dye, these monomers can polymerization prepare the high molecular fluorescent polymeric material under the initiation of free radical.This class coumarine dye itself has lovely luster, and fluorescence intensive characteristic has purposes more widely.

The general structure of series fragrant legumin dye monomer of the present invention is as follows:

In the formula:

X represents O, S, NH;

N is 0～3;

Y represents OR ₁, NHCOR ₂, NHSO ₂R ₃Or R wherein ₁, R ₂, R ₄,

R ₅Can represent hydrogen, alkyl respectively, have substituent or not have substituent cycloalkyl, aralkyl or aryl, and with A ring form thick and 5～7 yuan of rings, R ₂, R ₃Represent alkyl, have substituent or do not have substituent cycloalkyl, aralkyl or aryl;

Z represents NR ₆, NCOR ₇, O, S, wherein R ₆Represent hydrogen, alkyl, have substituent or do not have substituent cycloalkyl, aralkyl or 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 or two benzofuran ring;

R ' represents hydrogen, alkyl, aralkyl or aryl;

R " represents hydrogen, alkyl, aralkyl or aryl.

The monomeric 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), reaction obtained compound (III) in 1～3 hour under 10～180 ℃, the intermediate compound IV that contains amino or secondary amine then with ammonia, primary amine condensation prepared, and then obtain fluorescent coumarin dye monomer V with acrylate chloride, the acyl chlorides condensation that contains unsaturated link(age).Reaction process can be expressed as follows:

The present invention introduces the acid amides of band unsaturated double-bond in the structure in the tonka bean camphor molecule after, the about 15nm of maximum absorption wavelength generation red shift of dyestuff, the molar absorptivity of dyestuff increases by 10 ⁴Lmol ^-1Cm ^-1, dye uptake is greatly improved when dyeing keratin-fiber, and under the situation of no dyeing and printing auxiliary, dye uptake can reach 97%.Particularly in molecular structure, introduce double bond containing substituting group, contained two substituent fluorescent coumarin dyes of key and can be used for preparing polymeric fluorescent dye, had extraordinary application prospect.

Description of drawings: Fig. 1 is the product mass spectrum of embodiment 1.Fig. 2 is the nucleus magnetic hydrogen spectrum (HNMR) of the product of embodiment 1.

Embodiment:

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 (0.0143mol) (S1), structural formula is as follows:

Be added in 13.3 gram (0.114mol) chlorsulfonic acids, be warmed up to 120 ℃, 120～130 ℃ of insulations 1 hour, cool to 10 ℃, reaction mixture is added in the 120 gram ice, filters, use the frozen water washing leaching cake, be washed till neutrality, filter cake is added in the there-necked flask, dropping ammonia 10 grams, kept 2 hours at 0～10 ℃, filter, obtain Yellow fluorochrome, yield 97%.

The dyestuff of the above-mentioned preparation of 5 grams is added among 5 milliliters of DMSO, is dripping third rare acyl chlorides below 10 ℃, use in the triethylamine simultaneously and the hydrochloric acid that generates, raw material is added in the water and separates out after disappearing, and filters, and washes filter cake with water and obtains following product, yield 85%.

The structure of product is identified: the molecular weight M of product ⁺=483, M+1=484 among the figure sees Fig. 1; Product ¹HNMR: see Fig. 2,, the ownership of each hydrogen atom such as following table.

The explanation of table 1 1HNMR figure

Chemical shift ppm	1.0～1.3	5.9	6.1	3.0～3.3	5.8～6.1	6.6～6.8	7.0～7.3	7.6	8.0
										Ownership	6H (1)	2H (10)	1 (9)	4H (2)	2H (3,4)	1H (5)	2H (7,8)	1H (1 1)	1H (6)

Embodiment 2

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 (0.0143mol), be added in 13.3 gram (0.114mol) chlorsulfonic acids, be warmed up to 120 ℃, 120～130 ℃ of insulations 1 hour, cool to 10 ℃, reaction mixture is added in the 120 gram ice, filters, use the frozen water washing leaching cake, be washed till neutrality, filter cake is added in the there-necked flask, add 10 milliliters of DMSO, at room temperature add 10 gram acrylamides, stirred under the room temperature 2 hours, and added 20 ml waters and separate out yellow crystal, filter and obtain the product same with example 1.

Embodiment 3～10

Press and example 1 similar method and condition, adopt different raw materials can be prepared as follows monomeric compound (as shown in table 2).

Table 2 adopts the different different dye monomers of feedstock production

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
												??3	?C 2H 5	?C 2H 5	??H	??H	??H	??H	??H	??CH 3	??H	??H	??S
??4	?C 2H 5	?C 2H 5	??H	??H	??H	??H	??H	??Cl	??H	??H	??S
												??5	?C 2H 5	?C 2H 5	??H	??H	??H	??H	??H	??H	??H	??H	??O
??6	?C 2H 5	?C 2H 5	??H	??H	??H	??H	??H	??CH 3	??H	??H	??O
												??7	?C 2H 5	?C 2H 5	??H	??H	??H	??H	??H	??Cl	??H	??H	??O
??8	?C 2H 5	?C 2H 5	??H	??H	??H	??H	??H	??H	??H	??H	??NH
												??9	?C 2H 5	?C 2H 5	??H	??H	??H	??H	??H	??CH 3	??H	??H	??NH
??10	?C 2H 5	?C 2H 5	??H	??H	??H	??H	??H	??Cl	??H	??H	??NH

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:

X represents O, S, NH;

N is 0～3;

Y represents OR ₁, NHCOR ₂, NHSO ₂R ₃Or R wherein ₁, R ₂, R ₄, R ₅Can represent hydrogen, alkyl respectively, have substituent or not have substituent cycloalkyl, aralkyl or aryl, and with A ring form thick and 5～7 yuan of rings, R ₂, R ₃Represent alkyl, have substituent or do not have substituent cycloalkyl, aralkyl or aryl;

Z represents NR ₆, NCOR ₇, O, S, wherein R ₆Represent hydrogen, alkyl, have substituent or do not have substituent cycloalkyl, aralkyl or 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 or two benzofuran ring;

R ' represents hydrogen, alkyl, aralkyl or aryl;

R " represents hydrogen, alkyl, aralkyl or aryl.

2. the preparation method of a class fluorescent coumarin dye compound is characterized in that this fluorescent coumarin dye is by compound (II):

With the chlorsulfonic acid of 2～20 times (molecular ratios),, reacted 1～3 hour at 50～180 ℃, make the intermediate sulfonyl chloride compound, then with the alkylamide condensation that contains unsaturated double-bond, or make compound (I) with the alkyl acyl chloride condensation that contains unsaturated double-bond more earlier and after the ammonia condensation, its general formula is:

In the formula: A, B, X, Y, Z, R ', R " have a definition given in the claim 1.

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