Coumarin fluorescent yellow disperse dye and preparation method thereof

Abstract

The invention provides a coumarin fluorescent yellow disperse dye and a preparation method thereof. The coumarin fluorescent yellow disperse dye has a structure as shown in the following formula (I): # imgabs0 # in the formula (I), R1 represents O or NH; r2 represents O, S, NH or CONH; and R3 represents Cl, CH3 or H. The color fastness to artificial light, the fastness to dry heat and the fastness to rubbing of the coumarin fluorescent yellow disperse dye disclosed by the invention are obviously improved.

Description

Technical Field

[0001] The invention relates to a coumarin fluorescent yellow disperse dye and a preparation method thereof, and belongs to the technical field of organic dye synthesis. Background Art

[0002] In recent years, coumarin fluorescent compounds have developed rapidly. Due to their high fluorescence quantum efficiency, strong structural modifiability, high biological activity, and wide adjustable absorption wavelength range, they are widely used in the fields of medicine, fragrance, dye, analysis, etc. People use coumarin as a matrix to carry out substitutions at different sites to change the electron movement trend within the molecule, thereby achieving changes in the fluorescence properties of the dye. When an electron-withdrawing group is introduced at the 3- or 4-position of coumarin, and an electron-donating group is introduced at the 6- or 7-position at the same time, the absorption and emission spectra move toward the long-wave direction, producing fluorescence of different properties. It is reported that except for a few derivatives obtained by introducing an alkyl group at the 7-position of the coumarin parent ring that can be used as fluorescent brighteners, most derivatives can obtain dyes of different colors. Introducing benzimidazole, benzoxazole, and benzothiazole at the 3-position in the coumarin parent structure is a widely used brilliant green yellow dye.

[0003] Coumarin fluorescent dyes have been further explored and studied by more and more domestic and foreign researchers due to their advantages of high emission intensity, bright color, strong fluorescence, etc. At present, there are two main synthetic routes for the synthesis of coumarin dyes. One method is to prepare 4-methyl-7-diethylaminocoumarin by ring condensation of m-hydroxy-N,N-diethylaniline and ethyl acetoacetate under catalyst conditions (see CN 111548337A). Although the product obtained by this synthetic route has high purity, the amount of catalyst and solvent is large, and some functional groups need to be protected during the reaction process, which is easy to produce three wastes and has relatively high cost.

[0004] Another method is to condense 4-diethylamino salicylaldehyde and ethyl cyanoacetate to generate 3-cyano-7-diethylaminocoumarin, and then react the condensate with 1,8-diazobispiro[5.4.0]undec-7-ene and trimethylsilyl cyanide to obtain 3,4-dicyano-7-diethylaminocoumarin dye (see CN 117285493A). This synthetic route has a long reaction time, a complicated operation process, and a low product yield. Summary of the invention

[0005] Problem that the invention aims to solve

[0006] In view of the technical problems existing in the prior art, the present invention first provides a coumarin fluorescent yellow disperse dye. The coumarin fluorescent yellow disperse dye of the present invention has significantly improved color fastness to artificial light, dry heat fastness and rubbing fastness.

[0007] The present invention also provides a method for preparing a coumarin fluorescent yellow disperse dye, which has a simple process, high reaction activity, pure product and high product quality. Compared with the traditional method for preparing coumarin fluorescent yellow disperse dye, the amount of solvent and catalyst, functional group tolerance and substrate range are greatly improved. In addition, the preparation method of the present invention is simple and easy to carry out industrial production.

[0008] Solutions for solving problems

[0009] The present invention provides a coumarin fluorescent yellow disperse dye, wherein the coumarin fluorescent yellow disperse dye has a structure shown in the following formula (I):

[0010]

[0011] In formula (I), R1 represents O or NH; R2 represents O, S, NH or CONH; and R3 represents Cl, CH3 or H.

[0012] The present invention also provides a method for preparing the coumarin fluorescent yellow disperse dye according to the present invention, which comprises the following steps:

[0013] Step 1): mixing a basic catalyst, 4-(diethylamino) salicylaldehyde and cyanoacetamide in a first organic solvent to obtain a first mixture;

[0014] Step 2): allowing 4-(diethylamino) salicylaldehyde in the first mixture to undergo an aldol condensation reaction with cyanoacetamide to obtain a first reaction product;

[0015] Step 3): subjecting the first reaction product to a deamination condensation reaction with an ortho-amino derivative to obtain a first coumarin fluorescent yellow disperse dye; the ortho-amino derivative has the following structure wherein R2 represents O, S, NH or CONH; R3 represents Cl, CH3 or H;

[0016] Optionally, the preparation method further comprises step 4), wherein step 4) comprises subjecting the first coumarin fluorescent yellow disperse dye to a hydrolysis reaction to obtain a second coumarin fluorescent yellow disperse dye.

[0017] According to the preparation method of the present invention, wherein, in the step 1), the molar ratio of the 4-(diethylamino) salicylaldehyde, the alkaline catalyst and cyanoacetamide is 0.8-2:0.1-0.2:1.

[0018] According to the preparation method of the present invention, the alkaline catalyst is sodium hydroxide, anhydrous sodium carbonate or a combination of one or more of triethylamine and piperidine; and / or,

[0019] The first organic solvent includes one or a combination of two or more of acetonitrile, tetrahydrofuran, ethanol or methanol.

[0020] According to the preparation method of the present invention, the reaction conditions of the aldol condensation reaction in step 2) include heating the first mixture to 40-55° C. and reacting for 3-4 hours.

[0021] According to the preparation method of the present invention, wherein the step 3) is carried out in the presence of a condensation promoter for deamination condensation reaction; preferably, the molar mass ratio of the condensation promoter to the ortho-amino derivative is 0.8 to 1.4:1; more preferably, the condensation promoter comprises one or a combination of two or more of H2SO4, HCl, H3PO4, and glacial acetic acid.

[0022] According to the preparation method of the present invention, the reaction conditions of the deamination condensation reaction in step 3) include cooling the first reaction product to 0-10°C, then mixing it with the condensation promoter and the ortho-amino derivative, and then refluxing it at 60-65°C for 6-20 hours.

[0023] According to the preparation method of the present invention, wherein the step 3) further comprises the step of recrystallizing the first coumarin fluorescent yellow disperse dye; preferably, the first coumarin fluorescent yellow disperse dye is recrystallized using a second organic solvent; more preferably, the second organic solvent comprises N,N-dimethylformamide.

[0024] According to the preparation method of the present invention, the hydrolysis reaction in step 4) is carried out in an inorganic solvent in the presence of an acidic reagent; preferably, the acidic reagent includes hydrochloric acid and / or sulfuric acid; and / or,

[0025] The conditions of the hydrolysis reaction in step 4) include a hydrolysis reaction at 80-85° C. for 1-2 hours.

[0026] According to the preparation method of the present invention, the mass ratio of the first coumarin fluorescent yellow disperse dye to the inorganic solvent is 1:50-100, and the molar ratio of the first coumarin fluorescent yellow disperse dye to the acidic reagent is 1:0.3-8.

[0027] Effects of the Invention

[0028] The color fastness to artificial light, the color fastness to dry heat and the color fastness to rubbing of the coumarin fluorescent yellow disperse dye of the present invention are all significantly improved.

[0029] Compared with the conventional preparation method of coumarin fluorescent yellow disperse dye, the preparation method of the present invention has significant improvements in terms of the amount of solvent and catalyst, functional group tolerance and substrate range. In addition, the preparation method of the present invention is simple and easy to carry out industrial production. DETAILED DESCRIPTION

[0030] Various exemplary embodiments, features and aspects of the present invention will be described in detail below. The word "exemplary" used here means "used as an example, embodiment or illustrative". Any embodiment described here as "exemplary" is not necessarily interpreted as being superior or better than other embodiments.

[0031] In addition, in order to better illustrate the present invention, numerous specific details are provided in the following specific embodiments. It should be understood by those skilled in the art that the present invention can be implemented without certain specific details. In other examples, methods, means, equipment and steps well known to those skilled in the art are not described in detail in order to highlight the subject matter of the present invention.

[0032] Unless otherwise stated, the units used in this specification are all international standard units, and the numerical values ​​and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.

[0033] In this specification, the word "may" means both performing a certain process and not performing a certain process.

[0034] In this specification, the references to "some specific / preferred embodiments", "other specific / preferred embodiments", "embodiments", etc., mean that the specific elements (e.g., features, structures, properties and / or characteristics) described in connection with the embodiments are included in at least one embodiment described herein, and may or may not exist in other embodiments. In addition, it should be understood that the elements may be combined in various embodiments in any suitable manner.

[0035] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints A and B.

[0036] <First aspect>

[0037] A first aspect of the present invention provides a coumarin fluorescent yellow disperse dye, wherein the coumarin fluorescent yellow disperse dye has a structure shown in the following formula (I):

[0038]

[0039] In formula (I), R1 represents O or NH; R2 represents O, S, NH or CONH; and R3 represents Cl, CH3 or H.

[0040] The color fastness to artificial light, the color fastness to dry heat and the color fastness to rubbing of the coumarin fluorescent yellow disperse dye of the present invention are all significantly improved.

[0041] The coumarin fluorescent yellow disperse dye of the present invention has the most obvious feature that a strong electron-donating amino group is introduced at the 7-position, and a strong electron-withdrawing group benzimidazole or benzoxazole is introduced at the 3-position to form push-pull electrons, thereby obtaining a strong fluorescent active compound. The compound has the advantages of high fluorescence quantum yield, good light resistance, bright color, good leveling performance, and the like, and has good application prospects in dyes, fluorescent probes, and the like.

[0042] The present invention also provides a method for preparing the coumarin fluorescent yellow disperse dye according to the present invention, which comprises the following steps:

[0043] Step 1): mixing a basic catalyst, 4-(diethylamino) salicylaldehyde and cyanoacetamide in a first organic solvent to obtain a first mixture;

[0044] Step 2): subjecting 4-(diethylamino) salicylaldehyde and cyanoacetamide in the first mixture to an aldol condensation reaction to obtain a first reaction product;

[0045] Step 3): subjecting the first reaction product to a deamination condensation reaction with an ortho-amino derivative to obtain a first coumarin fluorescent yellow disperse dye; the ortho-amino derivative has the following structure wherein R2 represents O, S, NH or CONH; R3 represents Cl, CH3 or H;

[0046] Optionally, the preparation method further comprises step 4), wherein step 4) comprises subjecting the first coumarin fluorescent yellow disperse dye to a hydrolysis reaction to obtain the coumarin fluorescent yellow disperse dye.

[0047] The invention allows 4-(diethylamino) salicylaldehyde to undergo aldol condensation with cyanoacetamide under the action of an alkaline catalyst, wherein the conditions in the process are mild and controllable, and then the product is subjected to deamination condensation and ring closure with an ortho-amino derivative, thereby finally obtaining a first coumarin fluorescent yellow disperse dye (i.e., a coumarin imine dye), and finally, after a hydrolysis reaction, a second coumarin fluorescent yellow disperse dye is obtained.

[0048] Compared with the conventional preparation method of coumarin fluorescent yellow disperse dye, the preparation method of the present invention has significant improvements in terms of solvent and catalyst dosage, functional group tolerance and substrate range. In addition, the preparation method of the present invention is simple and easy to carry out industrial production.

[0049] In some specific embodiments, in step 1), the molar ratio of 4-(diethylamino) salicylaldehyde, alkaline catalyst and cyanoacetamide is 0.8-2:0.1-0.2:1, preferably 0.8-1:0.1-0.15:1, for example: 0.9-1.8:0.11-0.19:1, 1-1.6:0.13-0.17:1, 1.2-1.4:0.14-0.15:1, etc. When the molar ratio of 4-(diethylamino) salicylaldehyde, alkaline catalyst and cyanoacetamide is 0.8-2:0.1-0.2:1, the reaction can be carried out more effectively.

[0050] In some specific embodiments, the alkaline catalyst is a combination of one or more of sodium hydroxide, anhydrous sodium carbonate or triethylamine and piperidine. Preferably, the alkaline catalyst is piperidine. The main function of the alkaline catalyst of the present invention is to promote the transfer of protons, so that the α-position hydrogen of the aldehyde group is easily transferred to the electrophilic reagent, and accelerate the aldol condensation reaction. Compared with triethylamine and piperidine, firstly, since the pKa value of piperidine is 11.2, and the pKa value of triethylamine is 10.6, and the larger the pKa, the stronger the alkalinity, therefore, the alkalinity of piperidine is greater than that of triethylamine; secondly, although piperidine is a secondary amine and triethylamine is a tertiary amine, due to the steric effect, piperidine is cyclized, and the lone electron pair is more likely to accept protons, so piperidine is more conducive to the aldol condensation reaction.

[0051] Specifically, in the present invention, the first organic solvent includes one or a combination of two or more of acetonitrile, tetrahydrofuran, ethanol or methanol.

[0052] In some specific embodiments, the reaction conditions of the aldol condensation reaction in step 2) are to heat the first mixture to 40-55°C, preferably 50-55°C for 3-4 hours. Specifically, the temperature of the aldol condensation reaction can be 42°C, 45°C, 48°C, 50°C, 51°C, 52°C, 53°C, 54°C, etc.; the time of the aldol condensation reaction can be 3.1 hours, 3.3 hours, 3.5 hours, 3.7 hours, etc. When the reaction temperature is 40-55°C and the reaction time is 3-4 hours, 4-(diethylamino) salicylaldehyde and cyanoacetamide can react completely, and the yield of the obtained product is higher.

[0053] In some specific embodiments, the step 3) is reacted in the presence of a condensation promoter. Since most cyclization reactions always shed some simple small molecules, such as H2O, NH3, HCl, HBr, C2H5OH, H2, etc., when forming a cyclic knot. In order to promote the shedding of small molecules and achieve deamination cyclization, the present invention is carried out under the action of a condensation promoter. Specifically, in the present invention, the condensation promoter can include one or a combination of two or more of H2SO4, HCl, H3PO4, glacial acetic acid, etc.

[0054] Preferably, the molar mass ratio of the condensation accelerator to the ortho-amino derivative is 0.8 to 1.4:1, preferably 1 to 1.4:1; for example: 0.85:1, 0.9:1, 1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1, etc. When the molar mass ratio of the condensation accelerator to the ortho-amino derivative is 0.8 to 1.4:1, the effect of the condensation accelerator can be more effectively exerted.

[0055] Furthermore, since the condensation promoter will cause intense heat release when diluted with methanol solvent, and its density is greater than that of methanol, it may cause splashing; in addition, when methanol reacts with the condensation promoter, the strong oxidizing and dehydrating properties of the condensation promoter may cause side reactions. Therefore, in the present invention, the reaction conditions of the deamination condensation reaction in step 3) include cooling the first reaction product to 0-10°C, for example: 1°C, 3°C, 5°C, 7°C, etc.

[0056] In the present invention, after the first reaction product is cooled to 0-10°C, the first reaction product is mixed with a condensation promoter and an ortho-amino derivative, and refluxed at 60-65°C for 6-20 hours. Specifically, the temperature of the deamination condensation reaction can be 61°C, 62°C, 63°C, 64°C, etc.; the time of the aldol condensation reaction can be 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, etc. When the temperature of the deamination condensation reaction is 60-65°C and the time of the deamination condensation reaction is 6-20 hours, the first reaction product and the ortho-amino derivative can react completely, and the yield of the obtained product is higher.

[0057] In some specific embodiments, the step 3) further comprises the step of recrystallizing the first coumarin fluorescent yellow disperse dye; the inventors of the present invention have found that by recrystallizing the first coumarin fluorescent yellow disperse dye, the color and purity of the second coumarin fluorescent yellow disperse dye can be improved. Preferably, the first coumarin fluorescent yellow disperse dye is recrystallized using a second organic solvent; more preferably, the second organic solvent comprises N,N-dimethylformamide.

[0058] In some specific embodiments, the hydrolysis reaction of step 4) is carried out in an inorganic solvent in the presence of an acidic reagent. The first coumarin fluorescent yellow disperse dye can be hydrolyzed to a corresponding carbonyl under acidic conditions. Specifically, the acidic reagent can be hydrochloric acid and / or sulfuric acid. The inorganic solvent is water.

[0059] In some specific embodiments, the mass ratio of the first coumarin fluorescent yellow disperse dye to the inorganic solvent is 1:50-100, for example: 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, 1:85, 1:90, 1:95, etc. The molar ratio of the first coumarin fluorescent yellow disperse dye to the acidic reagent is 1:0.3-8, preferably 1:0.5-1.2, for example: 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, etc. When the mass ratio of the first coumarin fluorescent yellow disperse dye to the inorganic solvent is 1:50-100, and the molar ratio of the first coumarin fluorescent yellow disperse dye to the acidic reagent is 1:0.3-8, the reaction can be carried out better.

[0060] Further, in the present invention, the hydrolysis reaction conditions of step 4) are 80-85°C for 1-2 hours. Specifically, the temperature of the hydrolysis reaction can be 81°C, 82°C, 83°C, 84°C, etc.; the time of the hydrolysis reaction can be 1.1 hours, 1.3 hours, 1.5 hours, 1.7 hours, 1.9 hours, etc. When the temperature of the hydrolysis reaction is 80-85°C and the time of the hydrolysis reaction is 1-2 hours, the reaction can be complete and the yield of the product is higher.

[0061] Example

[0062] The embodiments of the present invention will be described in detail below in conjunction with the examples, but those skilled in the art will appreciate that the following examples are only used to illustrate the present invention and should not be considered to limit the scope of the present invention. If no specific conditions are specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be obtained commercially.

[0063] Example 1

[0064] (a) adding 90 ml of methanol solvent (MeOH), (0.53 g, 0.0062 mol) of basic catalyst piperidine (pip), (0.037 mol, 7.14 g) of 4-(diethylamino) salicylaldehyde and (0.044 mol, 3.73 g) of cyanoacetamide to a reaction vessel in sequence to obtain a first mixture;

[0065] (b) The first mixture was heated to 50°C for reaction and maintained for 3 hours, and the reaction endpoint was determined by HPLC. The specific reaction formula is as follows:

[0066]

[0067] (c) The product of step (b) was cooled to 10°C and an o-amino derivative (0.037 mol, 4.0 g) was added. and (98%, 3.7g) sulfuric acid; slowly heat to about 62°C and reflux for 6 hours. Cool to about 2°C to precipitate a yellow crystalline material, filter to obtain a filter cake, wash the filter cake with ice water until neutral to obtain coumarin imine dye (HPLC purity 97.76%, yield 92.15%), and recycle the methanol solvent in the mother liquor. The specific reaction formula is as follows:

[0068]

[0069] (d) Disperse 6 g of coumarin imine dye in 300 g of water, add 1.8 mL of 37% (mass fraction) concentrated hydrochloric acid, stir thoroughly to dissolve, and react at a temperature of about 82°C for 1 hour. Cool, filter, and wash to neutrality to obtain coumarin fluorescent yellow disperse dye (yield 88.71%, HPLC purity 99.43%). The specific reaction formula is as follows:

[0070]

[0071] Example 2

[0072] The difference between Example 2 and Example 1 is that in step (a), 90 ml of methanol solvent, 0.37 g of alkaline catalyst piperidine, 7.14 g of 4-(diethylamino) salicylaldehyde and 2.63 g of cyanoacetamide are added to the reaction container in sequence; the remaining steps, raw material composition and dosage are exactly the same as in Example 1.

[0073] The yield of coumarin fluorescent yellow disperse dye obtained by filtration and washing is about 82.2% and the HPLC purity is 95.9%.

[0074] Example 3

[0075] The difference between Example 3 and Example 1 is that in step (a), 0.6 g of basic catalyst triethylamine, 90 ml of methanol solvent, 7.14 g of 4-(diethylamino) salicylaldehyde and 3.73 g of cyanoacetamide are added to the reaction container in sequence to obtain a first mixture. The remaining steps, raw material composition and dosage are exactly the same as those in Example 1.

[0076] The yield of coumarin fluorescent yellow disperse dye obtained by filtration and washing is about 61.65% and the HPLC purity is 95.12%.

[0077] Example 4

[0078] The difference between Example 4 and Example 1 is that in step (b), the first mixture is heated to 40°C for reaction and maintained for 3 hours, and the reaction endpoint is determined by HPLC. The remaining steps, raw material composition and dosage are exactly the same as those in Example 1.

[0079] The yield of coumarin fluorescent yellow disperse dye obtained by filtration and washing is about 84.04% and the HPLC purity is 95.96%.

[0080] Example 5

[0081] Example 5 is different from Example 1 in that in step (c), (0.04 mol 5.8 g) of an o-amino derivative is added (CAS 95-85-2). The remaining steps, raw material composition and dosage are exactly the same as those in Example 1.

[0082] The yield of coumarin fluorescent yellow disperse dye obtained by filtration and washing is about 89.52% and the HPLC purity is 95.64%.

[0083] Example 6

[0084] The difference between Example 6 and Example 5 is that the reaction condition of step (c) is to heat the reaction to about 62° C. and maintain the reflux reaction for 20 hours. The remaining steps, raw material composition and dosage are exactly the same as those in Example 5.

[0085] The yield of coumarin fluorescent yellow disperse dye obtained by filtration and washing is about 91.13%, and the HPLC purity is 96.22%.

[0086] Example 7

[0087] The hydrolysis reaction step (d) of Example 6 was replaced by recrystallization, that is, 6 g of coumarin imine dye was added to 42 g of DMF for recrystallization. The remaining steps, raw material composition and dosage were exactly the same as those of Example 6.

[0088] The yield of the finished coumarin fluorescent yellow disperse dye obtained after recrystallization is about 73.09% and the HPLC purity is 99.69%.

[0089] Example 8

[0090] The hydrolysis reaction step (d) of Example 1 was replaced by recrystallization, that is, 6 g of coumarin imine dye was added to 42 g of DMF for recrystallization. The remaining steps, raw material composition and dosage were exactly the same as those of Example 1.

[0091] The yield of coumarin fluorescent yellow disperse dye obtained after recrystallization is about 73.43% and the HPLC purity is 98.89%.

[0092] Example 9

[0093] The difference between Example 9 and Example 1 is that in step (d), 6 g of coumarin imine dye is dispersed in 300 g of water, 0.5 mL of 37% (mass fraction) concentrated hydrochloric acid is added, stirred to dissolve, and stirred at 82° C. for 1 hour. The remaining steps, raw material composition and dosage are exactly the same as those in Example 1.

[0094] The yield of coumarin fluorescent yellow disperse dye obtained by filtration and washing is about 89.16%, and the HPLC purity is 95.51%.

[0095] Example 10

[0096] The difference between Example 10 and Example 1 is that in step (d), 6 g of coumarin imine dye is dispersed in 300 g of water, 11.73 mL of 37% (mass fraction) concentrated hydrochloric acid is added, stirred to dissolve, and stirred at 82° C. for 1 hour. The remaining steps, raw material composition and dosage are exactly the same as those in Example 1.

[0097] The yield of coumarin fluorescent yellow disperse dye obtained by filtration and washing is about 79.32%, and the HPLC purity is 98.97%.

[0098] Embodiment 11

[0099] The difference between Example 10 and Example 1 is that in step (c), only sulfuric acid is not added, and the remaining steps, raw material composition and dosage are exactly the same as those in Example 1.

[0100] The yield of coumarin fluorescent yellow disperse dye obtained by filtration and washing is about 83.43%, and the HPLC purity is 95.57%.

[0101] Performance Testing

[0102] 1. Extinction performance test

[0103] Use spectrophotometer to test the maximum absorption wavelength λ max ab , maximum excitation wavelength λ max ex and the maximum emission wavelength λ max em , and at the maximum absorption wavelength λ max ab The absorbance A was measured by a spectrophotometer, and then the molar extinction coefficient ε was calculated according to the Lambert-Beer law.

[0104] Calculate the maximum emission wavelength λ max em With the maximum excitation wavelength λ max ex The difference is the Stokes shift.

[0105] 2. Dyeing performance test

[0106] According to the test methods of GB / T8427-2008, GB / T5718-97 and GB / T3920-97, the color fastness to artificial light, the color fastness to dry heat (210°C) and the color fastness to rubbing of coumarin fluorescent yellow disperse dye were tested. The results are shown in Table 1 below.

[0107] Table 1

[0108]

[0109] In the present invention, the molar extinction coefficient actually reflects the maximum absorption wavelength λ of the dye. max ab The higher the molar extinction coefficient, the stronger the absorption capacity, the higher the energy obtained by the dye, the more fluorescent photons emitted, and the brighter the fluorescence.

[0110] It can be seen from Table 1 that as the substituent of R3 changes from H to Cl, its maximum absorption wavelength and maximum emission wavelength are both red-shifted, and the Stoke shift increases. This is because the electron-withdrawing substituent chlorine absorbs electrons in the conjugated bond system, which will deepen the color of the dye molecule. The addition of the electron-withdrawing substituent Cl has a greater impact on coumarin fluorescent yellow disperse dyes, which can increase the electron cloud density in the dye molecule, and thus play a positive role in increasing the absorption wavelength and excitation wavelength of the dye, and increasing the molar extinction coefficient.

[0111] In addition, it can be seen from Table 1 that the coumarin fluorescent yellow disperse dyes obtained in Examples 1-11 of the present invention have excellent color light fastness, dry heat fastness and rubbing fastness. In addition, when the substituent of R3 is Cl, its color light fastness, dry heat fastness and rubbing fastness are even better.

[0112] It should be noted that, although the technical solution of the present invention is introduced with specific examples, those skilled in the art will appreciate that the present invention should not be limited thereto.

[0113] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The selection of terms used herein is intended to best explain the principles of the embodiments, practical applications, or technical improvements in the market, or to enable other persons of ordinary skill in the art to understand the embodiments disclosed herein.

Claims

1. A coumarin fluorescent yellow disperse dye, characterized in that: The coumarin fluorescent yellow disperse dye has a structure shown in the following formula (I): In formula (I), R1 represents O or NH; R2 represents O, S, NH or CONH; and R3 represents Cl, CH3 or H.

2. A method for preparing the coumarin fluorescent yellow disperse dye according to claim 1, characterized in that: The following steps are involved: Step 1): mixing a basic catalyst, 4-(diethylamino) salicylaldehyde and cyanoacetamide in a first organic solvent to obtain a first mixture; Step 2): allowing 4-(diethylamino) salicylaldehyde in the first mixture to undergo an aldol condensation reaction with cyanoacetamide to obtain a first reaction product; Step 3): subjecting the first reaction product to a deamination condensation reaction with an ortho-amino derivative to obtain a first coumarin fluorescent yellow disperse dye; the ortho-amino derivative has the following structure wherein R2 represents O, S, NH or CONH; R3 represents Cl, CH3 or H; Optionally, the preparation method further comprises step 4), wherein step 4) comprises subjecting the first coumarin fluorescent yellow disperse dye to a hydrolysis reaction to obtain a second coumarin fluorescent yellow disperse dye.

3. The preparation method according to claim 2, characterized in that: In the step 1), the molar ratio of the 4-(diethylamino) salicylaldehyde, the alkaline catalyst and cyanoacetamide is 0.8-2:0.1-0.2:

1.

4. The preparation method according to claim 3, characterized in that: The alkaline catalyst is sodium hydroxide, anhydrous sodium carbonate or a combination of triethylamine and piperidine or more than two thereof; and / or, The first organic solvent includes one or a combination of two or more of acetonitrile, tetrahydrofuran, ethanol or methanol.

5. The preparation method according to any one of claims 2 to 4, characterized in that: The reaction conditions of the aldol condensation reaction in step 2) include heating the first mixture to 40-55° C. and reacting for 3-4 hours.

6. The preparation method according to any one of claims 2 to 5, characterized in that: The step 3) is to carry out a deamination condensation reaction in the presence of a condensation promoter; preferably, the molar mass ratio of the condensation promoter to the ortho-amino derivative is 0.8-1.4:1; more preferably, the condensation promoter includes one or a combination of two or more of H2SO4, HCl, H3PO4, and glacial acetic acid.

7. The preparation method according to claim 6, characterized in that: The reaction conditions of the deamination condensation reaction in step 3) include cooling the first reaction product to 0-10° C., then mixing it with the condensation accelerator and the ortho-amino derivative, and then refluxing it at 60-65° C. for 6-20 hours.

8. The preparation method according to any one of claims 2 to 7, characterized in that: The step 3) further comprises the step of recrystallizing the first coumarin fluorescent yellow disperse dye; preferably, the first coumarin fluorescent yellow disperse dye is recrystallized using a second organic solvent; more preferably, the second organic solvent comprises N,N-dimethylformamide.

9. The preparation method according to any one of claims 2 to 8, characterized in that: The hydrolysis reaction in step 4) is carried out in an inorganic solvent in the presence of an acidic reagent; preferably, the acidic reagent includes hydrochloric acid and / or sulfuric acid; and / or, The conditions of the hydrolysis reaction in step 4) include a hydrolysis reaction at 80-85° C. for 1-2 hours.

10. The preparation method according to claim 9, characterized in that: The mass ratio of the first coumarin fluorescent yellow disperse dye to the inorganic solvent is 1:50-100, and the molar ratio of the first coumarin fluorescent yellow disperse dye to the acidic reagent is 1:0.3-8.

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