A method for preparing azo disperse dyes

Abstract

The present disclosure relates to the field of dye chemical industry, and in particular to a method for preparing azo disperse dyes. The method provided by the present disclosure comprises the following steps: subjecting an aromatic compound containing a nitro group and a primary amine to a diazo reaction with a nitrous acid compound to obtain a diazo compound intermediate product; and subjecting the diazo compound intermediate product to a coupling reaction with a compound containing a tertiary amine under the action of a phase transfer catalyst to obtain an azo disperse dye.

Description

Technical Field

[0001] The present invention relates to the field of dye chemical industry, and in particular to a method for preparing azo disperse dyes. Background Art

[0002] Azo disperse dyes have the advantages of complete color spectrum, simple synthesis process, low cost, good dyeing performance, etc., so they occupy an important position in dye products, making them the largest type of industrial dyes in terms of variety and output, and the synthesis technology and new chemical structure are still developing. The method of manufacturing azo disperse dyes mainly includes two steps: diazotization reaction and coupling reaction.

[0003] The reaction of aromatic primary amines and nitrous acid to form diazonium salts is called diazotization reaction. Aromatic primary amines are often called diazo components, and nitrous acid is the diazotization reagent. Because nitrous acid is unstable, nitrosylsulfuric acid and sodium nitrite are usually used as diazotization agents in the presence of hydrochloric acid or sulfuric acid. The released nitrous acid immediately reacts with aromatic primary amines to avoid the decomposition of nitrous acid. The diazotization reaction of aromatic primary amines generates diazonium salts. The reaction of aromatic diazonium salts with phenols and aromatic amines to form azo compounds is called coupling reaction; phenols and aromatic amines are coupling components.

[0004] The diazotization reaction is carried out in the presence of an inorganic acid. The role of the inorganic acid is to dissolve the aromatic amine, then generate nitrous acid with sodium nitrite, or stabilize nitrosyl sulfuric acid; finally, it reacts with the aromatic amine to generate a diazonium salt. Diazo salts are easy to decompose under normal conditions and are relatively stable only in excess acid. The excess of acid depends on the alkalinity of the aromatic amine. The weaker the alkalinity, the more excess there is, generally exceeding 25% to 100%, and some excesses are even more. Since diazonium salts are unstable in the reaction system, they are prone to self-coupling and decomposition. Although the diazonium component and the coupling component are 1:1 in the chemical reaction formula, the diazonium component is often in excess in the actual reaction. The more excess there is, the lower the purity of the reaction product and the higher the raw material cost. Inhibiting the decomposition of diazonium salts and improving the reaction efficiency are effective ways to increase the yield of azo disperse dyes.

[0005] The coupling reaction is usually a solid-liquid reaction, and the reaction is mainly controlled by mass transfer. As the reaction proceeds, the concentration of the reactants continues to decrease, the reaction rate is also getting slower and slower, and there are more and more side reactions. In particular, the local pH value and temperature change greatly during the reaction, and the decomposition of the diazonium salt is more likely to occur. If a catalyst that can stabilize the diazonium salt intermediate and increase the reaction rate is found, the stability of the reaction system can be improved, the decomposition of the diazonium salt can be reduced, the reaction time can be shortened, and the product yield can be increased. Therefore, in the coupling reaction, a catalyst that can stabilize the diazonium salt intermediate and increase the coupling reaction rate is urgently needed. Summary of the invention

[0006] The purpose of the present disclosure is to provide a method for preparing azo disperse dyes to solve the above problems.

[0007] To achieve the above objectives, the present disclosure provides the following technical solutions:

[0008] According to a first aspect of an embodiment of the present disclosure, there is provided a method for preparing an azo disperse dye, the method comprising the following steps:

[0009] Step 1: subjecting an aromatic compound containing a nitro group and a primary amine to a diazotization reaction with a nitrous acid compound to obtain a diazo compound intermediate;

[0010] Step 2: Under the action of a phase transfer catalyst, coupling the diazo compound intermediate product with a compound containing a tertiary amine to obtain the azo disperse dye;

[0011] The aromatic compound containing a nitro group and a primary amine has the following chemical formula I (hereinafter referred to as Compound I):

[0012]

[0013] wherein Ar1 is selected from a C5-C12 aryl group or a 5-12 membered heteroaryl group; R1 is selected from a hydrogen, a halogen atom, an amino group, a nitro group, a hydroxyl group, a carboxyl group, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C1-C10 alkoxy group, a C3-12 cycloalkyl group or a 3-12 membered heterocyclic group;

[0014] The nitrite compound is selected from nitrosylsulfuric acid, sodium nitrite, calcium nitrite, potassium nitrite, ammonium nitrite or lead nitrite;

[0015] The tertiary amine-containing compound has the following chemical formula II (hereinafter referred to as compound II):

[0016]

[0017] wherein R2 and R3 are each independently selected from C1-C10 alkyl, C2-C10 alkenyl or C2-C10 alkynyl, and the C1-C10 alkyl, C2-C10 alkenyl or C2-C10 alkynyl is optionally substituted with one or more halogen atoms, amino, nitro, hydroxyl, carboxyl, cyano, C5-C12 aryl, 5-12 membered heteroaryl, C3-12 cycloalkyl or 3-12 membered heterocyclyl;

[0018] R4 and R5 are each independently selected from hydrogen, a halogen atom, an amino group, a nitro group, a hydroxyl group, a carboxyl group, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C1-C10 alkoxy group, a C3-12 cycloalkyl group, a 3-12 membered heterocyclic group or ; R 41Selected from C1-C10 alkyl or C2-C10 alkenyl;

[0019] The azo disperse dye has the following chemical formula III:

[0020]

[0021] In one aspect of the embodiments of the present disclosure, Ar1 is selected from phenyl, benzothiazolyl or benzimidazole; specifically, Ar1 is selected from phenyl or benzothiazolyl.

[0022] In one aspect of the embodiments of the present disclosure, R2 and R3 are each independently selected from C1-C10 alkyl or C2-C10 alkenyl; the C1-C10 alkyl or C2-C10 alkenyl is optionally substituted with a nitro, hydroxyl, cyano, phenyl or naphthyl.

[0023] In one aspect of the embodiments of the present disclosure, there is provided a method for preparing an azo disperse dye, the method comprising the following steps:

[0024] Step 1: adding the aromatic compound containing nitro and primary amine into an acidic solution and dissolving it, then cooling it to below 20° C., adding a nitrite compound under stirring to carry out a diazotization reaction, the reaction time is selected from 0.5-4 hours, to obtain an intermediate product;

[0025] Step 2: Under the action of a phase transfer catalyst, the intermediate product is subjected to a coupling reaction with a compound containing a tertiary amine to obtain the azo disperse dye.

[0026] In one aspect of the disclosed embodiments, the phase transfer catalyst has the following chemical formula IV:

[0027]

[0028] Wherein, R7 is selected from C5-C20 alkyl, R8 and R9 are each independently selected from C1-C10 alkyl or C2-C10 alkenyl; and X1 is selected from O, C or N.

[0029] In one aspect of the embodiments of the present disclosure, the phase transfer catalyst has the following chemical formulas of Formula IV-1 to Formula IV-4:

[0030]

[0031]

[0032]

[0033] In one aspect of the embodiments of the present disclosure, the molar ratio of the intermediate product to the catalyst is selected from 1:(0.01-0.1).

[0034] In one aspect of the embodiments of the present disclosure, there is provided a method for preparing an azo disperse dye, the method comprising the following steps:

[0035] Add an acidic solution and a nitrous acid compound to a three-necked flask, place the three-necked flask in ice water and cool to 20°C, slowly add an aromatic compound containing a nitro group and a primary amine under stirring conditions, and control the temperature to be 20°C-25°C. After the addition is completed, continue to stir and react at a temperature of 20°C-25°C for 20-40 minutes, use a dropper to take a small amount of the reaction solution and add it to the ice water and stir quickly and evenly. If it is completely dissolved in the ice water and becomes transparent and the reaction solution can turn starch potassium iodide blue, the reaction is terminated, and the reaction solution is cooled to 5°C for standby use;

[0036] Add water and a phase transfer catalyst into a beaker, add 2-N,N-diallyl-4-acetylaminoanisole under stirring, and beat at room temperature for 20-40 minutes to obtain a dispersion; cool the dispersion to -2°C-1°C with ice brine, slowly drop the reaction solution cooled to 5°C, keep the dropping temperature at -2°C-1°C, detect the end point of the coupling reaction when the remaining volume of the reaction solution is 8%-15% of the original volume, continue stirring for 20-40 minutes after reaching the end point of the coupling reaction, then heat to 40°C-55°C and keep stirring for 45-70 minutes, and then filter, wash to neutrality, and dry to obtain an azo disperse dye.

[0037] In one aspect of the embodiments of the present disclosure, the acidic solution is hydrochloric acid or sulfuric acid.

[0038] In one aspect of the embodiments of the present disclosure, specifically, the aromatic compound containing a nitro group and a primary amine is selected from 2,4-dinitro-6-chloroaniline, p-nitroaniline or 2-amino-6-nitro-benzothiazole.

[0039] In one aspect of the embodiments of the present disclosure, the phase transfer catalyst is prepared by the following steps:

[0040] Step 1-a: using o-phenylenediamine and dichloroacetic acid as raw materials to obtain intermediate product 1-a;

[0041]

[0042] Step 2-a: using a long-chain organic acid as a raw material to obtain an intermediate product 2-a; wherein n is selected from an integer from 7 to 15;

[0043]

[0044] Step 3-a: preparing intermediate product 3-a through intermediate product 2-a;

[0045]

[0046] Step 4-a: preparing the azo disperse dye through the intermediate product 2-a;

[0047]

[0048] According to a second aspect of the embodiments of the present disclosure, an azo disperse dye is provided, wherein the azo disperse dye is prepared by the aforementioned method.

[0049] The technical solution provided by the embodiments of the present disclosure may have the following beneficial effects:

[0050] It can be seen from the above embodiments that the present disclosure prepares a phase transfer catalyst that can stabilize the diazonium salt intermediate product and increase the coupling reaction rate in the coupling reaction. Through the phase transfer catalyst of the present disclosure, the present disclosure obtains a preparation method that can improve the purity and yield of azo disperse dyes.

[0051] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure. DETAILED DESCRIPTION

[0052] In order to make the purpose, technical solutions and advantages of the present disclosure clearer, the technical solutions of the present disclosure will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present disclosure, rather than all of the embodiments. The relevant embodiments described herein are illustrative in nature and are used to provide a basic understanding of the present disclosure. The embodiments of the present disclosure should not be interpreted as limiting the present disclosure. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present disclosure. On the contrary, they are merely examples of devices and methods consistent with some aspects of the present disclosure as detailed in the attached claims.

[0053] For simplicity, the present disclosure only specifically discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an undefined range; and any lower limit can be combined with other lower limits to form an undefined range, and any upper limit can be combined with any other upper limit to form an undefined range. In addition, each separately disclosed point or single value can itself be combined as a lower limit or upper limit with any other point or single value or with other lower limits or upper limits to form an undefined range.

[0054] In the present disclosure, the terms "comprises", "comprising" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further limitations, an element defined by the sentence "comprising a ..." does not exclude the presence of additional identical elements in the process, method, article or device comprising the element.

[0055] In the description of the present disclosure, unless otherwise specified, “above” and “below” include the present number.

[0056] Unless otherwise specified, the terms used in this disclosure have the commonly known meanings generally understood by those skilled in the art. Unless otherwise specified, the numerical values ​​of the various parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the embodiments of this disclosure).

[0057] The term "about" is used to describe and illustrate small changes. When used in conjunction with an event or situation, the term may refer to an example in which the event or situation occurs precisely and an example in which the event or situation occurs very approximately. For example, when used in conjunction with a numerical value, the term may refer to a range of variation less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. In addition, amounts, ratios, and other numerical values ​​are sometimes presented in the present disclosure in a range format. It should be understood that such a range format is for convenience and simplicity, and should be flexibly understood to include not only numerical values ​​explicitly designated as range limits, but also all individual numerical values ​​or subranges encompassed within the range, as if each numerical value and subrange were explicitly designated.

[0058] A list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items A and B are listed, the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B, and C are listed, the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

[0059] In the present disclosure, the term "alkyl" refers to an aliphatic hydrocarbon group, which can be straight or branched. Branched refers to one or more lower alkyl groups connected to a linear alkyl chain, such as methyl, ethyl or propyl. For example, the term "C3-C12 alkyl" includes, but is not limited to: n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, etc.

[0060] In the present disclosure, the term "alkenyl" refers to an aliphatic hydrocarbon group, which contains at least one carbon-carbon double bond, which can be straight or branched, containing about 2 to about 15 carbon atoms in the chain, and preferred alkenyls contain about 2 to about 12 carbon atoms in the chain, and more preferably contain about 2 to about 6 carbon atoms in the chain. Branched refers to one or more low alkyl groups connected to a linear alkenyl chain, such as methyl, ethyl or propyl. The non-limiting examples of suitable alkenyls include vinyl, propenyl, n-butenyl, 3-methylbut-2-enyl, n-pentenyl, octenyl and decenyl.

[0061] In the present disclosure, the term "alkynyl" refers to an aliphatic hydrocarbon group containing at least one carbon-carbon triple bond, which can be straight or branched, containing about 2 to about 15 carbon atoms in the chain, preferably alkynyl containing about 2 to about 12 carbon atoms in the chain, more preferably containing about 2 to about 4 carbon atoms in the chain. Branched refers to one or more lower alkyl groups, such as methyl, ethyl or propyl, attached to a linear alkynyl chain. Non-limiting examples of suitable alkynyl groups include ethynyl, propynyl, 2-butynyl, 3-methylbutynyl, n-pentynyl and decynyl.

[0062] In the present disclosure, the term "aryl" refers to an aromatic monocyclic or polycyclic ring system. The aryl group may be optionally substituted with one or more "ring system substituents", which may be the same or different, and are as defined in the present disclosure. Non-limiting examples of suitable aryl groups include phenyl and naphthyl.

[0063] In the present disclosure, the term "alkoxy" refers to -O-alkyl. Alkoxy can refer to a straight, branched or cyclic, saturated or unsaturated oxy-hydrocarbon chain, including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy and pentoxy. Alkoxy can be optionally substituted with one or more alkoxy substituents. For example, the term "C1-C8 alkyl" includes, but is not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy or n-hexoxy etc.

[0064] In the present disclosure, the term "cycloalkyl" refers to a non-aromatic mono- or polycyclic ring system containing about 3 to about 10 carbon atoms, preferably about 5 to about 10 carbon atoms, and the preferred cycloalkyl ring contains about 5 to about 7 ring atoms. The cycloalkyl group may be optionally substituted with one or more "ring system substituents", which may be the same or different and are defined as above. Non-limiting examples of suitable monocyclic cycloalkyls include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Non-limiting examples of suitable polycyclic cycloalkyls include 1-decalinyl, norbornyl, adamantyl, etc.

[0065] In the present disclosure, the term "heterocyclyl" refers to a non-aromatic saturated monocyclic or polycyclic ring system containing about 3 to about 10 ring atoms, preferably about 5 to about 10 ring atoms, wherein one or more of the ring atoms in the ring system is an element other than carbon, such as nitrogen, oxygen or sulfur, either alone or in combination. There are no adjacent oxygen and / or sulfur atoms in the ring system, and preferred heterocycles contain about 5 to about 6 ring atoms. The prefix aza, oxa or thia before the heterocyclyl root name indicates that at least one nitrogen, oxygen or sulfur atom, respectively, is present as a ring atom. The nitrogen or sulfur atom of the heterocyclyl may be optionally oxidized to the corresponding N-oxide, S-oxide or S,S-dioxide. Non-limiting examples of suitable monocyclic heterocyclyl rings include piperidinyl, pyrrolidinyl, piperazinyl, morpholinyl, thiomorpholinyl, thiazolidinyl, 1,3-dioxolanyl, 1,4-dioxacyclohexyl, tetrahydrofuranyl, tetrahydrophenylthio, tetrahydrothiopyranyl, and the like.

[0066] In this disclosure, the term "heteroaryl" refers to an aromatic monocyclic or polycyclic ring system containing about 5 to about 14 ring atoms, preferably about 5 to about 10 ring atoms, wherein one or more of the ring atoms is an element other than carbon, such as nitrogen, oxygen or sulfur, alone or in combination, with preferred heteroaryls containing about 5 to about 6 ring atoms. The prefix aza, oxa or thia before the heteroaryl root name means that at least one nitrogen, oxygen or sulfur atom, respectively, is present as a ring atom. The nitrogen atom of the heteroaryl group may be optionally oxidized to the corresponding N-oxide. Non-limiting examples of suitable heteroaryl groups include pyridinyl, pyrazinyl, furanyl, thiophenyl, pyrimidinyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrrolyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, 2,3-naphthyridinyl, imidazo[1,2-a]pyridinyl, imidazo[2,1-b]thiazolyl, benzofurazanyl, indolyl, azaindolyl, benzimidazolyl, benzothiophenyl, quinolinyl, imidazolyl, thienopyridinyl, quinazolinyl, thienopyrimidinyl, pyrrolopyridinyl, imidazopyridinyl, isoquinolinyl, benzazaindolyl, 1,2,4-triazinyl, benzothiazolyl, and the like.

[0067] The present disclosure provides compounds having formula IV-1 as catalysts:

[0068]

[0069] The preparation method of the compound comprises the following steps:

[0070] Step 1-a: using o-phenylenediamine and dichloroacetic acid as raw materials to obtain intermediate product 1-a;

[0071]

[0072] The reaction in step 1-a actually includes the following two steps:

[0073]

[0074] Specifically, the method includes: adding 27 mL of water, 37.5 mL of 30% (mass fraction) hydrochloric acid, 6.8 mL of dichloroacetic acid and 4.5 g of o-phenylenediamine to a 250 mL three-necked flask in sequence; reflux at 105°C-110°C for 10 hours; then cooling and adjusting the volume to 120 mL. Add 150 mL of water and 5 g of Na2CO3 to another 1000 mL three-necked flask, keep stirring and add 150 g of ice, adjust the temperature to below 5°C, add the above condensation liquid to the 250 mL three-necked flask in a thin stream, control the temperature below 10°C with an ice water bath, add it in about 1 hour, keep the bright yellow test paper red (pH≈8), otherwise, add Na2CO3 until the bright yellow test paper turns red; then add 500 mL of water, filter, wash the filter cake with water until the bright yellow test paper turns slightly red (neutral), dry, and obtain the product of step 1-a.

[0075] Step 2-a and step 3-a: using lauric acid (raw material 1) and diethylenetriamine as raw materials to prepare lauric acid imidazoline intermediate;

[0076]

[0077] Specifically, the method includes: weighing 40g of lauric acid (about 0.2 mol), measuring 40 mL of xylene and 24 mL of diethylenetriamine (about 0.24 mol) in a three-necked flask, assembling the reaction device with an electric heating jacket, a water separator and a spherical condenser, and heating. After heating to 170°C, react for 3h (step 2-a), then continue to heat to 210°C and react for 3h (step 3-a), cool it to room temperature under vacuum conditions, perform reduced pressure distillation and cool it to room temperature to obtain a lauric acid imidazoline intermediate.

[0078] Step 4-a: using the product of the lauric acid imidazoline intermediate and the intermediate 1-a to prepare a compound of formula IV-1;

[0079]

[0080] Specifically, the process comprises: adding 15 mL of the product of step 1-a to the lauric acid imidazoline intermediate, reacting at 80° C. for 3 hours under stirring, and then decolorizing and recrystallizing to obtain a white solid, which is the compound of formula IV-1.

[0081] In the present disclosure, the preparation process of compounds having formula IV-2, formula IV-3 and formula IV-4 is the same as that of the compound having formula IV-1, except that the raw material 1 used in step 2-a is different; the compound of formula IV-2 uses palmitic acid, the compound of formula IV-3 uses decanoic acid, and the compound of formula IV-4 uses nonanoic acid.

[0082] The present disclosure is further described below in conjunction with the examples. It should be understood that these examples are only used to illustrate the present disclosure and are not used to limit the scope of the present disclosure.

[0083] Embodiment and comparative example:

[0084] Embodiment 1:

[0085] In a 250mL three-necked flask, add 29g of concentrated sulfuric acid (content 98%) and 35.6g of nitrosylsulfuric acid (content 41%) in sequence, put the three-necked flask into ice water and cool it to 20℃, slowly add 25g of 2,4-dinitro-6-chloroaniline (content 98%) under stirring. In this process, the temperature must be strictly controlled between 20℃-25℃. After the addition is completed, continue to stir and react at 20℃-25℃ for 30min. Use a dropper to take 1mL of the reaction solution and add it to 100ml of ice water and stir quickly and evenly. If it is completely dissolved in the ice water and is transparent, and the reaction solution can turn starch potassium iodide blue, the reaction end point is reached, and the diazo solution is cooled to 5℃ for standby use.

[0086] Add 700ml of deionized water, 2g of fast penetrant T, 0.8g of phase transfer catalyst IV-1 to a 2000ml beaker, add 37.1g (content 75.5%) of 2-N,N-diallyl-4-acetylaminoanisole under stirring, and beat at room temperature for 30min. Cool the beaten dispersion to -2℃-1℃ with ice brine, slowly add the prepared diazo solution, keep the dropping temperature at -2℃-1℃, and start detecting the coupling end point when the diazonium salt is added by about 90%. After reaching the coupling end point, continue to keep warm and stir for 30min, then heat to 50℃, keep warm and stir at this temperature for 60min, filter, wash to neutral, and dry to obtain the filter cake of azo disperse dye. The chemical formula of the azo disperse dye prepared in Example 1 is as follows:

[0087]

[0088] Embodiment 2:

[0089] The steps of Example 2 are basically the same as those of Example 1, except that 0.82 g of the compound of formula IV-2 is used as a phase transfer catalyst.

[0090] Embodiment three:

[0091] The steps of Example 3 are basically the same as those of Example 1, except that 0.78 g of the compound of formula IV-3 is used as a phase transfer catalyst.

[0092] Comparative Example 1:

[0093] The steps of Comparative Example 1 are substantially the same as those of Example 1, except that an equimolar amount of benzyltriethylammonium chloride is used as a phase transfer catalyst.

[0094] Comparative Example 2:

[0095] The steps of Comparative Example 2 are substantially the same as those of Example 1, except that an equimolar amount of tetrabutylammonium chloride is used as a phase transfer catalyst.

[0096] Comparative Example 3:

[0097] The steps of Comparative Example 3 are substantially the same as those of Example 1, except that an equimolar amount of ethylene thiourea is used as a phase transfer catalyst.

[0098] Comparative Example 4:

[0099] The steps of Comparative Example 4 are substantially the same as those of Example 1, except that no phase transfer catalyst is used in Comparative Example 4.

[0100] The yields and product purities of Examples 1 to 3 and Comparative Examples 1 to 4 are shown in Table 1:

[0101] Table 1

[0102] Filter cake yield (g) Yield (%, based on coupling components) Filter cake purity (%, HPLC) Embodiment 1 51.2 97.3 96.1 Embodiment 2 51.9 98.7 96.7 Embodiment 3 51.5 97.9 96.6 Comparative Example 1 46.8 88.0 95.7 Comparative Example 2 45.9 85.8 95.0 Comparative Example 3 46.9 86.9 94.2 Comparative Example 4 36.9 65.7 90.5

[0103] Those skilled in the art will readily appreciate other embodiments of the present disclosure after considering the specification and practicing the disclosure disclosed herein. The present disclosure is intended to cover any variations, uses or adaptations of the present disclosure that follow the general principles of the present disclosure and include common knowledge or customary technical means in the art that are not disclosed in the present disclosure.

Claims

1. A method for preparing azo disperse dyes, characterized in that: The method comprises the following steps: Step 1: subjecting an aromatic compound containing a nitro group and a primary amine to a diazotization reaction with a nitrous acid compound to obtain a diazo compound intermediate; Step 2: Under the action of a phase transfer catalyst, coupling the diazo compound intermediate product with a compound containing a tertiary amine to obtain the azo disperse dye; The aromatic compound containing a nitro group and a primary amine has the following chemical formula I: wherein Ar1 is selected from a C5-C12 aryl group or a 5-12 membered heteroaryl group; R1 is selected from a hydrogen, a halogen atom, an amino group, a nitro group, a hydroxyl group, a carboxyl group, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C1-C10 alkoxy group, a C3-12 cycloalkyl group or a 3-12 membered heterocyclic group; The nitrite compound is selected from nitrosylsulfuric acid, sodium nitrite, calcium nitrite, potassium nitrite, ammonium nitrite or lead nitrite; The tertiary amine-containing compound has the following chemical formula II: wherein R2 and R3 are each independently selected from C1-C10 alkyl, C2-C10 alkenyl or C2-C10 alkynyl, and the C1-C10 alkyl, C2-C10 alkenyl or C2-C10 alkynyl is optionally substituted with one or more halogen atoms, amino, nitro, hydroxyl, carboxyl, cyano, C5-C12 aryl, 5-12 membered heteroaryl, C3-12 cycloalkyl or 3-12 membered heterocyclyl; R4 and R5 are each independently selected from hydrogen, a halogen atom, an amino group, a nitro group, a hydroxyl group, a carboxyl group, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C1-C10 alkoxy group, a C3-12 cycloalkyl group, a 3-12 membered heterocyclic group or R 41 Selected from C1-C10 alkyl or C2-C10 alkenyl; The azo disperse dye has the following chemical formula III: The phase transfer catalyst has the following chemical formulas of Formula IV-1 to Formula IV-4:

2. The method according to claim 1, characterized in that Ar1 is selected from phenyl, benzothiazolyl or benzimidazole; R2 and R3 are each independently selected from C1-C10 alkyl or C2-C10 alkenyl; the C1-C10 alkyl or C2-C10 alkenyl is optionally substituted with a nitro, hydroxyl, cyano, phenyl or naphthyl group.

3. The method according to claim 1, characterized in that The method comprises the following steps: Step 1: adding the aromatic compound containing nitro and primary amine into an acidic solution and dissolving it, then cooling it to below 20° C., adding a nitrite compound under stirring to carry out a diazotization reaction, the reaction time is selected from 0.5-4 hours, to obtain an intermediate product; Step 2: Under the action of a phase transfer catalyst, the intermediate product is subjected to a coupling reaction with a compound containing a tertiary amine to obtain the azo disperse dye.

4. The method according to claim 3, characterized in that The molar ratio of the intermediate product to the catalyst is selected from 1:(0.01-0.1).

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