CN114773289A - Nitrobenzoisothiazole azo compound and application thereof - Google Patents

Nitrobenzoisothiazole azo compound and application thereof Download PDF

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Publication number
CN114773289A
CN114773289A CN202210509384.4A CN202210509384A CN114773289A CN 114773289 A CN114773289 A CN 114773289A CN 202210509384 A CN202210509384 A CN 202210509384A CN 114773289 A CN114773289 A CN 114773289A
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end point
azo compound
nitrobenzoisothiazole
dye
coupling
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段玉辉
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Liaoning Yongxinda Dye Chemical Co ltd
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Liaoning Yongxinda Dye Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/04—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D275/06—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings condensed with carbocyclic rings or ring systems with hetero atoms directly attached to the ring sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
    • C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
    • C09B29/0085—Thiazoles or condensed thiazoles
    • C09B29/0088—Benzothiazoles
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
    • C09B29/08—Amino benzenes
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0002—Grinding; Milling with solid grinding or milling assistants
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0003—Drying, e.g. sprax drying; Sublimation of the solvent
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/008—Preparations of disperse dyes or solvent dyes

Abstract

The invention provides a nitrobenzoisothiazole azo compound and application thereof. The nitrobenzoisothiazole azo compound provided by the invention adopts a solvent method to synthesize a coupling component and a water system and solvent system coupling process, the dye structure can be biodegraded, the color development intensity of the dye is 2-2.5 times of that of anthraquinone dye, and the color fastness and sublimation fastness are far superior to those of anthraquinone disperse dye. The nitro benzisothiazole azo compound provided by the invention has the color light covering deep purple, light blue, deep blue and light green, and one or a mixture of several kinds of compounds can replace anthraquinone disperse dyes to be used as the disperse dyes prepared from the nitro benzisothiazole azo compound and aromatic amine substituted compounds for dyeing polyester superfine fiber materials and digital printing dyeing.

Description

Nitrobenzoisothiazole azo compound and application thereof
Technical Field
The invention relates to a dye compound, in particular to a nitrobenzoisothiazole azo compound and application thereof.
Background
The increasing demand and consumption of polyester, nylon and various modified synthetic fiber fabrics in synthetic fibers, especially the wide application prospect of polyester superfine fiber and digital printing, make the heterocyclic disperse dye become one of the most actively developed dyes in the world dye market at present, the disperse dye color system synthesized by nitroisothiazole can cover from red to green, can replace anthraquinone dye to use, and the color fastness and dyeing property are excellent. The anthraquinone dye has serious synthetic pollution, cannot be biodegraded, cannot treat some pollutants, has low color development intensity of the dye and has poor sublimation fastness.
The application performance of the dye is mainly determined by the dye structure, the bonding force between the disperse dye and the fiber is Van der Waals force, the planar structure of the nitroisothiazole has extremely strong hydrophobicity, and the longer substituent on the amino group of the coupling component has various hydrophobic groups, so that the dye structure and the polyester fiber have excellent similarity and intermiscibility, and the disperse dye has excellent dyeing fastness and becomes a hotspot of research and development.
Disclosure of Invention
The invention provides a nitrobenzoisothiazole azo compound, which has a structural formula (I):
Figure BDA0003638688680000021
wherein, R1 is ethyl or allyl;
r2 is ethyl butyrate, butylaminobutyl, cyanoethyl, allyl, or tetrahydrofurfuryl butyrate; r3 is hydrogen, methyl or methylsulfonylamino.
Preferably, the nitrobenzoisothiazole azo compound is one of the following structural formulas:
Figure BDA0003638688680000022
Figure BDA0003638688680000031
Figure BDA0003638688680000041
Figure BDA0003638688680000051
the invention also provides application of the nitrobenzoisothiazole azo compound in preparation of azo disperse dyes.
The nitrobenzoisothiazole azo compound provided by the invention adopts a solvent method to synthesize a coupling component and a water system and solvent system coupling process, the dye structure can be biodegraded, the color development intensity of the dye is 2-2.5 times of that of anthraquinone dye, and the color fastness and sublimation fastness are far superior to those of anthraquinone disperse dye.
The nitro-benzisothiazole azo compound provided by the invention has the color light covering deep purple, light blue, deep blue and light green, and one or a mixture of more of the nitro-benzisothiazole azo compound and the aromatic amine substituted compound can be used for replacing anthraquinone disperse dyes and is used for dyeing polyester superfine fiber materials and dyeing digital printing.
Detailed Description
The invention is further described below with reference to specific examples.
Example 1
This example provides a nitrobenzoisothiazole azo compound having the structure shown below.
Figure BDA0003638688680000052
The chemical synthesis route of the compound is as follows:
step one
Figure BDA0003638688680000061
Step two
Figure BDA0003638688680000062
The preparation of the compound comprises the following steps:
(1) and diazotization reaction: adding 30 g of water into a three-neck flask, slowly adding 48 ml of sulfuric acid with the mass concentration of 98% while stirring and cooling, keeping the temperature at 20 +/-5 ℃, adding 32.7 g of nitrosyl sulfuric acid with the mass concentration of 40%, cooling to 15 +/-5 ℃, controlling the system to be 15 +/-5 ℃, adding 0.1mol of 4-nitro-2-amino (2.1) -benzisothiazole, continuously keeping the temperature and stirring for reaction for 3 hours, detecting the end point according to the method, adding 100ml of ice water into a beaker, taking two drops of diazo from a test tube, dripping into the ice water, shaking uniformly, showing clarity and transparency, namely the reaction end point, adding 1 g of urea to eliminate excessive nitrosyl sulfuric acid after the end point is detected, and waiting for coupling;
(2) coupling reaction: adding 100 g of methanol, 0.102mol of coupling agent N-ethyl-N-ethyl butyrate-based aniline and 50 g of ice into a three-neck flask, keeping the temperature at 0-5 ℃, dropwise adding the diazonium salt synthesized in the first step, detecting the end point of the coupling reaction according to the following steps after stirring for 1 hour, dropping the coupling liquid on filter paper, dropping a drop of H acid solution (1-amino-8-hydroxy-3.6-disulfonic acid) with the mass concentration of 1% at the joint of two permeation rings to take the end point of no color development, heating to 60 ℃ after detecting the end point of the coupling reaction, filtering and washing to obtain a filter cake.
Example 2
This example provides a nitrobenzoisothiazole azo compound having the structure shown below.
Figure BDA0003638688680000071
Step one
Figure BDA0003638688680000072
Step two
Figure BDA0003638688680000073
The preparation of the compound comprises the following steps:
(1) and diazotization reaction: adding 30 g of water into a three-neck flask, slowly adding 48 ml of sulfuric acid with the mass concentration of 98% while stirring and cooling, keeping the temperature at 20 +/-5 ℃, adding 32.7 g of nitrosyl sulfuric acid with the mass concentration, cooling to 15 +/-5 ℃, controlling the temperature of a system to be 15 +/-5 ℃, adding 0.1mol of 4-nitro-2-amino (2.1) -benzisothiazole, continuously preserving heat and stirring for reaction for 3 hours after the addition is finished, detecting the end point according to the following method, adding 100ml of ice water into a beaker, taking two drops of diazo in a test tube, dripping the two drops of diazo into ice water, shaking uniformly, showing the state of clarity and transparency, namely the reaction end point, adding 1 g of urea to eliminate the excessive nitrosyl sulfuric acid after the detection of the end point, and waiting for coupling;
(2) and coupling reaction: 100 g of water, 12 ml of sulfuric acid with the mass concentration of 98%, 1 g of urea, 0.102mol of coupling agent N-ethyl-N-ethyl butyrate-ethyl m-toluidine and 50 g of ice are added into a three-neck flask, the diazo salt synthesized in the first step is dropwise added at 0-5 ℃, after the mixture is stirred for 1 hour, the end point of the coupling reaction is detected according to the following steps, the coupling liquid is taken and dripped on filter paper, then a drop of H acid solution with the mass concentration of 1% (1-amino-8-hydroxy-3.6-disulfonic acid) is dripped on the joint of two permeation rings, the end point of the coupling reaction is detected, the temperature is raised to 60 ℃, and the filter cake is obtained through filtration and washing.
Example 3
This example provides a nitrobenzoisothiazole azo compound having the structure shown below.
Figure BDA0003638688680000081
Step one
Figure BDA0003638688680000082
Step two
Figure BDA0003638688680000083
The preparation of the compound comprises the following steps:
(1) and diazotization reaction: adding 30 g of water into a three-neck flask, slowly adding 48 ml of sulfuric acid with the mass concentration of 98% while stirring and cooling, keeping the temperature at 20 +/-5 ℃, adding 32.7 g of nitrosyl sulfuric acid with the mass concentration, cooling to 15 +/-5 ℃, adding 0.1mol of 4-nitro-2-amino (2.1) -benzisothiazole at the temperature of 15 +/-5 ℃ of a control system, continuously keeping the temperature and stirring for reaction for 3 hours after the addition is finished, detecting the end point, adding 1 g of urea at the end point to eliminate excessive nitrosyl sulfuric acid, and waiting for coupling;
(2) and (3) coupling reaction: 100 g of methanol, 24.9 g of 0.102mol of coupling agent N-ethyl-N-butyrylaminobutylamine and 50 g of ice are added into a three-neck flask, the temperature is kept between 0 and 5 ℃, diazo salt synthesized in the first step is dripped, after the mixture is stirred for 1 hour, the coupling reaction end point is detected according to the following steps, coupling liquid is dripped on filter paper, then a drop of H acid solution (1-amino-8-hydroxy-3.6-disulfonic acid) with the mass concentration of 1 percent is dripped, the joint of two permeation rings does not develop color, the end point is detected, the temperature is raised to 60 ℃ after the coupling reaction end point is detected, and a filter cake is obtained through filtration and washing.
Example 4
This example provides a nitrobenzoisothiazole azo compound having the structure shown below.
Figure BDA0003638688680000091
Step one
Figure BDA0003638688680000092
Step two
Figure BDA0003638688680000101
The preparation of the compound comprises the following steps:
(1) and diazotization reaction: adding 30 g of water into a three-neck flask, slowly adding 48 ml of sulfuric acid with the mass concentration of 98% while stirring and cooling, keeping the temperature at 20 +/-5 ℃, adding 32.7 g of nitrosyl sulfuric acid with the mass concentration, cooling to 15 +/-5 ℃, controlling the temperature of a system to be 15 +/-5 ℃, adding 0.1mol of 4-nitro-2-amino (2.1) -benzisothiazole, continuously preserving heat and stirring for reaction for 3 hours after the addition is finished, detecting the end point according to the following method, adding 100ml of ice water into a beaker, taking two drops of diazo in a test tube, dripping the two drops of diazo into ice water, shaking uniformly, showing the state of clarity and transparency, namely the reaction end point, adding 1 g of urea to eliminate the excessive nitrosyl sulfuric acid after the detection of the end point, and waiting for coupling;
(2) and (3) coupling reaction: 100 g of water, 12 ml of sulfuric acid with the mass concentration of 98%, 1 g of urea, 0.102mol of coupling agent N-ethyl-N-butyrylaminobutyl-m-toluidine and 50 g of ice are added into a three-neck flask, the diazo salt synthesized in the first step is dropwise added at 0-5 ℃, after the mixture is stirred for 1 hour, the end point of the coupling reaction is detected according to the following steps, the coupling liquid is taken and dripped on filter paper, then a drop of H acid solution with the mass concentration of 1% (1-amino-8-hydroxy-3.6-disulfonic acid) is dripped on the joint of two permeation rings, the end point is not developed, the temperature is raised to 60 ℃ after the end point of the coupling reaction is detected, and a filter cake is obtained through filtration and washing.
Example 5
This example provides a nitrobenzoisothiazole azo compound having the structure shown below.
Figure BDA0003638688680000111
Step one
Figure BDA0003638688680000112
Step two
Figure BDA0003638688680000113
The preparation method of the compound comprises the following steps:
(1) and diazotization reaction: adding 30 g of water into a three-neck flask, slowly adding 48 ml of sulfuric acid with the mass concentration of 98% while stirring and cooling, keeping the temperature at 20 +/-5 ℃, adding 32.7 g of nitrosyl sulfuric acid with the mass concentration, cooling to 15 +/-5 ℃, controlling the temperature of a system to be 15 +/-5 ℃, adding 0.1mol of 4-nitro-2-amino (2.1) -benzisothiazole, continuously preserving heat and stirring for reaction for 3 hours after the addition is finished, detecting the end point according to the following method, adding 100ml of ice water into a beaker, taking two drops of diazo in a test tube, dripping the two drops of diazo into ice water, shaking uniformly, showing the state of clarity and transparency, namely the reaction end point, adding 1 g of urea to eliminate the excessive nitrosyl sulfuric acid after the detection of the end point, and waiting for coupling;
(2) and (3) coupling reaction: 100 g of water, 12 ml of sulfuric acid with the mass concentration of 98%, 1 g of urea, 0.102mol of coupling agent N-ethyl-N-cyanoethyl-m-methylsulfonylaminoaniline and 50 g of ice are added into a three-neck flask, the diazo salt synthesized in the first step is dropwise added at the temperature of 0-5 ℃, after the addition and the stirring are finished for 1 hour, the coupling reaction end point is detected according to the following steps, the coupling liquid is taken and dropwise added onto filter paper, then one drop of H acid solution with the mass concentration of 1% (1-amino-8-hydroxy-3.6-disulfonic acid) is dropwise added, the color is not developed at the joint of two permeation rings to be the end point, the temperature is raised to 60 ℃ after the coupling reaction end point is detected, and the filter cake is obtained through filtering and washing.
Example 6
This example provides a nitrobenzoisothiazole azo compound having the structure shown below.
Figure BDA0003638688680000121
Step one
Figure BDA0003638688680000122
Step two
Figure BDA0003638688680000131
The preparation method of the compound comprises the following steps:
(1) and diazotization reaction: adding 30 g of water into a three-neck flask, slowly adding 48 ml of sulfuric acid with the mass concentration of 98% while stirring and cooling, keeping the temperature at 20 +/-5 ℃, adding 32.7 g of nitrosyl sulfuric acid with the mass concentration, cooling to 15 +/-5 ℃, controlling the temperature of a system to be 15 +/-5 ℃, adding 0.1mol of 4-nitro-2-amino (2.1) -benzisothiazole, continuously preserving heat and stirring for reaction for 3 hours after the addition is finished, detecting the end point according to the following method, adding 100ml of ice water into a beaker, taking two drops of diazo in a test tube, dripping the two drops of diazo into ice water, shaking uniformly, showing the state of clarity and transparency, namely the reaction end point, adding 1 g of urea to eliminate the excessive nitrosyl sulfuric acid after the detection of the end point, and waiting for coupling;
(2) and (3) coupling reaction: 100 g of water, 1 g of urea, 0.102mol of N.N-dipropylene m-methylsulfonylaminoaniline and 50 g of ice are added into a three-neck flask, the temperature is kept between 0 and 5 ℃, the diazonium salt synthesized in the first step is dripped, after the diazo salt is stirred for 1 hour, the coupling reaction end point is detected according to the following steps, the coupling liquid is dripped on filter paper, then a drop of H acid solution (1-amino-8-hydroxy-3.6-disulfonic acid) with the mass concentration of 1 percent is dripped, the joint of two permeation rings does not develop color and is taken as the end point, the temperature is raised to 60 ℃ after the coupling reaction end point is detected, and a filter cake is obtained through filtration and washing.
Example 7
This example provides a nitrobenzoisothiazole azo compound having the structure shown below.
Figure BDA0003638688680000141
Step one
Figure BDA0003638688680000142
Step two
Figure BDA0003638688680000143
The preparation of the compound comprises the following steps:
(1) and diazotization reaction: adding 30 g of water into a three-neck flask, slowly adding 48 ml of sulfuric acid with the mass concentration of 98% while stirring and cooling, keeping the temperature at 20 +/-5 ℃, adding 32.7 g of nitrosyl sulfuric acid with the mass concentration, cooling to 15 +/-5 ℃, controlling the temperature of a system at 15 +/-5 ℃, adding 0.1mol of 4-nitro-2-amino (2.1) -benzisothiazole, continuously preserving heat and stirring for reacting for 3 hours, detecting the end point according to the following method, adding 100ml of ice water into a beaker, taking two drops of diazo ice water from a test tube, dripping the test tube into water, shaking uniformly, and obtaining clear and transparent reaction end point, adding 1 g of urea to eliminate excessive nitrosyl sulfuric acid after detecting the end point, and waiting for coupling;
(2) and (3) coupling reaction: 100 g of water, 1 g of urea, 0.102mol of coupling agent N-ethyl-N-ethyl butyrate-ethyl meta-methylsulfonylaminoaniline and 50 g of ice are added into a three-neck flask, the temperature is kept between 0 and 5 ℃, the diazonium salt synthesized in the first step is dropwise added, after stirring for 1 hour, the coupling reaction end point is detected according to the following steps, the coupling liquid is taken and dripped on filter paper, then a drop of H acid solution (1-amino-8-hydroxy-3.6-disulfonic acid) with the mass concentration of 1 percent is dripped, the joint of two permeation rings does not develop color as the end point, the temperature is raised to 60 ℃ after the detection of the coupling reaction end point, and a filter cake is obtained through filtration and washing.
Example 8
This example provides a nitrobenzoisothiazole azo compound having the structure shown below.
Figure BDA0003638688680000151
Step one
Figure BDA0003638688680000152
Step two
Figure BDA0003638688680000161
The preparation method of the compound comprises the following steps:
(1) and diazotization reaction: adding 30 g of water into a three-neck flask, slowly adding 48 ml of sulfuric acid with the mass concentration of 98% while stirring and cooling, keeping the temperature at 20 +/-5 ℃, adding 32.7 g of nitrosyl sulfuric acid with the mass concentration, cooling to 15 +/-5 ℃, controlling the temperature of a system to be 15 +/-5 ℃, adding 0.1mol of 4-nitro-2-amino (2.1) -benzisothiazole, continuously preserving heat and stirring for reaction for 3 hours after the addition is finished, detecting the end point according to the following method, adding 100ml of ice water into a beaker, taking two drops of diazo in a test tube, dripping the two drops of diazo into ice water, shaking uniformly, showing the state of clarity and transparency, namely the reaction end point, adding 1 g of urea to eliminate the excessive nitrosyl sulfuric acid after the detection of the end point, and waiting for coupling;
(2) and (3) coupling reaction: 100 g of water, 1 g of urea, 0.102mol of a coupling agent N-ethyl-N-butyrylaminobutyl-m-methylsulfonylaminoaniline and 50 g of ice are added into a three-neck flask, the temperature is kept between 0 and 5 ℃, the diazonium salt synthesized in the first step is dropwise added, after stirring for 1 hour, the end point of the coupling reaction is detected according to the following steps, the coupling liquid is taken and dripped on filter paper, then a drop of H acid solution (1-amino-8-hydroxy-3.6-disulfonic acid) with the mass concentration of 1 percent is dripped, the joint of two permeation rings does not develop color as the end point, the temperature is raised to 60 ℃ after the end point of the coupling reaction is detected, and a filter cake is obtained through filtration and washing.
Example 9
This example provides a nitrobenzoisothiazole azo compound having the structure shown below.
Figure BDA0003638688680000171
Step one
Figure BDA0003638688680000172
Step two
Figure BDA0003638688680000173
The preparation method of the compound comprises the following steps:
(1) and diazotization reaction: adding 30 g of water into a three-neck flask, slowly adding 48 ml of sulfuric acid with the mass concentration of 98% while stirring and cooling, keeping the temperature at 20 +/-5 ℃, adding 32.7 g of nitrosyl sulfuric acid with the mass concentration, cooling to 15 +/-5 ℃, controlling the temperature of a system at 15 +/-5 ℃, adding 0.1mol of 4-nitro-2-amino (2.1) -benzisothiazole, continuously preserving heat and stirring for reacting for 3 hours, detecting the end point according to the following method, adding 100ml of ice water into a beaker, taking two drops of diazo ice water from a test tube, dripping the test tube into water, shaking uniformly, and obtaining clear and transparent reaction end point, adding 1 g of urea to eliminate excessive nitrosyl sulfuric acid after detecting the end point, and waiting for coupling;
(2) and (3) coupling reaction: 100 g of water, 1 g of urea, 0.102mol of coupling agent N-ethyl-N-tetrahydrofurfuryl butyrate meta-methanesulfonamido aniline and 50 g of ice are added into a three-neck flask, the temperature is kept between 0 and 5 ℃, diazo salt synthesized in the first step is dropwise added, after stirring is finished for 1 hour, the coupling reaction end point is detected according to the following steps, coupling liquid is taken and dropwise added onto filter paper, then a drop of H acid solution (1-amino-8-hydroxy-3.6-disulfonic acid) with the mass concentration of 1 percent is dropwise added, the joint of two permeation rings does not develop color as the end point, the temperature is raised to 60 ℃ after the coupling reaction end point is detected, and a filter cake is obtained through filtering and washing.
Example 10
This example provides a nitrobenzoisothiazole azo compound having the structure shown below.
Figure BDA0003638688680000181
Step one
Figure BDA0003638688680000182
Step two
Figure BDA0003638688680000191
The preparation of the compound comprises the following steps:
(1) and diazotization reaction: adding 30 g of water into a three-neck flask, slowly adding 48 ml of sulfuric acid with the mass concentration of 98% while stirring and cooling, keeping the temperature at 20 +/-5 ℃, adding 32.7 g of nitrosyl sulfuric acid with the mass concentration, cooling to 15 +/-5 ℃, controlling the temperature of a system to be 15 +/-5 ℃, adding 0.1mol of 4-nitro-2-amino (2.1) -benzisothiazole, continuously preserving heat and stirring for reaction for 3 hours after the addition is finished, detecting the end point according to the following method, adding 100ml of ice water into a beaker, taking two drops of diazo in a test tube, dripping the two drops of diazo into ice water, shaking uniformly, showing the state of clarity and transparency, namely the reaction end point, adding 1 g of urea to eliminate the excessive nitrosyl sulfuric acid after the detection of the end point, and waiting for coupling;
(2) and (3) coupling reaction: 100 g of water, 1 g of urea, 0.102mol of coupling agent N-ethyl-N-tetrahydrofurfuryl butyrate m-toluidine and 50 g of ice are added into a three-neck flask, the temperature is kept between 0 ℃ and 5 ℃, diazo salt synthesized in the first step is dropwise added, after stirring for 1 hour, the coupling reaction end point is detected according to the following steps, coupling liquid is dropwise added onto filter paper, then a drop of H acid solution (1-amino-8-hydroxy-3.6-disulfonic acid) with the mass concentration of 1% is dropwise added, the joint of two permeation rings does not develop color as the end point, the temperature is raised to 60 ℃ after the coupling reaction end point is detected, and a filter cake is obtained through filtering and washing.
Example 11
This example provides a nitrobenzoisothiazole azo compound having the structure shown below.
Figure BDA0003638688680000201
Step one
Figure BDA0003638688680000202
Step two
Figure BDA0003638688680000203
The preparation of the compound comprises the following steps:
(1) and diazotization reaction: adding 30 g of water into a three-neck flask, slowly adding 48 ml of sulfuric acid with the mass concentration of 98% while stirring and cooling, keeping the temperature at 20 +/-5 ℃, adding 32.7 g of nitrosyl sulfuric acid with the mass concentration, cooling to 15 +/-5 ℃, controlling the temperature of a system at 15 +/-5 ℃, adding 0.1mol of 4-nitro-2-amino (2.1) -benzisothiazole, continuously preserving heat and stirring for reacting for 3 hours, detecting the end point according to the following method, adding 100ml of ice water into a beaker, taking two drops of diazo ice water from a test tube, dripping the test tube into water, shaking uniformly, and obtaining clear and transparent reaction end point, adding 1 g of urea to eliminate excessive nitrosyl sulfuric acid after detecting the end point, and waiting for coupling;
(2) and (3) coupling reaction: 100 g of water, 1 g of urea, 0.102mol of coupling agent N-ethyl-N-tetrahydrofurfuryl butyrate m-toluidine and 50 g of ice are added into a three-neck flask, the temperature is kept between 0 ℃ and 5 ℃, diazo salt synthesized in the first step is dropwise added, after stirring for 1 hour, the coupling reaction end point is detected according to the following steps, coupling liquid is dropwise added onto filter paper, then a drop of H acid solution (1-amino-8-hydroxy-3.6-disulfonic acid) with the mass concentration of 1% is dropwise added, the joint of two permeation rings does not develop color as the end point, the temperature is raised to 60 ℃ after the coupling reaction end point is detected, and a filter cake is obtained through filtering and washing.
Example 12
The embodiment provides application of the nitrobenzoisothiazole azo compound in preparing azo disperse dyes.
The dye filter cake prepared in the embodiment 1-11, the assistant and water are mixed and ground uniformly, the particle diameter is 1-1.5 μm, and the commercial dye is obtained by spray drying.
0.5 g of each commercial dye is dispersed in 500 ml of water, 20 ml of the commercial dye is absorbed and then mixed with 60 ml of water, the pH is adjusted to 4.5-5 by acetic acid, the temperature is raised to 70 ℃, 2 g of polyester fabric is added for dyeing, the temperature is raised from 70 ℃ to 130 ℃ within 30 minutes, the temperature is kept for 40 minutes, and the sampling is started after the temperature is cooled to below 90 ℃.
The color fastness to washing, rubbing, sunlight and color fastness are excellent by adopting an international AATCC standard test.
The results obtained are shown in the following table:
Figure BDA0003638688680000221

Claims (3)

1. a nitrobenzoisothiazole azo compound is shown in a structural formula (I):
Figure FDA0003638688670000011
wherein, R1 is ethyl or allyl;
r2 is ethyl butyrate, butylaminobutyl, cyanoethyl, allyl, or tetrahydrofurfuryl butyrate;
r3 is hydrogen, methyl or methylsulfonylamino.
2. A nitrobenzoisothiazole azo compound of claim 1 having one of the following structural formulas:
Figure FDA0003638688670000012
Figure FDA0003638688670000021
Figure FDA0003638688670000031
Figure FDA0003638688670000041
3. use of a nitrobenzoisothiazole-based azo compound according to claim 1 or 2 for the preparation of azo disperse dyes.
CN202210509384.4A 2022-05-11 2022-05-11 Nitrobenzoisothiazole azo compound and application thereof Pending CN114773289A (en)

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JPS54123186A (en) * 1978-02-24 1979-09-25 Hoechst Ag Photopolymerizable mixture
JPS60246885A (en) * 1984-05-22 1985-12-06 合成染料技術研究組合 Alkali resist style method
CN101125961A (en) * 2007-08-01 2008-02-20 浙江龙盛集团股份有限公司 Dye monomer compound and its preparation and application
CN101445667A (en) * 2008-12-30 2009-06-03 浙江龙盛染料化工有限公司 Nitrobenzoisothiazole dye monomer compound, application thereof and disperse dye composition
CN102898856A (en) * 2012-10-17 2013-01-30 江苏之江化工有限公司 Azo type heterocyclic ring disperse dye
CN110229541A (en) * 2019-07-22 2019-09-13 大连傲视化学有限公司 A kind of combination azo dispersion dyes and preparation method
CN111849194A (en) * 2020-07-27 2020-10-30 浙江青松轻纺股份有限公司 Benzisothiazole dye monomer compound, preparation method and application in hydrophobic fiber material dyeing
CN111995879A (en) * 2020-08-27 2020-11-27 青岛大学 Method for enhancing alkali resistance and oxidation resistance of benzisothiazole disperse dye

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54123186A (en) * 1978-02-24 1979-09-25 Hoechst Ag Photopolymerizable mixture
JPS60246885A (en) * 1984-05-22 1985-12-06 合成染料技術研究組合 Alkali resist style method
CN101125961A (en) * 2007-08-01 2008-02-20 浙江龙盛集团股份有限公司 Dye monomer compound and its preparation and application
CN101445667A (en) * 2008-12-30 2009-06-03 浙江龙盛染料化工有限公司 Nitrobenzoisothiazole dye monomer compound, application thereof and disperse dye composition
CN102898856A (en) * 2012-10-17 2013-01-30 江苏之江化工有限公司 Azo type heterocyclic ring disperse dye
CN110229541A (en) * 2019-07-22 2019-09-13 大连傲视化学有限公司 A kind of combination azo dispersion dyes and preparation method
CN111849194A (en) * 2020-07-27 2020-10-30 浙江青松轻纺股份有限公司 Benzisothiazole dye monomer compound, preparation method and application in hydrophobic fiber material dyeing
CN111995879A (en) * 2020-08-27 2020-11-27 青岛大学 Method for enhancing alkali resistance and oxidation resistance of benzisothiazole disperse dye

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