CN115073934B - Benzisothiazole heterocyclic azo dye and preparation method thereof - Google Patents
Benzisothiazole heterocyclic azo dye and preparation method thereof Download PDFInfo
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- 239000000987 azo dye Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 claims abstract description 40
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000007859 condensation product Substances 0.000 claims abstract description 25
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 22
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012043 crude product Substances 0.000 claims abstract description 21
- 238000005185 salting out Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000006482 condensation reaction Methods 0.000 claims abstract description 17
- 238000005859 coupling reaction Methods 0.000 claims abstract description 17
- LDTCWISGJYTXDC-UHFFFAOYSA-N 5-nitro-1,2-benzothiazol-3-amine Chemical compound C1=C([N+]([O-])=O)C=C2C(N)=NSC2=C1 LDTCWISGJYTXDC-UHFFFAOYSA-N 0.000 claims abstract description 15
- WRBMXBNVQFFEFI-UHFFFAOYSA-N NC1(NSC(C=C2)=C1C=C2[N+]([O-])=O)[N+]#N Chemical class NC1(NSC(C=C2)=C1C=C2[N+]([O-])=O)[N+]#N WRBMXBNVQFFEFI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000000967 suction filtration Methods 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000000975 dye Substances 0.000 claims description 30
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 24
- 238000006193 diazotization reaction Methods 0.000 claims description 13
- 235000011056 potassium acetate Nutrition 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 claims description 5
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- ZFRBZRZEKIOGQI-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1,3-disulfonic acid Chemical compound C1=CC(O)=C2C(N)=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1 ZFRBZRZEKIOGQI-UHFFFAOYSA-N 0.000 claims description 4
- ZUQOBHTUMCEQBG-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 ZUQOBHTUMCEQBG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000000980 acid dye Substances 0.000 abstract description 2
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 15
- 238000001914 filtration Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000000376 reactant Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- YDDGKXBLOXEEMN-IABMMNSOSA-N chicoric acid Chemical group O([C@@H](C(=O)O)[C@@H](OC(=O)\C=C\C=1C=C(O)C(O)=CC=1)C(O)=O)C(=O)\C=C\C1=CC=C(O)C(O)=C1 YDDGKXBLOXEEMN-IABMMNSOSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C09B29/0081—Isothiazoles or condensed isothiazoles
-
- 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
- C09B29/24—Monoazo dyes prepared by diazotising and coupling from coupling components containing both hydroxyl and amino directing groups
- C09B29/28—Amino naphthols
- C09B29/30—Amino naphtholsulfonic acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
The invention belongs to the technical field of chemical synthesis, and particularly relates to benzisothiazole heterocyclic azo dye and a preparation method thereof. The preparation method comprises the following steps: carrying out condensation reaction on acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid to obtain a condensation product; dropwise adding sodium nitrite into concentrated sulfuric acid under the ice salt bath condition, stirring, heating until the sodium nitrite is completely dissolved to prepare nitrosylsulfuric acid, cooling, gradually adding 3-amino-5-nitrobenzoisothiazole, and stirring for reaction to obtain 3-amino-5-nitrobenzoisothiazole diazonium salt; gradually dripping 3-amino-5-nitrobenzoisothiazole diazonium salt into a condensation product for coupling reaction, adding acetate solid in batches for salting out after the reaction is completed, carrying out suction filtration, airing a filter cake to obtain a crude product, regulating the pH value after redissolving the crude product, and carrying out salting out again to obtain the benzisothiazole heterocyclic azo dye. The heterocyclic azo acid dye has the advantages of simple synthesis process, high pH sensitivity, good selectivity and reversible color change.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to benzisothiazole heterocyclic azo dye and a preparation method thereof.
Background
Azo dyes are a very important class of dyes because of their readily available raw materials, simple synthesis, complete chromatography and high absorption coefficient. Many monoazo type water-soluble dyes are easy to generate tautomerism of azo-quinone hydrazone due to azo bonds, so that different color differences are often presented in different acid-base environments, and research on acid-base color change effects of the monoazo type dyes is also a research hotspot in the field of functional dyes. The 3-amino-5-nitrobenzoisothiazole has better dark effect due to the existence of sulfur atoms and nitrogen atoms with high electronegativity in the heterocyclic structure, better electron transfer capability of the heterocyclic system and strong electron-withdrawing effect of nitro substituent groups, and is often used as a diazo component for synthesizing water-insoluble dyes such as high-performance disperse dyes, but the structure has poorer water solubility, so that the 3-amino-5-nitrobenzoisothiazole heterocyclic structure cannot be applied to water-soluble dyes, and the application of the excellent performance of the 3-amino-5-nitrobenzoisothiazole heterocyclic structure in the dye field is greatly limited.
Therefore, the invention utilizes the dark effect of the 3-amino-5-nitrobenzoisothiazole heterocyclic structure, takes the 3-amino-5-nitrobenzoisothiazole heterocyclic structure as a diazonium component for synthesizing water-soluble azo dye, and introduces the diazonium component into the parent structure of amino naphthol sulfonic acid water-soluble dye to prepare the water-soluble heterocyclic azo acid-base color-changing dye with high pH sensitivity, good selectivity and reversible color change.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a benzisothiazole heterocyclic azo dye and a preparation method thereof, which are used for solving the problem that a 3-amino-5-nitrobenzoisothiazole heterocyclic structure is difficult to apply to water-soluble dye and widening the application of the 3-amino-5-nitrobenzoisothiazole heterocyclic structure in the dye field.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a benzisothiazole heterocyclic azo dye having the structure of formula i:
wherein n=1 or 2;
x is selected from-OCH 3 or-OPh.
According to a further embodiment of the invention, in the formula I, the amino naphthol disulfonic acid residue or amino naphthol sulfonic acid residue linked to X and the azo bond is selected from one of the following groups:
h acid residue, its structural formula is:
k acid residue, its structural formula is:
chicoric acid residues of the formula：
J acid residue, its structural formula is:
a gamma acid residue having the structural formula:
a method of preparing a benzisothiazole heterocyclic azo dye, the method comprising:
1) Condensation reaction
Carrying out condensation reaction on acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid to obtain a condensation product;
2) Diazotisation reaction
Dropwise adding sodium nitrite into concentrated sulfuric acid under the ice water bath condition, stirring, heating until the sodium nitrite is completely dissolved to prepare nitrosylsulfuric acid, cooling, gradually adding 3-amino-5-nitrobenzoisothiazole, and stirring for reaction to obtain 3-amino-5-nitrobenzoisothiazole diazonium salt;
3) Coupling reaction
Gradually dripping the 3-amino-5-nitrobenzoisothiazole diazonium salt obtained in the step 2) into the condensation product obtained in the step 1) for coupling reaction, adding acetate solid in batches after the reaction is completed for salting out, carrying out suction filtration, airing a filter cake to obtain a crude product, regulating the pH value after redissolving the crude product, and carrying out salting out again to obtain the benzisothiazole heterocyclic azo dye.
According to a further technical scheme, in the step 1), the amino naphthol disulfonic acid is one of H acid, K acid and chicago acid;
or, the amino naphthol sulfonic acid is one of J acid and gamma acid;
or, the molar ratio of the acetic anhydride or benzoyl chloride to the amino naphthol sulfonic acid is 2.5:1;
or the reaction temperature is 60-80 ℃.
According to a further technical scheme, nitrosylsulfuric acid is adopted as a diazotizing reagent in the diazotizing reaction in the step 2);
or, the molar ratio of the sodium nitrite to the 3-amino-5-nitrobenzoisothiazole is 1.05:1;
or, the molar ratio of the concentrated sulfuric acid to the 3-amino-5-nitrobenzoisothiazole is 11:1
Or the reaction time is 2-4 h;
or, the reaction temperature is 0 to 5 ℃.
According to a further technical scheme of the invention, in the step 3),
the molar ratio of the 3-amino-5-nitrobenzoisothiazole diazonium salt to the condensation product of acetic anhydride or benzoyl chloride and aminonaphthol disulfonic acid or aminonaphthol sulfonic acid is 1:1;
or the pH value of the reaction is 1-2;
or the reaction temperature is 0-5 ℃.
According to a further technical scheme, in the step 1), acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid are subjected to condensation reaction according to the following method: dropwise adding acetic anhydride or benzoyl chloride into an aqueous solution of amino naphthol disulfonic acid or amino naphthol sulfonic acid, wherein the molar ratio of the acetic anhydride or benzoyl chloride to the amino naphthol sulfonic acid is 2.5:1; heating to 60-80 deg.c, stirring to react, and detecting with ehrling reagent to determine the end point of the reaction to obtain the condensation product of acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid.
According to a further technical scheme, the diazotization reaction in the step 2) is specifically as follows: gradually adding sodium nitrite solid into concentrated sulfuric acid under the ice water bath condition of 0-5 ℃, stirring, heating to be completely dissolved, cooling to 0-5 ℃, gradually adding 3-amino-5-nitrobenzoisothiazole, wherein the molar ratio of sodium nitrite to 3-amino-5-nitrobenzoisothiazole is 1.05:1, the molar ratio of concentrated sulfuric acid to 3-amino-5-nitrobenzoisothiazole is 11:1, stirring and reacting for 2-4 hours, and adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed, thus obtaining the 3-amino-5-nitrobenzoisothiazole diazonium salt.
According to a further technical scheme, the coupling reaction in the step 3) is specifically as follows: gradually dripping 3-amino-5-nitrobenzoisothiazole diazonium salt into condensation products of acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid, wherein the molar ratio of the 3-amino-5-nitrobenzoisothiazole diazonium salt to the condensation products of acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid is 1:1, controlling the pH value to be 1-2, reacting at 0-5 ℃, adding a pH value buffer according to the mass ratio of the buffer to the volume ratio of the solution after the reaction is finished, adding potassium acetate solid in batches, detecting the salting-out condition of the dye by a ring permeation method, stirring, standing, suction filtering, airing a filter cake to obtain a crude product, and regulating the pH value to be 6.8-7.0 after redissolving the crude product, and salting out again to obtain the benzisothiazole heterocyclic azo dye.
The benzisothiazole heterocyclic azo dye and the preparation method thereof have the advantages that: the heterocyclic azo type water-soluble acid dye prepared by the invention has the advantages of simple synthesis process, high pH sensitivity, good selectivity and reversible color change, not only has the dark color effect brought by a 3-amino-5-nitrobenzoisothiazole heterocyclic structure, but also has water solubility and excellent acid-base color change performance, and widens the application of the 3-amino-5-nitrobenzoisothiazole heterocyclic structure in the dye field.
Drawings
FIG. 1 is an infrared spectrum of a benzisothiazole heterocyclic azo dye of example 1 of the present invention;
FIG. 2 is a graph showing the UV-visible absorption spectrum of the benzisothiazole heterocyclic azo dye of example 1 in accordance with the present invention without pH.
Detailed Description
The following description of the embodiments is provided in conjunction with the accompanying drawings.
The reagents and apparatus in the examples below were conventional experimental reagents and apparatus.
Example 1:
the specific structure of the benzisothiazole heterocyclic azo dye is as follows:
the preparation method of the benzisothiazole heterocyclic azo dye comprises the following steps:
diazotization reaction: placing 11.0g of concentrated sulfuric acid (0.11 mol, 98%) into a three-mouth bottle, cooling in an ice water bath at 0-5 ℃, gradually adding 0.73g of sodium nitrite solid (0.0105 mol), stirring for a period of time, heating until the solution is completely dissolved, stopping heating, cooling, gradually adding 2.01g of 3-amino-5-nitrobenzoisothiazole (0.01 mol, 97%) for continuous stirring reaction at 0-5 ℃, detecting the end point of the reaction by thin layer chromatography, and adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed;
condensation reaction: taking an aqueous solution containing 4.0g of H acid monosodium salt (0.01 mol, 85.6%), gradually adding 0.25mol of acetic anhydride according to the molar ratio of acetic anhydride to H acid of 2.5:1, heating to 60-80 ℃, stirring for reaction, and detecting by using an Ehrlich reagent to determine the end point of the reaction to obtain a condensation product of acetic anhydride and H acid;
coupling reaction: gradually dripping the 3-amino-5-nitrobenzoisothiazole diazonium salt into a condensation product, controlling the pH value to be between 1 and 2, reacting at 0 to 5 ℃, and detecting the reaction condition by a permeation ring method. After the reaction is completed, adding 1% (w/v) of pH buffer, adding potassium acetate solid in batches, detecting dye salting-out condition by using a ring permeation method, standing after stirring, carrying out suction filtration, washing for 3 times by using a proper amount of ethanol, and airing a filter cake to obtain a crude product. And (3) re-dissolving the crude product, regulating the pH value to 6.8-7.0, and re-salting out to obtain Dye1.
Measuring the ultraviolet-visible absorption spectrum of the dye solution at different pH values:
accurately weighing 0.1000g of dye benzisothiazole heterocyclic azo dye, adding a proper amount of deionized water for dissolution, adjusting the pH value to be neutral by using a dilute hydrochloric acid or sodium carbonate solution, transferring to a 100mL volumetric flask, adding deionized water to scale, fixing the volume, and shaking uniformly. And respectively transferring a certain volume of Dye liquor from the 100mL volumetric flask to a colorimetric tube, respectively preparing solutions containing Dye1 at different pH values, wherein the pH values are respectively 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0 and 11.0, and measuring the ultraviolet-visible absorption spectrums of the Dye solutions at different pH values, wherein the result is shown in figure 2.
Example 2:
the specific structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: the same as in example 1;
condensation reaction: taking an aqueous solution containing 4.0g of H acid monosodium salt (0.01 mol, 85.6%), gradually adding 0.25mol of benzoyl chloride according to the molar ratio of benzoyl chloride to H acid of 2.5:1, heating to 60-80 ℃, stirring for reaction, and detecting with an Ehrlich reagent to determine the end point of the reaction to obtain a condensation product of benzoyl chloride and H acid;
coupling reaction: and (3) adding potassium acetate to precipitate dye after the reaction is finished, filtering, redissolving the crude product, adjusting the pH value to 6.8-7.0, and salting out to obtain the product.
Example 3:
the specific structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: the same as in example 1;
condensation reaction: the preparation of the condensation product was carried out using K acid instead of H acid, the other reactants and reaction conditions being the same as those described in example 1 above;
coupling reaction: and (3) adding potassium acetate to precipitate dye after the reaction is finished, filtering, redissolving the crude product, adjusting the pH value to 6.8-7.0, and salting out to obtain the product.
Example 4:
the specific structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: the same as in example 1;
condensation reaction: the preparation of the condensation product was carried out with K acid instead of H acid, the other reactants and reaction conditions being the same as those described in example 2 above;
coupling reaction: and (3) adding potassium acetate to precipitate dye after the reaction is finished, filtering, redissolving the crude product, adjusting the pH value to 6.8-7.0, and salting out to obtain the product.
Example 5:
the specific structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: the same as in example 1;
condensation reaction: the condensation product was prepared using chicago acid instead of H acid, and the other reactants and reaction conditions were the same as in example 1 above;
coupling reaction: and (3) adding potassium acetate to precipitate dye after the reaction is finished, filtering, redissolving the crude product, adjusting the pH value to 6.8-7.0, and salting out to obtain the product.
Example 6:
the specific structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: the same as in example 1;
condensation reaction: the condensation product was prepared using chicago acid instead of H acid, and the other reactants and reaction conditions were the same as in example 2 above;
coupling reaction: and (3) adding potassium acetate to precipitate dye after the reaction is finished, filtering, redissolving the crude product, adjusting the pH value to 6.8-7.0, and salting out to obtain the product.
Example 7:
the specific structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: the same as in example 1;
condensation reaction: the condensation product was prepared with J acid instead of H acid, other reactants and reaction conditions were the same as those prepared in example 1 above;
coupling reaction: and (3) adding potassium acetate to precipitate dye after the reaction is finished, filtering, redissolving the crude product, adjusting the pH value to 6.8-7.0, and salting out to obtain the product.
Example 8:
the specific structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: the same as in example 1;
condensation reaction: the condensation product was prepared with J acid instead of H acid, other reactants and reaction conditions were the same as those prepared in example 2 above;
coupling reaction: and (3) adding potassium acetate to precipitate dye after the reaction is finished, filtering, redissolving the crude product, adjusting the pH value to 6.8-7.0, and salting out to obtain the product.
Example 9:
the specific structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: the same as in example 1;
condensation reaction: the preparation of the condensation product was carried out using gamma acid instead of H acid, the other reactants and reaction conditions being the same as those described in example 1 above;
coupling reaction: and (3) adding potassium acetate to precipitate dye after the reaction is finished, filtering, redissolving the crude product, adjusting the pH value to 6.8-7.0, and salting out to obtain the product.
Example 10:
the specific structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: the same as in example 1;
condensation reaction: the preparation of the condensation product was carried out using gamma acid instead of H acid, the other reactants and reaction conditions being the same as those described in example 2 above;
coupling reaction: and (3) adding potassium acetate to precipitate dye after the reaction is finished, filtering, redissolving the crude product, adjusting the pH value to 6.8-7.0, and salting out to obtain the product.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the essence of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. A benzisothiazole heterocyclic azo dye characterized by having the structure:
2. a process for the preparation of a benzisothiazole heterocyclic azo-type dye as described in claim 1, characterized in that the process comprises:
1) Condensation reaction
Carrying out condensation reaction on acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid to obtain a condensation product;
2) Diazotisation reaction
Dropwise adding sodium nitrite into concentrated sulfuric acid under the ice water bath condition, stirring, heating until the sodium nitrite is completely dissolved to prepare nitrosylsulfuric acid, cooling, gradually adding 3-amino-5-nitrobenzoisothiazole, and stirring for reaction to obtain 3-amino-5-nitrobenzoisothiazole diazonium salt;
3) Coupling reaction
Gradually dripping the 3-amino-5-nitrobenzoisothiazole diazonium salt obtained in the step 2) into the condensation product obtained in the step 1) for coupling reaction, adding acetate solid in batches after the reaction is completed for salting out, carrying out suction filtration, airing a filter cake to obtain a crude product, regulating the pH value after redissolving the crude product, and carrying out salting out again to obtain the benzisothiazole heterocyclic azo dye;
in the step 1), the amino naphthol disulfonic acid is one of H acid, K acid and chicago acid;
the amino naphthol sulfonic acid is one of J acid and gamma acid;
the molar ratio of the acetic anhydride or benzoyl chloride to the amino naphthol sulfonic acid is 2.5:1;
the reaction temperature is 60-80 ℃.
3. The method for preparing benzisothiazole heterocyclic azo dye according to claim 2, wherein the diazotization reaction in the step 2) adopts nitrosylsulfuric acid as diazotizing agent;
the molar ratio of the sodium nitrite to the 3-amino-5-nitrobenzoisothiazole is 1.05:1;
the molar ratio of the concentrated sulfuric acid to the 3-amino-5-nitrobenzoisothiazole is 11:1;
the reaction time is 2-4 h;
the reaction temperature is 0-5 ℃.
4. The process for preparing benzisothiazole heterocyclic azo dyes as claimed in claim 2, wherein in the step 3),
the molar ratio of the 3-amino-5-nitrobenzoisothiazole diazonium salt to the condensation product of acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid in the step 1) is 1:1;
the pH value of the reaction is 1-2, and the reaction temperature is 0-5 ℃.
5. The process for preparing benzisothiazole heterocyclic azo type dye according to claim 2, wherein the condensation reaction of acetic anhydride or benzoyl chloride and aminonaphthol disulfonic acid or aminonaphthol sulfonic acid in the step 1) is carried out as follows: dropwise adding acetic anhydride or benzoyl chloride into an aqueous solution of amino naphthol disulfonic acid or amino naphthol sulfonic acid, wherein the molar ratio of the acetic anhydride or benzoyl chloride to the amino naphthol sulfonic acid is 2.5:1; heating to 60-80 deg.c, stirring to react, and detecting with ehrling reagent to determine the end point of the reaction to obtain the condensation product of acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid.
6. The method for preparing benzisothiazole heterocyclic azo dye according to claim 2, wherein the diazotization reaction in the step 2) is specifically: gradually adding sodium nitrite solid into concentrated sulfuric acid under the ice water bath condition of 0-5 ℃, stirring, heating to be completely dissolved, cooling to 0-5 ℃, gradually adding 3-amino-5-nitrobenzoisothiazole, wherein the molar ratio of sodium nitrite to 3-amino-5-nitrobenzoisothiazole is 1.05:1, the molar ratio of concentrated sulfuric acid to 3-amino-5-nitrobenzoisothiazole is 11:1, stirring and reacting for 2-4 hours, and adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed, thus obtaining the 3-amino-5-nitrobenzoisothiazole diazonium salt.
7. The process for the preparation of benzisothiazole heterocyclic azo dyes according to claim 2, wherein the coupling reaction in step 3) is specifically: gradually dripping 3-amino-5-nitrobenzoisothiazole diazonium salt into condensation products of acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid, wherein the molar ratio of the 3-amino-5-nitrobenzoisothiazole diazonium salt to the condensation products of the acetic anhydride or benzoyl chloride and the amino naphthol disulfonic acid or amino naphthol sulfonic acid in the step 1) is 1:1, controlling the pH value to be 1-2, controlling the temperature to be 0-5 ℃, adding a pH value buffer agent according to the mass-volume ratio of the buffer agent to the solution to be 1% after the reaction is finished, then adding potassium acetate solid in batches, detecting the salting-out condition of the dye by a ring permeation method, standing after stirring, carrying out suction filtration, airing a filter cake to obtain a crude product, and regulating the pH value to be 6.8-7.0 after redissolving the crude product, and carrying out salting-out again to obtain the benzisothiazole heterocyclic azo dye.
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