CN115073934A - Benzisothiazole heterocyclic azo dye and preparation method thereof - Google Patents
Benzisothiazole heterocyclic azo dye and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000987 azo dye Substances 0.000 title claims abstract description 31
- 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 50
- 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 41
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 32
- 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
- 239000002253 acid Substances 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 22
- 238000005185 salting out Methods 0.000 claims abstract description 21
- 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
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 16
- WASBLYYABCWBNN-UHFFFAOYSA-N NN1C(SC2=C1C=C(C=C2)[N+](=O)[O-])[N+]#N Chemical class NN1C(SC2=C1C=C(C=C2)[N+](=O)[O-])[N+]#N WASBLYYABCWBNN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000012065 filter cake Substances 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 3
- 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 3
- 239000000975 dye Substances 0.000 claims description 44
- 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 17
- 235000011056 potassium acetate Nutrition 0.000 claims description 12
- FUARCQLZUVMPSL-UHFFFAOYSA-N 5-nitro-2h-1,3-benzothiazol-3-amine Chemical compound C1=C([N+]([O-])=O)C=C2N(N)CSC2=C1 FUARCQLZUVMPSL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- ZFRBZRZEKIOGQI-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1,3-disulfonic acid Chemical group 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 6
- ZUQOBHTUMCEQBG-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid Chemical group OS(=O)(=O)C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 ZUQOBHTUMCEQBG-UHFFFAOYSA-N 0.000 claims description 6
- HBZVNWNSRNTWPS-UHFFFAOYSA-N 6-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical group C1=C(S(O)(=O)=O)C=C(O)C2=CC(N)=CC=C21 HBZVNWNSRNTWPS-UHFFFAOYSA-N 0.000 claims description 6
- 239000006172 buffering agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000005457 ice water Substances 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 4
- 239000007864 aqueous solution Substances 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
- 230000035515 penetration Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical group OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000008859 change 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
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical group [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 16
- 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
- 239000002585 base Substances 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 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
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000000623 heterocyclic group Chemical group 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
- 239000003513 alkali Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 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 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
- 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
- 238000010189 synthetic method Methods 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- 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
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- 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; under the condition of ice salt bath, dropwise adding sodium nitrite into concentrated sulfuric acid, heating until the sodium nitrite is completely dissolved after stirring to prepare nitrosyl sulfuric acid, gradually adding 3-amino-5-nitrobenzoisothiazole after cooling, and stirring for reaction to obtain 3-amino-5-nitrobenzoisothiazole diazonium salt; gradually dripping 3-amino-5-nitrobenzothiazole diazonium salt into the condensation product for coupling reaction, adding acetate solid in batches after the reaction is finished, salting out, carrying out suction filtration, airing the filter cake to obtain a crude product, regulating the pH value of the crude product after the crude product is redissolved, and salting out again to obtain the benzisothiazole heterocyclic azo dye. The heterocyclic azo type 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 due to the readily available raw materials, simple synthetic methods, complete chromatograms, and high absorption coefficients. Many monoazo type water-soluble dyes are prone to tautomerism of azo-quinone hydrazone due to azo bonds, so different color differences are often presented in different acid and alkali environments, and the research on the acid-base discoloration effect of the azo type dyes also becomes a research hotspot in the field of functional dyes. The 3-amino-5-nitrobenzoisothiazole has good dark color effect due to the existence of sulfur atoms and nitrogen atoms with high electronegativity in a heterocyclic structure, good electron transfer capability of the heterocyclic system and strong electron withdrawing effect of a nitro substituent, and is often used as a diazo component for synthesizing water-insoluble dyes such as high-performance disperse dyes, but the structure has poor water solubility, so the structure cannot be applied to the water-soluble dyes, and the application of the excellent performance of the 3-amino-5-nitrobenzoisothiazole heterocyclic structure in the field of dyes is greatly limited.
Therefore, the invention utilizes the good dark color effect of the 3-amino-5-nitrobenzoisothiazole heterocyclic structure as the diazo component for synthesizing the water-soluble azo dye and introduces the diazo component into the parent structure of the amino naphthol sulfonic acid water-soluble dye to prepare the reversible water-soluble heterocyclic azo acid-base color-changing dye with high pH sensitivity, good selectivity and color change.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a benzisothiazole heterocyclic azo dye and a preparation method thereof, which aim to solve the problem that a 3-amino-5-nitrobenzothiazole heterocyclic structure is difficult to be applied to a water-soluble dye and widen the application of the 3-amino-5-nitrobenzothiazole heterocyclic structure in the dye field.
In order to achieve the purpose, the invention adopts the following technical scheme: a benzisothiazole heterocyclic azo dye has a structure of general formula I:
wherein n is 1 or 2;
x is selected from-OCH 3 or-OPh.
In a further technical scheme of the invention, in the formula I, the amino naphthol disulfonic acid residue or the amino naphthol sulfonic acid residue connected with the X and the azo bond is selected from one of the following groups:
an H acid residue having the formula:
a K acid residue of the formula:
a chicago acid residue having the formula:
j acid residue of the formula:
a gamma acid residue having the formula:
a process for the preparation of benzisothiazole heterocyclic azo type dyes, said process 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) diazotization reaction
Under the condition of ice water bath, dropwise adding sodium nitrite into concentrated sulfuric acid, heating until the sodium nitrite is completely dissolved after stirring to prepare nitrosyl sulfuric acid, gradually adding 3-amino-5-nitrobenzoisothiazole after cooling, and stirring for reaction to obtain 3-amino-5-nitrobenzoisothiazole diazonium salt;
3) coupling reaction
Gradually dripping the 3-amino-5-nitrobenzothiazole diazonium salt obtained in the step 2) into the condensation product obtained in the step 1) for coupling reaction, adding acetate solid in batches for salting out after the reaction is finished, performing suction filtration, drying a filter cake to obtain a crude product, re-dissolving the crude product, adjusting the pH value, and re-salting out to obtain the benzisothiazole heterocyclic azo dye.
According to a further technical scheme, in the step 1), the aminonaphthol 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 the 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, nitrosyl sulfuric acid is used as a diazotization reagent in the diazotization 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-nitrobenzothiazole is 11:1
Or, the reaction time is 2-4 h;
or the reaction temperature is 0-5 ℃.
In the further technical scheme of the invention, in the step 3),
the molar ratio of the 3-amino-5-nitrobenzothiazole diazonium salt to the condensation product of acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid is 1: 1;
or, the reaction pH value is 1-2;
or the reaction temperature is 0-5 ℃.
According to a further technical scheme, the condensation reaction of acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid in the step 1) is carried out according to the following method: dropwise adding acetic anhydride or benzoyl chloride into an aqueous solution of aminonaphthol disulfonic acid or aminonaphthol sulfonic acid, wherein the molar ratio of the acetic anhydride or benzoyl chloride to the aminonaphthol sulfonic acid is 2.5: 1; heating to 60-80 ℃, stirring for reaction, and detecting by using an Ehrlich reagent to determine a reaction end point to obtain a condensation product of acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid.
According to a further technical scheme of the invention, the diazotization reaction in the step 2) is specifically as follows: under the condition of ice water bath at 0-5 ℃, adding sodium nitrite solid into concentrated sulfuric acid gradually, heating until the sodium nitrite solid is completely dissolved after stirring, cooling to 0-5 ℃, adding 3-amino-5-nitrobenzothiazole gradually, wherein the molar ratio of sodium nitrite to 3-amino-5-nitrobenzothiazole is 1.05:1, the molar ratio of concentrated sulfuric acid to 3-amino-5-nitrobenzothiazole is 11:1, stirring for reaction for 2-4 h, and adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed, thereby obtaining the 3-amino-5-nitrobenzothiazole diazonium salt.
According to a further technical scheme of the invention, the coupling reaction in the step 3) is specifically as follows: gradually dropping 3-amino-5-nitrobenzothiazole diazonium salt into a condensation product 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-nitrobenzothiazole diazonium salt to the condensation product of the acetic anhydride or benzoyl chloride and the amino naphthol disulfonic acid or the amino naphthol sulfonic acid is 1:1, controlling the pH value to be 1-2, reacting at 0-5 ℃, adding a pH value buffering agent according to the mass ratio of the buffering agent to the volume ratio of the solution of 1% after the reaction is completed, then adding potassium acetate solid in batches, detecting the salting-out condition of the dye by a ring penetration method, stirring, standing, performing suction filtration, drying a filter cake to obtain a crude product, re-dissolving the crude product, adjusting the pH value to be 6.8-7.0, and re-salting out 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, has a dark color effect brought by a 3-amino-5-nitrobenzoisothiazole heterocyclic structure, has water solubility and excellent acid-base color changing performance, and widens the application of the 3-amino-5-nitrobenzoisothiazole heterocyclic structure in the field of dyes.
Drawings
FIG. 1 is an infrared spectrum of a benzisothiazole heterocyclic azo type dye of example 1 of the present invention;
FIG. 2 is a graph showing UV-visible absorption spectra of benzisothiazole heterocyclic azo type dye of example 1 of the present invention without pH.
Detailed Description
The following description of the embodiments is provided in connection with the accompanying drawings.
The reagents and instruments in the following examples are all conventional laboratory reagents and instruments.
Example 1:
the concrete 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 (0.11mol and 98%) in a three-neck flask, cooling at 0-5 ℃ in an ice water bath, gradually adding 0.73g of sodium nitrite solid (0.0105mol), stirring for a period of time, heating until the sodium nitrite solid is completely dissolved, stopping heating, cooling, gradually adding 2.01g of 3-amino-5-nitrobenzoisothiazole (0.01mol and 97%), continuously stirring at 0-5 ℃ for reaction, detecting the reaction end point by thin-layer chromatography, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid;
condensation reaction: taking an aqueous solution containing 4.0g of H acid monosodium salt (0.01mol, 85.6%), gradually adding 0.25mol of acetic anhydride according to the molar ratio of the acetic anhydride to the H acid of 2.5:1, heating to 60-80 ℃, stirring for reaction, and detecting by using an Ehrlich reagent to determine a reaction end point to obtain a condensation product of the acetic anhydride and the H acid;
coupling reaction: gradually dripping the 3-amino-5-nitrobenzothiazole diazonium salt into a condensation product, controlling the pH value to be 1-2, reacting at 0-5 ℃, and detecting the reaction condition by using a ring penetration method. After the reaction is finished, adding a pH value buffering agent of 1% (w/v), adding potassium acetate solid in batches, detecting the salting-out condition of the dye by a ring permeation method, stirring, standing, performing suction filtration, washing with a proper amount of ethanol for 3 times, and drying a filter cake to obtain a crude product. And (3) re-dissolving the crude product, adjusting the pH value to 6.8-7.0, and re-salting out to obtain Dye 1.
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 dissolving, adjusting the pH value to be neutral by using dilute hydrochloric acid or sodium carbonate solution, transferring the solution to a 100mL volumetric flask, adding deionized water to scale, fixing the volume and shaking up. A certain volume of Dye solution was transferred from the above 100mL volumetric flasks into the colorimetric cylinder, solutions containing Dye1 having different pH values of 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0 and 11.0 were prepared, respectively, and the uv-vis absorption spectra of the Dye solutions at different pH values were measured, and the results are shown in fig. 2.
Example 2:
the concrete structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: same preparation as in example 1;
condensation reaction: taking an aqueous solution containing 4.0g of H acid monosodium salt (0.01mol, 85.6%), gradually adding 0.25mol of benzoyl chloride according to the molar ratio of the benzoyl chloride to the H acid of 2.5:1, heating to 60-80 ℃, stirring for reaction, and detecting by using an Ehrlich reagent to determine a reaction end point to obtain a condensation product of the benzoyl chloride and the H acid;
coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the product is obtained by salting out.
Example 3:
the concrete structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: same preparation as in example 1;
condensation reaction: the condensation product was prepared by substituting the K acid for the H acid, and the other reactants and reaction conditions were the same as in the above example 1;
coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the product is obtained by salting out.
Example 4:
the concrete structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: same preparation as in example 1;
condensation reaction: the condensation product was prepared by substituting the K acid for the H acid, and the other reactants and reaction conditions were the same as in the above example 2;
coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the product is obtained by salting out.
Example 5:
the concrete structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: same preparation as in example 1;
condensation reaction: chicago acid was used in place of H acid in the preparation of the condensation product, and other reactants and reaction conditions were the same as in the preparation of example 1 above;
coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the product is obtained by salting out.
Example 6:
the concrete structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: same preparation as in example 1;
condensation reaction: chicago acid was used in place of H acid in the preparation of the condensation product, and other reactants and reaction conditions were the same as in the preparation of example 2 above;
coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the product is obtained by salting out.
Example 7:
the concrete structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: same preparation as in example 1;
condensation reaction: the condensation product was prepared by substituting J acid for H acid, and the other reactants and reaction conditions were the same as in the above preparation of example 1;
coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the product is obtained by salting out.
Example 8:
the concrete structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: same preparation as in example 1;
condensation reaction: the condensation product was prepared by substituting J acid for H acid, and the other reactants and reaction conditions were the same as in the above example 2;
coupling reaction: and (3) adding potassium acetate to precipitate a dye after the reaction is finished, filtering, re-dissolving the crude product, adjusting the pH value to be 6.8-7.0, and salting out to obtain the product, which is the same as the preparation in the embodiment 1.
Example 9:
the concrete structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: same preparation as in example 1;
condensation reaction: the condensation product was prepared by substituting gamma acid for H acid, and the other reactants and reaction conditions were the same as those in example 1 above;
coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the product is obtained by salting out.
Example 10:
the concrete structure of the benzisothiazole heterocyclic azo dye is as follows:
diazotization reaction: same preparation as in example 1;
condensation reaction: the condensation product was prepared by substituting gamma acid for H acid, and the other reactants and reaction conditions were the same as those in example 2 above;
coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the product is obtained by salting out.
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.
Claims (9)
1. A benzisothiazole heterocyclic azo dye having the structure of formula I:
wherein n is 1 or 2;
x is selected from-OCH 3 or-OPh.
2. Benzisothiazole heterocyclic azo dyes according to claim 1, wherein the aminonaphthol disulfonic acid residue or the aminonaphthol sulfonic acid residue linked to X and the azo bond in formula I is selected from one of the following groups:
an H acid residue having the formula:
a K acid residue of the formula:
a chicago acid residue having the structural formula:
j acid residue of the formula:
a gamma acid residue of the formula:
3. a method for producing a benzisothiazole heterocyclic azo type dye having the structure of any one of claims 1 to 2, 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) diazotization reaction
Under the condition of ice water bath, dropwise adding sodium nitrite into concentrated sulfuric acid, heating until the sodium nitrite is completely dissolved after stirring to prepare nitrosyl sulfuric acid, gradually adding 3-amino-5-nitrobenzoisothiazole after cooling, and stirring for reaction to obtain 3-amino-5-nitrobenzoisothiazole diazonium salt;
3) coupling reaction
Gradually dripping the 3-amino-5-nitrobenzothiazole diazonium salt obtained in the step 2) into the condensation product obtained in the step 1) for coupling reaction, adding acetate solid in batches for salting out after the reaction is finished, performing suction filtration, drying a filter cake to obtain a crude product, re-dissolving the crude product, adjusting the pH value, and re-salting out to obtain the benzisothiazole heterocyclic azo dye.
4. A process for the preparation of benzisothiazole heterocyclic azo dyes according to claim 3, characterized in that: in the step 1), the aminonaphthol 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 the benzoyl chloride to the amino naphthol sulfonic acid is 2.5: 1;
or the reaction temperature is 60-80 ℃.
5. The process for preparing benzisothiazole heterocyclic azo type dye according to claim 3, wherein the diazotization reaction in the step 2) is performed using nitrosylsulfuric acid as a diazotizing agent;
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-nitrobenzothiazole is 11: 1;
or, the reaction time is 2-4 h;
or the reaction temperature is 0-5 ℃.
6. The process for preparing benzisothiazole heterocyclic azo type dyes according to claim 3, wherein in step 3),
the molar ratio of the 3-amino-5-nitrobenzothiazole diazonium salt to the condensation product of acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid is 1: 1;
or the reaction pH value is 1-2, and the reaction temperature is 0-5 ℃.
7. The process for preparing benzisothiazole heterocyclic azo dyes according to claim 3, wherein the condensation reaction of acetic anhydride or benzoyl chloride with aminonaphthol disulfonic acid or aminonaphthol sulfonic acid in step 1) is carried out as follows: dropwise adding acetic anhydride or benzoyl chloride into an aqueous solution of aminonaphthol disulfonic acid or aminonaphthol sulfonic acid, wherein the molar ratio of the acetic anhydride or benzoyl chloride to the aminonaphthol sulfonic acid is 2.5: 1; heating to 60-80 ℃, stirring for reaction, and detecting by using an Ehrlich reagent to determine a reaction end point to obtain a condensation product of acetic anhydride or benzoyl chloride and amino naphthol disulfonic acid or amino naphthol sulfonic acid.
8. The process for preparing benzisothiazole heterocyclic azo type dye according to claim 3, wherein the diazotization reaction in the step 2) is specifically: under the condition of ice water bath at 0-5 ℃, adding sodium nitrite solid into concentrated sulfuric acid gradually, heating until the sodium nitrite solid is completely dissolved after stirring, cooling to 0-5 ℃, adding 3-amino-5-nitrobenzothiazole gradually, wherein the molar ratio of sodium nitrite to 3-amino-5-nitrobenzothiazole is 1.05:1, the molar ratio of concentrated sulfuric acid to 3-amino-5-nitrobenzothiazole is 11:1, stirring for reaction for 2-4 h, and adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed, thereby obtaining the 3-amino-5-nitrobenzothiazole diazonium salt.
9. The process for preparing benzisothiazole heterocyclic azo dyes according to claim 3, wherein the coupling reaction in step 3) is specifically: gradually dropping 3-amino-5-nitrobenzothiazole diazonium salt into a condensation product 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-nitrobenzothiazole diazonium salt to the condensation product of the acetic anhydride or benzoyl chloride and the amino naphthol disulfonic acid or the amino naphthol sulfonic acid is 1:1, controlling the pH value to be 1-2, reacting at 0-5 ℃, adding a pH value buffering agent according to the mass ratio of the buffering agent to the volume ratio of the solution of 1% after the reaction is completed, then adding potassium acetate solid in batches, detecting the salting-out condition of the dye by a ring penetration method, stirring, standing, performing suction filtration, drying a filter cake to obtain a crude product, re-dissolving the crude product, adjusting the pH value to be 6.8-7.0, and re-salting out to obtain the benzisothiazole heterocyclic azo dye.
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