CN113683901B - Benzothiazole heterocycle azo type water-soluble dye and preparation method thereof - Google Patents
Benzothiazole heterocycle azo type water-soluble dye and preparation method thereof Download PDFInfo
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- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 238000006482 condensation reaction Methods 0.000 claims abstract description 64
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000005859 coupling reaction Methods 0.000 claims abstract description 43
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 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 35
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 32
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007859 condensation product Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- GPNAVOJCQIEKQF-UHFFFAOYSA-N 6-nitro-1,3-benzothiazol-2-amine Chemical compound C1=C([N+]([O-])=O)C=C2SC(N)=NC2=C1 GPNAVOJCQIEKQF-UHFFFAOYSA-N 0.000 claims abstract description 15
- VMKJWLXVLHBJNK-UHFFFAOYSA-N cyanuric fluoride Chemical compound FC1=NC(F)=NC(F)=N1 VMKJWLXVLHBJNK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 173
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 84
- 239000000243 solution Substances 0.000 claims description 52
- 230000001276 controlling effect Effects 0.000 claims description 51
- 239000007787 solid Substances 0.000 claims description 50
- 239000012043 crude product Substances 0.000 claims description 49
- 238000005185 salting out Methods 0.000 claims description 46
- 238000001914 filtration Methods 0.000 claims description 42
- 235000011056 potassium acetate Nutrition 0.000 claims description 42
- 238000006193 diazotization reaction Methods 0.000 claims description 39
- 238000004519 manufacturing process Methods 0.000 claims description 37
- 239000003153 chemical reaction reagent Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- 239000011734 sodium Substances 0.000 claims description 27
- 238000004809 thin layer chromatography Methods 0.000 claims description 25
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- MQXMFFRUJDMLOR-UHFFFAOYSA-N NC1(SC2=C(N1)C=CC(=C2)[N+](=O)[O-])[N+]#N Chemical class NC1(SC2=C(N1)C=CC(=C2)[N+](=O)[O-])[N+]#N MQXMFFRUJDMLOR-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 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 12
- 235000010288 sodium nitrite Nutrition 0.000 claims description 11
- 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 9
- 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 9
- 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 9
- 239000000047 product Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 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 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 150000001448 anilines Chemical class 0.000 claims description 6
- 125000001246 bromo group Chemical group Br* 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000006174 pH buffer Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims 2
- 239000000975 dye Substances 0.000 abstract description 148
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 150000004982 aromatic amines Chemical class 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 239000012954 diazonium Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 abstract 1
- 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 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 241000605314 Ehrlichia Species 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 20
- 239000000376 reactant Substances 0.000 description 12
- NNRSYETYEADPBW-UHFFFAOYSA-N cyhalodiamide Chemical compound CC1=CC(C(F)(C(F)(F)F)C(F)(F)F)=CC=C1NC(=O)C1=CC=CC(Cl)=C1C(=O)NC(C)(C)C#N NNRSYETYEADPBW-UHFFFAOYSA-N 0.000 description 11
- 238000010907 mechanical stirring Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 4
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 125000002560 nitrile group Chemical group 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 3
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 2
- KVCQTKNUUQOELD-UHFFFAOYSA-N 4-amino-n-[1-(3-chloro-2-fluoroanilino)-6-methylisoquinolin-5-yl]thieno[3,2-d]pyrimidine-7-carboxamide Chemical compound N=1C=CC2=C(NC(=O)C=3C4=NC=NC(N)=C4SC=3)C(C)=CC=C2C=1NC1=CC=CC(Cl)=C1F KVCQTKNUUQOELD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- SQYUJKVKVFILNB-UHFFFAOYSA-N methyl 2-amino-4-[(2,5-dichlorophenyl)carbamoyl]benzoate Chemical compound C1=C(N)C(C(=O)OC)=CC=C1C(=O)NC1=CC(Cl)=CC=C1Cl SQYUJKVKVFILNB-UHFFFAOYSA-N 0.000 description 2
- 239000006179 pH buffering agent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229950000244 sulfanilic acid Drugs 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
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 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
- 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
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 238000005406 washing 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
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
- C09B29/0011—Monoazo dyes prepared by diazotising and coupling from diazotized anilines from diazotized anilines directly substituted by a heterocyclic ring (not condensed)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/82—Nitrogen atoms
-
- 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
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3691—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing nitrogen and sulfur as heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
The invention relates to the technical field of dyes, in particular to benzothiazole heterocycle azo type water-soluble dye and a preparation method thereof. The weak alkaline aromatic amine containing heterocyclic structure in the molecule is used as diazonium component to be introduced into the water-soluble acid or active dye structure, so that the acid-base color-changing dye is formed. The preparation method comprises the following steps: the condensation reaction of cyanuric chloride, cyanuric fluoride, acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid to obtain condensation products; diazotizing 2-amino-6-nitrobenzothiazole; coupling of diazotized reaction products with condensation products. The benzothiazole heterocycle azo type water-soluble dye provided by the invention has excellent acid-base color-changing performance, is simple in synthesis process, can be used for rapidly detecting the pH value of a solution directly through naked eye observation without any optical device, has the advantages of high sensitivity, good selectivity, rapidness, reversibility, visible naked eyes and the like, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of dyes, in particular to benzothiazole heterocycle azo type water-soluble 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, and high absorption coefficient. Because azo bonds are easy to generate tautomerism of azo-quinone hydrazone structures, a plurality of monoazo water-soluble dyes often show different color differences in different acid-base environments, and research on pH color change effects of azo structural dyes also becomes a research hot spot in the dye field. 2-amino-6-nitrobenzothiazole is often used as a diazo component for synthesizing high-performance azo dyes in water-insoluble dyes such as disperse dyes, direct dyes and the like due to the existence of sulfur or nitrogen atoms with slightly higher electronegativity in a heterocyclic structure, better electron transfer capability of a heterocyclic system and nitro electron-withdrawing action, but has few applications in active and acid dyes with wide application.
Disclosure of Invention
Aiming at the defects existing in the prior art, the technical problem to be solved by the invention is to provide benzothiazole heterocycle azo type water-soluble dye and a preparation method thereof, wherein 2-amino-6-nitrobenzothiazole is used as a diazo component to be introduced into a water-soluble acid or active dye structure so as to become an acid-base color-changing dye.
The technical scheme adopted by the invention for achieving the purpose is as follows: a benzothiazole heterocyclic azo type water-soluble dye having a structure of general formula (I):
Wherein,
a is selected from-OCH 3 -OPh or formula (ii-a);
n=1 or 2;
in the general formula (II-a),
x is selected from-Cl or-F;
y is selected from-Cl, -F, -NH 2 、-NHCH 3 、-NHCH 2 CH 3 、-NHCH 2 COOH、-NHCH(CH 3 )COOH、-OH、-OCH 3 、-OCH 2 CH 3 Or of the general formula (II-b);
in the general formula (II-b),
R 1 selected from-H, carboxyl, sulfonic acid group, methyl, methoxy, nitro, nitrile group, amino, -Cl or-Br;
R 2 selected from-H, carboxyl, sulfonic acid group, methyl, methoxy, nitro, nitrile group, amino, -Cl, -Br, -CH 2 COOH、-COCH 2 Cl、-COCH 2 CH 2 Cl、-NHCOCH 2 Cl、-NHCOCH 2 CH 2 Cl、-NHCOCH＝CH 2 、-NHCOC(Br)＝CH 2 、-NHCH 2 CH(OH)CH 2 Cl、-NHSO 2 CH＝CH 2 、-N(CH 3 )SO 2 CH 2 CH 2 M、-SO 2 CH＝CH、-SO 2 CH 2 CH 2 M、-SO 2 CH 2 CH 2 OSO 3 M、-SO 2 NHCH 2 CH 2 M or-SO 2 N(CH 3 )CH 2 CH 2 M; wherein M is selected from-Cl, -F or-OSO 3 R 3 ，R 3 Selected from-H, -Na or-K.
Further, in the formula (I), the amino naphthol sulfonic acid residue or amino naphthol disulfonic acid residue connected with A is selected from one of the following groups:
h acid residue, its structural formula is:
j acid residue, its structural formula is:
a gamma acid residue having the structural formula:
k acid residue, its structural formula is:
a chicagonic acid residue having the structural formula:
the invention also comprises a method for preparing the benzothiazole heterocycle azo type water-soluble dye,
1) Condensation reaction
The condensation reaction of cyanuric chloride, cyanuric fluoride, acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid to obtain condensation products;
2) Diazotisation reaction
Gradually adding sodium nitrite solid into concentrated sulfuric acid under the ice salt bath condition, stirring, heating to be completely dissolved, cooling to 0-5 ℃, gradually adding 2-amino-6-nitrobenzothiazole, stirring for reaction, adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed, and obtaining 2-amino-6-nitrobenzothiazole diazonium salt;
3) Coupling reaction
Gradually dripping the 2-amino-6-nitrobenzothiazole diazonium salt obtained in the step 2) into the condensation product obtained in the step 1), controlling pH, reacting, adding a pH buffering agent after the reaction is completed, then adding potassium acetate or sodium acetate solid in a divided manner, stirring, standing, suction filtering, airing a filter cake to obtain a crude product, re-dissolving the crude product, adjusting the pH, and re-salting out to obtain the benzothiazole heterocyclic azo type water-soluble dye.
Further, in the step 1), the condensation reaction of cyanuric chloride or cyanuric fluoride and amino naphthol sulfonic acid is a primary condensation reaction or a secondary condensation reaction;
the amino naphthol sulfonic acid is one of H acid, J acid, gamma acid, K acid or Chicago acid.
Further, the primary condensation reaction is as follows: adding 10% amino naphthol sulfonic acid solution into cyanuric chloride or cyanuric fluoride solution, stirring and reacting at 0-5 ℃, controlling the pH value of the solution to be 4-5 in the reaction process, and detecting a condensation reaction end point by using an Ehrlich reagent to obtain a condensation product;
the secondary condensation reaction is as follows: adding unsubstituted or substituted aminobenzene or aliphatic amine into the first-shrink product, raising the temperature to 15-30 ℃, controlling the pH value to 5-6 for reaction, and detecting the end point of the second-shrink reaction by thin layer chromatography to obtain the second-shrink product.
Further, the method comprises the steps of,
the molar ratio of the cyanuric chloride or the cyanuric fluoride to the amino naphthol sulfonic acid is 1.02:1;
the molar ratio of the monocondensation product to the unsubstituted or substituted aminobenzene or fatty amine is 1:1.
Further, in the step 1), the condensation reaction of acetic anhydride or benzoyl chloride and aminonaphthol sulfonic acid is as follows: and (3) dropwise adding acetic anhydride or benzoyl chloride into the aqueous solution of the amino naphthol sulfonic acid, 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 the acetic anhydride or benzoyl chloride and the amino naphthol sulfonic acid.
Further, the molar ratio of the acetic anhydride or the benzoyl chloride to the amino naphthol sulfonic acid is 2-3:1;
the molar ratio of the acetic anhydride or benzoyl chloride to the amino naphthol sulfonic acid is 2.5:1.
Further, the diazotization reaction in the step 2) specifically includes: gradually adding sodium nitrite solid into 11.0g of concentrated sulfuric acid under the ice salt bath condition of-5 to-10 ℃, stirring, heating to be completely dissolved, cooling to 0-5 ℃, gradually adding 2-amino-6-nitrobenzothiazole, stirring for reacting for 2-4 hours, and adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed to obtain 2-amino-6-nitrobenzothiazole diazonium salt;
The molar ratio of the sodium nitrite to the 2-amino-6-nitrobenzothiazole is 1.05:1.
Further, the coupling reaction in the step 3) is specifically: gradually dripping 2-amino-6-nitrobenzothiazole diazonium salt into the condensation product in the step 1), controlling the pH value to be 1-2, reacting at 0-5 ℃, and adding 1% (w/v) Na after the reaction is completed 2 HPO 4 -NaH 2 PO 4 Adding potassium acetate or sodium acetate solid in batches, detecting dye salting-out condition by using a permeation ring, stirring, standing, suction-filtering, airing 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 benzothiazole heterocycle azo type water-soluble dye.
The benzothiazole heterocycle azo type water-soluble dye and the preparation method thereof have the beneficial effects that: the benzothiazole heterocycle azo type water-soluble dye provided by the invention has excellent acid-base color-changing performance, is simple in synthesis process, can be used for rapidly detecting the pH value of a solution directly through naked eye observation without any optical device, has the advantages of high sensitivity, good selectivity, rapidness, reversibility, visible naked eyes and the like, and has a wide application prospect.
Drawings
FIG. 1 is a graph showing the UV-visible absorption spectrum of the blue Dye1 obtained in example 1 of the present invention under different pH conditions;
FIG. 2 is an infrared spectrum of a blue Dye1 obtained in example 1 of the present invention.
Detailed Description
The invention will be described in further detail with reference to the accompanying drawings and specific examples;
example 1
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: cooling 11.0g of concentrated sulfuric acid with the mass fraction of 98% under the ice bath condition of 0-5 ℃, gradually adding 0.73g of sodium nitrite solid, stirring, heating until the sodium nitrite solid is completely dissolved, stopping heating and cooling, gradually adding 1.99g of 2-amino-6-nitrobenzothiazole (0.01 mol, 98%), stirring, then continuing the reaction at 0-5 ℃, detecting the reaction end point by Thin Layer Chromatography (TLC), and adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed;
condensation reaction of cyanuric chloride: 1.90g cyanuric chloride (0.0103 mol) and 20g of small ice cubes are taken, mechanically stirred at 0-5 ℃ until the mixture is milky, then an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt is added, the pH of the solution is regulated to be between 4 and 5, and an ehrlichia reagent is used for detecting and determining the end point of the reaction; after the reaction is finished, adding 2.81g of p- (beta-sulfuric acid ester ethyl sulfone) aniline (0.01 mol), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using 10% sodium carbonate solution, and detecting the reaction end point by TLC after 3-4 hours of reaction (developing agent is n-butanol, isopropanol, ethyl acetate, water=2:4:1:3, v/v);
Coupling reaction: gradually dripping the 2-amino-6-nitrobenzothiazole diazonium salt into a condensation product of cyanuric chloride, controlling the pH value between 1 and 2, reacting at 0 to 5 ℃, and detecting the reaction condition by a ring permeation 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 permeation ring, stirring, standing, suction filtering, washing by using proper amount of ethanol for 3 times, 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 the blue Dye1.
FIG. 1 is a graph showing the UV-visible absorption spectrum of the blue Dye1 obtained in example 1 of the present invention under different pH conditions;
FIG. 2 is an infrared spectrum of a blue Dye1 obtained in example 1 of the present invention.
Example 2
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: 1.90g cyanuric chloride (0.0103 mol) and 20g of small ice cubes are taken, mechanically stirred at 0-5 ℃ until the mixture is milky, then an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt is added, the pH of the solution is regulated to be between 4 and 5, and an ehrlichia reagent is used for detecting and determining the end point of the reaction; after the reaction is finished, adding 2.81g of meta (beta-sulfuric acid ester ethyl sulfone) aniline (0.01 mol), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using 10% sodium carbonate solution, and detecting the reaction end point by TLC after 3-4 hours of reaction (developing agent is n-butanol, isopropanol, ethyl acetate, water=2:4:1:3, v/v);
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 blue solid.
Example 3
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: 1.90g cyanuric chloride (0.0103 mol) and 20g of small ice cubes are taken, mechanically stirred at 0-5 ℃ until the mixture is milky, then an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt is added, the pH of the solution is regulated to be between 4 and 5, and an ehrlichia reagent is used for detecting and determining the end point of the reaction; after the reaction is finished, adding 1.77g of o-aminobenzenesulfonic acid (0.01 mol, 98%), raising the temperature to 20-30 ℃, controlling the pH value to 5-6 by using 10% sodium carbonate solution, and detecting the reaction end point by TLC after 3-4 hours of reaction (developing agent is n-butanol, isopropanol, ethyl acetate, water=2:4:1:3, v/v);
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 blue solid.
Example 4
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: 1.90g cyanuric chloride (0.0103 mol) and 20g of small ice cubes are taken, mechanically stirred at 0-5 ℃ until the mixture is milky, then an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt is added, the pH of the solution is regulated to be between 4 and 5, and an ehrlichia reagent is used for detecting and determining the end point of the reaction; after the reaction is finished, adding 1.75g of metaaminobenzenesulfonic acid (0.01 mol, 99%), raising the temperature to 20-30 ℃, controlling the pH value to 5-6 by using 10% sodium carbonate solution, and detecting the reaction end point by TLC after 3-4 hours of reaction (developing agent is n-butanol, isopropanol, ethyl acetate, water=2:4:1:3, v/v);
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 blue solid.
Example 5
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
Diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: 1.90g cyanuric chloride (0.0103 mol) and 20g of small ice cubes are taken, mechanically stirred at 0-5 ℃ until the mixture is milky, then an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt is added, the pH of the solution is regulated to be between 4 and 5, and an ehrlichia reagent is used for detecting and determining the end point of the reaction; after the reaction is finished, adding 1.73g of sulfanilic acid (0.01 mol, 99.8%), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using 10% sodium carbonate solution, and detecting the reaction end point by TLC after 3-4 hours of reaction (developing agent is n-butanol, isopropanol, ethyl acetate, water=2:4:1:3, v/v);
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 blue solid.
Example 6
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: 1.90g cyanuric chloride (0.0103 mol) and 20g of small ice cubes are taken, mechanically stirred at 0-5 ℃ until the mixture is milky, then an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt is added, the pH of the solution is regulated to be between 4 and 5, and an ehrlichia reagent is used for detecting and determining the end point of the reaction; after the reaction is finished, adding 2.67g of aniline-2, 5-disulfonic acid (0.01 mol, 92.0%), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using 10% sodium carbonate solution, and detecting the reaction endpoint by TLC after 3-4 hours of reaction (developing agent is n-butanol, isopropanol, ethyl acetate, water=2:4:1:3, v/v);
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 blue solid.
Example 7
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: 1.90g cyanuric chloride (0.0103 mol) and 20g of small ice cubes are taken, mechanically stirred at 0-5 ℃ until the mixture is milky, then an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt is added, the pH of the solution is regulated to be between 4 and 5, and an ehrlichia reagent is used for detecting and determining the end point of the reaction; after the reaction is finished, 1.40g of p-aminobenzoic acid (0.01 mol, 98%) is added, the temperature is raised to 20-30 ℃, the pH value is controlled to be 5-6 by using 10% sodium carbonate solution, after the reaction is finished for 3-4 hours, the TLC detects the end point of the reaction (developing agent is n-butanol, isopropanol, ethyl acetate, water=2:4:1:3, v/v);
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 blue solid.
Example 8
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: 1.90g cyanuric chloride (0.0103 mol) and 20g of small ice cubes are taken, mechanically stirred at 0-5 ℃ until the mixture is milky, then an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt is added, the pH of the solution is regulated to be between 4 and 5, and an ehrlichia reagent is used for detecting and determining the end point of the reaction; after the reaction is finished, 0.93g of aniline (0.01 mol) is added, the temperature is raised to 20-30 ℃, the pH value is controlled to be 5-6 by using 10% sodium carbonate solution, after the reaction is carried out for 3-4 hours, the TLC detects the end point of the reaction (developing agent is n-butanol, isopropanol, ethyl acetate, water=2:4:1:3, v/v);
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 blue solid.
Example 9
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
Diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: 1.90g cyanuric chloride (0.0103 mol) and 20g of small ice cubes are taken, mechanically stirred at 0-5 ℃ until the mixture is milky, then an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt is added, the pH of the solution is regulated to be between 4 and 5, and an ehrlichia reagent is used for detecting and determining the end point of the reaction; after the reaction is finished, 0.64g of ethylamine (0.01 mol, 70%) is added, the temperature is raised to 20-30 ℃, the pH value is controlled to be 5-6 by using 10% sodium carbonate solution, after the reaction is carried out for 3-4 hours, the TLC detects the end point of the reaction (developing agent is n-butanol, isopropanol, ethyl acetate, water=2:4:1:3, v/v);
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 blue solid.
Example 10
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: 1.90g cyanuric chloride (0.0103 mol) and 20g of small ice cubes are taken, mechanically stirred at 0-5 ℃ until the mixture is milky, then an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt is added, the pH of the solution is regulated to be between 4 and 5, and an ehrlichia reagent is used for detecting and determining the end point of the reaction; after the reaction is finished, adding 0.75g glycine (0.01 mol), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using 10% sodium carbonate solution, and detecting the reaction end point by TLC after 3-4 hours of reaction (developing agent is n-butanol, isopropanol, ethyl acetate, water=2:4:1:3, v/v);
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 blue solid.
Example 11
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: adding dissolved 4.0g (0.01 mol, 85.6%) H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103 mol) of cyhalodiamide under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process 2 CO 3 Controlling the pH value of the solution to be 4-5, and detecting and determining the reaction end point by using an ehrlichia reagent; after the reaction, 2.81g of p- (beta-sulfate ethyl sulfone) aniline (0.01 mol) was added thereto, the temperature was raised to 15 to 20℃and 10% of Na was used 2 CO 3 Controlling the pH value of the solution to be between 5 and 6, and detecting the reaction end point by TLC after reacting for 3 to 4 hours;
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 blue solid.
Example 12
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: adding dissolved 4.0g (0.01 mol, 85.6%) H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103 mol) of cyhalodiamide under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process 2 CO 3 Controlling the pH value of the solution to be 4-5, and detecting and determining the reaction end point by using an ehrlichia reagent; after the reaction, 2.81g of meta (. Beta. -sulfate ethylsulfone) aniline (0.01 mol) was added thereto, the temperature was raised to 15 to 20℃and 10% of Na was used 2 CO 3 Controlling the pH value of the solution to be between 5 and 6, and detecting the reaction end point by TLC after reacting for 3 to 4 hours;
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 blue solid.
Example 13
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
A process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: adding dissolved 4.0g (0.01 mol, 85.6%) H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103 mol) of cyhalodiamide under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process 2 CO 3 Controlling the pH value of the solution to be 4-5, and detecting and determining the reaction end point by using an ehrlichia reagent; after the reaction was completed, 1.77g of o-aminobenzenesulfonic acid (0.01 mol, 98%) was added thereto, and the temperature was increasedRaising the temperature to 15-20 ℃ and using 10% of Na 2 CO 3 Controlling the pH value of the solution to be between 5 and 6, and detecting the reaction end point by TLC after reacting for 3 to 4 hours;
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 blue solid.
Example 14
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
Condensation reaction of the cyanuric oxide: adding dissolved 4.0g (0.01 mol, 85.6%) H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103 mol) of cyhalodiamide under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process 2 CO 3 Controlling the pH value of the solution to be 4-5, and detecting and determining the reaction end point by using an ehrlichia reagent; after the reaction, 1.75g of metaaminobenzenesulfonic acid (0.01 mol, 99%) was added thereto, the temperature was raised to 15 to 20℃and 10% of Na was used 2 CO 3 Controlling the pH value of the solution to be between 5 and 6, and detecting the reaction end point by TLC after reacting for 3 to 4 hours;
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 blue solid.
Example 15
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: adding dissolved 4.0g (0.01 mol, 85.6%) H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103 mol) of cyhalodiamide under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process 2 CO 3 Controlling the pH value of the solution to be 4-5, and detecting and determining the reaction end point by using an ehrlichia reagent; after the reaction, 1.73g of sulfanilic acid (0.01 mol, 99.8%) was added, the temperature was raised to 15 to 20℃and 10% Na was used 2 CO 3 Controlling the pH value of the solution to be between 5 and 6, and detecting the reaction end point by TLC after reacting for 3 to 4 hours;
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 blue solid.
Example 16
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: adding dissolved 4.0g (0.01 mol, 85.6%) H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103 mol) of cyhalodiamide under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process 2 CO 3 Controlling the pH value of the solution to be 4-5, and detecting and determining the reaction end point by using an ehrlichia reagent; after the reaction is finished 2.67g of aniline-2, 5-disulfonic acid (0.01 mol, 92.0%) was added, the temperature was raised to 15-20℃and 10% Na was used 2 CO 3 Controlling the pH value of the solution to be between 5 and 6, and detecting the reaction end point by TLC after reacting for 3 to 4 hours;
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 blue solid.
Example 17
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: adding dissolved 4.0g (0.01 mol, 85.6%) H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103 mol) of cyhalodiamide under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process 2 CO 3 Controlling the pH value of the solution to be 4-5, and detecting and determining the reaction end point by using an ehrlichia reagent; after the reaction, 1.40g of p-aminobenzoic acid (0.01 mol, 98%) was added, the temperature was raised to 15 to 20℃and 10% Na was used 2 CO 3 Controlling the pH value of the solution to be between 5 and 6, and detecting the reaction end point by TLC after reacting for 3 to 4 hours;
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 blue solid.
Example 18
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: adding dissolved 4.0g (0.01 mol, 85.6%) H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103 mol) of cyhalodiamide under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process 2 CO 3 Controlling the pH value of the solution to be 4-5, and detecting and determining the reaction end point by using an ehrlichia reagent; after the reaction, 0.93g of aniline (0.01 mol) was added thereto, the temperature was raised to 15 to 20℃and 10% of Na was used 2 CO 3 Controlling the pH value of the solution to be between 5 and 6, and detecting the reaction end point by TLC after reacting for 3 to 4 hours;
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 blue solid.
Example 19
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: adding dissolved 4.0g (0.01 mol, 85.6%) H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103 mol) of cyhalodiamide under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process 2 CO 3 The pH value of the solution is controlled to be 4-5 by using the Ehrlich testDetecting the reagent to determine a reaction end point; after the reaction was completed, 0.64g of ethylamine (0.01 mol, 70%) was added thereto, the temperature was raised to 15 to 20℃and 10% of Na was used 2 CO 3 Controlling the pH value of the solution to be between 5 and 6, and detecting the reaction end point by TLC after reacting for 3 to 4 hours;
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 blue solid.
Example 20
A benzothiazole heterocycle azo type water-soluble dye has the following specific structure:
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
Diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: adding dissolved 4.0g (0.01 mol, 85.6%) H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103 mol) of cyhalodiamide under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process 2 CO 3 Controlling the pH value of the solution to be 4-5, and detecting and determining the reaction end point by using an ehrlichia reagent; after the reaction, 0.75g of glycine (0.01 mol) was added thereto, the temperature was raised to 15 to 20℃and 10% of Na was used 2 CO 3 Controlling the pH value of the solution to be between 5 and 6, and detecting the reaction end point by TLC after reacting for 3 to 4 hours;
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 blue solid.
Examples 21 to 30
Benzothiazole heterocycle azo type water-soluble dye with specific structure shown in table 1:
TABLE 1 Structure of benzothiazole heterocyclic azo Water-soluble dye synthesized in examples 21-30
A process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
Condensation reaction of cyanuric chloride: in the preparation of the polycondensate, 2.66g of J acid (0.01 mol, 89.7%) was used in place of H acid, and the other reactants and reaction conditions were the same as in example 1, and the preparation of the polycondensate was the same as in examples 1 to 10, respectively;
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 blue solid.
Examples 31 to 40
Benzothiazole heterocycle azo type water-soluble dye with specific structure shown in table 2:
TABLE 2 Structure of benzothiazole heterocyclic azo type Water-soluble dye synthesized in examples 31 to 40
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A process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: in the preparation of the polycondensate, 2.66g of J acid (0.01 mol, 89.7%) was used in place of H acid, and the other reactants and reaction conditions were the same as in example 11, and the preparation of the polycondensate was the same as in examples 11 to 20, respectively;
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 blue solid.
Examples 41 to 50
Benzothiazole heterocycle azo type water-soluble dye with specific structure shown in table 3:
TABLE 3 Structure of benzothiazole heterocyclic azo type Water-soluble dye synthesized in examples 41-50
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A process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: in the preparation of the polycondensate, 2.68g of gamma acid (0.01 mol, 89%) was used instead of H acid, and the other reactants and reaction conditions were the same as in example 1, and the preparation of the polycondensate was the same as in examples 1 to 10, respectively;
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 blue solid.
Examples 51 to 60
Benzothiazole heterocycle azo type water-soluble dye with specific structure shown in table 4:
TABLE 4 Structure of benzothiazole heterocyclic azo type Water-soluble dye synthesized in examples 51 to 60
A process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: in the preparation of the polycondensate, 2.68g of gamma acid (0.01 mol, 89%) was used instead of H acid, and other reactants and reaction conditions were the same as in example 11, and the preparation of the polycondensate was the same as in examples 11 to 20, respectively;
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 blue solid.
Examples 61 to 70
Benzothiazole heterocycle azo type water-soluble dye with specific structure shown in table 5:
TABLE 5 Structure of benzothiazole heterocycle azo type Water-soluble dye synthesized in examples 61-70
A process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: in the preparation of the polycondensate, 4.0g of K acid (0.01 mol, 85%) was used instead of H acid, and the other reactants and reaction conditions were the same as in example 1, and the preparation of the polycondensate was the same as in examples 1 to 10, respectively;
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 blue solid.
Examples 71 to 80
Benzothiazole heterocycle azo type water-soluble dye with specific structure shown in table 6:
TABLE 6 Structure of benzothiazole heterocyclic azo type Water-soluble dye synthesized in examples 71-80
A process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: in the preparation of the first polycondensate, 4.0. 4.0g K acid (0.01 mol, 85%) was used instead of H acid, and other reactants and reaction conditions were the same as in example 11, and the preparation of the second polycondensate was the same as in examples 11 to 20, respectively;
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 blue solid.
Examples 81 to 90
Benzothiazole heterocycle azo type water-soluble dye with specific structure shown in Table 7:
TABLE 7 Structure of benzothiazole heterocyclic azo type Water-soluble dye synthesized in examples 81-90
A process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: preparation of the first polycondensate 4.0g of chicago acid (0.01 mol, 85%) was used instead of H acid, the other reactants and reaction conditions were the same as in example 1, and the preparation of the second polycondensate was the same as in examples 1 to 10, respectively, 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 blue solid.
Examples 91 to 100
Benzothiazole heterocycle azo type water-soluble dye with specific structure shown in table 8:
TABLE 8 Structure of benzothiazole heterocyclic azo Water-soluble dye synthesized in examples 91-100
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A process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: preparation of the first polycondensate 4.0g of chicago acid (0.01 mol, 85%) was used instead of H acid, the other reactants and the reaction conditions were the same as in example 11, and the preparation of the second polycondensate was the same as in examples 11-20, respectively, 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 blue solid.
Example 101
A benzothiazole heterocycle azo type water-soluble dye, the specific structure of which is shown in Table 9,
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
Diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103 mol) and 20g of small ice cubes, mechanically stirring at 0-5 ℃ until the mixture is milky, then adding an aqueous solution containing 4.0g (0.01 mol, 85.6%) of monosodium salt of H acid, regulating the pH value of the solution to be between 4 and 5, and detecting and determining the end point of the reaction by using an Ehrlich reagent to obtain a condensate of cyanuric 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 blue solid.
Examples 102 to 105
A benzothiazole heterocycle azo type water-soluble dye, the specific structure of which is shown in Table 9,
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of cyanuric chloride: examples 102 to 105 were prepared by substituting J acid, gamma acid, K acid and chicago acid for H acid, respectively, and the other reactants and reaction conditions were the same as those in example 101;
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 blue solid.
Example 106
A benzothiazole heterocycle azo type water-soluble dye, the specific structure of which is shown in Table 9,
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction of the cyanuric oxide: adding an aqueous solution containing a certain mass of H-acid monosodium salt into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103 mol) of cyhalodiamide under mechanical stirring, continuously adding crushed ice in the reaction process, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process 2 CO 3 Controlling the pH value of the solution to be 4-5, and detecting and determining the reaction end point by using an ehrlichia reagent to obtain a condensate of the cyanuric chloride and the 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 blue solid.
Examples 107 to 110
A benzothiazole heterocycle azo type water-soluble dye, the specific structure of which is shown in Table 9,
TABLE 9 Structure of benzothiazole heterocycle azo type Water-soluble dye synthesized in examples 101 to 110
A process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
Diazotization reaction: the same as in example 1;
condensation reaction: examples 106 to 110 were prepared by substituting J acid, gamma acid, K acid and chicago acid for H acid, respectively, and the other reactants and reaction conditions were the same as those in example 106;
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 blue solid.
Example 111
A benzothiazole heterocycle azo type water-soluble dye, the specific structure of which is shown in Table 10,
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction: taking an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt, 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 ℃ for stirring 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 amino naphthol sulfonic 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 blue solid.
Examples 112 to 115
A benzothiazole heterocycle azo type water-soluble dye, the specific structure of which is shown in Table 10,
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction: examples 112 to 115 were prepared by substituting J acid, gamma acid, K acid and chicago acid for H acid, respectively, and the other reactants and reaction conditions were the same as those in example 111 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 blue solid.
Example 116
A benzothiazole heterocycle azo type water-soluble dye, the specific structure of which is shown in Table 10,
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction: taking an aqueous solution containing 4.0g (0.01 mol, 85.6%) of H acid monosodium salt, 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 by using an Ehrlich reagent to determine the end point of the reaction to obtain a condensation product of benzoyl chloride and amino naphthol sulfonic 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 blue solid.
Examples 117 to 120
A benzothiazole heterocycle azo type water-soluble dye, the specific structure of which is shown in Table 10,
a process for preparing the benzothiazole heterocyclic azo type water-soluble dye:
diazotization reaction: the same as in example 1;
condensation reaction: examples 117 to 120 were prepared by substituting J acid, gamma acid, K acid and chicago acid for H acid, respectively, and the other reactants and reaction conditions were the same as those of example 116;
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 blue solid.
Table 10 Structure of benzothiazole heterocyclic azo Water-soluble dye synthesized in examples 111-120
Example 121:
a benzothiazole heterocyclic azo type water-soluble dye having a structure of general formula (I):
wherein,
a is selected from-OCH 3 -OPh or formula (ii-a);
n=1 or 2;
in the general formula (II-a),
x is selected from-Cl or-F;
y is selected from-Cl, -F, -NH 2 、-NHCH 3 、-NHCH 2 CH 3 、-NHCH 2 COOH、-NHCH(CH 3 )COOH、-OH、-OCH 3 、-OCH 2 CH 3 Or of the general formula (II-b);
in the general formula (II-b),
R 1 selected from-H, carboxyl, sulfonic acid group, methyl, methoxy, nitro, nitrile group, amino, -Cl or-Br;
R 2 selected from-H, carboxyl, sulfonic acid group, methyl, methoxy, nitro, nitrile group, amino, -Cl, -Br, -CH 2 COOH、-COCH 2 Cl、-COCH 2 CH 2 Cl、-NHCOCH 2 Cl、-NHCOCH 2 CH 2 Cl、-NHCOCH＝CH 2 、-NHCOC(Br)＝CH 2 、-NHCH 2 CH(OH)CH 2 Cl、-NHSO 2 CH＝CH 2 、-N(CH 3 )SO 2 CH 2 CH 2 M、-SO 2 CH＝CH、-SO 2 CH 2 CH 2 M、-SO 2 CH 2 CH 2 OSO 3 M、-SO 2 NHCH 2 CH 2 M or-SO 2 N(CH 3 )CH 2 CH 2 M; wherein M is selected from-Cl, -F or-OSO 3 R 3 ，R 3 Selected from-H, -Na or-K.
In the formula (I), the amino naphthol sulfonic acid residue or amino naphthol disulfonic acid residue connected with the A is selected from one of the following groups:
h acid residue, its structural formula is:
j acid residue, its structural formula is:
a gamma acid residue having the structural formula:
k acid residue, its structural formula is:
a chicagonic acid residue having the structural formula:
the invention also comprises a method for preparing the benzothiazole heterocycle azo type water-soluble dye,
1) Condensation reaction
The condensation reaction of cyanuric chloride, cyanuric fluoride, acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid to obtain condensation products;
2) Diazotisation reaction
Gradually adding sodium nitrite solid into concentrated sulfuric acid under the ice salt bath condition, stirring, heating to be completely dissolved, cooling to 0-5 ℃, gradually adding 2-amino-6-nitrobenzothiazole, stirring for reaction, adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed, and obtaining 2-amino-6-nitrobenzothiazole diazonium salt;
3) Coupling reaction
Gradually dripping the 2-amino-6-nitrobenzothiazole diazonium salt obtained in the step 2) into the condensation product obtained in the step 1), controlling pH, reacting, adding a pH buffering agent after the reaction is completed, then adding potassium acetate or sodium acetate solid in a divided manner, stirring, standing, suction filtering, airing a filter cake to obtain a crude product, re-dissolving the crude product, adjusting the pH, and re-salting out to obtain the benzothiazole heterocyclic azo type water-soluble dye.
In the step 1), the condensation reaction of cyanuric chloride or cyanuric fluoride and amino naphthol sulfonic acid is a primary condensation reaction or a secondary condensation reaction;
the amino naphthol sulfonic acid is one of H acid, J acid, gamma acid, K acid or Chicago acid.
The primary condensation reaction is as follows: adding 10% amino naphthol sulfonic acid solution into cyanuric chloride or cyanuric fluoride solution, stirring and reacting at 0-5 ℃, controlling the pH value of the solution to be 4-5 in the reaction process, and detecting a condensation reaction end point by using an Ehrlich reagent to obtain a condensation product;
the secondary condensation reaction is as follows: adding unsubstituted or substituted aminobenzene or aliphatic amine into the first-shrink product, raising the temperature to 15-30 ℃, controlling the pH value to 5-6 for reaction, and detecting the end point of the second-shrink reaction by thin layer chromatography to obtain the second-shrink product.
The molar ratio of the cyanuric chloride or the cyanuric fluoride to the amino naphthol sulfonic acid is 1.02:1;
the molar ratio of the monocondensation product to the unsubstituted or substituted aminobenzene or fatty amine is 1:1.
In the step 1), the condensation reaction of acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid is as follows: and (3) dropwise adding acetic anhydride or benzoyl chloride into the aqueous solution of the amino naphthol sulfonic acid, 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 the acetic anhydride or benzoyl chloride and the amino naphthol sulfonic acid.
The molar ratio of the acetic anhydride or benzoyl chloride to the amino naphthol sulfonic acid is 2.5:1.
The diazotization reaction in the step 2) is specifically as follows: gradually adding sodium nitrite solid into 11.0g of concentrated sulfuric acid under the ice salt bath condition of-5 to-10 ℃, stirring, heating to be completely dissolved, cooling to 0-5 ℃, gradually adding 2-amino-6-nitrobenzothiazole, stirring for reacting for 2-4 hours, and adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed to obtain 2-amino-6-nitrobenzothiazole diazonium salt;
the molar ratio of the sodium nitrite to the 2-amino-6-nitrobenzothiazole is 1.05:1.
The coupling reaction in the step 3) is specifically as follows: gradually dripping 2-amino-6-nitrobenzothiazole diazonium salt into the condensation product in the step 1), controlling the pH value to be 1-2, reacting at 0-5 ℃, and adding 1% (w/v) Na after the reaction is completed 2 HPO 4 -NaH 2 PO 4 Adding potassium acetate or sodium acetate solid in batches, detecting dye salting-out condition by using a permeation ring, stirring, standing, suction-filtering, airing 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 benzothiazole heterocycle azo type water-soluble dye.
The invention utilizes the characteristics of good deep color effect, high light absorption coefficient and the like of the 2-amino-6-nitrobenzothiazole structure, and introduces the 2-amino-6-nitrobenzothiazole into a water-soluble dye matrix structure to prepare the acid-base color-changing dye.
The experimental methods used in the above examples are conventional methods unless otherwise specified.
The materials and reagents used in the above examples were obtained commercially or synthesized from commercially available starting materials unless otherwise specified.
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 benzothiazole heterocycle azo type water-soluble dye, characterized in that the benzothiazole heterocycle azo type water-soluble dye has the structure of general formula (i):
Wherein,
a is selected from-OCH 3 -OPh or formula (ii-a);
n=1 or 2;
in the general formula (II-a),
x is selected from-Cl or-F;
y is selected from-Cl, -F, -NH 2 、-NHCH 3 、-NHCH 2 CH 3 、-NHCH 2 COOH、-NHCH(CH 3 )COOH、-OH、-OCH 3 、-OCH 2 CH 3 Or of the general formula (II-b);
in the general formula (II-b),
R 1 selected from-H, carboxyl, methyl, methoxy, nitro, nitrile, amino, -Cl or-Br;
R 2 selected from-H, carboxyl, methyl, methoxy, nitro, nitrile, amino, -Cl, -Br, -CH 2 COOH、-COCH 2 Cl、-COCH 2 CH 2 Cl、-NHCOCH 2 Cl、-NHCOCH 2 CH 2 Cl、-NHCOCH＝CH 2 、-NHCOC(Br)＝CH 2 、-NHCH 2 CH(OH)CH 2 Cl、-NHSO 2 CH＝CH 2 、-N(CH 3 )SO 2 CH 2 CH 2 M、-SO 2 CH＝CH、-SO 2 CH 2 CH 2 M、-SO 2 CH 2 CH 2 OSO 3 M、-SO 2 NHCH 2 CH 2 M or-SO 2 N(CH 3 )CH 2 CH 2 M; wherein M is selected from-Cl, -F or-OSO 3 R 3 ，R 3 Selected from-H, -Na or-K;
in the formula (I), the amino naphthol sulfonic acid residue or amino naphthol disulfonic acid residue connected with the A is selected from one of the following groups:
j acid residue, its structural formula is:
a gamma acid residue having the structural formula:
k acid residue, its structural formula is:
a chicagonic acid residue having the structural formula:
2. a process for preparing the benzothiazole heterocyclic azo type water-soluble dye of claim 1, characterized in that:
1) Condensation reaction
The condensation reaction of cyanuric chloride, cyanuric fluoride, acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid to obtain condensation products;
2) Diazotisation reaction
Gradually adding sodium nitrite solid into concentrated sulfuric acid under the ice salt bath condition, stirring, heating to be completely dissolved, cooling to 0-5 ℃, gradually adding 2-amino-6-nitrobenzothiazole, stirring for reaction, adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed, and obtaining 2-amino-6-nitrobenzothiazole diazonium salt;
3) Coupling reaction
Gradually dripping the 2-amino-6-nitrobenzothiazole diazonium salt obtained in the step 2) into the condensation product obtained in the step 1), controlling pH, reacting, adding a pH buffer after the reaction is completed, then adding potassium acetate or sodium acetate solid in a separated mode, stirring, standing, suction-filtering, airing a filter cake to obtain a crude product, regulating the pH after redissolving the crude product, and re-salting out to obtain the benzothiazole heterocyclic azo type water-soluble dye;
in the step 1), the condensation reaction of cyanuric chloride or cyanuric fluoride and amino naphthol sulfonic acid is a primary condensation reaction or a secondary condensation reaction;
the amino naphthol sulfonic acid is one of J acid, gamma acid, K acid or chicago acid;
the primary condensation reaction is as follows: adding 10% amino naphthol sulfonic acid solution into cyanuric chloride or cyanuric fluoride solution, stirring and reacting at 0-5 ℃, controlling the pH value of the solution to be 4-5 in the reaction process, and detecting a condensation reaction end point by using an Ehrlich reagent to obtain a condensation product;
the secondary condensation reaction is as follows: adding unsubstituted or substituted aminobenzene or fatty amine into the first-shrink product, raising the temperature to 15-30 ℃, controlling the pH value to 5-6 for reaction, and detecting the end point of the second-shrink reaction by thin layer chromatography to obtain a second-shrink product;
The molar ratio of the cyanuric chloride or the cyanuric fluoride to the amino naphthol sulfonic acid is 1.02:1;
the molar ratio of the monocondensation product to the unsubstituted or substituted aminobenzene or fatty amine is 1:1.
3. The method for preparing benzothiazole heterocycle azo type water-soluble dye according to claim 2, wherein in the step 1), the condensation reaction of acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid is: and (3) dropwise adding acetic anhydride or benzoyl chloride into the aqueous solution of the amino naphthol sulfonic acid, 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 the acetic anhydride or benzoyl chloride and the amino naphthol sulfonic acid.
4. The method for preparing benzothiazole heterocycle azo type water-soluble dye according to claim 3, characterized in that:
the molar ratio of the acetic anhydride or the benzoyl chloride to the amino naphthol sulfonic acid is 2-3:1.
5. The method for preparing benzothiazole heterocycle azo type water-soluble dye according to claim 2, wherein the diazotization reaction in the step 2) is specifically: gradually adding sodium nitrite solid into 11.0g of concentrated sulfuric acid under the ice salt bath condition of-5 to-10 ℃, stirring, heating to be completely dissolved, cooling to 0-5 ℃, gradually adding 2-amino-6-nitrobenzothiazole, stirring for reacting for 2-4 hours, and adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is completed to obtain 2-amino-6-nitrobenzothiazole diazonium salt;
The molar ratio of the sodium nitrite to the 2-amino-6-nitrobenzothiazole is 1.05:1.
6. The method for preparing benzothiazole heterocycle azo type water-soluble dye according to claim 2, wherein the coupling reaction in the step 3) is specifically: gradually dripping 2-amino-6-nitrobenzothiazole diazonium salt into the condensation product in the step 1), controlling the pH value to be 1-2, reacting at 0-5 ℃, and adding 1% (w/v) Na after the reaction is completed 2 HPO 4 -NaH 2 PO 4 Adding potassium acetate or sodium acetate solid in batches, detecting dye salting-out condition by using a permeation ring, stirring, standing, suction-filtering, airing 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 benzothiazole heterocycle azo type water-soluble dye.
7. The method for preparing benzothiazole heterocycle azo type water-soluble dye according to claim 4, wherein the molar ratio of acetic anhydride or benzoyl chloride to amino naphthol sulfonic acid is 2.5:1.
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