CN1050374C - Temporary soluble blue dispersed dye and synthesis method thereof - Google Patents
Temporary soluble blue dispersed dye and synthesis method thereof Download PDFInfo
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- CN1050374C CN1050374C CN95110173A CN95110173A CN1050374C CN 1050374 C CN1050374 C CN 1050374C CN 95110173 A CN95110173 A CN 95110173A CN 95110173 A CN95110173 A CN 95110173A CN 1050374 C CN1050374 C CN 1050374C
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- MCPLVIGCWWTHFH-UHFFFAOYSA-M disodium;4-[4-[[4-(4-sulfoanilino)phenyl]-[4-(4-sulfonatophenyl)azaniumylidenecyclohexa-2,5-dien-1-ylidene]methyl]anilino]benzenesulfonate Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)O)=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-M 0.000 title claims description 6
- 238000001308 synthesis method Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000975 dye Substances 0.000 claims abstract description 27
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010189 synthetic method Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- QZZSAWGVHXXMID-UHFFFAOYSA-N 1-amino-4-bromo-9,10-dioxoanthracene-2-sulfonic acid Chemical compound C1=CC=C2C(=O)C3=C(Br)C=C(S(O)(=O)=O)C(N)=C3C(=O)C2=C1 QZZSAWGVHXXMID-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- -1 iron powder compound Chemical class 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000005576 amination reaction Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 4
- 238000003916 acid precipitation Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 abstract description 2
- 239000000986 disperse dye Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract description 2
- 159000000000 sodium salts Chemical class 0.000 abstract description 2
- 150000004982 aromatic amines Chemical class 0.000 abstract 1
- 238000005831 deiodination reaction Methods 0.000 abstract 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 150000003568 thioethers Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 23
- 239000012065 filter cake Substances 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 150000003457 sulfones Chemical class 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- QDXZMQKBSROXKE-UHFFFAOYSA-N 2-(chloromethyl)-1-ethoxy-4-nitrobenzene Chemical compound CCOC1=CC=C([N+]([O-])=O)C=C1CCl QDXZMQKBSROXKE-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229920004935 Trevira® Polymers 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006114 decarboxylation reaction Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- SSYDSTKMOYVTMW-UHFFFAOYSA-N 2-(chloromethyl)-1-methoxy-4-nitrobenzene Chemical compound COC1=CC=C([N+]([O-])=O)C=C1CCl SSYDSTKMOYVTMW-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-Methylanthraquinone Natural products C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- AWLVTQRRKPBQEQ-UHFFFAOYSA-N 2-benzylsulfanylacetic acid Chemical compound OC(=O)CSCC1=CC=CC=C1 AWLVTQRRKPBQEQ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- YRCKMNSQBUJMIX-UHFFFAOYSA-N NC(C1=CC=CC=C1)S(CC(O)=O)(=O)=O Chemical compound NC(C1=CC=CC=C1)S(CC(O)=O)(=O)=O YRCKMNSQBUJMIX-UHFFFAOYSA-N 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- APGGSERFJKEWFG-UHFFFAOYSA-N 1-(chloromethyl)-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(CCl)=C1 APGGSERFJKEWFG-UHFFFAOYSA-N 0.000 description 1
- NWPKEYHUZKMWKJ-UHFFFAOYSA-N 1-ethoxy-4-nitrobenzene Chemical compound CCOC1=CC=C([N+]([O-])=O)C=C1 NWPKEYHUZKMWKJ-UHFFFAOYSA-N 0.000 description 1
- DNNDZIBLDXKITM-UHFFFAOYSA-N 2-(1-carboxy-2-phenylethyl)sulfanyl-3-phenylpropanoic acid Chemical compound C=1C=CC=CC=1CC(C(O)=O)SC(C(=O)O)CC1=CC=CC=C1 DNNDZIBLDXKITM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RJXSDWABPXPYPK-UHFFFAOYSA-N C1=CC=C(C=C1)C([N+](=O)[O-])S(=O)(=O)CC(=O)O Chemical compound C1=CC=C(C=C1)C([N+](=O)[O-])S(=O)(=O)CC(=O)O RJXSDWABPXPYPK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
- C09B1/26—Dyes with amino groups substituted by hydrocarbon radicals
- C09B1/32—Dyes with amino groups substituted by hydrocarbon radicals substituted by aryl groups
- C09B1/325—Dyes with no other substituents than the amino groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention proposes water temporary solubility blue disperse dye shown in a formula (I). A product is obtained by that 2-chloromethyl-4-nitrophenylalkyl is condensed with mercaptoacetic acid, is oxidized by thioether, is reduced by nitryl, is in arylamine, is in deiodination reaction, etc. The present invention has the advantages of convenient synthetic method, high yield, and good water solubility for ammonium salt or sodium salt of the product, can dye polyester fiber under the condition of general use, and has fine color fixation rate, wherein R=-CH3,-C2Holes,-C2H4OCH3.
Description
The invention provides the temporary soluble blue dispersed dye and the synthetic method thereof of a class practicality.
The dispersed dye of selling on market at present all are non-water-soluble, and they are former dyestuff a kind of water dispersible commodity that sand milling processes in water medium in the presence of dispersion agent of certain crystal formation, are mainly used in the dyeing of trevira.
We proposed a class temporarily water-soluble disperse dye [Pan Xin, chemical industry journal, (1), 26 (1982)], they have water-soluble characteristics, and at high temperature decarboxylize be transformed into dispersed dye and on dye trevira, but its blue kind needs higher decarboxylation temperature, has influenced its practicality.
The invention provides a class temporary soluble blue dispersed dye, its ammonium salt or sodium salt have better water solubility; Can under the common condition, dye trevira; Degree of fixation is preferably arranged; Synthesizing of its intermediate and dyestuff is comparatively convenient, and yield is also high.
This type of blue dyes general structure is:
Wherein R is: I
a-CH
3I
b-C
2H
5I
c-C
2H
4OCH
3Building-up process can be expressed as follows:
Synthetic intermediate (II) with the following method:
Raw material 2-chloromethyl-4-nitro-alkyl ether benzene (V) can be produced with the high yield of Cholromethylation method by 4-nitrophenyl alkyl oxide.Japanese Patent JPn.Kokai, JP60-32,750 (1983) have reference value.
Raw material (V) through the alcohols recrystallization carries out condensation reaction in water medium with under the Thiovanic acid normal pressure, yield can reach 99%, and (weight percent concentration, the following percentage concentration of this specification sheets is weight percent concentration.)
DMF is a dimethyl formamide in the reaction formula, hereinafter to be referred as DMF.
Also the methylated crude product of available chlorine directly carries out condensation reaction.The impurity that is generated during chloromethylation can be removed at the condensation reaction after-filtration, and yield also can reach 82～97%.
Condensation reaction can be at solvent, as carrying out in the methyl alcohol, add a small amount of DMF and can add fast response, the consumption of DMF is V: DMF=1: 0.1-0.22 (mol ratio), and the starting point concentration of Thiovanic acid is advisable with 10～13% during reaction, and raw material (V) is 1: 1～1.05 with the mol ratio of Thiovanic acid, condensation reaction is carried out at 40～70 ℃, be advisable with 60～62 ℃, the pH during condensation is 8～9, and the pH value does not become terminal point.Condensation product is chilled to room temperature, uses the hydrochloric acid acid out, filters washing, drying, gets white precipitate.Crude product its content of efficient liquid phase chromatographic analysis.
The sulfide oxidation that contains carboxymethyl becomes the reaction of corresponding sulfone, can carry out easily under the normal pressure in water medium, and yield can reach 85～98%.
Carboxylic sulfide compound can be water-soluble under neutrallty condition, can carry out the homogeneous oxidizing reaction with hydrogen peroxide, generates corresponding sulfone.The starting point concentration of reactant (VI) is generally 15～22%, is advisable with 20%, often adopts deionized water to reduce the decomposition of metal ion to hydrogen peroxide.
Hydrogen peroxide with 30% can react, and its consumption is VI: H
2O
2=1: 2.2～2.6 (mol ratios), the purity of visual response thing (VI) and feed rate are and different, and the high consumption of purity is few, and feed rate is suitable, and consumption is few.
Be reflected at 60～70 ℃, pH 5～6.7 carries out, and generally at 62～65 ℃, carry out pH5.5～6.7.
Catalyzer WO
3Participate in the sodium wolframate form with this understanding, it is oxidized to the sulfone stage at sulfoxide and plays an important role, and its existence can significantly reduce the excessive value of hydrogen peroxide.Be not subject to the group of hydrogen peroxide oxidation owing to there is other in the structure of reactant (VI), carry out comparatively smoothly, but the time that oxidation is reached home fully is subjected to the influence of selective oxidation position in the structure, need 12～20 hours so react.
Catalyzer WO
3Consumption is VI: WO
3=1: 0.005～0.01 (mol ratio), visual response consumption and deciding, consumption is got big value for a short time, and consumption gets the small value greatly and gets final product, and can add quantitative sodium hydroxide solution and be made into sodium tungstate solution and once add before oxidation or add when oxidation in batches.
(stationary phase is a silica GF254 to the oxidation terminal point with thin-layer chromatography control; Developping agent is a benzene: ethyl acetate: acetate=5: 5: 1), cooperate the potassium iodide starch test paper inspection.
Crude product its content of efficient liquid phase chromatographic analysis.
Nitroreduction becomes amino can adopt general iron powder-water reduction method, and yield is more than 87%.
Nitro-compound is reduced into corresponding aminocompound with iron powder under the normal pressure in water medium be general method commonly used, contains the water soluble group carboxyl in the structure, not only makes the amine of generation not volatile; And help owing to reaction back carboxylate salt is soluble in water and the separating of iron mud.
Raw material (VII) should be added in batches in the mixture of iron powder and water and go, and higher concentration helps rapid reaction, and generally 19～23%, as catalyzer, consumption is 0.01 moles/mole (VII) with acetic acid.
Iron powder reducing often adopts boiling reflux, because the singularity of raw material (VII) structure, it is easy in high temperature generation decarboxylation side reaction, therefore needs control reaction temperature, be generally 60～92 ℃, be preferably in 88～90 ℃ of reactions, exothermic heat of reaction is so early stage can be in the following reinforced limit reaction of low slightly temperature, make it to reach home 90 ℃ of reactions at last, with thin-layer chromatography (the same oxidizing reaction of developping agent) control terminal point, be terminal point to there not being raw material (VII), about 2.5～3 hours of process.
It is 9 that reactant adds adjusting PH with base, and with iron mud filtering separation, the filtrate that contains (VIII) is directly used in next step aryl amination after diazotization is analyzed content.
Filtrate also can be separated out white precipitate after vacuum concentration, decolouring, cooling, use the alcohol-water recrystallization.
Amine and bromamine acid carry out the aryl amination reaction under the normal pressure in water medium be the common method that obtains blue dyes.
The height of aryl amination yield is strong and weak relevant with the alkalescence of amine.Used its amino contraposition of amine of the present invention has alkoxyl group, so amino alkalescence is strong, reaction is easy, and the yield height can reach more than 96%.
Generally the concentration at amine is 18～20%, and bromamine acid is under the reinforced concentration of 9～12% solution, bromamine acid: amine (II)=1: 1.25 (mol ratio), 70～75 ℃ of temperature are reacted and can be reached home in 1～1.5 hour.
Bromamine acid adds with solution state and helps improving yield, therefore is made into the pyritous strong solution and adds.
The consumption of amine is a bromamine acid: amine (II)=1: 1.2～1.25 (mol ratios), if the amine consumption is few, then speed of response is slow, removes the bromamine acid difficulty of not participating in reaction.
The aryl amination temperature is 65～80 ℃, is advisable with 70～75 ℃.
Catalyst consumption is bromamine acid: CuSO
4: FeSO
4=1: 0.2: 0.18 (mol ratio), be made into the aqueous solution and when its temperature is 70～75 ℃, add, be that catalyst reaction speed is fast with the cuprous chloride, but CuSO
4-FeSO
4Convenient and the low price of catalyst preparation.
The used in amounts of sodium bicarbonate and yellow soda ash changes with the alkalescence of amine is strong and weak during aryl amination, and carboxyl is to the influence of catalyzer in the amine in order to reduce, and yellow soda ash increases to some extent with respect to the amount of sodium bicarbonate, bromamine acid: NaHCO
3: Na
2CO
3=1: 1.7: 1.9 (mol ratio).
The thin plate chromatography control of aryl amination terminal point, use butanols: acetic acid: water=4: 1: 5 (upper strata) is developping agent, bromamine acid disappears and is terminal point.
Reaction product by saltout-acid out separates, filters, with 1: 10 dilute hydrochloric acid flush away filtrate, filter cake by dissolve, saltout-acid out, wash come refining.
Its β of dyes of anthraquinone-position sulfonic group can remove with V-Brite B (being commonly called as vat powder) in the alkalescent water medium under normal pressure usually.
Dyestuff (IV) still contains carboxylic methylsulfonyl (SO owing to do not have sulfonic group in the structure
2CH
2COOH), thus dyestuff still have water-soluble, only this carboxyl be subjected to sulfuryl electrophilic influence to be easy to be heated remove.
Because its carboxylic methylsulfonyl is not directly to be associated on the aromatic ring of band imino-, but link by methylene radical, the power supply base that is encircled influences and reduces, therefore its decarboxylation temperature just can be reduced to (205 ℃ of general hot melting temperature conditions, 1.5 divide), under general " High Temperature High Pressure " dyeing condition, also can remove, so can be used for the dyeing of polyster fibre.
The concentration of dyestuff is 7% when taking off sulphur, and transferring pH is 7.5, adds gradually in the mode of uniform mixture batch charging under temperature of reaction of vat powder and sodium bicarbonate.Its consumption is dyestuff (III): Na
2S
2O
4: NaHCO
3=1: 1.9～2: 5.7～6 (mol ratio), 25～90 ℃ of temperature of reaction are advisable with 32～34 ℃, with thin-layer chromatography (the same aryl amination of developping agent) control terminal point, to all taking off till the sulphur.
With saltout-the acid out method separates out dyestuff, and is refining with the dissolving acid-precipitation method again, dyestuff (I), yield is more than 96%.
The embodiment of the invention is as follows:
Embodiment 1, in 250 milliliters of four-hole boiling flasks of agitator, thermometer, dropping funnel and hydrogen chloride gas absorption unit are housed, add p-Nitromethoxybenzene 38.3 successively and restrain (0.255 mole of (0.25 mole), Zinc Chloride Anhydrous 10.2 grams (0.075 mole), trioxymethylene 7.65 gram, amount to into formaldehyde, down together) and 23.6 milliliters of 36.5% hydrochloric acid (0.275 mole).In water-bath, heat, be warmed up to 60 ℃ gradually, start and be stirred and heated to 70 ℃.Dripped 96% 36.1 milliliters of the vitriol oils (0.65 mole) in 100～110 minutes gradually, temperature remains on 69～71 ℃.Continue to stir 5 minutes after dripping sulfuric acid, drip 1 ml water.Stirring is cooled to 20 ℃.Filter with acid funnel, drain,, drain with 10 milliliters of washings of 70% sulfuric acid.Filter cake is transferred in the frozen water, stirred 10 minutes, filter, filter cake washes with water to neutrality, and drying obtains 2-chloromethyl-4-Nitroanisole (V
a).Liquid-phase chromatographic analysis content is 95.38%, yield 94.1%.Fusing point: 80～81 ℃ (methyl alcohol).The ultimate analysis value [experimental value (theoretical value) %, down together.]：C47.76(47.66)；H3.90(4.00)；N6.82(6.95)。
Example 2, the method for use-case 1, raw material makes p-Nitrophenetole into, and each molar ratio of material is all identical with reaction conditions, working method, obtains 2-chloromethyl-4-nitrophenetol (V
b).Liquid-phase chromatographic analysis content is 96.49%, yield 95.7%, fusing point: 69～70 ℃ (ethanol), ultimate analysis value: C50.09 (50.13); H4.42 (4.67); N6.77 (6.50).
Example 3 adds 4-oil of mirbane-'beta '-methoxy ether 25 grams (0.127 mole), Zinc Chloride Anhydrous 4.33 grams (0.03175 mole), trioxymethylene 3.89 gram (0.13 mole) and 16.5 milliliters of 36.5% hydrochloric acid (0.14 mole) successively in the same device.Be warmed up to 65 ℃ under the heating in water bath, start to stir and be warmed up to 70 ℃,, stirred 5 minutes after dripping sulfuric acid, drip 1 milliliter in water again at 21.1 milliliters of the vitriol oils (0.38 mole) that in 100～120 minutes, drip 96% under this temperature gradually.Stirring is cooled to 5 ℃ (using ice-water bath when being lower than room temperature instead).Filter with acid funnel, drain, filter cake changes in the frozen water, stirs 10 minutes, filters, and is washed till neutrality with frozen water.Get 4-nitro-2-chloromethylbenzene-'beta '-methoxy ether (V after the drying
c).Liquid-phase chromatographic analysis content is 95.96%, yield 84.7%, fusing point: 33～35 ℃.Ultimate analysis value: C48.30 (48.89); H4.58 (4.92); N5.72 (5.70).
Example 4, in 150 milliliters of four-hole boiling flasks of agitator, reflux exchanger, thermometer and dropping funnel are housed, Thiovanic acid 13 grams (0.125 mole) that add content 88%, 60 milliliters in water, 18.8 milliliters in 30% sodium hydroxide (about 0.187 mole), 2-chloromethyl-4-Nitroanisole 24 grams (0.119 mole) that add use-case 1 preparation then, N, 1.2 milliliters of dinethylformamides (DMF) (0.0156 mole).Stirred under the room temperature 30 minutes, and be warmed up to 60 ℃ gradually, pH reduces to and dripped 6.2 milliliters in 30% sodium hydroxide (0.062 mole) at 8～8.5 o'clock with 6.2 milliliters of water-reducible solution, maintenance pH8～8.5, and 60～62 ℃ of temperature are till no longer descending to pH.Add 30 milliliters in 60 ℃ of water, 2 gram gacs stirred 10 minutes, were cooled to room temperature.Filter, filtrate with 12 milliliters of 36.5% hydrochloric acid (0.14 mole) with 12 milliliters of water-reducible solution acid outs to pH1, left standstill 30 minutes, filter, filter cake washs with dilute hydrochloric acid, wash, drying, must (2 '-methoxyl group-5 '-nitro) benzyl carboxymethyl thioether (VI
a).Liquid-phase chromatographic analysis content 96.7%, yield are 94.4%.Fusing point: 114-115 ℃ (alcohol-water).Ultimate analysis value: C46.77 (46.69); H4.30 (4.31); N5.45 (5.44); S12.66 (12.46).
Example 5 with the operation of example 4, adds 88% Thiovanic acid 4.82 grams (0.0461 mole), 30 milliliters in water, 6.8 milliliters in 30% sodium hydroxide (about 0.068 mole) in four-hole bottle.Add pure 2-chloromethyl-4-nitrophenetol 9.47 grams (0.0439 mole) then, DMF0.75 milliliter (0.0097 mole).Stir half an hour under the room temperature, be warmed up to 60 ℃ gradually in half an hour, pH reduced to 8～8.5 o'clock, drip 2.42 milliliters in 30% sodium hydroxide (0.0242 mole) with 2.4 milliliters of water-reducible solution, keep pH8～8.5,60～62 ℃ of temperature are ended when pH no longer descends.Add 10 milliliters in 60 ℃ of water, 0.8 gram gac stirred 10 minutes, cool to room temperature, filter, in filtrate, drip 5 milliliters of water-reducible solution of 5 milliliters of usefulness of 36.5% hydrochloric acid, acid out to pH be 1, leave standstill, filter, filter cake washs with dilute hydrochloric acid, washing, drying, (2 '-oxyethyl group-5 '-nitro) benzyl carboxymethyl thioether (VI
b), yield is 99%, fusing point: 134～136 ℃ (alcohol-water), ultimate analysis value: C48.70 (48.70); H4.92 (4.83); N5.08 (5.16); S11.80 (11.82).
Example 6 is with the operation of example 5.In four-hole bottle, add 88% Thiovanic acid, 12.6 grams (0.1205 mole), 60 milliliters in water, 18 milliliters in 30% sodium hydroxide (0.18 mole) adds 2-chloromethyl-4-nitrophenetol (V that use-case 2 prepares then
b) 24.8 grams (0.115 mole), DMF0.89 milliliter (0.0115 mole) stirred 30 minutes under the room temperature, be warmed up to 60 ℃ gradually, pH reduces to and dripped 6 milliliters in 30% sodium hydroxide (0.06 mole) at 8～8.5 o'clock with 6 milliliters of water-reducible solution, keeps pH8～8.5,60～62 ℃ of temperature till no longer descending to pH, add 60 ℃ 50 milliliters in water, gac 2 grams, stirred 10 minutes, cool to room temperature filters, filter cake washs with dilute hydrochloric acid, washing, drying, yield 97.2%.
Example 7 adds sodium hydroxide 7.83 grams (0.196 mole) in 250 milliliters of four-hole bottles, methyl alcohol makes it dissolving for 120 milliliters, drips Thiovanic acid 9 grams (0.0978 mole), is heated to backflow, drips the 2-chloromethyl-4-oil of mirbane-'beta '-methoxy ether V of fusing gradually
c(example 3 products) 24 grams (0.0978 mole) added the back back flow reaction 4.5 hours, and reaction mixture is poured in the 200g mixture of ice and water, remove by filter insolubles, filtrate is used the dilute hydrochloric acid acid out, washing, drying, (5 '-nitro-2 '-the 'beta '-methoxy oxyethyl group) benzyl-carboxymethyl thioether (VI
c), liquid-phase chromatographic analysis content 92.9%, yield 82.12%, fusing point: 116～117.5 ℃ (alcohol-water).Ultimate analysis value: C48.01 (47.84); H5.06 (5.02); N4.64 (4.65); S10.33 (10.64).
Example 8, in being housed, 250 milliliters of four-hole bottles of agitator, thermometer add 2 '-methoxyl group-5 '-nitro-benzyl carboxymethyl thioether (VI
a) 28.3 grams (0.11 mole), 110 milliliters of deionized waters with 11 milliliters in 30% sodium hydroxide (0.11 mole) pH6.7 that neutralizes, add wolframic acid (WO in 50 ml beakers
3) 0.178 gram (0.00077 mole), 10 milliliters of deionized waters, it is neutral transferring pH with several sodium hydroxide solutions, make it dissolving, this solution is poured in the four-hole bottle, heating in water bath to 62 ℃, at reaction solution pH is 6～6.7 dropping 28.6 milliliters in 30% hydrogen peroxide (0.286 mole), and reactant is reached home fully, and hydrogen peroxide need drip 10 hours approximately, be oxidized to terminal point, add gac 1 gram, stirred cooling 10 minutes, filter, filtrate is 1 with hcl acidifying to pH, separates out white precipitate, places half an hour, filter, filter cake is washed with 50 milliliters of dilute hydrochloric acid, and washing press dry, drying, 2 '-methoxyl group-5 ' nitro-benzyl carboxymethyl sulfone (VII
a), liquid-phase chromatographic analysis content is 92.53%, yield 98.5%, fusing point: 192～193 ℃ (alcohol-water).Ultimate analysis value: C42.11 (41.52); H3.98 (3.82); N4.96 (4.84); S11.23 (11.08)
Example 9, in 1000 milliliters of four-hole bottles, add 2 '-oxyethyl group-5 '-nitro-benzyl carboxymethyl thioether (VI
b) 127.4 grams (0.47 mole), 452 milliliters of deionized waters, transfer pH 6～7 in 50 ml beakers, to add 20 milliliters of deionized waters with 47 milliliters in 30% sodium hydroxide (0.47 mole), wolframic acid 0.544 gram (0.00235 mole), addend drips sodium hydroxide solution transfers neutral stirring and dissolving, then this solution is poured in the four-hole bottle into heating in water bath for reaction thing to 62 ℃, be 6.8～6.5 at pH and drip 108 milliliters in 30% hydrogen peroxide (1.08 moles), to terminal point, add gac 5 grams with the chromatograph controlled oxidation, stirred 10 minutes, cooling, filter, filtrate is 1 with the hydrochloric acid acid out to pH, separates out white precipitate, filter, filter cake is washed with 200 milliliters of dilute hydrochloric acid, and washing press dry, drying, 2 '-oxyethyl group-5 '-nitro-benzyl carboxymethyl sulfone (VII
b), liquid-phase chromatographic analysis content is 91.51%, yield 96.5%, fusing point: 161～162 ℃ (alcohol-water).Ultimate analysis value: C43.62 (43.56); H4.32 (4.40); N4.70 (4.62); S10.59 (10.57).
Example 10, use-case 7 is resulting 5 '-nitro-2 '-'beta '-methoxy ethoxy benzyl-carboxymethyl thioether (VI
c), with above-mentioned oxidation style obtain white powdery 5 '-nitro-2 '-'beta '-methoxy ethoxy benzyl-carboxymethyl sulfone (VII
c), liquid-phase chromatographic analysis content is 93.01%, yield 85%, fusing point: 148～149 ℃ (alcohol-water), ultimate analysis value: C42.98 (43.24); H4.56 (4.54); N4.17 (4.20); S9.43 (9.62).
Example 11, in 500 milliliters of four-hole bottles, add 160 milliliters of entry, 0.92 milliliter of acetic acid (0.0016 mole), adding total amount then is 1/3 amount-24 grams of the iron powder of 72 grams, warming-in-water to 62 ℃, add the resulting oxide compound 2 of method of use-case 8 '-methoxyl group-5 '-nitrobenzyl carboxymethyl sulfone (VII
a) total amount is 1/4 amount of 46.2 (0.16 moles), exothermic heat of reaction, temperature rise, and alternately add iron powder and sulfone then, are lower than 90 ℃ with the feed rate control reaction temperature, in the process with 40 ml waters towards Xian's bottleneck.Control reaction end with chromatograph, when the nitro Restore All becomes amino, end.Add 30% sodium hydroxide about 18 milliliters (0.18 moles) and transfer pH to 9, add gac 5 grams, stirred filtered while hot 10 minutes.Filter cake is with 20 milliliters of hot washes.Merging filtrate and washing lotion, 2 '-methoxyl group-5 '-sodium salt solution (II of aminobenzyl carboxymethyl sulfone
a), analyze content, yield 90% with the diazotization method.Filtrate can be directly used in next step aryl amination reaction.
Filtrate is behind hcl acidifying and vacuum concentration, and the freezing white precipitate of separating out is used the alcohol-water recrystallization, gets the white plates crystallization.Fusing point: 180～182 ℃ of decomposition (alcohol-water).Ultimate analysis value: C46.08 (46.32); H4.90 (5.05); N5.21 (5.40); S12.06 (12.36).
Example 12, the method for use-case 11 and a mole proportioning, can be with 2 '-oxyethyl group-5 '-nitrobenzyl carboxymethyl sulfone (VII
b) be reduced into 2 '-oxyethyl group-5-amino-benzyl carboxymethyl sulfone (IIb), yield 93.6%, also can separate out white precipitate by acidifying, decolouring, vacuum concentration, refrigerated method, after with the alcohol-water recrystallization, its fusing point: 174 ℃ of decomposition (alcohol-water), ultimate analysis value: C47.88 (48.34); H5.44 (5.53); N5.00 (5.12); S11.73 (11.73),
Example 13, the method of use-case 11 and mole proportioning, can with 5 of example 10 gained '-nitro-2 '-'beta '-methoxy ethoxy benzyl carboxymethyl sulfone (VIIc) is reduced into 5 '-amino-2 '-'beta '-methoxy ethoxy benzyl carboxymethyl sulfone (IIc), yield 86%, fusing point: 182～183 ℃ of decomposition (alcohol-water).Ultimate analysis value: C47.61 (47.52); H5.70 (5.65); N4.65 (4.62); S10.64 (10.57).
Example 14, add in 2000 milliliters of four-hole bottles that the method for use-case 11 makes 2 '-methoxyl group-5 '-amino-benzyl carboxymethyl sulfone sodium salt (IIa) filtrate, 191.8 milliliters of content 19.9% (concentration of volume percent) (0.1358 mole), warming-in-water to 68 ℃, three groups of compounds below balancedly adding: sodium bromaminate 43.87 gram (0.1086 mole) 85 ℃ of solution in 430 ml waters; The mixture of sodium bicarbonate 15.5 grams (0.1846 mole) and yellow soda ash 21.9 grams (0.2063 mole); Ferrous 5.43 gram (0.0195 mole) the 72 ℃ of solution in 100 ml waters of cupric sulfate crystals 5.43 grams (0.02172 mole) and crystalline sulfuric acid; control reaction temperature is 70～75 ℃; being stirred to bromamine acid disappears; about 90～120 minutes; in reaction solution, add 800 milliliters of 70 ℃ of hot water; stirred 3 minutes; filtered while hot; about 1600 milliliters of filtrate cumulative volume; adding refined salt 60 grams saltouts; add 45 milliliters of acid outs of 36.5% hydrochloric acid when being cooled to 50 ℃, 40 ℃ of filtrations are with 200 milliliters of washing leaching cakes of 1: 10 hydrochloric acid; filter cake with dissolve-saltout/method of acid out is refining; pure dye 1-amino-4-anilino-4 '-methoxyl group-3 '-carboxymethyl sulfonyl tectoquinone-2-sulfonic acid (IIIa), yield 96%
Example 15, the method of use-case 14,2 of use-case 12 gained '-oxyethyl group-5 '-sodium salt (IIb) filtrate of amino-benzyl carboxymethyl sulfone, 221 milliliters of content 18.13% (concentration expressed in percentage by volume) (0.1358 mole), be warmed up to 70 ℃, balancedly add three groups of compounds: the mixture of sodium bicarbonate 15.5 grams (0.1846 mole) and yellow soda ash 21.9 grams (0.2063 mole); Sodium bromaminate 43.87 grams (0.1086 mole) are at 84 ℃ of solution of 307 ml waters and 10 milliliter of 10% peregal; Ferrous 5.43 gram (0.0195 mole) the 72 ℃ of solution in 100 ml waters of cupric sulfate crystals 5.43 grams (0.02172 mole) and crystalline sulfuric acid; control reaction temperature is 70～72 ℃; be stirred to bromamine acid disappearance on the chromatograph; about 90 minutes; aftertreatment is with example 14; 1-amino-4-anilino-4 '-oxyethyl group-3 '-carboxymethyl sulfonyl tectoquinone-2-sulfonic acid (IIIb), yield 96.7%
Example 16, the method for use-case 15 can get 1-amino-4-anilino-4 '-'beta '-methoxy oxyethyl group-3 '-carboxymethyl sulfonyl tectoquinone-2-sulphur sulphur (IIIc), yield 85%,
Example 17; in 400 ml beakers, add dyestuff (IIIa) 16.7 grams (0.0298 mole) by example 14 method gained; 200 milliliters in water; transfer pH to 7.5 for 6 milliliters with 30% sodium hydroxide; make dyestuff molten entirely, be warmed up to 32 ℃, the mixture of take a policy gradually powder 9.85 grams (0.0566 mole) and sodium bicarbonate 14.3 grams (0.1698 mole); take off fully to the chromatograph till the sulphur; filter, filter cake washs with 5% salt solution, and filter cake is taken out; add 200 milliliters in water; add 5 milliliters of making beating of 36.5% hydrochloric acid, filter, filter cake washs with 1: 300 dilute hydrochloric acid solution; do not end to there being inferior sulfate radical; again with a small amount of washing, drying, dyestuff 1-amino-4-anilino-4 '-methoxyl group-3 '-carboxymethyl sulfonyl methyl-anthraquinone (Ia); yield 99%
Example 18, dyestuff (IIIb) 64.5 grams (0.1032 mole) that the method for adding use-case 15 makes in 1500 ml beakers, 800 milliliters in water, 23 milliliters in 30% sodium hydroxide transfers pH7.5 to molten entirely, is warmed up to 32 ℃, powder 35.5 grams (0.204 mole) and sodium bicarbonate 51.4 grams (0.612 mole) gradually take a policy, add 200 milliliters in water in the middle of the process, taking off sulphur to the chromatograph ends fully, with salt 10 grams, add 60 milliliters of 36.5% hydrochloric acid, filter, filter cake is washed with 1: 50 dilute hydrochloric acid solution, press dry.
Above-mentioned filter cake is added water to 700 milliliters of cumulative volumes; stirring adds 5 milliliters of making beating of 36.5% hydrochloric acid; be heated to 40 ℃, stirred 2 hours, filter; filter cake is washed till no inferior sulfate radical with 1: 300 dilute hydrochloric acid solution to be ended; a small amount of washing press dry drying; dyestuff 1-amino-4-anilino-4 '-oxyethyl group-3 '-carboxymethyl sulfonyl tectoquinone (Ib), yield 95.9%.
Example 19, the method for use-case 18 can get dyestuff 1-amino-4-anilino-4 '-'beta '-methoxy oxyethyl group-3 '-carboxymethyl sulfonyl tectoquinone (Ic), yield 92.6%.
Claims (2)
1. temporary soluble blue dispersed dye, its structural formula is:
R=-CH wherein
3,-C
2H
5,-C
2H
4OCH
3
2. the synthetic method of a temporary soluble blue dispersed dye is characterized in that:
A. 2-chloromethyl-4-nitro-alkyl ether benzene (V) and Thiovanic acid are carried out condensation in alkaline medium, obtain 2 '-alkoxyl group-5 '-nitro-benzyl carboxymethyl thioether (VI), the temperature of this condensation reaction is 40～70 ℃, the pH value is 8～9, raw material (V) is 1: 1～1.05 with the mol ratio of Thiovanic acid, and the starting point concentration of Thiovanic acid is 10～13% (weight percents); Wherein alkyl is-CH
3,-C
2H
5,-C
2H
4OCH
3, as follows;
B. in water medium, be catalyzer with compound (VI) with the tungstic oxide, with hydrogen peroxide oxidation become 2 '-alkoxyl group-5 '-nitro-benzyl carboxymethyl sulfone (VII), the starting point concentration of reactant (VI) is 15～22% (weight percents), hydrogen peroxide concentration is 30% (weight percent), and consumption is VI: H
2O
2=1: 2.2～2.6 (mol ratios), temperature are 60～70 ℃, and pH is 5～6.7, and the reaction times is 12～20 hours, and catalyst levels is VI: WO
3=1: 0.005～0.01 (mol ratio);
C. in water medium, with iron powder compound (VII) reduction is made 2 '-alkoxyl group-5 '-amino-benzyl carboxymethyl sulfone (II), adding acetic acid is catalyzer, consumption is 0.01 moles/mole (VII), temperature is 60～92 ℃, the time is 2.5～3 hours;
D. with compound (II) and 1-amino-4-bromo-anthraquinone-2-sulfonic acid at NaHCO
3And Na
2CO
3Exist down; carry out catalysis aryl amination reaction, obtain 1-amino-4-anilino-4 '-alkoxyl group-3 '-carboxymethyl sulfonyl tectoquinone-2-sulfonic acid (III), temperature of reaction is 65～80 ℃; bromamine acid: amine (II)=1: 1.2～1.25 (mol ratios), the catalysts consumption is bromamine acid: CuSO
4: FeSO
4=1: 0.2: 0.18 (mol ratio), bromamine acid: NaHCO
3: Na
2CO
3=1: 1.7: 1.9 (mol ratio);
E. with compound (III) and V-Brite B at NaHCO
3Exist and to take off sulphur down and react, obtain 1-amino-4 anilino-4 '-alkoxyl group-3 '-carboxymethyl sulfonyl methyl-anthraquinone (I), temperature of reaction is 25～90 ℃, compound (III): Na
2S
2O
4: NaHCO
3=1: 1.9～2: 5.7～6 (mol ratio); With saltout-the acid out method separates out dyestuff, again with the refining product (I) that obtains of acid-precipitation method.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN1050374C true CN1050374C (en) | 2000-03-15 |
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| CN102154846B (en) * | 2011-03-11 | 2013-03-27 | 河南洛染股份有限公司 | Application of orange temporarily water-soluble disperse dye in preparation of inkjet printing ink |
| CN102174271B (en) * | 2011-03-11 | 2013-06-05 | 河南洛染股份有限公司 | Temporarily water-soluble disperse dye and preparation method and application thereof |
| CN102161833A (en) * | 2011-03-11 | 2011-08-24 | 河南洛染股份有限公司 | Red temporary water-soluble disperse dye and manufacturing method and use thereof |
| CN102199364B (en) * | 2011-03-11 | 2014-04-09 | 河南洛染股份有限公司 | Blue temporary water-soluble disperse dye, preparation method thereof and application thereof |
| CN104559309B (en) * | 2013-10-12 | 2017-01-18 | 湖北华丽染料工业有限公司 | Method for preparing blue reactive dyes |
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