CN116355434B - Method for preparing direct dye by replacing benzidine - Google Patents
Method for preparing direct dye by replacing benzidine Download PDFInfo
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- CN116355434B CN116355434B CN202310089219.2A CN202310089219A CN116355434B CN 116355434 B CN116355434 B CN 116355434B CN 202310089219 A CN202310089219 A CN 202310089219A CN 116355434 B CN116355434 B CN 116355434B
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- Prior art keywords
- fluorenone
- diamino
- solution
- acid
- hydroxynaphthalene
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000982 direct dye Substances 0.000 title claims abstract description 25
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 title abstract description 15
- GWTJRFCUTIHVPX-UHFFFAOYSA-N 2,7-diaminofluoren-9-one Chemical compound C1=C(N)C=C2C(=O)C3=CC(N)=CC=C3C2=C1 GWTJRFCUTIHVPX-UHFFFAOYSA-N 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 44
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 24
- -1 7-amino-4-hydroxy-3- ((7-amino-9-fluorenonyl) diazenyl) naphthalene-2-sulfonic acid Chemical compound 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000012954 diazonium Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 150000001989 diazonium salts Chemical class 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- 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 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 235000010288 sodium nitrite Nutrition 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 8
- HIVUAOXLSJITPA-UHFFFAOYSA-N 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=C(S(O)(=O)=O)C(N)=CC=C21 HIVUAOXLSJITPA-UHFFFAOYSA-N 0.000 claims description 7
- HGWQOFDAUWCQDA-UHFFFAOYSA-N 4-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(O)=CC=C(S(O)(=O)=O)C2=C1 HGWQOFDAUWCQDA-UHFFFAOYSA-N 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 230000008878 coupling Effects 0.000 claims description 7
- 238000010168 coupling process Methods 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- NRZRRZAVMCAKEP-UHFFFAOYSA-N naphthionic acid Chemical compound C1=CC=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 NRZRRZAVMCAKEP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 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 claims description 6
- 238000004537 pulping Methods 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 23
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 abstract description 13
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 24
- 238000000862 absorption spectrum Methods 0.000 description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000012266 salt solution Substances 0.000 description 18
- 230000031700 light absorption Effects 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- 150000002829 nitrogen Chemical class 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 238000006193 diazotization reaction Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000006149 azo coupling reaction Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- VWEYLNZGUPHCNP-UHFFFAOYSA-O COC1=C(C(=CC=C1N)C1=CC(=C(N)C=C1)OC)[N+]#N Chemical class COC1=C(C(=CC=C1N)C1=CC(=C(N)C=C1)OC)[N+]#N VWEYLNZGUPHCNP-UHFFFAOYSA-O 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 229940079101 sodium sulfide Drugs 0.000 description 4
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 4
- HDVGAFBXTXDYIB-UHFFFAOYSA-N 2,7-dinitrofluoren-9-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C2=C1 HDVGAFBXTXDYIB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SJODITPGMMSNRF-UHFFFAOYSA-N 2-aminofluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC(N)=CC=C3C2=C1 SJODITPGMMSNRF-UHFFFAOYSA-N 0.000 description 1
- GCJCNFYTHYPWQM-UHFFFAOYSA-N 2-methoxy-4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=C(OC)C(N)=CC=2)=C1 GCJCNFYTHYPWQM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000012062 aqueous buffer Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PHBXSOKXCTZJBO-UHFFFAOYSA-L disodium 7-amino-4-hydroxy-3-[[4-[4-[(1-hydroxy-4-sulfonatonaphthalen-2-yl)diazenyl]-3-methoxyphenyl]-2-methoxyphenyl]diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].COc1cc(ccc1N=Nc1cc(c2ccccc2c1O)S([O-])(=O)=O)-c1ccc(N=Nc2c(O)c3ccc(N)cc3cc2S([O-])(=O)=O)c(OC)c1 PHBXSOKXCTZJBO-UHFFFAOYSA-L 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography 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
- C09B29/0018—Monoazo dyes prepared by diazotising and coupling from diazotized aminopolycyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- 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
- C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
- C09B29/16—Naphthol-sulfonic acids
-
- 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
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/039—Disazo dyes characterised by the tetrazo component
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing direct dye by replacing benzidine. The method uses 2, 7-diamino-9-fluorenone to replace 3,3' -dimethoxy benzidine as a connecting group to prepare direct dye, and the prepared product has similar optical performance with that of a benzidine direct dye compound. The 2, 7-diamino-9-fluorenone has stable structure, difficult decomposition, difficult absorption, safety and low toxicity, can replace benzidine, and realizes the purpose of simply and effectively preparing direct dye with long absorption wavelength.
Description
Technical Field
The invention relates to the technical field of dye preparation, in particular to a method for preparing a direct dye by using 2, 7-diamino-9-fluorenone to replace 3,3' -dimethoxy benzidine as a connecting group.
Background
Benzidine can be used for preparing disazo salt through one-time diazotization, and the production and the manufacture of a polyazo product are easy to finish. Benzidine is an important raw material for preparing dyes with long absorption wavelength, and many successful commercial dyes are prepared by using benzidine monomers including benzidine, 3 '-dimethylbenzidine, 3' -dimethoxy aniline and the like as raw materials, such as C.I direct yellow 1, C.I direct brown 95, C.I direct blue 168, C.I direct black 91, C.I acid black 29 and the like. However, benzidine-based dyes are degraded to easily reform benzidine, and have serious carcinogenic effects, so that the production and use of dyes made from benzidine have been prohibited.
The diamine monomer can be used for selectively preparing mono-diazonium salt or double-diazonium salt by adjusting the condition of diazotization reaction, and various azo dyes can be prepared by selecting different coupling reagents, so that the preparation method has the advantage of product diversity. On the other hand, the diamine monomer can easily obtain long absorption wavelength products through the conjugation of the monomer, can simplify the synthesis path of the products, and has the advantages of shortening the production route and saving the manufacturing cost. Therefore, the method has important significance in developing safe and low-toxicity diamine monomer to replace benzidine monomer and realizing the synthesis and preparation of direct dye compounds.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing a direct dye by using 2, 7-diamino-9-fluorenone to replace 3,3' -dimethoxy benzidine as a connecting group. The method can simply and effectively prepare the direct dye with long absorption wavelength.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a direct dye compound as shown in formula i or formula II:
wherein R 1 is OH, ONa or NH 2,R2 is H or NH 2,R3 is H, SO 3 H or SO 3Na,R4 is H, SO 3 H or SO 3Na,R5 is H or SO 3 Na.
Preferably, the direct dye is selected from one of 7-amino-4-hydroxy-3- ((7-amino-9-fluorenone) diazenyl) naphthalene-2-sulfonic acid, 3, 7-diazenyl (7-amino-4-hydroxynaphthalene-2-sulfonic acid) -9-fluorenone, 3, 7-diazenyl (7-amino-4-hydroxynaphthalene-2, 8-disulfonic acid) -9-fluorenone, 3, 7-diazenyl (1-aminonaphthalene-4-sulfonic acid) -9-fluorenone, 3, 7-diazenyl (1-hydroxynaphthalene-4-sulfonic acid) -9-fluorenone, or a sulfonate thereof.
The invention also provides a preparation method of the direct dye compound, which comprises the following steps:
(1) 2, 7-diamino-9-fluorenone is prepared by reducing 2, 7-binitro-9-fluorenone;
(2) 2, 7-diamino-9-fluorenone is prepared into a diazonium salt intermediate through diazotization reaction;
(3) Diazo coupling is carried out on the diazonium salt prepared in the step (2) and naphthol in alkaline aqueous solution, and the diazonium salt reacts for 20-120 minutes at the temperature of 10-50 ℃ to obtain the direct dye compound.
The preparation reaction formula of the direct dye is shown in a formula III:
Wherein R 1 is OH, ONa or NH 2,R2 is H or NH 2,R3 is H or SO 3 H or SO 3Na,R4 is H or SO 3 H or SO 3Na,R5 is H or SO 3 Na.
Preferably, the specific preparation steps of the 2, 7-diamino-9-fluorenone in the step (1) are as follows: a) Adding methanol into 2, 7-binitro-9-fluorenone, uniformly stirring, slowly dripping a reducing agent solution into the mixture, and heating and stirring for reaction after the dripping is finished to obtain a 2, 7-diamino-9-fluorenone solution for later use; b) Evaporating the 2, 7-diamino-9-fluorenone solution to dryness to obtain a crude product, and pulping the crude product by using an organic solvent to obtain the 2, 7-diamino-9-fluorenone.
Further preferably, the amount of methanol used in step (a) is 25mL/g, and the reducing agent is one of ascorbic acid, sodium sulfide, iron powder and zinc powder, more preferably ascorbic acid or sodium sulfide; the molar ratio of the reducing agent to the 2, 7-dinitro-9-fluorenone is 1.0 to 5.0:1, more preferably 3.0 to 4.0:1; the heating temperature is 40-65deg.C, more preferably 55-65deg.C; the reaction time is 1 to 5 hours, more preferably 3 to 4 hours.
Further preferably, the 2, 7-diamino-9-fluorenone solution is evaporated to dryness in step (b) at a temperature of 40 to 60 ℃, more preferably 50 to 55 ℃; the organic solvent is one or a mixture of methanol, ethanol, acetone, petroleum ether and tetrahydrofuran, more preferably a mixture of methanol and petroleum ether, and methanol: the volume ratio of petroleum ether is 1:5-20.
Preferably, the specific steps for preparing the diazonium salt intermediate from the 2, 7-diamino-9-fluorenone in the step (2) are as follows: c) Dissolving 2, 7-diamino-9-fluorenone in an acidic solution for later use; d) Then dropwise adding sodium nitrite solution at low temperature, and continuing to react for a period of time after the completion of the dropwise adding, thus obtaining diazonium salt solution.
Further preferably, the acid used in step (c) is one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid or a mixed acid thereof, more preferably hydrochloric acid or acetic acid; the molar ratio of acid to 2, 7-diamino-9-fluorenone is 3.0 to 5.0:1, more preferably 3.0 to 4.0:1;
It is further preferred that the concentration of the sodium nitrite solution in step (d) is in the range of 0.1 to 2M, more preferably in the range of 0.5 to 1.0M, the molar ratio of sodium nitrite to 2, 7-diamino-9-fluorenone is in the range of 0.5 to 5.0:1, more preferably in the range of 0.75 to 1.5:1 for monoazo salts, more preferably in the range of 2.5 to 4.0:1 for bisazo salts, the reaction temperature is in the range of 0 to 20 ℃, more preferably in the range of 5 to 15 ℃, and the reaction time is in the range of 0.5 to 3 hours, more preferably in the range of 1 to 2 hours.
Preferably, the naphthol in the step (3) is one of 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid and 1-aminonaphthalene-4-sulfonic acid; the molar ratio of diazonium salt to naphthol is 1:0.5-2.5, more preferably 1:0.75-1.5 for monoazo salt, and more preferably 1:2.0-2.5 for disazo salt; the alkaline aqueous solution is one of saturated sodium bicarbonate aqueous solution, saturated sodium carbonate aqueous solution and 0.1-1.0M sodium hydroxide aqueous solution, more preferably saturated sodium carbonate aqueous solution, and the concentration is 0.25-0.5M.
The invention takes 2, 7-binitro-9-fluorenone as raw material, sodium sulfide or ascorbic acid as reducer, methanol as solvent, reacting for 3-4 hours at 55-65 ℃, monitoring the reaction by thin layer chromatography, evaporating the solvent at 50-55 ℃ after the reaction reaches the end point, refining by pulping the mixed solvent of ethanol/petroleum ether to obtain pure 2, 7-diamino-9-fluorenone, and characterizing the product by nuclear magnetic resonance hydrogen spectrum. 2, 7-diamino-9-fluorenone is dissolved in hydrochloric acid or acetic acid aqueous solution, reacts with sodium nitrite solution for 1-2 hours at 5-15 ℃ to prepare monoazo salt or disazo salt, characterization of the azo salt is carried out through nuclear magnetic resonance hydrogen spectrum, and the azo salt and naphthol compound comprise 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid or 1-aminonaphthalene-4-sulfonic acid are coupled to prepare monoazo or disazo direct dye.
The invention also protects the application of the direct dye compound in dyeing. The direct dye prepared by the invention and the product prepared by the control example are subjected to optical performance characterization through an ultraviolet-visible light absorption spectrum, the test solvent is an aqueous buffer solution system, the test concentration is 10ppm, the test concentration can be confirmed through the ultraviolet-visible light absorption spectrum, the 2, 7-diamino-9-fluorenone and the 3,3 '-dimethoxy benzidine have similar effects, the prepared azo compound has a near maximum absorption wavelength and similar absorption peaks, and the 2, 7-diamino-9-fluorenone can replace the 3,3' -dimethoxy benzidine in the application of dye preparation.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the 2, 7-diamino-9-fluorenone provided by the invention has the advantages of mild condition, environment friendliness, simple treatment, simple process, less equipment investment, high yield and low cost. The direct dye compound is prepared by using 2, 7-diamino-9-fluorenone as a linking group, and the product has optical properties similar to those of the biphenyl amine direct dye compound. The 2, 7-diamino-9-fluorenone has stable structure, difficult decomposition, difficult absorption, safety and low toxicity, can replace benzidine, and realizes the purpose of simply and effectively preparing direct dye with long absorption wavelength.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 2, 7-diamino-9-fluorenone prepared by the present invention.
FIG. 2 is a nuclear magnetic carbon spectrum of 2, 7-diamino-9-fluorenone prepared by the present invention.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the 2, 7-diamino-9-fluorenone monodiazonium salt prepared by the present invention.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the 2, 7-diamino-9-fluorenone double diazonium salt prepared by the present invention.
FIG. 5 is a nuclear magnetic resonance spectrum of 3,3' -dimethoxybenzidine monodiazonium salt prepared in comparative example 1 according to the present invention.
FIG. 6 is a nuclear magnetic resonance spectrum of a dual nitrogen salt of 3,3' -dimethoxy benzidine prepared in comparative example 2 of the present invention.
FIG. 7 is a graph showing the ultraviolet-visible light absorption spectrum of the product produced in application example 1 of the present invention.
FIG. 8 is a graph showing the ultraviolet-visible light absorption spectrum of the product produced in application example 2 of the present invention.
FIG. 9 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in application example 3 of the present invention.
FIG. 10 is a graph showing the ultraviolet-visible light absorption spectrum of the product produced in application example 4 of the present invention.
FIG. 11 is a graph showing the ultraviolet-visible light absorption spectrum of the product produced in application example 5 of the present invention.
FIG. 12 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in comparative example 1, which was used in the present invention.
FIG. 13 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in comparative example 2, which was used in the present invention.
FIG. 14 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in comparative example 3, which was used in the present invention.
FIG. 15 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in comparative example 4, which was used in the present invention.
FIG. 16 is a graph showing the absorption spectrum of ultraviolet-visible light of the product produced in comparative example 5, which was used in the present invention.
Detailed Description
The following examples are further illustrative of the invention and are not intended to be limiting thereof.
Example 1
The method for preparing 2, 7-diamino-9-fluorenone by reducing ascorbic acid comprises the following steps:
(1) 2, 7-dinitro-9-fluorenone (2.7 g,10 mmol) was weighed into a 250mL round bottom flask, dissolved by adding 70mL methanol, and then transferred to a 60℃oil bath with heating and stirring for 15 minutes; then slowly dripping ascorbic acid solution (5.3 g,30 mmol) into the mixture for five times, continuing to react for 4 hours after the dripping is finished, stopping heating, naturally cooling to room temperature, and performing post-treatment;
(2) Transferring to a rotary evaporator, removing methanol under reduced pressure at 50deg.C to obtain black viscous solid, transferring to a vacuum oven at 50deg.C to thoroughly remove solvent to obtain grey brown solid, pulping with 50mL of mixed solvent (petroleum ether/methanol=10/1, volume ratio), and suction filtering to obtain grey solid 1.7g with 80% yield. Product nuclear magnetism 1H NMR(500MHz,DMSO-d6)δ7.1(d,J＝7.9Hz,2H),6.7(d,J＝2.2Hz,2H),6.6(dd,J＝7.9,2.3Hz,2H),5.3(s,4H).13C NMR(125MHz,DMSO)δ195.36,148.66,135.05,133.74,120.34,119.10,110.13,40.25,40.08,39.91,39.75,39.58.( fig. 1, fig. 2).
Example 2
The method for preparing 2, 7-diamino-9-fluorenone by reducing sodium sulfide comprises the following steps:
(1) 2, 7-dinitro-9-fluorenone (2.7 g,10 mmol) was weighed into a 250mL round bottom flask, dissolved by adding 70mL methanol, and then transferred to a 60℃oil bath with heating and stirring for 15 minutes; then dropwise adding sodium sulfide nonahydrate solution (9.6 g,40 mmol) into the mixture for five times, continuing to react for 4 hours after the dropwise adding is finished, stopping heating, naturally cooling to room temperature, and carrying out post-treatment;
(2) Transferring to a rotary evaporator, removing methanol under reduced pressure at 50deg.C to obtain black viscous solid, transferring to a vacuum oven at 50deg.C to thoroughly remove solvent to obtain grey brown solid, pulping with 50mL of mixed solvent (petroleum ether/methanol=10/1, volume ratio), and vacuum filtering to obtain grey solid 1.7g with a yield of 60%. Product nuclear magnetism 1H NMR(500MHz,DMSO-d6)δ7.1(d,J＝7.9Hz,2H),6.7(d,J＝2.2Hz,2H),6.6(dd,J＝7.9,2.3Hz,2H),5.3(s,4H).13C NMR(125MHz,DMSO)δ195.36,148.66,135.05,133.74,120.34,119.10,110.13,40.25,40.08,39.91,39.75,39.58.( fig. 1, fig. 2).
Example 3
The method for preparing 2, 7-diamino-9-fluorenone monodiazonium salt by diazotization reaction comprises the following steps:
(1) Weighing 2, 7-diamino-9-fluorenone (2.1 g,10 mmol) in a 100mL beaker, adding 50mL deionized water, stirring and dispersing, then adding concentrated hydrochloric acid (37 wt%,4mL,40 mmol), ultrasonically dissolving, transferring to ice water bath, and cooling to 5 ℃ for standby;
(2) Sodium nitrite (0.56 g,8 mmol) is weighed and dissolved in 50mL of deionized water, then slowly added dropwise into the 2, 7-diamino-9-fluorenone acid solution, and the mixture is continuously stirred for reaction for 1 hour after the dropwise addition is finished, so that 2, 7-diamino-9-fluorenone monodiazonium salt solution is obtained and is directly used for the next reaction. 2, 7-diamino-9-fluorenone monodiazonium salt solution nuclear magnetism 1H NMR(500MHz,D2O)δ8.8(d,J＝13.1Hz,2H),8.4(d,J＝8.3Hz,1H),7.7(d,J＝8.0Hz,1H),7.5(s,1H),7.5(d,J＝8.1Hz,1H).( figure 3).
Example 4
The method for preparing the 2, 7-diamino-9-fluorenone double nitrogen salt by diazotization reaction comprises the following steps:
(1) Weighing 2, 7-diamino-9-fluorenone (2.1 g,10 mmol) in a 100mL beaker, adding 50mL deionized water, stirring and dispersing, then adding concentrated hydrochloric acid (37 wt%,4mL,40 mmol), ultrasonically dissolving, transferring to ice water bath, and cooling to 5 ℃ for standby;
(2) Sodium nitrite (2.5 g,35 mmol) is weighed and dissolved in 50mL of deionized water, then slowly added dropwise into the 2, 7-diamino-9-fluorenone acid solution, and the mixture is continuously stirred for reaction for 1 hour after the dropwise addition is finished, so that 2, 7-diamino-9-fluorenone double nitrogen salt solution is obtained and is directly used for the next reaction. 2, 7-diamino-9-fluorenone double nitrogen salt solution nuclear magnetism 1 H NMR (500 mhz, d2 o) δ9.1-8.6 (m, 4H), 8.5 (d, j=8.3 hz, 2H) (fig. 4).
Comparative example 1
The method for preparing 3,3' -dimethoxy benzidine monodiazonium salt by diazotization reaction comprises the following steps:
(1) Weighing 3,3' -dimethoxy benzidine (2.4 g,10 mmol) in a 100mL beaker, adding 50mL of deionized water, stirring for dispersion, then adding concentrated hydrochloric acid (37 wt%,4mL,40 mmol), ultrasonically dissolving, transferring to ice water bath, and cooling to 5 ℃ for standby;
(2) Sodium nitrite (0.69 g,10 mmol) is weighed and dissolved in 50mL of deionized water, then slowly added dropwise into 3,3 '-dimethoxy benzidine acid solution, and after the dropwise addition, the reaction is continued for 1 hour with stirring, so as to obtain 3,3' -dimethoxy benzidine monodiazonium salt solution, which is directly used for the next reaction. 3,3' -dimethoxy benzidine monodiazonium salt solution nuclear magnetism 1H NMR(500MHz,D2O)δ8.4(d,J＝8.7Hz,1H),7.7(s,1H),7.6(d,J＝8.7Hz,1H),7.3(d,J＝8.1Hz,1H),7.3(d,J＝1.8Hz,1H),7.2(dd,J＝8.1,1.8Hz,1H),4.2(s,3H),3.9(s,3H).( fig. 5).
Comparative example 2
The method for preparing the 3,3' -dimethoxy benzidine double nitrogen salt by diazotization reaction comprises the following steps:
(1) Weighing 3,3' -dimethoxy benzidine (2.4 g,10 mmol) in a 100mL beaker, adding 50mL of deionized water, stirring for dispersion, then adding concentrated hydrochloric acid (37 wt%,4mL,40 mmol), ultrasonically dissolving, transferring to ice water bath, and cooling to 5 ℃ for standby;
(2) Sodium nitrite (2.1 g,30 mmol) was weighed and dissolved in 50mL of deionized water, then slowly added dropwise to the 3,3 '-dimethoxybenzidine acid solution, and the reaction was continued for 1 hour after the dropwise addition to obtain a double nitrogen salt solution of 3,3' -dimethoxybenzidine, which was directly used in the next reaction. Nuclear magnetism 1 H NMR (500 MHz, D2O) delta 8.4 (d, J=8.8 Hz, 2H), 7.7 (s, 2H), 7.6 (dd, J=8.7, 1.5Hz, 2H), 4.2 (s, 6H) of 3,3' -dimethoxybenzidine double nitrogen salt solution (FIG. 6).
Application example 1
A process for diazotizing coupling to prepare 7-amino-4-hydroxy-3- ((7-amino-9-fluorenonyl) diazenyl)) naphthalene-2-sulfonic acid comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-7-sulfonic acid (2.4 g,10 mmol) in a 500mL beaker, then adding 200mL of saturated sodium carbonate aqueous solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-7-sulfonic acid solution; then, 2, 7-diamino-9-fluorenone monodiazonium salt solution (100 mL,0.1mol/L,10 mmol) prepared in example 3 was added thereto and coupled at 20℃for 1 hour to obtain the product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the mixture to salt out, and after stirring for 1 hour, the mixture was allowed to stand, centrifuged and dried to obtain 4.1g of a product with a yield of 90%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 551nm (FIG. 7).
Application example 2
A process for diazotizing coupling to prepare 3, 7-diazenyl (7-amino-4-hydroxynaphthalene-2-sulfonic acid) -9-fluorenone, comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-7-sulfonic acid (4.8 g,20 mmol) in a 500mL beaker, then adding 200mL of saturated sodium carbonate aqueous solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-7-sulfonic acid solution; then, 2, 7-diamino-9-fluorenone double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) prepared in example 4 was added thereto and coupled at 20℃for 1 hour to obtain the product;
(2) Sodium chloride solids (45 g,15 wt%) were added to salt out, stirred for 1 hour, then allowed to stand, centrifuged, and dried to give 5.0g of the product in 70% yield.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 540nm (FIG. 8).
Application example 3
A process for diazotising a coupling to prepare 3, 7-diazenyl (7-amino-4-hydroxynaphthalene-2, 8-disulfonic acid) -9-fluorenone comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid (6.8 g,20 mmol) in a 500mL beaker, then adding 200mL saturated sodium carbonate solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid solution; then, 2, 7-diamino-9-fluorenone double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) prepared in example 4 was added thereto and coupled at 20℃for 1 hour to obtain the product;
(2) Sodium chloride solids (45 g,15 wt%) were added to salt out, stirred for 1 hour, then allowed to stand, centrifuged, and dried to give 5.5g of product in 60% yield.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 545nm (FIG. 9).
Application example 4
A process for the diazo coupling preparation of 3, 7-diazenyl (1-hydroxynaphthalene-4-sulfonic acid) -9-fluorenone comprising the steps of:
(1) 1-hydroxynaphthalene-4-sulfonic acid (4.9 g,20 mmol) was weighed into a 500mL beaker, then 200mL of saturated sodium carbonate solution was added, and after ultrasonic dissolution, 1-hydroxynaphthalene-4-sulfonic acid solution was obtained; then, 2, 7-diamino-9-fluorenone double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) prepared in example 4 was added thereto and coupled at 20℃for 1 hour to obtain the product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the mixture to salt out, and after stirring for 1 hour, the mixture was allowed to stand, centrifuged and dried to obtain 5.8g of a product with a yield of 80%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 556nm (FIG. 10).
Application example 5
A process for the diazo coupling preparation of 3, 7-diazenyl (1-aminonaphthalene-4-sulfonic acid) -9-fluorenone comprising the steps of:
(1) 1-aminonaphthalene-4-sulfonic acid (4.9 g,20 mmol) was weighed into a 500mL beaker, then 200mL of saturated sodium carbonate solution was added, and after ultrasonic dissolution, 1-aminonaphthalene-4-sulfonic acid solution was obtained; then, 2, 7-diamino-9-fluorenone double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) prepared in example 4 was added thereto and coupled at 20℃for 1 hour to obtain the product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the solution, and after stirring for 1 hour, the solution was allowed to stand, centrifuged and dried to obtain 2.9g of a product with a yield of 40%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 467nm (FIG. 11).
Comparative example 1 was used
A process for diazotizing coupling to prepare 7-amino-4-hydroxy-3- ((3, 3 '-dimethoxy-4' -aminobiphenyl) diazenyl)) naphthalene-2-sulfonic acid comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-7-sulfonic acid (2.4 g,10 mmol) in a 500mL beaker, then adding 200mL of saturated sodium carbonate solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-7-sulfonic acid solution; then, 3' -methoxybenzidine monodiazonium salt solution (100 mL,0.1mol/L,10 mmol) prepared in comparative example 1 was added thereto, and coupling was performed at 20℃for 1 hour to obtain a product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the solution, and after stirring for 1 hour, the solution was allowed to stand, centrifuged and dried to obtain 4.5g of a product with a yield of 90%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 558nm (FIG. 12).
Comparative example 2
A process for the diazo coupling preparation of 4,4 '-diazenyl (7-amino-4-hydroxynaphthalene-2-sulfonic acid) -3,3' -biphenyl comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-7-sulfonic acid (4.8 g,20 mmol) in a 500mL beaker, then adding 200mL of saturated sodium carbonate solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-7-sulfonic acid solution; then, a double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) of 3,3' -methoxybenzidine prepared in comparative example 2 was added thereto, and the mixture was coupled at 20℃for 1 hour to obtain a product;
(2) Sodium chloride solids (45 g,15 wt%) were added to salt out, stirred for 1 hour, then allowed to stand, centrifuged, and dried to give 5.3g of the product in 70% yield.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 569nm (FIG. 13).
Comparative example 3
A process for the diazo coupling preparation of 4,4 '-diazenyl (7-amino-4-hydroxynaphthalene-2, 8-disulfonic acid) -3,3' -biphenyl comprising the steps of:
(1) Weighing 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid (6.8 g,20 mmol) in a 500mL beaker, then adding 200mL saturated sodium carbonate solution, and performing ultrasonic dissolution to obtain 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid solution; then, a double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) of 3,3' -methoxybenzidine prepared in comparative example 2 was added thereto, and the mixture was coupled at 20℃for 1 hour to obtain a product;
(2) Sodium chloride solids (45 g,15 wt%) were added to salt out, stirred for 1 hour, then allowed to stand, centrifuged, and dried to give 5.7g of the product in 60% yield.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 553nm (FIG. 14).
Comparative example 4
A process for the diazo coupling preparation of 4,4 '-diazenyl (1-hydroxy-4-naphthalenesulfonic acid) -3,3' -biphenyl comprising the steps of:
(1) 1-hydroxynaphthalene-4-sulfonic acid (4.9 g,20 mmol) was weighed into a 500mL beaker, then 200mL of saturated sodium carbonate solution was added, and after ultrasonic dissolution, 1-hydroxynaphthalene-4-sulfonic acid solution was obtained; then, a double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) of 3,3' -methoxybenzidine prepared in comparative example 2 was added thereto, and the mixture was coupled at 20℃for 1 hour to obtain a product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the mixture to salt out, and after stirring for 1 hour, the mixture was allowed to stand, centrifuged and dried to obtain 6.4g of a product with a yield of 80%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 564nm (FIG. 15).
Comparative example 5
A process for the diazo coupling preparation of 4,4 '-diazenyl (1-amino-4-naphthalenesulfonic acid) -3,3' -biphenyl comprising the steps of:
(1) 1-aminonaphthalene-4-sulfonic acid (4.9 g,20 mmol) was weighed into a 500mL beaker, then 200mL of saturated sodium carbonate solution was added, and after ultrasonic dissolution, 1-aminonaphthalene-4-sulfonic acid solution was obtained; then, a double nitrogen salt solution (100 mL,0.1mol/L,10 mmol) of 3,3' -methoxybenzidine prepared in comparative example 2 was added thereto, and the mixture was coupled at 20℃for 1 hour to obtain a product;
(2) Sodium chloride solid (45 g,15 wt%) was added to the solution, and after stirring for 1 hour, the solution was allowed to stand, centrifuged and dried to obtain 2.8g of a product with a yield of 35%.
(3) The product was dissolved in deionized water to prepare a 10ppm aqueous solution, and the ultraviolet-visible light absorption spectrum was measured by an ultraviolet-visible light spectrometer, and the maximum absorption wavelength was 419nm (FIG. 16).
The maximum absorption wavelength and the color of the products obtained in the above application examples 1 to 5 and application comparative examples 1 to 5 are shown in Table 1.
TABLE 1 maximum absorption wavelength and color of the products of application examples 1-5/application comparative examples 1-5
The products obtained in application examples 1 to 5 and application comparative examples 1 to 5 were weighed and dissolved in deionized water to prepare 10ppm aqueous solutions, and colorimetric control was performed, and the results are summarized in Table 1, and the colors of the application examples and the comparative examples are substantially the same, and the colors of the application examples and the comparative examples are purple, mauve, purple, purplish blue, and orange sequentially with increasing numbers. The application example is similar to the peak type of the ultraviolet-visible light absorption spectrum line of the comparison example, and the maximum absorption wavelength is close, so that the preparation method of the 2, 7-diamino-9-fluorenone and the application of the preparation method to diazotization reaction as a diamine monomer can replace benzidine to prepare azo dye, and the purpose of simply and effectively preparing direct dye with long absorption wavelength is realized.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (2)
1. A process for the preparation of a direct dye compound comprising the steps of:
(1) 2, 7-diamino-9-fluorenone is prepared by reducing 2, 7-binitro-9-fluorenone:
a) Adding methanol into 2, 7-binitro-9-fluorenone, wherein the dosage of the methanol is 25mL/g, slowly dripping a reducing agent solution into the mixture after stirring uniformly, wherein the reducing agent is ascorbic acid or sodium sulfide, the mol ratio of the reducing agent to the 2, 7-binitro-9-fluorenone is 3.0-4.0:1, and heating and stirring at 55-65 ℃ for 3-4 hours after the dripping is finished to obtain the 2, 7-diamino-9-fluorenone solution for later use;
b) Evaporating the 2, 7-diamino-9-fluorenone solution at 50-55 ℃ to obtain a crude product, and pulping the crude product by using an organic solvent to obtain 2, 7-diamino-9-fluorenone; the organic solvent is a mixture of methanol and petroleum ether according to the volume ratio of 1:5-20;
(2) Preparation of 2, 7-diamino-9-fluorenone by diazotisation to give diazonium salt intermediates:
c) Dissolving 2, 7-diamino-9-fluorenone in an acidic solution for later use; the acid is hydrochloric acid or acetic acid; the molar ratio of the acid to the 2, 7-diamino-9-fluorenone is 3.0 to 4.0:1;
d) Then dropwise adding 0.5-1.0M sodium nitrite solution at low temperature, wherein the molar ratio of sodium nitrite to 2, 7-diamino-9-fluorenone is 0.5-5.0:1, the molar ratio of sodium nitrite to 2, 7-diamino-9-fluorenone is 0.75-1.5:1 for monoazo salt preparation, and the molar ratio of sodium nitrite to 2, 7-diamino-9-fluorenone is 2.5-4.0:1 for disazo salt preparation, and continuously reacting for 1-2 hours at 5-15 ℃ after dropwise adding to obtain diazonium salt solution;
(3) Diazotizing coupling is carried out on the diazonium salt prepared in the step (2) and naphthol in an alkaline aqueous solution, and the diazonium salt reacts for 20-120 minutes at the temperature of 10-50 ℃ to obtain the direct dye compound; the naphthol is one of 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-5-hydroxynaphthalene-1, 7-disulfonic acid, 1-hydroxynaphthalene-4-sulfonic acid and 1-aminonaphthalene-4-sulfonic acid; the molar ratio of the diazonium salt to the naphthol is 1:0.5-2.5, for monoazo salt preparation, the molar ratio of the diazonium salt to the naphthol is 1:0.75-1.5, and for disazo salt preparation, the molar ratio of the diazonium salt to the naphthol is 1:2.0-2.5; the alkaline aqueous solution is 0.25-0.5M saturated sodium carbonate aqueous solution.
2. The method according to claim 1, wherein the direct dye compound is selected from one of 7-amino-4-hydroxy-3- ((7-amino-9-fluorenonyl) diazenyl) naphthalene-2-sulfonic acid, 3, 7-diazenyl (7-amino-4-hydroxynaphthalene-2, 8-disulfonic acid) -9-fluorenone, 3, 7-diazenyl (1-aminonaphthalene-4-sulfonic acid) -9-fluorenone, 3, 7-diazenyl (1-hydroxynaphthalene-4-sulfonic acid) -9-fluorenone, and a sulfonate thereof.
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| CN202310089219.2A CN116355434B (en) | 2023-02-09 | 2023-02-09 | Method for preparing direct dye by replacing benzidine |
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| JPH02300756A (en) * | 1989-05-15 | 1990-12-12 | Fuji Photo Film Co Ltd | Electrophotograhic sensitive body |
| JP2000147808A (en) * | 1998-11-09 | 2000-05-26 | Ricoh Co Ltd | Photoconductor, organic pigment-dispersed liquid and manufacture of photoconductor by using same, electrophotographic method and apparatus |
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| "Disazo direct dyes containing cyclic amido, keto and amino groups";Jerzy Szadowski;Dyes and Pigments;第14卷(第3期);217-224 * |
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