CN110396303A - A kind of preparation and application of triarylmethane class compound - Google Patents
A kind of preparation and application of triarylmethane class compound Download PDFInfo
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- CN110396303A CN110396303A CN201910626075.3A CN201910626075A CN110396303A CN 110396303 A CN110396303 A CN 110396303A CN 201910626075 A CN201910626075 A CN 201910626075A CN 110396303 A CN110396303 A CN 110396303A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 title claims description 18
- -1 -disubstituted amido diphenyl-methane Chemical compound 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 14
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000975 dye Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 6
- 150000002989 phenols Chemical class 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical class CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000692870 Inachis io Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000001003 triarylmethane dye Substances 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
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
- C09B11/14—Preparation from aromatic aldehydes, aromatic carboxylic acids or derivatives thereof and aromatic amines
-
- 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
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/22—Amino derivatives of triarylmethanes containing OH groups bound to an aryl nucleus and their ethers and esters
-
- 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
Abstract
This application discloses a kind of preparation methods of triarylmethane class dyestuff, with 4,4 '-N, N '-disubstituted amido diphenyl-methane (bass) and arylamine class or substituted aroma amine compound, phenols or substituted phenol compound are in a solvent, catalyst is made with metal complex and tetrachloroquinone, using oxygen as oxidant, it is reacted 5-8 hours under acid condition and certain temperature, one step obtains product triarylmethane class dyestuff, using the product being commercialized is further processed, meet the use demand of different field.This method is simple and safe, high income, and the three wastes are few.
Description
Technical field
This application involves organic synthesis field more particularly to a kind of preparations and application of triarylmethane class compound.
Background technique
Triarylmethane based dye is characterized in that very distinct and colour rendering is high, by the color as purple, blue or green
Material and be used for various coating, aqueous ink, oiliness ink, inkjet, ink, ink for color filter and printed wiring board and semiconductor preparation
Colour developing in the process is also used to the purposes such as the dyeing of the cell DNA of biological field.Foremost peacock in triarylmethane compound dyestuff
It is green to be just developed early in 1877, it has used till now more than 100 years.Typical method is to replace aromatic aldehyde and N
Aniline reacts in acid condition, then under catalytic condition, obtains product triarylmethane dye, oxygen using the method for oxidation
Some has used lead during changing, and chromium, the heavy metals such as manganese are as oxidant；Preparing for the raw material aromatic aldehyde used in such methods is normal
Normal damage ratio is heavier, so the preparation process of entire product is restricted.Another kind of method is exactly with aromatic amine compounds and rice
Then family name's ketone compounds add arylamine first by michaelis ketone and phosphorus oxychloride reaction for raw material, the reaction was continued, obtains product；
This method has used toxicity and the relatively high phosphorus oxychloride raw material of risk, while producing containing phosphor contaminant, and processing is relatively more tired
Difficulty, while the raw material michaelis ketone used is relatively expensive.On the whole, existing method wants damage ratio in preparation process heavier,
It is exactly that the cost of raw material is relatively high, is not suitable with existing environmentally protective manufacture policy.
Summary of the invention
The application technical problems to be solved are to provide the preparation and application of a kind of triarylmethane class compound, the present invention
Product can be obtained by one-step method, technical process is simple, and at low cost, high income, the three wastes are few, has complied with current environmentally protective
With safe and reliable new situations and new policy.
In order to solve the above-mentioned technical problem, this application provides a kind of preparation method of triarylmethane class compound, packets
Include following steps:
With 4,4 '-N of formula (1), the arylamine class or substituted aroma of N '-disubstituted amido diphenyl-methane (bass) and formula (2)
Aminated compounds is raw material, in a solvent, makees catalyst with metal complex and tetrachloroquinone, using oxygen as oxidant, In
It is reacted at acid condition and 30-100 DEG C, the triarylmethane class compound of formula (4) is obtained after fully reacting,
Or with 4,4 '-N of formula (1), the phenols or substituted phenol compound of N '-disubstituted amido diphenyl-methane and formula (3)
Catalyst is done with metal complex and tetrachloroquinone in a solvent for raw material, using oxygen as oxidant, acid condition with
And reacted at 30-100 DEG C, the triarylmethane class compound of formula (5) is obtained after fully reacting,
Wherein, formula (1)-(5) are as follows respectively:
Wherein R1For the alkyl of C1-C5；R2、R3Alkyl independently selected from hydrogen or C1-C5；R4For hydrogen, C1-C10 alkyl,
Alkoxy, alkylamino, phenyl or Benzoheterocyclic compounds；R5For hydrogen or the alkyl of C1-C5；R6For hydrogen, C1-C10 alkyl, alcoxyl
Base, alkylamino, phenyl or Benzoheterocyclic compounds；X is acid group.
Further, the arylamine class or substituted aroma of the 4 of formula (1), 4 '-N, N '-disubstituted amido diphenyl-methane and formula (2)
The molar ratio of aminated compounds is 1.5:1:1.
Further, the phenols or substituted phenol of the 4 of formula (1), 4 '-N, N '-disubstituted amido diphenyl-methane and formula (3)
The molar ratio for closing object is 1.5:1:1.
Further, X is halogen, sulfuric acid, nitric acid, waits the acid ion of inorganic acids, and such as oxalic acid,
The acid ion of the organic acids such as acetic acid.
Further, the solvent is one or more of alcohols, ketone and halogenated hydrocarbon compound.Preferably, alcohol
Class compound is methanol, ethyl alcohol, propyl alcohol, butanol etc.；Ketone compounds are acetone, butanone etc.；Halogenated hydrocarbon compound is dichloro
Methane, chloroform, carbon tetrachloride, 1,2- dichloroethanes, trichloroethanes etc..
Further, the 4 of formula (1), 4 '-N, the N '-concentration of disubstituted amido diphenyl-methane in a solvent are 5-70%, excellent
It is selected as 15-40%.
Further, the metal complex be 4, the 1-8% of 4 '-N, N '-disubstituted amido diphenyl-methane mass fraction,
The metal complex is the complex that iron, cobalt, nickel, copper, zinc or manganese and Salen or Salprn are formed.Preferably, metal combination
Object is 4,4 '-N, the 2-5% of N '-disubstituted amido diphenyl-methane mass fraction.
Further, the dosage of tetrachloroquinone is 4, the 1- of 4 '-N, N '-disubstituted amido diphenyl-methane mass fraction
10%, preferably 2-6%.
Further, the pH value of acid condition is 1-5, preferably 1-3.
Further, it is reacted in air or pure oxygen atmosphere.The flow velocity of air is 30-50mL/min in reaction；Oxygen
Flow velocity be 10-20mL/min.
Preferably, reaction temperature is 50-80 DEG C.
Further, in reaction process by HPLC track investigate raw material bass amount come judge react performance, one
As the reaction time be 5-8 hours.
Further, after fully reacting, it is distilled to recover solvent, suitable sodium hydrate aqueous solution is added, solid is precipitated, then
It is adjusted with different acid to pH to acidity, is filtered at 70 DEG C, after filtrate crystallisation by cooling, obtain final product after purification.
The present invention is also claimed using triarylmethane class compound prepared by above-mentioned preparation method as dyestuff
Using.
The beneficial effect of the application is:
The present invention provides a kind of methods of one-step synthesis method triarylmethane compound compound, and this method solve triaryl methanes
Seriously polluted problem in dyestuff preparation process, and it is at low cost, and Atom economy is good.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention and cooperation, detailed description is as follows below.
Specific embodiment
The application is described further combined with specific embodiments below, so that those skilled in the art can be preferably
Understand the application and can be practiced, but illustrated embodiment is not as the restriction to the application.
Embodiment 1
Thermometer is housed in 250mL, in the reaction flask of reflux condenser and magnetic agitation, is put into 26.66g (0.11mol)
N, N '-dimethyl aniline, 50.87g (0.1mol) 4,4 '-bis- (N, N '-dimethyl)-diphenyl-methanes (methane bass), anhydrous second
Alcohol 100mL, Salprn cobalt complex 1.0g, tetrachloroquinone 1.5g, 5mL concentrated hydrochloric acid, is heated to 65 DEG C under stiring, is passed through oxygen
Gas, flow 15mL/min react 5 hours, and by HPLC sampling analysis, methane bass reaction conversion completely, stops reaction, steams
Ethyl alcohol is distillated, 50mL water and 10mL concentrated hydrochloric acid is added, is heated to 75 DEG C, filtering, filtrate is cooled to room temperature, crystallizes, and filtering obtains
To the crystallization with metallic luster, weigh after dry, 78.1g, yield 95.7%.Its characterization result is as follows:
Found:C,73.70；H,7.41；N, 10.39, Calc.for C25H30N3Cl:C,73.62；H,7.36；N,
10.31%.1H NMR(300MHz；CDCl3；ppm)δH:3.28(18H,s,-CH3), 6.86 (6H, d, J=9Hz, Ar H),
7.32 (6H, d, J=9Hz, Ar H)13C NMR(75MHz；CDCl3；ppm)δC:40.56,112.36,126.65,139.74,
155.58；m/z(EI):372.6(M+-Cl-+1)。
Embodiment 2
Thermometer is housed in 250mL, in the reaction flask of reflux condenser and magnetic agitation, is put into 26.66g (0.11mol)
N, N '-dimethyl aniline, 50.87g (0.1mol) 4,4 '-bis- (N, N '-dimethyl)-diphenyl-methanes (methane bass), anhydrous second
Alcohol 100mL, Salen iron complex 1.0g, tetrachloroquinone 1.5g, 5mL concentrated hydrochloric acid, is heated to 65 DEG C under stiring, is passed through oxygen,
Flow is 20mL/min, is reacted 4 hours, and by HPLC sampling analysis, methane bass reaction conversion completely, stops reaction, distillation
50mL water and 10mL concentrated hydrochloric acid is added in ethyl alcohol out, is heated to 70 DEG C, and filtering, filtrate is cooled to room temperature, crystallizes, and filtering obtains
Crystallization with metallic luster is weighed after dry, 75.48g, yield 92.5%.Its characterization result is as follows:
EA Found:C,73.70；H,7.41；N,10.39.Calc.for C25H30N3Cl:C,73.62；H,7.36；N,
10.31%.1H NMR(300MHz；CDCl3；ppm)δH:3.28(18H,s,-CH3), 6.86 (6H, d, J=9Hz, Ar H),
7.32 (6H, d, J=9Hz, Ar H)13C NMR(75MHz；CDCl3；ppm)δC:40.56,112.36,126.65,139.74,
155.58；m/z(EI):372.6(M+-Cl-+1)。
Embodiment 3
Thermometer is housed in 250mL, in the reaction flask of reflux condenser and magnetic agitation, is put into 16.42g (0.11mol)
N, N '-ethyl aniline, 31.05g (0.1mol) 4,4 '-bis- (N, N '-diethyl)-diphenyl-methanes (ethane bass), chloroform
100mL, Salen cobalt complex 0.5g, tetrachloroquinone 1.0g, 10mL acetic acid, are heated to 65 DEG C under stiring, are passed through oxygen, flow
It for 18mL/min, reacts 6 hours, by HPLC sampling analysis, ethane bass reaction conversion completely, stops reaction, distills out chlorine
50mL water and 10mL concentrated hydrochloric acid is added in imitative and acetic acid, is heated to 80 DEG C, and filtering, filtrate is cooled to room temperature, crystallizes, and filtering obtains
To the crystallization with metallic luster, weigh after dry, 44.93g, yield 91.3%.Its characterization result is as follows:
EA Found:C,75.57；H,8.72；N,8.61.Calc.for C31H42N3Cl:C,75.66；H,8.60；N,
8.54%；m/z(EI):456.6(M+-Cl-+1)。
Embodiment 4
Thermometer is housed in 250mL, in the reaction flask of reflux condenser and magnetic agitation, is put into 18.84g (0.11mol)
N-ethylnaphthylamine, 31.05g (0.1mol) 4,4 '-bis- (N, N '-diethyl)-diphenyl-methanes (ethane bass), chloroform 100mL,
Salen iron complex 0.5g, tetrachloroquinone 1.0g, 10mL acetic acid, is heated to 60 DEG C under stiring, is passed through air, flow is
45mL/min reacts 5 hours, and by HPLC sampling analysis, ethane bass reaction conversion completely, stops reaction, distills out chloroform
And acetic acid, 50mL water and 15mL concentrated hydrochloric acid is added, is heated to 75 DEG C, filtering, filtrate is cooled to, salting-out crystallization, and filtering obtains
Crystallization with metallic luster is weighed after dry, 48.22g, yield 93.8%.Its characterization result is as follows:
EA Found:C,77.13；H,7.97；N,8.23；Calc.for C33H40N3Cl:C,77.09；H,7.84；N,
8.17%.；m/z(EI):478.3(M+-Cl-+1)。
Embodiment 5
Thermometer is housed in 250mL, in the reaction flask of reflux condenser and magnetic agitation, is put into 11.90g (0.11mol)
Methyl phenyl ethers anisole, 31.05g (0.1mol) 4,4 '-bis- (N, N '-diethyl)-diphenyl-methanes (ethane bass), chloroform 80mL, Salprn
Iron complex 0.5g, tetrachloroquinone 1.0g, 10mL acetic acid, is heated to 55 DEG C under stiring, is passed through oxygen, flow 40mL/
Min reacts 6 hours, and by HPLC sampling analysis, ethane bass reaction conversion completely, stops reaction, distills out chloroform and second
50mL water and 15mL concentrated hydrochloric acid is added in acid, is heated to 75 DEG C, and filtering, filtrate is cooled to, salting-out crystallization, and filtering is had
The crystallization of metallic luster is weighed after dry, 48.22g, yield 93.8%.Its characterization result is as follows:
EA Found:C,74.53；H,7.90；N,6.23；Calc.for C28H35N2OCl:C,74.56；H,7.82；N,
6.21%.；m/z(EI):415.3(M+-Cl-+1)。
Embodiment described above is only the preferred embodiment lifted to absolutely prove the application, the protection model of the application
It encloses without being limited thereto.Those skilled in the art made equivalent substitute or transformation on the basis of the application, in the application
Protection scope within.The protection scope of the application is subject to claims.
Claims (10)
1. a kind of preparation method of triarylmethane class compound, which comprises the following steps:
With 4,4 '-N of formula (1), the arylamine class or substituted aroma amine compound of N '-disubstituted amido diphenyl-methane and formula (2)
For raw material, or
With the 4 of formula (1), the phenols or substituted phenol compound of 4 '-N, N '-disubstituted amido diphenyl-methane and formula (3) are raw material,
In a solvent, catalyst is done with metal complex and tetrachloroquinone, using oxygen as oxidant, in acid condition and
It is reacted at 30-100 DEG C, the triarylmethane class compound of formula (4) or formula (5) is obtained after fully reacting, wherein formula (1)-(5)
It is as follows respectively:
Wherein R1For the alkyl of C1-C5；R2、R3Alkyl independently selected from hydrogen or C1-C5；R4For hydrogen, C1-C10 alkyl, alcoxyl
Base, alkylamino, phenyl or Benzoheterocyclic compounds；R5For hydrogen or the alkyl of C1-C5；R6For hydrogen, C1-C10 alkyl, alkoxy, alkane
Amino, phenyl or Benzoheterocyclic compounds；X is acid group.
2. preparation method as described in claim 1, which is characterized in that the 4 of formula (1), 4 '-N, N '-disubstituted amido hexichol first
The molar ratio of the arylamine class or substituted aroma amine compound of alkane and formula (2) is 1.5:1:1.
3. preparation method as described in claim 1, which is characterized in that the 4 of formula (1), 4 '-N, N '-disubstituted amido hexichol first
The molar ratio of the phenols or substituted phenol compound of alkane and formula (3) is 1.5:1:1.
4. preparation method as described in claim 1, which is characterized in that X is the acid ion of inorganic acid or the acid group of organic acid
Ion.
5. preparation method as described in claim 1, which is characterized in that the solvent is alcohols, ketone and halogenated hydrocarbon chemical combination
One or more of object.
6. preparation method as described in claim 1, which is characterized in that the metal complex is 4, and 4 '-N, N '-two replace ammonia
The 1-8% of base diphenyl-methane mass fraction, the metal complex are iron, cobalt, nickel, copper, zinc or manganese and Salen or Salprn shape
At complex.
7. preparation method as described in claim 1, which is characterized in that the pH value of acid condition is 1-5.
8. preparation method as described in claim 1, which is characterized in that reacted in air or pure oxygen atmosphere.
9. preparation method as described in claim 1, which is characterized in that the reaction time is 5-8 hours.
10. triarylmethane class compound is as dyestuff prepared by preparation method of any of claims 1-9
Using.
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