CN105237362A - Method for catalytic preparation of triarylmethane compounds by using [EG]2[ZnCl2] - Google Patents

Method for catalytic preparation of triarylmethane compounds by using [EG]2[ZnCl2] Download PDF

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CN105237362A
CN105237362A CN201510608512.0A CN201510608512A CN105237362A CN 105237362 A CN105237362 A CN 105237362A CN 201510608512 A CN201510608512 A CN 201510608512A CN 105237362 A CN105237362 A CN 105237362A
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ethyl acetate
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王爱玲
邢鹏飞
郑学仿
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Dalian University
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Dalian University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation

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Abstract

The invention relates to a method for catalytic preparation of triarylmethane compounds by using [EG]2[ZnCl2], especially to a method for catalytic preparation of the triarylmethane compounds by using a deep eutectic solvent [EG]2[ZnCl2] through Friedel-Crafts alkylation. Electron-rich aromatic hydrocarbons and diarylcarbinols are used as substrates, [EG]2[ZnCl2] is used as both the reaction solvent and catalyst, and Friedel-Crafts alkylation is carried out to prepare the triarylmethane compounds. According to the invention, [EG]2[ZnCl2] used in the method has high catalytic activity, high selectivity and high reaction yield, can effectively reduce the usage amounts of other organic solvents and toxic catalysts and alleviates corrosivity of the catalyst to equipment, and post-treatment is simple and convenient.

Description

Utilize [EG] 2[ZnCl 2] catalysis prepares triarylmethane compounds
Technical field
The present invention relates to a kind of method that triarylmethane compounds is prepared in catalysis, more particularly, relate to and a kind ofly utilize dark congruent melting solvent to generate method to triarylmethane compounds by the catalysis of Friedel-Crafts alkylated reaction.
Background technology
Triarylmethane compounds is medicine, the important intermediate of fuel and materials chemistry aspect.Such as, magenta is a kind of triarylmethane compounds, can be used to the materials such as staining for collagen fiber.Triarylmethane compounds cetirizine is the useful Claritin etc. of a class.In addition, some triarylmethane compounds also have certain biological activity, and antiviral, anti-tumor aspect has important application.
Because triarylmethane compounds serves many purposes, its synthetic method has a lot of report.Current primary synthetic methods has: Friedel-Crafts alkylated reaction, linked reaction, reduction reaction etc.Wherein, having higher atom utilization and only have water to be by product due to Friedel-Crafts alkylated reaction, is a kind of conventional method preparing triarylmethane compounds.The selection of current catalyzer is the key issue of restriction Friedel-Crafts alkylated reaction, and traditional catalyzer is generally protonic acid or Lewis acid, such as AlCl 3, AuCl 3, SnCl 4, TfOH, Yb (OTf) 3deng.But this kind of catalyzer has some inevitable shortcomings, e.g., cannot recycle, need to produce corrosive gases and a large amount of waste liquid in use volatile organic solvent, aftertreatment complexity, process, cause severe contamination etc. to environment.
The green clean medium of searching replaces traditional solvent and catalyzer to carry out organic synthesis and catalyzed reaction is more and more subject to people's attention.In recent years, a kind of novel green solvent--dark congruent melting solvent (DeepEutecticSolvents, DES), the concern receiving scientists is paid attention to.Dark congruent melting solvent is that its fusing point is lower than raw material fusing point by two or three material by intermolecular hydrogen bonding association melting and the solvent stability formed mutually.Compared with conventional organic solvents, have cheap, preparation simply, not volatile, nonflammable, easy storage, the plurality of advantages such as nontoxic.
In this patent, develop a kind of method using green solvent catalysis Friedel-Crafts alkylated reaction to prepare triarylmethane compounds.
Summary of the invention
The object of the invention is a kind of environmentally friendly reaction system newly of development for Friedel-Crafts alkylated reaction, this reaction system uses DES ([EG] 2[ZnCl 2]) as reaction medium, avoid and use easy volatile organic solvent, environmentally harmful traditional catalyst, has invented the preparation method of cheap, the eco-friendly triarylmethane compounds of a kind of safety.This system is applied widely, simple to operate, inexpensive safety, productive rate are higher, environmentally friendly.
The present invention with electron rich aromatic hydrocarbons and diarylcarbinols for substrate, DES ([EG] 2[ZnCl 2]) doublely do reaction solvent and catalyzer, prepare triarylmethane compounds by Friedel-Crafts alkylated reaction.Reaction expression is as follows:
I is electron rich arene compounds, and II is diarylcarbinols compounds, and III is triarylmethane compounds, and DES is [EG] 2[ZnCl 2].
Compared with traditional technology method, beneficial effect of the present invention is mainly reflected in:
(1) reaction conditions is gentle, easy to operate.The present invention is 60-and can carry out Friedel-Crafts alkylated reaction at 120 DEG C, for the good electron rich aromatic hydrocarbons of activity and diarylcarbinols compound, reaction 1h can obtain the triarylmethane class product of high yield.
(2) catalyzer makes simple, and safe ready, can reuse.Compared with traditional Lewis acid or bronsted acid catalyst, used catalyst cheaper starting materials of the present invention is easy to get, stable, nontoxic in water, environmentally friendly, 4 times can be reused when catalysis Friedel-Crafts alkylated reaction prepares triarylmethane compounds.
(3) whole process is environmentally friendly, pollution-free, and aftertreatment is simple.The method of triaryl methane compounds is prepared in traditional use Friedel-Crafts alkylation, need to add poisonous, easy volatile organic solvent in reaction process as reaction solvent, aftertreatment bothers and can produce a large amount of waste liquid, certain harm is caused to environment, the DES ([EG] used in scheme provided by the invention 2[ZnCl 2]) not only make reaction solvent but also make catalysts, avoid with an organic solvent, during post-reaction treatment, do not need to be acidified with acid, directly extract, dry, underpressure distillation, post is separated can obtain triarylmethane compounds, is a kind of synthetic method of environmental protection.
Embodiment
The present invention's following examples illustrate, but the present invention is not limited to following embodiment, and under the scope not departing from the described aim in front and back, change is included in technical scope of the present invention.
Embodiment 1
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2 successively, 4-trimethoxy-benzene and 368mg (2.0mmol) benzhydrol, magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction.Discovery does not have product to generate, and is not namely having to react under DES existence condition not carry out.
Reaction equation:
Embodiment 2
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2,4-trimethoxy-benzene and 368mg (2.0mmol) benzhydrol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 1h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 1h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 85%.
Reaction equation:
Embodiment 3
Experimental technique: by the water evaporate to dryness of aqueous phase in example 2, will reclaim after obtaining catalyzer vacuum-drying and uses.To reclaim [EG] that obtain 2[ZnCl 2] repeat the step of embodiment 2.Repetition like this 4 times, the productive rate of products therefrom is respectively 84%, 81%, 78%, 73%.
Reaction equation:
Embodiment 4
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2,4-trimethoxy-benzene and 368mg (2.0mmol) benzhydrol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 0.5h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 0.5h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 46%.
Reaction equation:
Embodiment 5
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2,4-trimethoxy-benzene and 368mg (2.0mmol) benzhydrol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 2h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 2h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 83%.
Reaction equation:
Embodiment 6
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2,4-trimethoxy-benzene and 368mg (2.0mmol) benzhydrol successively, then adds 1.56g (6.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 1h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 1 mole, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 1h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 85%.
Reaction equation:
Embodiment 7
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2,4-trimethoxy-benzene and 368mg (2.0mmol) benzhydrol successively, then adds 0.52g (2.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 1h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 1 mole, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 1h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 61%.
Reaction equation:
Embodiment 8
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2,4-trimethoxy-benzene and 368mg (2.0mmol) benzhydrol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 60 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 1h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 60 DEG C, and the reaction times is 1h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 44%.
Reaction equation:
Embodiment 9
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2,4-trimethoxy-benzene and 368mg (2.0mmol) benzhydrol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 80 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 1h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 80 DEG C, and the reaction times is 1h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 81%.
Reaction equation:
Embodiment 10
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2,4-trimethoxy-benzene and 368mg (2.0mmol) benzhydrol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 100 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 1h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 100 DEG C, and the reaction times is 1h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 85%.
Reaction equation:
Embodiment 11
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2,4-trimethoxy-benzene and 368mg (2.0mmol) benzhydrol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 120 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 1h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 120 DEG C, and the reaction times is 1h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 82%.
Reaction equation:
Embodiment 12
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2,4-trimethoxy-benzene and 548mg (2.0mmol) 2,3,5-trimethoxy benzhydrol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 1.5h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 1.5h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 81%.
Reaction equation:
Embodiment 13
Experimental technique: get 25mL round-bottomed flask, add 336mg (2.0mmol) 1 successively, 2,4-trimethoxy-benzene and 608mg (2.0mmol) 4-p-methoxy-phenyl-(2,3,5-trimethoxyphenyl) methyl alcohol, then add 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 1.5h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 1.5h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 83%.
Reaction equation:
Embodiment 14
Experimental technique: get 25mL round-bottomed flask, adds 276mg (2.0mmol) meta-methoxy benzene and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 1.5h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 1.5h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 78%.
Reaction equation:
Embodiment 15
Experimental technique: get 25mL round-bottomed flask, adds 248mg (2.0mmol) 2-methoxyphenol and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 3h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 3h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 73%.
Reaction equation:
Embodiment 16
Experimental technique: get 25mL round-bottomed flask, adds the bromo-3-anisole of 374mg (2.0mmol) 1-and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 2h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 2h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 69%.
Reaction equation:
Embodiment 17
Experimental technique: get 25mL round-bottomed flask, adds 216mg (2.0mmol) methyl-phenoxide and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 3h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 3h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain colorless oil, productive rate 71%.
Reaction equation:
Embodiment 18
Experimental technique: get 25mL round-bottomed flask, adds 276mg (2.0mmol) O-methoxy benzene and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 2h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 2h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 77%.
Reaction equation:
Embodiment 19
Experimental technique: get 25mL round-bottomed flask, adds 340mg (2.0mmol) phenyl ether and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.04g (4.0mmol) [EG] 2[ZnCl 2], magnetic agitation, stirs at oil bath control temperature 90 DEG C, by the progress of tlc monitoring reaction, and stopped reaction after reaction 3h.Be standard based on 1 mole of electron rich arene compounds, DES ([EG] 2[ZnCl 2]) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 90 DEG C, and the reaction times is 3h.
Aftertreatment, adds 10mL distilled water after being cooled to room temperature and 10mL ethyl acetate extracts, [EG] 2[ZnCl 2] be soluble in the aqueous phase, product is dissolved in ethyl acetate layer, separatory, ethyl acetate layer with saturated common salt water washing once, anhydrous magnesium sulfate drying, underpressure distillation removing ethyl acetate, carry out column separating purification afterwards, obtain white solid, productive rate 61%.
Reaction equation:

Claims (6)

1. the synthetic method of a triarylmethane compounds, use electron rich aromatic hydrocarbons and diarylcarbinols as reactant, by Friedel-Crafts alkylated reaction synthesis triarylmethane compounds, it is characterized in that, in reaction process, use DES ([EG] 2[ZnCl 2]) as catalyzer.
2. in method according to claim 1, it is characterized in that, described electron rich aromatic hydrocarbons comprises: 1,2,4-trimethoxy-benzene, meta-methoxy benzene, O-methoxy benzene, 2-hydroxyanisol, 3-bromoanisole, methyl-phenoxide, phenyl ether, described diarylcarbinols comprises: diphenyl-carbinol, 2,3,5-trimethoxy benzhydrol, 4-p-methoxy-phenyl-(2,3,5-trimethoxyphenyl) methyl alcohol, described DES ([EG] 2[ZnCl 2]) be ethylene glycol (EG): zinc chloride (ZnCl 2) mol ratio equals the dark congruent melting solvent of 2:1.
3. in method according to claim 1, it is characterized in that, is standard based on 1 mole of electron rich arene compounds, described DES ([EG] 2[ZnCl 2]) consumption is 1.0-3.0 moles, be more preferably 2.0 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 60-120 DEG C, is more preferably 90 DEG C, and the reaction times is 0.5-3h.
4. in method according to claim 1, it is characterized in that, described DES ([EG] 2[ZnCl 2]) not only make reaction solvent but also make catalysts.
5. in method according to claim 1, it is characterized in that, described DES ([EG] 2[ZnCl 2]) 4 times can be reused.
6. in method according to claim 1, it is characterized in that, described post-reaction treatment is simple, directly extracts, dry, underpressure distillation, and post is separated can obtain triarylmethane compounds.
CN201510608512.0A 2015-09-14 2015-09-14 Method for catalytic preparation of triarylmethane compounds by using [EG]2[ZnCl2] Pending CN105237362A (en)

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Citations (2)

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CN102643176A (en) * 2012-04-01 2012-08-22 南京哈柏医药科技有限公司 Synthesis method of 4-methoxytriphenylchloromethane
CN104045541A (en) * 2014-06-18 2014-09-17 大连大学 Method for synthesizing aromatic ketone compound

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102643176A (en) * 2012-04-01 2012-08-22 南京哈柏医药科技有限公司 Synthesis method of 4-methoxytriphenylchloromethane
CN104045541A (en) * 2014-06-18 2014-09-17 大连大学 Method for synthesizing aromatic ketone compound

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