CN105061164A - Method for preparing triarylmethane compounds by utilizing catalysis of [ChCl][ZnCl2]2 - Google Patents
Method for preparing triarylmethane compounds by utilizing catalysis of [ChCl][ZnCl2]2 Download PDFInfo
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- CN105061164A CN105061164A CN201510582722.7A CN201510582722A CN105061164A CN 105061164 A CN105061164 A CN 105061164A CN 201510582722 A CN201510582722 A CN 201510582722A CN 105061164 A CN105061164 A CN 105061164A
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- WBTOQBDUHJIBFS-UHFFFAOYSA-N COc(cc1OC)c(C(c2ccccc2)c2ccccc2)cc1OC Chemical compound COc(cc1OC)c(C(c2ccccc2)c2ccccc2)cc1OC WBTOQBDUHJIBFS-UHFFFAOYSA-N 0.000 description 1
- AGIQIOSHSMJYJP-UHFFFAOYSA-N COc(cc1OC)ccc1OC Chemical compound COc(cc1OC)ccc1OC AGIQIOSHSMJYJP-UHFFFAOYSA-N 0.000 description 1
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
Abstract
The invention relates to a method for preparing triarylmethane compounds by utilizing the catalysis of [ChCl][ZnCl2]2, in particular to the method for generating the triarylmethane compounds by utilizing the catalysis of a deep eutectic solvent ([ChCl][ZnCl2]2) through a Friedel-Crafts alkylation reaction. The method is characterized in that by taking electron-rich arenes and diaryl methanols as substrates, and taking the [ChCl][ZnCl2]2 as a reaction solvent and a catalyst, the triarylmethane compounds are prepared by the Friedel-Crafts alkylation reaction. The [ChCl][ZnCl2]2 used by the method disclosed by the invention has the advantages of high catalytic activity, high selectivity and high reaction yield; the use of other solvents and toxic catalysts can be effectively reduced, and the corrosion of the catalyst on equipment is reduced; the simplicity and the convenience in posttreatment are realized.
Description
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 ([ChCl] [ZnCl
2]
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 synthetic method of a kind of triarylmethane compounds of the present invention, 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 ([ChCl] [ZnCl
2]
2) as catalyzer.
According in above-described method, preferably, described electron rich aromatic hydrocarbons comprises: 1,2,4-trimethoxy-benzene, meta-methoxy benzene, O-methoxy benzene, to anisole, 2-hydroxyanisol, 3-bromoanisole, methyl-phenoxide, 4-bromophenol, phenol, phenyl ether, described diarylcarbinols comprises: diphenyl-carbinol, 2,3,5-trimethoxy benzhydrol, 4-p-methoxy-phenyl-(2,3,5-trimethoxyphenyl) methyl alcohol, described DES ([ChCl] [ZnCl
2]
2) be choline chloride 60 (ChCl): zinc chloride (ZnCl
2) mol ratio equals the dark congruent melting solvent of 1:2.
According in above-described method, preferably, be standard based on 1 mole of electron rich arene compounds, described DES ([ChCl] [ZnCl
2]
2) consumption is 0.5-2.5 moles, be more preferably 2.0 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 40-120 DEG C, is more preferably 80 DEG C, and the reaction times is 0.5-3h.
According in above-described method, preferably, described DES ([ChCl] [ZnCl
2]
2) not only make reaction solvent but also make catalysts.
According in above-described method, preferably, described DES ([ChCl] [ZnCl
2]
2) 4 times can be reused.
According in above-described method, preferably, described post-reaction treatment is simple, directly extracts, dry, underpressure distillation, and post is separated can obtain triarylmethane compounds.
The present invention with electron rich aromatic hydrocarbons and diarylcarbinols for substrate, DES ([ChCl] [ZnCl
2]
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 [ChCl] [ZnCl
2]
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 40-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 in water, biodegradable, nontoxic, 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 in reaction process, easy volatile organic solvent is as reaction solvent, aftertreatment bothers and can produce a large amount of waste liquid, certain harm is caused to environment, the DES used in scheme provided by the invention not only makes reaction solvent but also make catalysts, avoid with an organic solvent, during post-reaction treatment, do not need to be acidified with acid, direct extraction, dry, underpressure distillation, post is separated can obtain triarylmethane compounds, it 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 80 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 1.65g (4.0mmol) [ChCl] [ZnCl
2]
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 ([ChCl] [ZnCl
2]
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 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 95%.
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.[the ChCl] [ZnCl obtained will be reclaimed
2]
2repeat the step of embodiment 2.Repetition like this 4 times, finds [ChCl] [ZnCl
2]
2catalytic effect substantially remain unchanged.The productive rate of products therefrom is respectively 93%, 92%, 90%, 88%.
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 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 80 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 ([ChCl] [ZnCl
2]
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 0.5h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 55%.
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 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 80 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 ([ChCl] [ZnCl
2]
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 2h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 91%.
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 0.83g (2.0mmol) [ChCl] [ZnCl
2]
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 ([ChCl] [ZnCl
2]
2) consumption is 1 mole, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 80 DEG C, and the reaction times is 1h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 76%.
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 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 40 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 ([ChCl] [ZnCl
2]
2) consumption is 2 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 40 DEG C, and the reaction times is 1h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 42%.
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 1.65g (4.0mmol) [ChCl] [ZnCl
2]
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 ([ChCl] [ZnCl
2]
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 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 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 1.65g (4.0mmol) [ChCl] [ZnCl
2]
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 ([ChCl] [ZnCl
2]
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 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 94%.
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 1.65g (4.0mmol) [ChCl] [ZnCl
2]
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 ([ChCl] [ZnCl
2]
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 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 92%.
Reaction equation:
Embodiment 11
Experimental technique: get 25mL round-bottomed flask, adds 336mg (2.0mmol) 1,2 successively, 4-trimethoxy-benzene and 548mg (2.0mmol) 2,3,5-trimethoxy benzhydrol, then add 1.65g (4.0mmol) [ChCl] [ZnCl
2]
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 ([ChCl] [ZnCl
2]
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 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 93%.
Reaction equation:
Embodiment 12
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 1.65g (4.0mmol) [ChCl] [ZnCl
2]
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 ([ChCl] [ZnCl
2]
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 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 92%.
Reaction equation:
Embodiment 13
Experimental technique: get 25mL round-bottomed flask, adds 276mg (2.0mmol) meta-methoxy benzene and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 80 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 ([ChCl] [ZnCl
2]
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 1.5h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 94%.
Reaction equation:
Embodiment 14
Experimental technique: get 25mL round-bottomed flask, adds 248mg (2.0mmol) 2-methoxyphenol and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 80 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 ([ChCl] [ZnCl
2]
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 2h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 90%.
Reaction equation:
Embodiment 15
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 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 80 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 ([ChCl] [ZnCl
2]
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 1.5h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 86%.
Reaction equation:
Embodiment 16
Experimental technique: get 25mL round-bottomed flask, adds 216mg (2.0mmol) methyl-phenoxide and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 80 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 ([ChCl] [ZnCl
2]
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 2h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 86%.
Reaction equation:
Embodiment 17
Experimental technique: get 25mL round-bottomed flask, adds 276mg (2.0mmol) O-methoxy benzene and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 80 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 ([ChCl] [ZnCl
2]
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 1.5h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 91%.
Reaction equation:
Embodiment 18
Experimental technique: get 25mL round-bottomed flask, adds 276mg (2.0mmol) successively to anisole and 368mg (2.0mmol) diphenyl-carbinol, then adds 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 80 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 ([ChCl] [ZnCl
2]
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 1.5h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 90%.
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 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 80 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 ([ChCl] [ZnCl
2]
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 3h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 74%.
Reaction equation:
Embodiment 20
Experimental technique: get 25mL round-bottomed flask, adds 346mg (2.0mmol) 4-bromophenol and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 80 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 ([ChCl] [ZnCl
2]
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 3h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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 21
Experimental technique: get 25mL round-bottomed flask, adds 188mg (2.0mmol) phenol and 368mg (2.0mmol) diphenyl-carbinol successively, then adds 1.65g (4.0mmol) [ChCl] [ZnCl
2]
2, magnetic agitation, stirs at oil bath control temperature 80 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 ([ChCl] [ZnCl
2]
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 2h.
Aftertreatment, adds 5mL distilled water after being cooled to room temperature and 5mL ethyl acetate extracts, [ChCl] [ZnCl
2]
2be 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:
。
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 ([ChCl] [ZnCl
2]
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, to anisole, 2-hydroxyanisol, 3-bromoanisole, methyl-phenoxide, 4-bromophenol, phenol, phenyl ether, described diarylcarbinols comprises: diphenyl-carbinol, 2,3,5-trimethoxy benzhydrol, 4-p-methoxy-phenyl-(2,3,5-trimethoxyphenyl) methyl alcohol, described DES ([ChCl] [ZnCl
2]
2) be choline chloride 60 (ChCl): zinc chloride (ZnCl
2) mol ratio equals the dark congruent melting solvent of 1:2.
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 ([ChCl] [ZnCl
2]
2) consumption is 0.5-2.5 moles, be more preferably 2.0 moles, the amount of described diarylcarbinols is 1 mole, and temperature of reaction is 40-120 DEG C, is more preferably 80 DEG C, and the reaction times is 0.5-3h.
4. in method according to claim 1, it is characterized in that, described DES ([ChCl] [ZnCl
2]
2) not only make reaction solvent but also make catalysts.
5. in method according to claim 1, it is characterized in that, described DES ([ChCl] [ZnCl
2]
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.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109894152A (en) * | 2019-03-20 | 2019-06-18 | 曲阜师范大学 | It is a kind of for the method for preparing catalyst and its gained catalyst of synthesizing tetrahydrofuran and application |
| CN113976177A (en) * | 2021-11-26 | 2022-01-28 | 华东理工大学 | Eutectic solvent and preparation method and application thereof |
| CN115466165A (en) * | 2022-08-16 | 2022-12-13 | 江苏极易新材料有限公司 | Synthetic method of 4,4' -biphenol |
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2015
- 2015-09-14 CN CN201510582722.7A patent/CN105061164A/en active Pending
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| Title |
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| AILING WANG ET AL.: "Deep eutectic solvent catalyzed Friedel-Crafts alkylation of electron-rich arenes with aldehydes", 《RSC ADV.》 * |
| 王爱玲等: "深共融溶剂在有机合成中的应用", 《化学进展》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109894152A (en) * | 2019-03-20 | 2019-06-18 | 曲阜师范大学 | It is a kind of for the method for preparing catalyst and its gained catalyst of synthesizing tetrahydrofuran and application |
| CN109894152B (en) * | 2019-03-20 | 2021-11-05 | 曲阜师范大学 | Preparation method of catalyst for synthesizing tetrahydrofuran, catalyst obtained by preparation method and application of catalyst |
| CN113976177A (en) * | 2021-11-26 | 2022-01-28 | 华东理工大学 | Eutectic solvent and preparation method and application thereof |
| CN113976177B (en) * | 2021-11-26 | 2023-07-04 | 华东理工大学 | Eutectic solvent and preparation method and application thereof |
| CN115466165A (en) * | 2022-08-16 | 2022-12-13 | 江苏极易新材料有限公司 | Synthetic method of 4,4' -biphenol |
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