CN101519339A - Method for preparing 1,2-diphenylethane by coupling reaction of benzyl chloride and reduced iron powder with copper chloride as latent catalyst - Google Patents
Method for preparing 1,2-diphenylethane by coupling reaction of benzyl chloride and reduced iron powder with copper chloride as latent catalyst Download PDFInfo
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- CN101519339A CN101519339A CN200910130426A CN200910130426A CN101519339A CN 101519339 A CN101519339 A CN 101519339A CN 200910130426 A CN200910130426 A CN 200910130426A CN 200910130426 A CN200910130426 A CN 200910130426A CN 101519339 A CN101519339 A CN 101519339A
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- diphenylethane
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Abstract
The invention provides a method for preparing 1,2-diphenylethane by a coupling reaction of benzyl chloride and reduced iron powder with copper chloride as a latent catalyst. The invention is characterized in that a copper chloride hydrochloric acid solution is fully mixed with a reduced iron powder aqueous sizing agent at a room temperature to prepare the reduced iron powder aqueous sizing agent containing the mixed catalyst of copper and cuprous chloride; and then, the benzyl chloride and the reduced iron powder finish the coupling reaction under the action of the mixed catalyst of the copper and the cuprous chloride to prepare the 1,2-diphenylethane. The method has simple, convenient and high-efficiency operation and uses little catalyst, therefore the 1,2-diphenylethane product has low raw material cost.
Description
Technical field
The present invention relates to a kind of 1, the preparation method of 2-diphenylethane, particularly cupric chloride is as potential catalyst, the linked reaction of catalytic chlorination benzyl and reduced iron powder preparation 1, the method for 2-diphenylethane belongs to the chemosynthesis production technical field.
Technical background
1, it is a kind of broad-spectrum Chemicals that the 2-diphenylethane is called bibenzyl again, through the acid catalyzed bromination reaction of Lewis, can prepare the TDE fire retardant.Can prepare 2-phenyl methyl phenyl ketone through optical chlorinating reaction and hydrolysis reaction; can prepare 1 through catalytic dehydrogenating reaction; the 2-toluylene; can also adopt preparation such as nitration reaction, sulfonation reaction or acylation reaction various 1; the 2-diphenyl ethane derivative is used for responsive to visible light material, white dyes, luminescent material, high-performance polymer etc.
1, the 2-diphenylethane has two kinds of industrial processes:
1. aluminum trichloride (anhydrous) class Lewis acid is as catalyzer, and with 1, the Friedel-Crafts of 2-ethylene dichloride reaction obtains 1 in excessive benzene, the mixture of 2-diphenylethane and multi-ethyl phenenyl, high temperature rectifying separation preparation 1,2-diphenylethane.The shortcoming of this method is 1, and 2-diphenylethane product purity is low, and product yield is low.Benzene and 1, there is phenomenon inductive phase in the Friedel-Crafts reaction of 2-ethylene dichloride, and operation is out of control easily, causes material spray.
2. the linked reaction of reduced iron powder and Benzyl Chloride.In water medium, copper and cuprous chloride are as mixed catalyst, and the linked reaction of reduced iron powder and Benzyl Chloride obtains 1,2-diphenylethane product.Copper and cuprous chloride must could use after pulverizing in industrial production.Mostly between 0.1～1 millimeter, specific surface area is little for the commodity copper powder size, and catalytic activity is low.Yet the too small copper powder of particle diameter is in storage, transportation and use, and oxidation by air easily forms ventilation breather.Cuprous chloride also is oxidized to basic copper chloride easily and loses catalytic activity in air.
At above problem, the present invention proposes a kind of cupric chloride as potential catalyst, and Benzyl Chloride and reduced iron powder are feedstock production 1, the novel method of 2-diphenylethane.
Summary of the invention
The active ability of chemistry that one of skill in the art knows copper does not have iron strong, so the required catalyst copper powder of the linked reaction of reduced iron powder and Benzyl Chloride can adopt the replacement(metathesis)reaction method of cupric chloride and iron powder and make.And if with in the copper chloride solution impouring reduced iron powder water slurry, the copper that replacement(metathesis)reaction produces will be deposited on the iron powder surface with atomic state, can significantly improve the specific surface area of copper powder catalyst, reduce same catalyst levels relatively.Therefore, it is considered herein that cupric chloride can be used as the potential catalyst of the linked reaction of reduced iron powder and Benzyl Chloride.
One of skill in the art knows reduced iron powder after storing for some time, and the reduced iron powder surface will produce basic carbonate iron or ferric oxide film, and this will influence the linked reaction process of reduced iron powder and Benzyl Chloride.For this reason, the pickling of reduced iron powder is ten necessity.Use cupric chloride and hydrochloric acid mixed solution washing reduced iron powder, produces two kinds of effects: 1. salt acid elution reduced iron powder surface, desalination derusts, realization reduced iron powder cleaning surfacesization; 2. hydrochloric acid and iron produce the reaction that replacement(metathesis)reaction is produced hydrogen, and newborn hydrogen can reduce cupric chloride and generate the cuprous chloride deposition, thereby makes the needed catalyzer cuprous chloride of linked reaction of reduced iron powder and Benzyl Chloride.Therefore, it is considered herein that cupric chloride can be used as the potential catalyst of the linked reaction of reduced iron powder and Benzyl Chloride.
Cupric chloride provided by the invention is as the linked reaction potential catalyst preparation 1 of reduced iron powder and Benzyl Chloride, and the concrete steps of 2-diphenylethane are as follows:
The 1. cleaning of reduced iron powder and the preparation of copper and cuprous chloride mixed catalyst of step
Under the room temperature, be that 0.05～5% hydrochloric acid soln and mass percent are 30～50% copper chloride solution thorough mixing with mass percent, preparation cupric chloride hydrochloric acid soln.In the slow impouring reduced iron powder of the cupric chloride hydrochloric acid soln water slurry that preparation is obtained, fully mix, can finish the preparation process of reduced iron powder surface cleaning and copper and cuprous chloride mixed catalyst, obtain containing the reduced iron powder water slurry of copper and cuprous chloride mixed catalyst.
The mass ratio of hydrochloric acid soln of the present invention and copper chloride solution is 5～1:1.
Reduced iron powder water slurry of the present invention is that to sneak into 20～100 gram particles by 100 grams in the water directly be that 0.1～0.5 millimeter reduced iron powder is made.
The mass ratio of copper chloride solution of the present invention and reduced iron powder water slurry is 1: 15～50.
Step is linked reaction and 1 2., the preparation of 2-diphenylethane
In the reduced iron powder water slurry that contains copper and cuprous chloride mixed catalyst, behind the input Benzyl Chloride, 80～85 ℃ of heat temperature raisings, stirring reaction 2～10 hours can be finished the catalytic Benzyl Chloride linked reaction of copper and cuprous chloride, makes linked reaction product system.
Benzyl Chloride of the present invention is 1:0.5～5 with the mass ratio that contains the reduced iron powder water slurry of copper and cuprous chloride mixed catalyst.
Step 3. 1, the separation of 2-diphenylethane is with refining
80～85 ℃ of insulations of linked reaction product system that 2. step makes were left standstill 0.5～2 hour, and what tell lower floor is the reduced iron powder water slurry that contains catalyzer, recycles; What tell the middle level is the light green ferrous chloride aqueous solution, is used for the preparation of iron protochloride; Tell upper strata 1, the 2-diphenylethane melts the liquid crude product.Use relatively 1, the 2-diphenylethane melts 80～85 ℃ of hot water of 1～5 times of liquid quality to 1, and the 2-diphenylethane melts liquid washing 1～3 time, use relative 1, the mass percent that the 2-diphenylethane melts 1～5 times of liquid quality be 75～95% ethanol to 1,2-diphenylethane recrystallization 1～3 time filters 1, the crystallization of 2-diphenylethane, deliver to vacuum drying oven, under 0.085～0.09Mpa pressure, 30～35 ℃ of dryings 3～10 hours, make 1,2-diphenylethane product.
Cupric chloride provided by the invention prepares 1 as the linked reaction that potential catalyst is used for Benzyl Chloride and reduced iron powder, and the distinguishing feature of 2-diphenylethane is:
1. directly commodity in use copper and cuprous chloride as catalyzer, avoided the secondary grinding and processing process of the commercial copper of purchasing and cuprous chloride.
2. the cupric chloride hydrochloric acid soln is sneaked in the reduced iron powder water slurry, the disposable multinomial processes such as preparation of finishing reduced iron powder surface cleaning, copper atom attitude deposition and cuprous chloride.The iron protochloride that this process produces together enters in the Benzyl Chloride linked reaction system, does not influence the Benzyl Chloride coupling reaction process, and the iron protochloride that produces with reduced iron powder and Benzyl Chloride linked reaction enters the iron protochloride removal process.
3. cupric chloride provided by the invention prepares 1 as potential catalyst, the method for 2-diphenylethane, and the mass ratio that it is characterized in that reduced iron powder and Benzyl Chloride is 0.3～1.5:1.The atomic state copper catalyst that the purpose of excessive use reduced iron powder is to finish after the linked reaction still is deposited on the excessive reduced iron powder surface, is convenient to Separation and Recovery and uses.
4. method of the present invention is easy and simple to handle efficient, and the no three wastes produce, and catalyst levels is few, and 1,2-diphenylethane products material cost is low.
Following embodiment further specifies cupric chloride provided by the invention and prepares 1, the method for 2-diphenylethane as the linked reaction that potential catalyst is used for Benzyl Chloride and reduced iron powder.
Embodiment 1
In 1000 milliliters of reactors, add entry 400 gram, reduced iron powder 180 grams, open and stir, slowly flow into the mass percents that contain 10 gram cupric chlorides under the room temperature and be 0.1% hydrochloric acid soln 100 grams, after 10 minutes, add Benzyl Chloride 500 grams again.Heat temperature raising is kept 80～85 ℃ of material in reactor temperature, stirring reaction 3 hours.Insulation was left standstill 30 minutes, isolate respectively have neither part nor lot in reaction contain catalyzer iron powder, absinthe-green ferrous chloride aqueous solution, and 1,2-diphenylethane crude product.After this, add clear water 280 grams in 1,2～diphenylethane crude product, kept 60～85 ℃ of agitator treatings of material in reactor temperature 10 minutes, insulation was left standstill 1 hour, told washing water, water washing 1, and 2-diphenylethane crude product repeats 1～2 time.1, be 95% ethanol 200 gram with mass percent behind the 2-diphenylethane crude product, keep 60～85 ℃ of agitator treatings of material in reactor temperature after 10 minutes, lower the temperature naturally, 1,2-diphenylethane needle crystal is separated out.Filter, filter cake is delivered to vacuum drying oven, and 30～35 ℃ of dryings are 3 hours under 0.085～0.09Mpa pressure, make white needles 1,2-diphenylethane product 334.6 grams, yield 93.0%, 51.3 ℃ of fusing points.
Embodiment 2
In 1000 milliliters of reactors, add entry 400 grams, reduced iron powder 180 grams, open and stir, the impouring mass percent is 0.1% hydrochloric acid soln 70 grams under the room temperature, then add mass percent slowly and be 38% copper chloride solution 30 grams, stirs after 10 minutes, add Benzyl Chloride 500 again and restrain.Heat temperature raising is kept 80～85 ℃ of material in reactor temperature, stirring reaction 3 hours.Remaining last handling process makes white needles 1 with reference to embodiment 1,2-diphenylethane product 329.2 grams, yield 91.5%, 51.1 ℃ of fusing points.
Embodiment 3
In 1000 milliliters of reactors, add entry 400 gram, reduced iron powder 180 grams, open and stir, two-way adding mass percent is that 0.1% hydrochloric acid soln 70 grams and mass percent are that 38% copper chloride solution 30 restrains under the room temperature, stir after 10 minutes, add Benzyl Chloride 500 grams again.Heat temperature raising is kept 80～85 ℃ of material in reactor temperature, stirring reaction 3 hours.Remaining last handling process makes white needles 1 with reference to embodiment 1,2-diphenylethane product 334.9 grams, yield 93.1%, 51.5 ℃ of fusing points.
Claims (6)
1. potential catalyst catalytic chlorination benzyl linked reaction preparation 1, the method of 2-diphenylethane, it is characterized in that: under the room temperature, mass percent is that 0.05～5% hydrochloric acid soln and mass percent are 30～50% copper chloride solution and reduced iron powder water slurry thorough mixing, makes the reduced iron powder water slurry that contains copper and cuprous chloride mixed catalyst; Thereafter, under the effect of copper and cuprous chloride mixed catalyst, 80～85 ℃ of temperature controls, Benzyl Chloride and reduced iron powder water slurry are finished linked reaction; Insulation was left standstill 0.5～2 hour, isolate respectively have neither part nor lot in linked reaction contain catalyst reduction iron powder water slurry, absinthe-green ferrous chloride aqueous solution, and 1,2-diphenylethane crude product; After this, 1,2-diphenylethane crude product is used aqueous ethanolic solution recrystallization 1～3 time with 80～85 ℃ of hot washes 1～3 time, filter 1, vacuum drying oven is delivered in the crystallization of 2-diphenylethane, under 0.085～0.09Mpa pressure, 30～35 ℃ of dryings 3～10 hours make 1,2-diphenylethane product.
2. according to the described potential catalyst catalytic chlorination of claim 1 benzyl linked reaction preparation 1, the method of 2-diphenylethane is characterized in that described reduced iron powder water slurry is that to sneak into 20～100 gram particles in the water directly be that 0.1～0.5 millimeter reduced iron powder is made to 100 grams.
3. according to the described potential catalyst catalytic chlorination of claim 1 benzyl linked reaction preparation 1, the method of 2-diphenylethane, the mass ratio that it is characterized in that described hydrochloric acid soln, copper chloride solution, reduced iron powder water slurry, Benzyl Chloride is 5～1:1:15～50:5～50.
4. according to the described potential catalyst catalytic chlorination of claim 1 benzyl linked reaction preparation 1, the method for 2-diphenylethane is characterized in that described washing water quality is 1,1～5 times of 2-diphenylethane crude product quality.
5. according to the described potential catalyst catalytic chlorination of claim 1 benzyl linked reaction preparation 1, the method for 2-diphenylethane is characterized in that described aqueous ethanolic solution is meant that mass percent is 75～95% aqueous ethanolic solution.
6. according to the described potential catalyst catalytic chlorination of claim 1 benzyl linked reaction preparation 1, the method for 2-diphenylethane is characterized in that described aqueous ethanolic solution quality is 1,1～5 times of 2-diphenylethane crude product quality.
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| CN2009101304268A CN101519339B (en) | 2009-04-05 | 2009-04-05 | Method for preparing 1,2-diphenylethane by coupling reaction of benzyl chloride and reduced iron powder with copper chloride as latent catalyst |
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| CN2009101304268A CN101519339B (en) | 2009-04-05 | 2009-04-05 | Method for preparing 1,2-diphenylethane by coupling reaction of benzyl chloride and reduced iron powder with copper chloride as latent catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432424A (en) * | 2011-09-30 | 2012-05-02 | 山东天一化学股份有限公司 | Method for producing diphenylethane and ferric chloride solution by using benzyl chloride |
| CN110483224A (en) * | 2019-08-01 | 2019-11-22 | 顾小星 | The synthetic method of 1,2- bis- (4- ethenylphenyl) ethane |
| CN117447288A (en) * | 2023-12-20 | 2024-01-26 | 寿光卫东腾冠化工有限公司 | High-yield preparation method of 1, 2-diphenylethane |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4929785A (en) * | 1989-03-20 | 1990-05-29 | Ethyl Corporation | Process for preparing diphenylalkane |
| CN101318873B (en) * | 2008-07-15 | 2011-07-20 | 寿光市鲁源盐化有限公司 | Process for preparing 1,2-diphenyl ethane |
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2009
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432424A (en) * | 2011-09-30 | 2012-05-02 | 山东天一化学股份有限公司 | Method for producing diphenylethane and ferric chloride solution by using benzyl chloride |
| CN110483224A (en) * | 2019-08-01 | 2019-11-22 | 顾小星 | The synthetic method of 1,2- bis- (4- ethenylphenyl) ethane |
| CN117447288A (en) * | 2023-12-20 | 2024-01-26 | 寿光卫东腾冠化工有限公司 | High-yield preparation method of 1, 2-diphenylethane |
| CN117447288B (en) * | 2023-12-20 | 2024-04-12 | 寿光卫东腾冠化工有限公司 | High-yield preparation method of 1, 2-diphenylethane |
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