CN102718624B - Method for synthesizing triphenylchloromethane - Google Patents
Method for synthesizing triphenylchloromethane Download PDFInfo
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- CN102718624B CN102718624B CN201210211516.1A CN201210211516A CN102718624B CN 102718624 B CN102718624 B CN 102718624B CN 201210211516 A CN201210211516 A CN 201210211516A CN 102718624 B CN102718624 B CN 102718624B
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Abstract
The invention discloses a method for synthesizing triphenylchloromethane. The method comprises the following steps of: (1) mixing aluminum powder and pure benzene, and introducing hydrogen chloride gas to act on the aluminum powder till the hydrogen chloride is not absorbed any more, and thus obtaining benzene suspension of aluminum trichloride; (2) slowly adding carbon tetrachloride into the benzene suspension of the aluminum trichloride, stirring till hydrogen chloride gas is not released any more, and thus obtaining a reaction solution of an aluminum trichloride complex containing the triphenylchloromethane, wherein the hydrogen chloride gas released in the reaction process is recycled; and (3) performing post treatment on the reaction solution obtained in the (2), and thus obtaining the triphenylchloromethane. According to the method, the aluminum powder is used as an initial raw material, and only a small amount of anhydrous aluminum trichloride is required for supplementing the loss of the hydrogen chloride in the production process, so that the whole production process can be continuously implemented, equivalently most of the aluminum trichloride required to be consumed in the conventional production method is replaced by the same mole of aluminum powder, and the atom economy of the whole synthetic route is improved.
Description
(1) technical field
The present invention relates to a kind of synthetic method of triphenylmethyl chloride.
(2) background technology
Triphenylmethyl chloride is an important Organic Chemicals, and its main application is for forming trityl ether with primary hydroxyl, realizing the selective protection of primary hydroxyl.
About the prior synthesizing method of triphenylmethyl chloride, reference Organic Syntheses, Coll.Vol.3, p.841 (1955) provide a kind of comparatively practical triphenylmethyl chloride preparation method, taking aluminum trichloride (anhydrous) as catalyzer, taking tetracol phenixin, purified petroleum benzin as raw material, there is Friedel-Crafts reaction in the method, the complex compound that produces triphenylmethyl chloride and aluminum chloride, aftertreatment obtains triphenylmethyl chloride.The method is a kind of conventional at present method.
Due to aluminum chloride in reaction process and triphenylmethyl chloride formation 1:1 complex compound, aluminum chloride is because of complexing inactivation simultaneously, therefore the method needs to consume the aluminum chloride of at least 1 equivalent in theory, produces per kilogram the finished product and need to consume 0.48 kilogram of aluminum trichloride (anhydrous).
(3) summary of the invention
The object of the invention is to provide a kind of improved triphenylmethyl chloride synthetic method, utilize tetracol phenixin in its production process to react with aluminium powder with the by-product hydrogen chloride that purified petroleum benzin generation Friedel-Crafts reaction produces, prepare aluminum trichloride (anhydrous), gained aluminum trichloride (anhydrous) is again for the Friedel-Crafts reaction of catalysis tetracol phenixin and purified petroleum benzin.
Concrete technical scheme of the present invention is:
A synthetic method for triphenylmethyl chloride, described method comprises the steps:
(1), aluminium powder is mixed with purified petroleum benzin, pass into hydrogen chloride gas and react with aluminium powder to absorbing hydrogen chloride (after passing into hydrogen chloride gas, pressure is not declining) no longer, obtain the benzene suspension of aluminum chloride;
(2), slowly add tetracol phenixin in the benzene suspension of the aluminum chloride that obtains to step (1), be stirred to and no longer emit hydrogen chloride gas, obtain the reaction solution containing the aluminum chloride complex compound of triphenylmethyl chloride; Recovery of the hydrogen chloride gas of emitting in reaction process, the raw material of step (1) when passing into gas reservoir and preparing as next batch;
(3), reaction solution step (2) Suo Shu is carried out to aftertreatment, obtain triphenylmethyl chloride.
Further, the weight ratio that feeds intake of aluminium powder and purified petroleum benzin described in step (1) is 1:13 ~ 18.
Further, step (1) can also be added alternatively aluminum trichloride (anhydrous) and mixes with aluminium powder and purified petroleum benzin, and adding of described aluminum trichloride (anhydrous) can be added alternatively.
Further, the weight ratio of adding aluminum trichloride (anhydrous) and aluminium powder in step (1) is 0 ~ 2:1, and the implication of 0:1 is all to use aluminium powder here.
Further, step (1) is no more than extremely no longer absorbing hydrogen chloride gas (after passing into hydrogen chloride gas, pressure remains unchanged) of reaction under 0.5MPa condition at pressure, obtains the benzene suspension of aluminum chloride.
Further, in step (2), in the add-on of tetracol phenixin and step (1), aluminium powder is 0.98 ~ 1.1 with the total molar ratio of aluminum chloride (being the theoretical molar amount of the aluminum chloride in aluminum chloride suspension) of adding, preferably 1.0 ~ 1.1:1.
Further, described in step (2), under the temperature condition of 20 ~ 60 DEG C, add tetracol phenixin.
Further, in step (3), the typical post-treating method of reaction solution is: step (2) gained reaction solution is cooled to 30 DEG C, add purified petroleum benzin dilute reaction solution, then suction 2N hydrochloric acid, insulated and stirred 30min, stratification, removes lower aqueous layer, adds sulfur oxychloride reflux 30min to upper strata organic layer, add again the gac processing of decolouring, filter, the concentrated solvent of removing 50% quality of filtrate decompression, concentrated solution is cooled to 10 DEG C, be incubated 10 ~ 15 DEG C of crystallizations 1 hour, filter, filter cake, in 50 DEG C of vacuum-dryings to constant weight, obtains triphenylmethyl chloride; The purified petroleum benzin weight of described dilution use is 4.0 ~ 4.2 times of tetracol phenixin charging capacity weight, preferably 4 times, the weight of the 2N hydrochloric acid adding is 3.4 ~ 3.5 times of tetracol phenixin charging capacity weight, preferably 3.5 times, the weight of the gac adding is 0.026 times of tetracol phenixin charging capacity weight, the sulfur oxychloride weight adding is 0.77 ~ 0.79 times of tetracol phenixin charging capacity weight, preferably 0.77 times.
Further, the synthetic method of triphenylmethyl chloride of the present invention recommends to carry out as follows: (1) is by purified petroleum benzin, aluminium powder adds in pressure reaction still with mass ratio 1:12 ~ 19, rapid stirring borehole cooling to 15 DEG C, hydrogen chloride gas in gas reservoir is passed into reactor, until still internal pressure reaches 0.5MPa (gauge pressure), then stop passing into hydrogenchloride, airtight stirring 20 minutes, pressure no longer obviously declines, continue to stir 10 minutes, the pressure valve of starting discharging is emitted gas reactor, the remaining preparation of hydrogen chloride 2N hydrochloric acid of gas water absorption of residual of emitting, the operation of repetition " passing into hydrogen chloride gas-venting release " 10 ~ 12 times, after now passing into hydrogen chloride gas, still internal pressure no longer declines, show no longer absorbing hydrogen chloride gas, react completely, obtain the benzene suspension of aluminum chloride,
(2) in the benzene suspension of above-mentioned aluminum chloride, slowly add tetracol phenixin, in adition process, controlling temperature of reaction kettle is 20 ~ 60 DEG C, within about 2 hours, add complete, continue insulated and stirred to no longer emitting hydrogen chloride gas, the hydrogen chloride gas producing in reaction process all enters air pump and inputs hydrogen chloride gas storage tank through reactor pneumatic outlet, to recycle;
(3) step (2) reaction solution is transferred in another reactor, be cooled to 30 DEG C, suction purified petroleum benzin dilute reaction solution, then suction 2N hydrochloric acid, stir stratification after 30 minutes, point sub-cloud water layer adds sulfur oxychloride in reactor, reflux 30 minutes, add gac, reflux decolour is processed 0.5 hour, filters, the concentrated solvent steaming except 50% quality of filtrate decompression, gained concentrated solution is cooled to 10 DEG C, is incubated 10 ~ 15 DEG C of stirred crystallization 1 hour, filter, filter cake, in 50 DEG C of vacuum-dryings to constant weight, obtains triphenylmethyl chloride; The purified petroleum benzin weight of described dilution use is 4 times of tetracol phenixin charging capacity weight, the weight of the 2N hydrochloric acid adding is 3.5 times of institute's tetracol phenixin charging capacity weight, the weight of the gac adding is 0.026 times of tetracol phenixin charging capacity weight, and the sulfur oxychloride weight adding is 0.77 times of tetracol phenixin charging capacity weight.
Triphenylmethyl chloride synthetic method of the present invention is taking aluminium powder as raw material, add alternatively a small amount of aluminum chloride, obtain aluminum trichloride (anhydrous) with hydrogen chloride gas precursor reactant, then reacting for catalysis tetracol phenixin and purified petroleum benzin, after the gas chlorination hydrogen gas reservoir collection that this reaction is emitted, for the preparation of aluminum chloride, reaction formula is:
Compared with prior art, beneficial effect of the present invention is mainly reflected in: it is starting raw material that novel process of the present invention is used aluminium powder, only need to consume a small amount of aluminum trichloride (anhydrous) in order to supplement the hydrogenchloride loss in production process, can make whole production process can continue to carry out, the major part being equivalent in the aluminum chloride of the required consumption of conventional production methods is replaced by equimolar aluminium powder, has improved the Atom economy of whole synthetic route.
(4) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1
Purified petroleum benzin 88.0kg, aluminium powder 6.8kg are added in 300L pressure reaction still to rapid stirring borehole cooling to 15 DEG C.Hydrogen chloride gas in gas reservoir is passed into reactor, until still internal pressure reaches 0.5MPa (gauge pressure), then stop passing into hydrogenchloride, airtight stirring 20 minutes, pressure no longer obviously declines, and continues to stir 10 minutes.The pressure valve of starting discharging is emitted gas reactor, the remaining preparation of hydrogen chloride 2N hydrochloric acid of gas water absorption of residual of emitting.Repeat the operation 12 times of " passing into hydrogen chloride gas-venting release ", now pass into hydrogen chloride gas after still internal pressure no longer decline, show no longer absorbing hydrogen chloride gas, react completely, obtain the benzene suspension of aluminum chloride.
In the benzene suspension of above-mentioned aluminum chloride, slowly add tetracol phenixin 38.0kg, in adition process, controlling temperature of reaction kettle is 40 ~ 50 DEG C, within about 2 hours, adds completely, continues insulated and stirred 6 hours, now no longer emits hydrogen chloride gas.The hydrogen chloride gas producing in reaction process all enters air pump and inputs hydrogen chloride gas storage tank through reactor pneumatic outlet, to recycle.
Reaction solution is transferred in another 500L reactor, be cooled to 30 DEG C, suction purified petroleum benzin 160kg dilute reaction solution, then suction 2N hydrochloric acid 130kg, stir stratification after 30 minutes, divide sub-cloud water layer, in reactor, add 30.2kg sulfur oxychloride, reflux 30 minutes, add 1.0kg gac, reflux decolour is processed 0.5 hour, filter, filtrate decompression is concentrated steams except 150kg solvent, gained concentrated solution is cooled to 10 DEG C, be incubated 10 ~ 15 DEG C of stirred crystallization 1 hour, filter, filter cake is in 50 DEG C of vacuum-dryings to constant weight, obtain triphenylmethyl chloride 57.1kg, yield 83% (by tetracol phenixin), HPLC purity 99.1%.
Embodiment 2
Purified petroleum benzin 88.0kg, aluminium powder 6.2kg are added in 300L reactor, add 3.0kg aluminum chloride, rapid stirring borehole cooling to 15 DEG C.Hydrogen chloride gas in gas reservoir is passed into reactor, until still internal pressure reaches 0.5MPa (gauge pressure), then stop passing into hydrogenchloride, airtight stirring 20 minutes, pressure no longer obviously declines, and continues to stir 10 minutes.The pressure valve of starting discharging is emitted gas reactor, the remaining preparation of hydrogen chloride 2N hydrochloric acid of gas water absorption of residual of emitting.Repeat the operation 11 times of " passing into hydrogen chloride gas-venting release ", now pass into hydrogen chloride gas after still internal pressure no longer decline, show no longer absorbing hydrogen chloride gas, react completely, obtain the benzene suspension of aluminum chloride.
In the benzene suspension of above-mentioned aluminum chloride, slowly add tetracol phenixin 38.0kg, in adition process, controlling temperature of reaction kettle is 20 ~ 30 DEG C, within about 2.5 hours, adds completely, continues insulated and stirred 12 hours, now no longer emits hydrogen chloride gas.The hydrogen chloride gas producing in reaction process all enters air pump and inputs hydrogen chloride gas storage tank through reactor pneumatic outlet, to recycle.
Post-processing operation, with embodiment 1, finally obtains triphenylmethyl chloride 58.5kg, yield 85%, HPLC purity 99.3%.
Embodiment 3
Purified petroleum benzin 88.0kg, aluminium powder 6.6kg are added in 300L reactor, add 1.0kg aluminum chloride, rapid stirring borehole cooling to 15 ° C left and right.Hydrogen chloride gas in gas reservoir is passed into reactor, until still internal pressure reaches 0.5MPa (gauge pressure), then stop passing into hydrogenchloride, airtight stirring 20 minutes, pressure no longer obviously declines, and continues to stir 10 minutes.The pressure valve of starting discharging is emitted gas reactor, the remaining preparation of hydrogen chloride 2N hydrochloric acid of gas water absorption of residual of emitting.Repeat the operation 11 times of " passing into hydrogen chloride gas-venting release ", now pass into hydrogen chloride gas after still internal pressure no longer decline, show no longer absorbing hydrogen chloride gas, react completely, obtain the benzene suspension of aluminum chloride.
In the benzene suspension of above-mentioned aluminum chloride, slowly add tetracol phenixin 38.0kg, in adition process, controlling temperature of reaction kettle is 50 ~ 60 DEG C, within about 2 hours, adds completely, continues insulated and stirred 6 hours, now no longer emits hydrogen chloride gas.The hydrogen chloride gas producing in reaction process all enters air pump and inputs hydrogen chloride gas storage tank through reactor pneumatic outlet, to recycle.
Post-processing operation, with embodiment 1, finally obtains triphenylmethyl chloride 55.0kg, yield 80%, HPLC purity 99.0%.
Embodiment 4
Purified petroleum benzin 88.0kg, aluminium powder 4.8kg are added in 300L reactor, add 10.0kg aluminum chloride, rapid stirring borehole cooling to 15 ° C left and right.Hydrogen chloride gas in gas reservoir is passed into reactor, until still internal pressure reaches 0.5MPa (gauge pressure), then stop passing into hydrogenchloride, airtight stirring 20 minutes, pressure no longer obviously declines, and continues to stir 10 minutes.The pressure valve of starting discharging is emitted gas reactor, the remaining preparation of hydrogen chloride 2N hydrochloric acid of gas water absorption of residual of emitting.Repeat the operation 10 times of " passing into hydrogen chloride gas-venting release ", now pass into hydrogen chloride gas after still internal pressure no longer decline, show no longer absorbing hydrogen chloride gas, react completely, obtain the benzene suspension of aluminum chloride.
In the benzene suspension of above-mentioned aluminum chloride, slowly add tetracol phenixin 42.8kg, in adition process, controlling temperature of reaction kettle is 40 ~ 50 DEG C, within about 2.5 hours, adds completely, continues insulated and stirred 6 hours, now no longer emits hydrogen chloride gas.The hydrogen chloride gas producing in reaction process all enters air pump and inputs hydrogen chloride gas storage tank through reactor pneumatic outlet, to recycle.
Post-processing operation with the consumption of other material of embodiment 1(also with embodiment 1), finally obtain triphenylmethyl chloride 62.0kg, yield 80%, HPLC purity 99.0%.
Claims (6)
1. a synthetic method for triphenylmethyl chloride, is characterized in that described method comprises the steps:
(1), aluminium powder is mixed with purified petroleum benzin, pass into hydrogen chloride gas and react with aluminium powder to absorbing hydrogen chloride no longer, obtain the benzene suspension of aluminum chloride; The weight ratio that feeds intake of described aluminium powder and purified petroleum benzin is 1:13～18;
(2), slowly add tetracol phenixin in the benzene suspension of the aluminum chloride that obtains to step (1), be stirred to and no longer emit hydrogen chloride gas, obtain the reaction solution containing the aluminum chloride complex compound of triphenylmethyl chloride; The hydrogen chloride gas of emitting in reaction process reclaims and repeats to apply mechanically;
(3), reaction solution step (2) Suo Shu is cooled to 30 DEG C, add purified petroleum benzin dilute reaction solution, then suction 2N hydrochloric acid, insulated and stirred 30min, stratification, removes lower aqueous layer, in the organic layer of upper strata, add sulfur oxychloride reflux 30min, then add the gac processing of decolouring, filter, the concentrated solvent of removing 50% quality of filtrate decompression, concentrated solution is cooled to 10 DEG C, is incubated 10～15 DEG C of crystallizations 1 hour, filters, filter cake, in 50 DEG C of vacuum-dryings to constant weight, obtains triphenylmethyl chloride; The purified petroleum benzin weight of described dilution use is 4 times of tetracol phenixin charging capacity weight, the weight of the 2N hydrochloric acid adding is 3.5 times of institute's tetracol phenixin charging capacity weight, the weight of the gac adding is 0.026 times of tetracol phenixin charging capacity weight, and the sulfur oxychloride weight adding is 0.77 times of tetracol phenixin charging capacity weight.
2. the synthetic method of triphenylmethyl chloride as claimed in claim 1, is characterized in that: step (1) also comprises that adding aluminum trichloride (anhydrous) mixes with aluminium powder and purified petroleum benzin.
3. the synthetic method of triphenylmethyl chloride as claimed in claim 2, is characterized in that aluminum trichloride (anhydrous) that described step (1) is added and the weight ratio of aluminium powder are 0～2:1.
4. the synthetic method of triphenylmethyl chloride as claimed in claim 1, is characterized in that: step (1) is no more than under 0.5MPa condition and reacts at pressure.
5. the synthetic method of triphenylmethyl chloride as claimed in claim 1, is characterized in that: in step (2), the total molar ratio of the add-on of tetracol phenixin and the described aluminium powder of step (1) and the aluminum chloride of adding is 1～1.1:1.
6. the synthetic method of triphenylmethyl chloride as claimed in claim 1, is characterized in that: in step (2), under 20～60 DEG C of temperature condition, add tetracol phenixin.
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| CN107935813A (en) * | 2017-11-03 | 2018-04-20 | 苏州艾缇克药物化学有限公司 | A kind of preparation method of triphenylchloromethane |
| CN110204413A (en) * | 2019-06-05 | 2019-09-06 | 临海市华南化工有限公司 | It is a kind of to prepare triphenylchloromethane recycled technique |
| CN112979411A (en) * | 2021-03-09 | 2021-06-18 | 江西华飞医药科技有限公司 | Process for preparing triphenylchloromethane |
| CN116730798B (en) * | 2023-01-29 | 2024-03-19 | 江苏飞宇医药科技股份有限公司 | Synthesis method of triphenylchloromethane |
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| CN101717324A (en) * | 2009-12-07 | 2010-06-02 | 浙江工业大学 | Green synthesizing method of triphenylchloromethane |
| CN101759523A (en) * | 2010-01-12 | 2010-06-30 | 广德县中信化工厂 | Preparation method for triphenylchloromethane |
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| JPS6357540A (en) * | 1986-08-29 | 1988-03-12 | Daicel Chem Ind Ltd | Production of triphenylchloromethane |
| FR2817255A1 (en) * | 2000-11-27 | 2002-05-31 | Atofina | PROCESS FOR THE PREPARATION OF DICHLORODIARYLMETHANES |
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| CN101717324A (en) * | 2009-12-07 | 2010-06-02 | 浙江工业大学 | Green synthesizing method of triphenylchloromethane |
| CN101759523A (en) * | 2010-01-12 | 2010-06-30 | 广德县中信化工厂 | Preparation method for triphenylchloromethane |
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