CN105801348B - Between 5 bromine benzotrifluoride and preparation method thereof - Google Patents
Between 5 bromine benzotrifluoride and preparation method thereof Download PDFInfo
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- CN105801348B CN105801348B CN201610248975.5A CN201610248975A CN105801348B CN 105801348 B CN105801348 B CN 105801348B CN 201610248975 A CN201610248975 A CN 201610248975A CN 105801348 B CN105801348 B CN 105801348B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C25/13—Monocyclic aromatic halogenated hydrocarbons containing fluorine
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Abstract
The invention discloses the preparation method of an inter-species 5 bromine benzotrifluoride, comprise the following steps：(1) by benzotrifluoride and composite catalyst input reactor, composite catalyst quality is the 0.05 0.5% of benzotrifluoride quality；(2) mass concentration is added as 30% hydrobromic acid and 5mol/L sulfuric acid 200ml；(3) it is 5 15 DEG C to control temperature under agitation, while it is 10 20% sodium chlorite solutions to instill mass concentration；(4) feed intake complete, after being incubated at low ambient temperatures, carry out temperature reaction；(5) stand, split-phase：Product after temperature reaction is divided into organic phase and aqueous phase, and organic phase pickling is stood afterwards to neutral；(6) dry, obtain crude product；(7) crude product is obtained into a 5 bromine benzotrifluoride through rectification under vacuum.The invention also discloses 5 bromine benzotrifluoride between prepared by above-mentioned preparation method, preparation method of the present invention reduces the generation of volatile, strong toxicity and not tractable bromine, and bromine atoms utilization rate reaches more than 90%.
Description
Technical field
The present invention relates to organic chemical industry to synthesize field, and in particular to inter-species 5 bromine benzotrifluoride and preparation method thereof.
Background technology
Between 5 bromine benzotrifluoride be a kind of very important chemical intermediate, mainly for the production of agricultural chemicals, medicine and other fields, such as
Synthesize slimming medicine fenfluramine and benfluorex etc..
Between bromine trifluoromethylbenzene mainly have two kinds of synthetic methods：1) direct bromination.This method raw material is benzotrifluoride, bromine
Element, using iron powder as catalyst.Wherein the mol ratio of benzotrifluoride and bromine is 1: 1.52, and iron powder weight is benzotrifluoride
20%, the trifluoromethylbenzene yield about 80% of preparation.This method has that low production efficiency, process dangerous be big, the three wastes (solid waste, liquid
Useless, gas gives up) discharge the problems such as more.2) mamino-trifluoromethyl benzene diazotising, displacement method.This method is to delay mamino-trifluoromethyl benzene
In the slow hydrobromic acid for adding 50 DEG C, sodium nitrite solution is added after being cooled to 10 DEG C, keeping temperature to diazotising terminates.By diazonium
Liquid is added in the cuprous bromide and hydrobromic acid solution boiled, is steamed organic matter using vapor.Its organic layer is taken, using dense sulphur
Acid, water, sig water are washed to neutrality.Oil reservoir is dehydrated through anhydrous calcium chloride, filters, be evaporated under reduced pressure after, collect 73-74.5 DEG C
(6.0kPa) cut, obtains trifluoromethylbenzene.There is production cost is high, process route is long, the dangerous big, three wastes for this method
The problems such as more, energy loss is done.
The content of the invention
Goal of the invention：The invention aims to make up the deficiency of existing investigative technique, there is provided an inter-species bromine trifluoro
The preparation method of toluene.
Technical scheme：The preparation method of one inter-species 5 bromine benzotrifluoride, comprises the following steps：
(1) by benzotrifluoride and composite catalyst input reactor, composite catalyst quality is benzotrifluoride quality
0.05-0.5%；
(2) mass concentration is added as 30% hydrobromic acid and 5mol/L sulfuric acid 200ml；
(3) it is 5-15 DEG C to control temperature under agitation, while it is molten for 10-20% sodium chlorites to instill mass concentration
Liquid；
(4) feed intake complete, after being incubated at low ambient temperatures, carry out temperature reaction；
(5) stand, split-phase：Product after temperature reaction is divided into organic phase and aqueous phase, after organic phase pickling to neutrality
Stand；
(6) dry, obtain crude product；
(7) crude product is obtained into a 5 bromine benzotrifluoride through rectification under vacuum.
Preferably, the composite catalyst described in step (1) is ferrum-based catalyst.
Preferably, in step (3), reaction generation sodium chlorite aoxidizes bromide ion, can generate the atom of high activity moment
Bromine, and reacted immediately with benzotrifluoride, benzotrifluoride, hydrobromic acid and the mass ratio of sodium chlorite solution are 1: 1.05-1.25:
1.20-1.35。
Preferably, in step (3), described sodium chlorite solution should be gradually added, to be started to control with ferrum-based catalyst one
The generation of isomers processed or more bromo-derivatives.
Preferably, in step (4), after feeding intake, in 5-15 DEG C of insulation reaction 1-2h；20-25 DEG C is warming up to again instead
Answer 1-2h；
Preferably, in step (5), organic phase will be washed successively, the bicarbonate that is 5%-10% with mass concentration
Sodium water solution is washed, is washed to neutrality again.
The invention also discloses 5 bromine benzotrifluoride between made by above-mentioned preparation method.
Beneficial effect：The invention belongs to green chemistry, using cheap and less toxic harmless inorganic acid, alkali, salt (hydrogen
Bromic acid, sodium chlorite, sodium acid carbonate etc.), reduce the generation of volatile, strong toxicity and not tractable bromine, and bromine atoms
Utilization rate reaches more than 90%.Present invention process mild condition is controllable, and it is terminating reaction to stop that sodium chlorite is added dropwise.
Embodiment
In the present invention, ferrum-based catalyst is self-control, and Homemade method is：Titanium dioxide is soaked with liquor ferri trichloridi, filtering,
Washing, then drying, calcination, is made efficient iron-base catalyst.
Embodiment 1：
The preparation method of one inter-species 5 bromine benzotrifluoride, comprises the following steps：
(1) by benzotrifluoride and ferrum-based catalyst input reactor, ferrum-based catalyst quality is benzotrifluoride quality
0.05%；
(2) mass concentration is added as 30% hydrobromic acid and 5mol/L sulfuric acid 200ml；
(3) it is 5-15 DEG C to control temperature under agitation, while it is 10-20% sodium chlorites progressively to instill mass concentration
Solution；To control the generation of isomers or more bromo-derivatives together with ferrum-based catalyst；
(4) feed intake complete, in 5 DEG C of insulation reaction 1-2h；20 DEG C of reaction 1-2h are warming up to again；
(5) stand, split-phase：Product after temperature reaction is divided into organic phase and aqueous phase, and organic phase will successively be washed, used
Mass concentration is that 5%-10% sodium bicarbonate aqueous solution is washed, is washed to neutrality again；
(6) dry, obtain crude product, its content reaches more than 96%, selectively reaches more than 99%；
(7) crude product is obtained into a 5 bromine benzotrifluoride, content 99.2%, yield 92.4% through rectification under vacuum.
In step (3), reaction generation sodium chlorite aoxidizes bromide ion, can generate the atom bromine of high activity moment, and immediately
Reacted with benzotrifluoride, benzotrifluoride, hydrobromic acid and the mass ratio of sodium chlorite solution are 1: 1.05: 1.20.
The present invention provides a kind of design more reasonable, the preparation of 5 bromine benzotrifluoride between preparation condition is simple, safe, controllable
Method.This method uses the bromine source of high activity, avoids big, volatile, high price bromine the use of toxicity, while inhibit isomery
The generation of body and more bromo-derivatives.Product has the characteristics of high controllability and high income.
Embodiment 2：
The preparation method of one inter-species 5 bromine benzotrifluoride, comprises the following steps：
(1) by benzotrifluoride and ferrum-based catalyst input reactor, ferrum-based catalyst quality is benzotrifluoride quality
0.5%；
(2) mass concentration is added as 30% hydrobromic acid and 5mol/L sulfuric acid 200ml；
(3) it is 15 DEG C to control temperature under agitation, while it is that 10-20% sodium chlorites are molten progressively to instill mass concentration
Liquid；To control the generation of isomers or more bromo-derivatives together with ferrum-based catalyst
(4) feed intake complete, in 5 DEG C of insulation reaction 1-2h；20 DEG C of reaction 1-2h are warming up to again；
(5) stand, split-phase：Product after temperature reaction is divided into organic phase and aqueous phase, and organic phase will successively be washed, used
Mass concentration is that 5%-10% sodium bicarbonate aqueous solution is washed, is washed to neutrality again；
(6) dry, obtain crude product, its content reaches more than 96.7%, selectively reaches more than 99.2%；
(7) crude product is obtained into a 5 bromine benzotrifluoride, content 99% through rectification under vacuum.
In step (3), reaction generation sodium chlorite aoxidizes bromide ion, can generate the atom bromine of high activity moment, and immediately
Reacted with benzotrifluoride, benzotrifluoride, hydrobromic acid and the mass ratio of sodium chlorite solution are 1: 1.25: 1.35.
Embodiment 3：
The preparation method of one inter-species 5 bromine benzotrifluoride, comprises the following steps：
(1) by benzotrifluoride and ferrum-based catalyst input reactor, ferrum-based catalyst quality is benzotrifluoride quality
0.3%；
(2) mass concentration is added as 30% hydrobromic acid and 5mol/L sulfuric acid 200ml；
(3) it is 10 DEG C to control temperature under agitation, while it is that 10-20% sodium chlorites are molten progressively to instill mass concentration
Liquid；To control the generation of isomers or more bromo-derivatives together with ferrum-based catalyst；
(4) feed intake complete, in 15 DEG C of insulation reaction 1-2h；25 DEG C of reaction 1-2h are warming up to again；
(5) stand, split-phase：Product after temperature reaction is divided into organic phase and aqueous phase, and organic phase will successively be washed, used
Mass concentration is that 5%-10% sodium bicarbonate aqueous solution is washed, is washed to neutrality again；
(6) dry, obtain crude product；
(7) crude product is obtained into a 5 bromine benzotrifluoride, content 99% through rectification under vacuum.
In step (3), reaction generation sodium chlorite aoxidizes bromide ion, can generate the atom bromine of high activity moment, and immediately
Reacted with benzotrifluoride, benzotrifluoride, hydrobromic acid and the mass ratio of sodium chlorite solution are 1: 1.2: 1.3.
Embodiment 4：
The preparation method of one inter-species 5 bromine benzotrifluoride, comprises the following steps：
(1) by benzotrifluoride and ferrum-based catalyst input reactor, ferrum-based catalyst quality is benzotrifluoride quality
0.4%；
(2) mass concentration is added as 30% hydrobromic acid and 5mol/L sulfuric acid 200ml；
(3) it is 5 DEG C to control temperature under agitation, while it is that 10-20% sodium chlorites are molten progressively to instill mass concentration
Liquid；To control the generation of isomers or more bromo-derivatives together with ferrum-based catalyst；
(4) feed intake complete, in 10 DEG C of insulation reaction 1-2h；23 DEG C of reaction 1-2h are warming up to again；
(5) stand, split-phase：Product after temperature reaction is divided into organic phase and aqueous phase, and organic phase will successively be washed, used
Mass concentration is that 5%-10% sodium bicarbonate aqueous solution is washed, is washed to neutrality again；
(6) dry, obtain crude product；
(7) crude product is obtained into a 5 bromine benzotrifluoride, content 99% through rectification under vacuum.
In step (3), reaction generation sodium chlorite aoxidizes bromide ion, can generate the atom bromine of high activity moment, and immediately
Reacted with benzotrifluoride, benzotrifluoride, hydrobromic acid and the mass ratio of sodium chlorite solution are 1: 1.1: 1.25.
Claims (2)
1. the preparation method of an inter-species 5 bromine benzotrifluoride, it is characterised in that：Comprise the following steps：
(1) by benzotrifluoride and composite catalyst input reactor, composite catalyst quality is benzotrifluoride quality
0.05-0.5%, described composite catalyst is ferrum-based catalyst；
(2) mass concentration is added as 30% hydrobromic acid and 200ml 5mol/L sulfuric acid；
(3) it is 5-15 DEG C to control temperature under agitation, while it is 10-20% sodium chlorite solutions to instill mass concentration, sub-
Sodium chlorate oxidation bromide ion can generate the atom bromine of high activity moment, and be reacted immediately with benzotrifluoride, benzotrifluoride, hydrobromic acid
Mass ratio with sodium chlorite solution is 1:1.05-1.25:1.20-1.35；
(4) feed intake complete, in 5-15 DEG C of insulation reaction 1-2h, then be warming up to 20-25 DEG C of reaction 1-2h；
(5) stand, split-phase：Product after temperature reaction is divided into organic phase and aqueous phase, and organic phase is washed successively, uses quality
The sodium bicarbonate aqueous solution that concentration is 5% -10% is washed, is washed to neutrality again, stands afterwards；
(6) dry, obtain crude product；
(7) crude product is obtained into a 5 bromine benzotrifluoride through rectification under vacuum.
2. the preparation method of according to claim 15 bromine benzotrifluoride, it is characterised in that：In step (3), described Asia
Sodium chlorate solution should be gradually added, to control the generation of isomers or more bromo-derivatives together with ferrum-based catalyst.
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| CN108558597A (en) * | 2018-06-07 | 2018-09-21 | 天门楚天精细化工有限公司 | The synthetic method of 5 bromine benzotrifluoride between a kind of highly effective |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6506951B1 (en) * | 1999-04-20 | 2003-01-14 | Central Glass Company, Limited | Process for producing brominated trifluoromethylbenzenes |
| CN105439811A (en) * | 2015-12-23 | 2016-03-30 | 成都中恒华铁科技有限公司 | Synthesis method of trifluperidol drug intermediate m-bromobenzotrifluoride |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6506951B1 (en) * | 1999-04-20 | 2003-01-14 | Central Glass Company, Limited | Process for producing brominated trifluoromethylbenzenes |
| CN105439811A (en) * | 2015-12-23 | 2016-03-30 | 成都中恒华铁科技有限公司 | Synthesis method of trifluperidol drug intermediate m-bromobenzotrifluoride |
Non-Patent Citations (2)
| Title |
|---|
| 一些对-、邻-和间-三氟甲基桂皮酰胺的合成及其抗惊活性;李安良 等;《药学学报》;19841231;第19卷(第12期);第888-893页 * |
| 间三氟甲基溴苯的合成新方法;陈红飙 等;《中国医药工业杂志》;20011231;第32卷(第10期);第473页 * |
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