CN103910639A - A method of preparing 2,6-dichloro-4-trifluoromethyl phenylamine - Google Patents
A method of preparing 2,6-dichloro-4-trifluoromethyl phenylamine Download PDFInfo
- Publication number
- CN103910639A CN103910639A CN201410095067.8A CN201410095067A CN103910639A CN 103910639 A CN103910639 A CN 103910639A CN 201410095067 A CN201410095067 A CN 201410095067A CN 103910639 A CN103910639 A CN 103910639A
- Authority
- CN
- China
- Prior art keywords
- acid
- solvent
- reaction
- dichlor
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method of preparing 2,6-dichloro-4-trifluoromethyl phenylamine. The method is characterized by comprising steps of: adding 4-aminobenzotrifluoride into a solvent, adding an inorganic acid or an organic acid into the solvent so that the inorganic acid or the organic acid reacts with the 4-aminobenzotrifluoride to obtain a corresponding inorganic salt or a corresponding organic salt, feeding chlorine into the reaction mixture, performing a chlorination reaction, washing with water to remove the inorganic acid or the organic acid after the reaction is finished, removing the solvent from an organic phase, and performing vacuum rectification to obtain the 2,6-dichloro-4-trifluoromethyl phenylamine. The method largely reduces side products of direct chlorination of the 4-aminobenzotrifluoride in traditional processes, thus increasing the conversion rate of the raw materials and the selectivity of the 2,6-dichloro-4-trifluoromethyl phenylamine and largely simplifying purification and separation of the product. The method is low in production cost, good in product quality and simple in production operation, and has a good industrial application prospect.
Description
Technical field
The present invention relates to one and prepare the method for 2,6-dichlor-4-trifluoromethyl aniline, be specifically related to a kind of processing method that adopts chloridization process to make 2,6-dichlor-4-trifluoromethyl aniline.
Background technology
2,6-dichlor-4-trifluoromethyl aniline is a kind of important organic intermediate, is mainly used in synthetic ethiprole, the fluorine-containing organic pesticide such as second worm nitrile.Ethiprole and second worm nitrile are all broad spectrum pesticides, can prevent and treat subterranean pest-insect, can prevent and treat again insect on the ground, can be used for seed treatment and foliar spray, and these two agricultural chemicals all have efficiently, long-acting feature, particularly second worm nitrile, to environment and person poultry safety, has wide market outlook.The main preparation method of 2,6-dichlor-4-trifluoromethyl aniline has following several:
(1), taking 4-5-trifluoromethylaniline as raw material, in acetic acid or ethylene dichloride equal solvent, pass into chlorine and carry out chlorination reaction and make 2,6-dichlor-4-trifluoromethyl aniline.This preparation method is simple to operate, the wherein method taking ethylene dichloride as solvent, and molar product yield higher (approximately 80%), is the preparation method that current production plant generally adopts, and still, still exists by product more, product separation is refined difficult problem.And more as reaction solvent side reaction taking acetic acid, molar product yield is lower.
(2), taking 4-chlorobenzotrifluoride as raw material, first react with DMF and make 4-trifluoromethyl-N, accelerine, then reacts with SULPHURYL CHLORIDE and makes 2,6-dichlor-4-trifluoromethyl-N, accelerine, last demethylation generates 2,6-dichlor-4-trifluoromethyl aniline.This preparation method's reactions steps is many, production operation complexity, and total molar yield is low.
(3) with 3,4-, bis-chlorobenzotrifluorides for raw material, first react with hydrazine hydrate and make the chloro-4-trifluoromethyl phenyl hydrazine of 2-, then in autoclave pressure, hydrogenating reduction makes the chloro-4-5-trifluoromethylaniline of 2-, finally chlorination makes 2,6-dichlor-4-trifluoromethyl aniline.This preparation method's complex process, production operation is had relatively high expectations, and total molar yield is lower.
(4) with 3,4,5-trichlorobenzotrifluoride for raw material, make 2,6-dichlor-4-trifluoromethyl aniline by high pressure ammonia solution.This preparation method's yield is not high, and needs High Temperature High Pressure ammonolysis reaction, and equipment is had higher requirements.
Therefore, hope can overcome many deficiencies of prior art, provides a kind of yield high, and production operation is simple, be easy to industrialized 2, the preparation method of 6-dichlor-4-trifluoromethyl aniline.
Summary of the invention
The invention provides one and prepare 2, the method of 6-dichlor-4-trifluoromethyl aniline, it comprises the following steps: 4-5-trifluoromethylaniline is joined in solvent, then in solvent, add mineral acid or organic acid and 4-5-trifluoromethylaniline to generate corresponding inorganic salt or organic salt, then carry out chlorination reaction to passing into chlorine in reaction mixture, after having reacted, above-mentioned mineral acid or organic acid are removed in washing, desolvation from organic phase again, carry out again rectification under vacuum and obtain 2,6-dichlor-4-trifluoromethyl aniline.
Solvent of the present invention is toluene, methylene dichloride, and ethylene dichloride, chloroform, any one or two kinds of and above mixed solvent in tetracol phenixin, is wherein preferably the one in chloroform or ethylene dichloride.
The temperature of chlorination reaction of the present invention is 60～80 DEG C.
The chlorination reaction time of the present invention is 8～16h.
Acid of the present invention is hydrogenchloride, sulfuric acid, and formic acid, any one or two kinds of and above mixing acid in acetic acid, is wherein preferably the one in hydrogenchloride or sulfuric acid.
Chemical equation of the present invention is, to use HCl as example:
Compared with prior art, the invention has the advantages that:
(1) traditional 4-5-trifluoromethylaniline direct chlorination prepares 2, the method of 6-dichlor-4-trifluoromethyl aniline, main by product is the reactions such as oxidation to have occurred due to the amino on phenyl ring cause, method provided by the invention by 4-Mr. 5-trifluoromethylaniline salify after, carry out again chlorination reaction, so by product is few, the selectivity of the transformation efficiency of 4-5-trifluoromethylaniline and generation 2,6-dichlor-4-trifluoromethyl aniline is all high;
(2) the present invention prepares 2, the method of 6-dichlor-4-trifluoromethyl aniline, because by product is few, the refining of product is very easy to, after chlorination after reactants water eccysis acid, desolvation, just can obtain more than 99.5% 2 of GC purity by simple rectifying again, 6-dichlor-4-trifluoromethyl aniline, and prepared by traditional technology 2,6-dichlor-4-trifluoromethyl aniline chlorated liquid, because by product is many, needs complicated aftertreatment and could obtain more than 99.5% product of GC purity to the very high complex distillation of equipment requirements;
(3) the present invention prepares the method for 2,6-dichlor-4-trifluoromethyl aniline, because yield is high, refining simple, so production cost is starkly lower than traditional method.In a word, the inventive method good product quality, production operation is simple, and production cost is low, has good industrial applications prospect.
Embodiment
The present invention is described in detail in detail by the following examples, and these embodiment are only clear open the present invention, but not as limitation of the present invention.
Embodiment 1
In reaction flask, add 1000g chloroform, 200g4-5-trifluoromethylaniline, under stirring, pass into hydrogen chloride gas, after stirring, be warmed up to 70 DEG C, pass into chlorine, GC monitors reaction, in the time that 4-trifluoromethylbenzene amine content is less than the chloro-4-trifluoromethylbenzene of 0.1%, 2-amine content and is less than 0.3%, stopped reaction, now 2,6-dichlor-4-trifluoromethyl aniline content approximately 98.5%, about 11h of reaction times.Reaction solution cooling washing, 30% aqueous sodium hydroxide washes is washed, and after distillation desolvation, rectification under vacuum obtains 2,6-dichlor-4-trifluoromethyl aniline 259g, GC purity 99.6%, molar yield 91%.
Embodiment 2
In reaction flask, add 1000g ethylene dichloride, 200g4-5-trifluoromethylaniline, under stirring, add the vitriol oil, after stirring, be warmed up to 60 DEG C, pass into chlorine, GC monitors reaction, in the time that 4-trifluoromethylbenzene amine content is less than the chloro-4-trifluoromethylbenzene of 0.1%, 2-amine content and is less than 0.3%, stopped reaction, now 2,6-dichlor-4-trifluoromethyl aniline content approximately 98%, about 16h of reaction times.Reaction solution cooling washing, 30% aqueous sodium hydroxide washes is washed, and after distillation desolvation, rectification under vacuum obtains 2,6-dichlor-4-trifluoromethyl aniline 253g, GC purity 99.5%, molar yield 89%.
Embodiment 3
In reaction flask, add 1000g ethylene dichloride, 200g4-5-trifluoromethylaniline, under stirring, add acetic acid, after stirring, be warmed up to 80 DEG C, pass into chlorine, GC monitors reaction, in the time that 4-trifluoromethylbenzene amine content is less than the chloro-4-trifluoromethylbenzene of 0.1%, 2-amine content and is less than 0.3%, stopped reaction, now 2,6-dichlor-4-trifluoromethyl aniline content approximately 96.8%, about 9h of reaction times.Reaction solution cooling washing, 30% aqueous sodium hydroxide washes is washed, and after distillation desolvation, rectification under vacuum obtains 2,6-dichlor-4-trifluoromethyl aniline 247g, GC purity 99.5%, molar yield 87%.
Comparative example 1
This comparative example is carried out according to the art methods of background technology part (1), wherein uses pure acetic acid as solvent.In reaction flask, add 1000g acetic acid and 200g4-5-trifluoromethylaniline, after stirring, be warmed up to 70 DEG C, pass into chlorine, GC monitors reaction, when 4-trifluoromethylbenzene amine content is less than 0.1%, when the chloro-4-trifluoromethylbenzene of 2-amine content is less than 0.5%, stopped reaction, now 2,6-dichlor-4-trifluoromethyl aniline content approximately 75.6%, about 17h of reaction times.Reaction solution cooling washing, 30% aqueous sodium hydroxide washes is washed, and after distillation desolvation, rectification under vacuum obtains 2,6-dichlor-4-trifluoromethyl aniline 182g, GC purity 99.5%, molar yield 64%.
Embodiment 3 is visible compared with comparative example 1, in embodiment 3, taking ethylene dichloride as solvent, using acetic acid as salt forming agent and after 4-5-trifluoromethylaniline salify, then carry out chlorination reaction, target product molar yield is very high, can reach 87%.But in comparative example 1 in the time using using pure acetic acid as solvent, although its also can with 4-5-trifluoromethylaniline salify, after chlorination reaction, target product molar yield is very low, is only 64%.And in art methods, when using ethylene dichloride as solvent but not using acid, target product molar yield can only be in 80% left and right, it should be noted that, although also can some HCl of by-product in chlorination process, this HCl produces in chlorination reaction process, and the HCl of the embodiment of the present invention 1 before chlorination reaction for 4-5-trifluoromethylaniline salify is deliberately added, from final effect, between the two, difference is huge.In this explanation the present invention, may exist certain synergy between acetic acid and solvent ethylene dichloride, cause target product yield very high, this exceeds technician and expects.
In other embodiment test, find, select toluene, methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin or its mixture as solvent, and add mineral acid or organic acid first to generate corresponding inorganic salt or organic salt with 4-5-trifluoromethylaniline, then carry out chlorination reaction to passing into chlorine in reaction mixture, also can obtain 1 to the embodiment 3 akin good test effect with embodiment.
Claims (6)
1. prepare 2 for one kind, the method of 6-dichlor-4-trifluoromethyl aniline, it is characterized in that: 4-5-trifluoromethylaniline is joined in solvent, then in solvent, add mineral acid or organic acid to generate corresponding inorganic salt or organic salt with 4-5-trifluoromethylaniline, then carry out chlorination reaction to passing into chlorine in reaction mixture, after having reacted, above-mentioned mineral acid or organic acid are removed in washing, desolvation from organic phase again, then carry out rectification under vacuum and obtain 2,6-dichlor-4-trifluoromethyl aniline.
2. method claimed in claim 1, is characterized in that: described solvent is selected from toluene, methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin or its mixture.
3. method claimed in claim 1, is characterized in that: described solvent is chloroform or ethylene dichloride.
4. method claimed in claim 1, is characterized in that: chlorination reaction is carried out at the temperature of 60～80 DEG C, and the chlorination reaction time is 8～16h.
5. method claimed in claim 1, is characterized in that: described acid is selected from hydrogenchloride, sulfuric acid, formic acid, acetic acid or its mixture.
6. method claimed in claim 1, is characterized in that: described acid is selected from hydrogenchloride or sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410095067.8A CN103910639A (en) | 2014-03-13 | 2014-03-13 | A method of preparing 2,6-dichloro-4-trifluoromethyl phenylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410095067.8A CN103910639A (en) | 2014-03-13 | 2014-03-13 | A method of preparing 2,6-dichloro-4-trifluoromethyl phenylamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103910639A true CN103910639A (en) | 2014-07-09 |
Family
ID=51036690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410095067.8A Pending CN103910639A (en) | 2014-03-13 | 2014-03-13 | A method of preparing 2,6-dichloro-4-trifluoromethyl phenylamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103910639A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845340A (en) * | 2019-11-07 | 2020-02-28 | 苏州开元民生科技股份有限公司 | Preparation method of fipronil intermediate |
| CN111875503A (en) * | 2020-08-06 | 2020-11-03 | 浙江巍华新材料股份有限公司 | Preparation method of 2, 6-dichloro-4-trifluoromethylaniline |
| CN114507147A (en) * | 2022-03-16 | 2022-05-17 | 浙江巍华新材料股份有限公司 | Method for preparing 2, 6-dichloro-4-trifluoromethylaniline |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001064623A1 (en) * | 2000-03-01 | 2001-09-07 | Rhodia Chimie | Chlorination of an aniline in ortho in a hydrofluoric medium |
| CN1705632A (en) * | 2002-10-25 | 2005-12-07 | 拜尔农科股份有限公司 | Novel process for the preparation of a synthetic intermediate for pesticides |
| CN101045709A (en) * | 2006-03-31 | 2007-10-03 | 江苏春江农化有限公司 | New method for industrial producing aminopyrazole |
| CN102863342A (en) * | 2012-10-17 | 2013-01-09 | 湖北美天生物科技有限公司 | Preparation method of high-purity 2, 6-dichloro-4-trifluoromethyl aniline |
-
2014
- 2014-03-13 CN CN201410095067.8A patent/CN103910639A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001064623A1 (en) * | 2000-03-01 | 2001-09-07 | Rhodia Chimie | Chlorination of an aniline in ortho in a hydrofluoric medium |
| CN1705632A (en) * | 2002-10-25 | 2005-12-07 | 拜尔农科股份有限公司 | Novel process for the preparation of a synthetic intermediate for pesticides |
| CN101045709A (en) * | 2006-03-31 | 2007-10-03 | 江苏春江农化有限公司 | New method for industrial producing aminopyrazole |
| CN102863342A (en) * | 2012-10-17 | 2013-01-09 | 湖北美天生物科技有限公司 | Preparation method of high-purity 2, 6-dichloro-4-trifluoromethyl aniline |
Non-Patent Citations (6)
| Title |
|---|
| 严中杰 等: "2,6-二氯-4-甲基三氟苯胺", 《农药》, vol. 47, no. 3, 31 March 2008 (2008-03-31), pages 174 - 175 * |
| 严中杰: "2,6-二氯-4-三氟甲基苯胺的合成", 《农化新世纪》, no. 7, 8 July 2008 (2008-07-08) * |
| 严传鸣 等: "2,6-二氯-4-三氟甲基苯胺的合成", 《现代农药》, vol. 2, no. 5, 31 October 2003 (2003-10-31) * |
| 刘宇: "2,6-二氯-4-三氟甲基苯胺的合成", 《农药》, vol. 41, no. 6, 25 June 2002 (2002-06-25), pages 21 * |
| 张腊腊 等: "2,6-二氯-4-三氟甲基苯胺的合成", 《化工中间体》, no. 6, 15 June 2011 (2011-06-15), pages 58 - 60 * |
| 陆阳 等: "催化氧化合成氟虫腈新工艺", 《化工技术与开发》, vol. 38, no. 5, 31 May 2009 (2009-05-31), pages 11 - 15 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110845340A (en) * | 2019-11-07 | 2020-02-28 | 苏州开元民生科技股份有限公司 | Preparation method of fipronil intermediate |
| CN110845340B (en) * | 2019-11-07 | 2022-03-22 | 苏州开元民生科技股份有限公司 | Preparation method of fipronil intermediate |
| CN111875503A (en) * | 2020-08-06 | 2020-11-03 | 浙江巍华新材料股份有限公司 | Preparation method of 2, 6-dichloro-4-trifluoromethylaniline |
| CN111875503B (en) * | 2020-08-06 | 2023-06-30 | 浙江巍华新材料股份有限公司 | Preparation method of 2, 6-dichloro-4-trifluoromethyl aniline |
| CN114507147A (en) * | 2022-03-16 | 2022-05-17 | 浙江巍华新材料股份有限公司 | Method for preparing 2, 6-dichloro-4-trifluoromethylaniline |
| CN114507147B (en) * | 2022-03-16 | 2024-03-19 | 浙江巍华新材料股份有限公司 | Method for preparing 2, 6-dichloro-4-trifluoromethyl aniline |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103910639A (en) | A method of preparing 2,6-dichloro-4-trifluoromethyl phenylamine | |
| CN102001952A (en) | Preparation method of high-purity paranitroaniline | |
| CN111732520A (en) | Preparation method of 3-methyl-2-aminobenzoic acid | |
| CN103224451B (en) | Method for synthesizing 3,5-dichlorobenzoic acid | |
| CN104129764B (en) | The method of azanol or hydroxylammonium salt is prepared from ketone, ammonia and hydrogen peroxide | |
| CN109232411A (en) | A method of preparing boscalid | |
| CN104129765A (en) | Reaction-extraction coupling method for preparation of hydroxylamine salt / hydroxylamine | |
| CN103553884B (en) | Method for preparing trifluoromethoxybenzene | |
| CN110818603B (en) | Preparation method of methomyl oxime | |
| CN102924244A (en) | Production technique of high-quality trimethyl orthoacetate | |
| CN105037186A (en) | Preparation method of aminomethylbenzoic acid | |
| CN108530301B (en) | Synthetic method of 2,4, 6-trifluorobenzylamine | |
| CN108164423B (en) | Preparation method of naftifine hydrochloride | |
| CN106699522A (en) | Production process of high-quality trimethyl orthoacetate | |
| CN104045521B (en) | A kind of parachlorometacresol green synthesis process | |
| CN114702391A (en) | Method for preparing cyclopropylamine by performing Hofmann rearrangement by using hydrogen peroxide | |
| EP3154933B1 (en) | Process for the preparation of 2-(trihalomethyl) benzamide | |
| CN103724213B (en) | A kind of synthetic method of 2,6-di-isopropyl-4-phenoxybenzamine | |
| CN105315127B (en) | A kind of preparation method of 4 tert-butyl group bromobenzyl | |
| CN113968792A (en) | Novel method for synthesizing 2-chloro-5-aminophenol | |
| CN103408437A (en) | Method for preparing 2,6-dichloro-4-trifluoromethyl phenylamine | |
| CN107098817A (en) | 2,6- of one kind dichlor-4-trifluoromethyl anilines lead to chlorine production technology | |
| CN107698503A (en) | A kind of preparation method of 8 fluorine quinoline and the preparation method of the fluorine quinoline of 3 iodine 8 | |
| CN103752209A (en) | Cashew nut based amide surfactant and preparation method thereof | |
| CN105418391B (en) | A kind of preparation method of p-trifluoromethyl benzaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140709 |