CN104341326A - Preparation method for 2-substituted 6-(trifluoromethyl)benzenesulphonyl chloride - Google Patents
Preparation method for 2-substituted 6-(trifluoromethyl)benzenesulphonyl chloride Download PDFInfo
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- CN104341326A CN104341326A CN201310343913.9A CN201310343913A CN104341326A CN 104341326 A CN104341326 A CN 104341326A CN 201310343913 A CN201310343913 A CN 201310343913A CN 104341326 A CN104341326 A CN 104341326A
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Abstract
A disclosed preparation method for 2-substituted 6-(trifluoromethyl)benzenesulphonyl chloride comprises preparation of 2-fluoro-6-(trifluoromethyl)benzenesulphonyl chloride. Concretely, the preparation method comprises: step 1, under protection of an inert gas, cooling an anhydrous solution of 3-substituted benzotrifluoride to -100 DEG C to -20 DEG C, and slowly adding a strong alkali into the solution; step 2, keeping warm for a period, dropwise adding sulfuryl chloride into the solution obtained in the step 1, and keeping a low temperature during dropwise adding; and step 3, performing washing, drying and desolventizing on the reaction solution obtained in the step 2, and directly performing a next-step reaction. A reaction general formula is shown in the specification.
Description
Technical field
The present invention relates to a kind of preparation method that the present invention relates to 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride.
Background technology
1-(2,2-difluoroethoxy)-6-trifluoromethyl-N-(5,8-dimethoxy [1,2,4] triazole [1,5-C] pyrimidine-2-) benzsulfamide, its chemical structure is as follows:
1-(2,2-difluoroethoxy)-6-trifluoromethyl-N-(5,8-dimethoxy [1,2,4] triazole [1,5-C] pyrimidine-2-) benzsulfamide is with weedicide after the seedling developed by Tao Nongke company of the U.S. (DowAgro-Sciences), it works by suppressing acetolactate synthestase (ALS), it is translocated herbicide, through stem, leaf, bud and Root Absorption, conducts to meristematic tissue by xylem and phloem, suppress plant strain growth, make vegetative point chlorosis, downright bad, and then kill whole strain plant.It is the kind that in current herbicide for rice field, herbicide spectrum is the widest.
Tao Nongke company of the U.S. (DowAgro-Sciences) 1999 United States Patent (USP) (US5858924) disclose 1-(2,2-difluoroethoxy)-6-trifluoromethyl-N-(5,8-dimethoxy [1,2,4] triazole [1,5-C] pyrimidine-2-) benzsulfamide and penoxsuam, it is by preparing intermediate 2-fluoro-6-trifluoromethyl benzene sulfonyl chloride, finally synthesizing through amination, alcoholysis.But key intermediate 2-fluoro-6-trifluoromethyl benzene sulfonyl chloride be with 6-trifluoromethyl-2-fluoroaniline for raw material, finally obtain with not high yield through diazotization, sulfonylation, chlorination.6-trifluoromethyl-2-fluoroaniline is expensive and market degree is not high, and this reaction yield is low, complex operation, therefore causes certain difficulty to this method synthesis sulphur grass amine.Its key intermediate 2-fluoro-6-trifluoromethyl benzene sulfonyl chloride also can prepare (Bioorganic and Medicinal Chemistry by the bromo-3-fluoride trifluoro toluene of 2-, 2008,16(3), 1345-1358), but be faced with expensive and market-oriented low, the problem that reaction yield is not high of 2-bromo-3-fluoride trifluoro toluene equally.
Summary of the invention
The object of this invention is to provide a kind of with the preparations and applicatio method of common raw material, efficiently synthesis 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride.
Concrete scheme provided by the invention is: a kind of preparation method of 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride, is characterized in that, comprise the preparation of 2-fluoro-6-trifluoromethyl benzene sulfonyl chloride:
Step 1: under protection of inert gas, by the anhydrous solvent Jiang Wen – 100 ~-20 DEG C of 3-substituting group phenylfluoroform, adds highly basic slowly wherein;
Step 2: to the step 1 gained solution of insulation for some time, drop to sulfuryl chloride, the process that drips keeps low temperature;
Step 3: by step 2 gained reaction solution after washing, drying, precipitation, directly carry out the next step;
Reaction expression is as follows:
X represents halogen; Alkali represents highly basic.
As preferably, highly basic used in described step 1 is one or several mixing separately such as butyllithium (as n-Butyl Lithium, tert-butyl lithium etc.), lithium diisopropylamine (LDA), hexamethyldisilazane lithium.
As preferably, described step 3 can replace to: by step 2 gained reaction solution after washing, dry, precipitation, be further purified and obtain sterling.
As preferably, in described step 1, the mol ratio of 3-substituting group phenylfluoroform and highly basic is 1:0.8 ~ 1.2.
As preferably, in described step 2, the mol ratio of 3-substituting group phenylfluoroform and sulfuryl chloride is 1:1.0 ~ 3.0.
As preferably, described reaction can be carried out under condition of no solvent.
As preferably, described reaction can be carried out under described organic solvent is the condition of aromatic hydrocarbons, alkane or ether.
As preferably, described reaction can be carried out within the scope of-100 ~-20 DEG C, and optimal reaction temperature is-60 –-100 DEG C.
The invention has the beneficial effects as follows:
The present invention is for raw material with the cheap 3-fluoride trifluoro toluene, a trifluoro-benzene phenolic ester, a trifluoro-benzene phenolic ether etc. of market at prices; react through organic bases (as butyllithium, Lithamide etc.) effect and sulfuryl chloride and directly generate 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride; cost is low; the present invention is simultaneously by directly preparing benzsulfamide intermediate 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride; simplify synthesis step; optimum synthesis technique; improve reaction yield; reduce production cost, thus greatly improve the combined coefficient of five happinesses sulphur grass amine.
Embodiment
Below by way of embodiment, the invention will be further described, but it should not be construed as limiting the scope of the invention.
Embodiment 1:
The preparation of 2-fluoro-6-trifluoromethyl benzene sulfonyl chloride
Under nitrogen protection, by 164.10g(1.00mol) between fluoride trifluoro toluene be dissolved in 3000mL anhydrous tetrahydro furan and be placed in 10000mL four-hole bottle.-80 DEG C, under induction stirring, in slow four-hole bottle, drip the tert-butyl lithium hexane solution 440mL(1.10mol of 2.5mol/L).Dropwise, at-80 DEG C, insulation 1h.
Under nitrogen protection, slowly by 202.50g(0.15mol) during the sulfuryl chloride reaction solution that drops to above-mentioned fluoride trifluoro toluene and tert-butyl lithium moves.Dropping process keeps less than-80 DEG C, insulation 2h.Reaction solution rises to room temperature gradually.Add saturated aqueous common salt 100mL magnetic agitation 5min.Stratification, organic layer saturated sodium bicarbonate aqueous solution washs, anhydrous sodium sulfate drying, and decompression precipitation, obtains reddish-brown oily matter.Purity 95%, yield 90%(is in a fluoride trifluoro toluene).
1HNMR(400MHz,CDCl
3)δ7.87(dd,J=5.2,8.0Hz,1H),7.78(d,J=8.0Hz,1H),7.58–7.63(m,1H)。
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
- The preparation method of 1.2-substituting group-6-trifluoromethyl benzene sulfonyl chloride, is characterized in that, comprise the preparation of 2-fluoro-6-trifluoromethyl benzene sulfonyl chloride:Step 1: under protection of inert gas, by the anhydrous solvent Jiang Wen – 100 ~-20 DEG C of 3-substituting group phenylfluoroform, adds highly basic slowly wherein;Step 2: step 1 gained solution after insulation for some time, drops to sulfuryl chloride, the process that drips keeps low temperature;Step 3: by step 2 gained reaction solution after washing, drying, precipitation, directly carry out the next step;Reaction expression is as follows:X represents halogen; Alkali represents highly basic.
- 2. the preparation method of 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride according to claim 1, it is characterized in that, highly basic used in described step 1 is one or several mixing separately such as butyllithium (as n-Butyl Lithium, tert-butyl lithium etc.), lithium diisopropylamine (LDA), hexamethyldisilazane lithium.
- 3. the preparation method of 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride according to claim 1, it is characterized in that, described step 3 can replace to: by step 2 gained reaction solution after washing, drying, precipitation, be further purified and obtain sterling.
- 4. the preparation method of 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride according to claim 1, it is characterized in that, in described step 1, the mol ratio of 3-substituting group phenylfluoroform and highly basic is 1:0.8 ~ 1.2.
- 5. the preparation method of 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride according to claim 1, it is characterized in that, in described step 2, the mol ratio of 3-substituting group phenylfluoroform and sulfuryl chloride is 1:1.0 ~ 3.0.
- 6. the preparation method of 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride according to claim 1, it is characterized in that, described reaction can be carried out under condition of no solvent.
- 7. the preparation method of 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride according to claim 1, it is characterized in that, described reaction can be carried out under described organic solvent is the condition of aromatic hydrocarbons, alkane or ether.
- 8. the preparation method of 2-substituting group-6-trifluoromethyl benzene sulfonyl chloride according to claim 1, it is characterized in that, described reaction can be carried out within the scope of-100 ~-20 DEG C, and optimal reaction temperature is-60 –-100 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961662A (en) * | 2015-06-11 | 2015-10-07 | 湖南化工研究院有限公司 | Preparation method of 2-fluoro-6-trifluoromethyl benzenesulfonyl chloride |
| CN105294515A (en) * | 2015-11-13 | 2016-02-03 | 天津现代职业技术学院 | Preparation method of 2-(2',2'-difluoroethoxy)-6-(trifluoromethyl)benzene-1-sulfonyl chloride |
| CN106478464A (en) * | 2016-08-30 | 2017-03-08 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of 2 fluorine, 6 trifluoromethyl benzene sulfonyl chloride |
| CN107935891A (en) * | 2018-01-24 | 2018-04-20 | 邯郸市赵都精细化工有限公司 | A kind of preparation method of 2 fluorine, 6 trifluoromethyl benzene sulfonyl chloride |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961662A (en) * | 2015-06-11 | 2015-10-07 | 湖南化工研究院有限公司 | Preparation method of 2-fluoro-6-trifluoromethyl benzenesulfonyl chloride |
| CN104961662B (en) * | 2015-06-11 | 2017-05-03 | 湖南化工研究院有限公司 | Preparation method of 2-fluoro-6-trifluoromethyl benzenesulfonyl chloride |
| CN105294515A (en) * | 2015-11-13 | 2016-02-03 | 天津现代职业技术学院 | Preparation method of 2-(2',2'-difluoroethoxy)-6-(trifluoromethyl)benzene-1-sulfonyl chloride |
| CN106478464A (en) * | 2016-08-30 | 2017-03-08 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of 2 fluorine, 6 trifluoromethyl benzene sulfonyl chloride |
| CN106478464B (en) * | 2016-08-30 | 2018-06-05 | 黄河三角洲京博化工研究院有限公司 | A kind of preparation method of the fluoro- 6- trifluoromethyls benzene sulfonyl chlorides of 2- |
| CN107935891A (en) * | 2018-01-24 | 2018-04-20 | 邯郸市赵都精细化工有限公司 | A kind of preparation method of 2 fluorine, 6 trifluoromethyl benzene sulfonyl chloride |
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Application publication date: 20150211 |