CN102001979A - Preparation method of 2-(2', 2'-difluoroethoxyl)-6-trifluoromethyl phenyl propyl sulfide - Google Patents
Preparation method of 2-(2', 2'-difluoroethoxyl)-6-trifluoromethyl phenyl propyl sulfide Download PDFInfo
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Abstract
The invention provides a preparation method of 2-(2', 2'-difluoroethoxyl)-6-trifluoromethyl phenyl propyl sulfide, having the following processes: reacting m-trifluoromethyl phenol with p-toluenesulfonyl chloride, trifluoromethanesulfonic anhydride or 3, 5-dinitrobenzol sulfonyl chloride in a solvent containing organic base or a solvent containing triethylamine hydrochloride and organic base, and then, collecting a compound having a formula (III) from reaction products, dissolving the compound in butylene oxide, adding tetramethyl ethylene diamine and diisopropylamine, at a temperature range from -25 DEG C to -100 DEG C, adding butyl lithium cyclohexane solution for reaction, and then, adding dipropyldisulfide, and collecting a compound having a formula (II); reacting the compound having the formula (II) with 4-nitrogen, nitrogen-dimethyl pyridine and difluoroethanol for catalytic reaction in the solvent, and then, collecting a compound having a formula (I) from the reaction products. The invention simplifies reaction conditions, optimizes the technology, reduces production cost, and improves synthesis effects. The general formula of the reaction is as follows.
Description
Technical field
The present invention relates to prepare 1-(2, the 2-difluoroethoxy)-6-trifluoromethyl-N-(method of benzsulfamide key intermediate 2-(2 ', 2 '-difluoroethoxy)-6-trifluoromethyl propyl group thioether of [1,2,4] triazole [1,5-C] pyrimidine-2-).
Background technology
1-(2, the 2-difluoroethoxy)-6-trifluoromethyl-N-(benzsulfamide of [1,2,4] triazole [1,5-C] pyrimidine-2-), its chemical structure is as follows:
1-(2, the 2-difluoroethoxy)-6-trifluoromethyl-N-([1,2,4] triazole [1,5-C] benzsulfamide of pyrimidine-2-) is to use weedicide behind the seedling of being developed by U.S. Tao Nongke company (Dow Agro-Sciences), it is the triazolopyrimidine sulfonamide weedicide, works by suppressing acetolactate synthestase (ALS).Remove the leather agent as the rice field with wide spectrum, can effectively prevent and kill off barnyard grass grass (comprising barnyard grass grass), Semen Euphorbiae and annual sedge weed to Stam F-34, quinclorac and anti-acetyl-CoA carboxylase tool resistance, and effective to numerous broadleaf weedss, give birth to different stamen flower (Heteranthera limosa), carp intestines (Eclipta prostrata), sesbania (Sesbania exaltata), ring flower (Commelina diffusa), Sheathed Monochoria (Monochoria vaginalis) etc. as the natural pond.Simultaneously, it also can prevent and kill off anti-benbbensulfuronmethyl weeds in the rice field, and many broad-leaveds and sedge weed and barnyard grass grass etc. are had residual activity, for composing the widest kind with killing grass in the weedicide in present rice field.
1-(2, the 2-difluoroethoxy)-6-trifluoromethyl-N-([1,2,4] triazole [1,5-C] pyrimidine-2-) benzsulfamide is disclosed (US5858924) by U.S. Tao Nongke company (Dow Agro-Sciences) at United States Patent (USP)s in 1999, and the preparation of related penoxsuam is to be the raw material preparation 6-trifluoromethyl-2-fluorobenzene SULPHURYL CHLORIDE of setting out by the 6-trifluoromethyl-2-fluoroaniline that costs an arm and a leg and market degree is not high in this patent;
Mentioned the synthetic method of making the phenolic hydroxyl group protecting group with the methoxyl group METHYLENE CHLORIDE respectively in two parts of patents (US20050215570 and US20020037811) in addition in the Dow Chemical Company; but increased de-protected step in synthetic; the introducing of difluoroethoxy needs with costliness and does not have 2 of the marketization in addition, and 2-difluoro monobromethane is as reagent.
The applicant finds that 2-(2 ', 2 '-difluoroethoxy)-6-trifluoromethyl propyl group thioether can be used as the key intermediate of preparation penoxsuam, and its chemical structure is as follows:
But the preparation method of present 2-(2 ', 2 '-difluoroethoxy)-6-trifluoromethyl propyl group thioether is as Timothy C.Johnson, Bioorganic; There is the increase reactions steps of leaving away of blocking group in the method for Medicinal Chemistry 17 (2009) bibliographical informations, makes the defective that yield is lower and cost increases, and can not satisfy need of industrial production.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of 2-(2 ', 2 '-difluoroethoxy)-6-trifluoromethyl propyl group thioether is to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
(1) in containing the solvent of organic bases, perhaps in the solvent that contains triethylamine hydrochloride and organic bases, under the inert atmosphere (nitrogen), with m-trifluoromethyl phenol and p-methyl benzene sulfonic chloride, trifluoromethanesulfanhydride anhydride or 3, the reaction of 5-dinitrophenyl chloride, from reaction product, collect the compound of general formula (III) then, that is: 1-(4-Methyl benzenesulfonyl oxygen base)-3-(trifluoromethyl) benzene;
Described organic bases is selected from triethylamine, pyridine, N, dinethylformamide or N, accelerine;
Described solvent is selected from methylene dichloride, trichloromethane, acetonitrile or hexanaphthene;
The weight ratio of each component is:
M-trifluoromethyl phenol: p-methyl benzene sulfonic chloride=1: 0.5～1;
M-trifluoromethyl phenol: trifluoromethanesulfanhydride anhydride or 3,5-dinitrophenyl chloride=1: 0.2～0.8;
M-trifluoromethyl phenol: organic bases=1: 0.1～0.7;
The weightmeasurement ratio of triethylamine hydrochloride and organic bases is 4.0～5.0mg/ml;
In the solvent, the volume content of organic bases is 20～50%;
(2) under the inert atmosphere (nitrogen),, be dissolved in tetrahydrofuran (THF) (THF) with the compound of general formula (III), add Tetramethyl Ethylene Diamine and Diisopropylamine, under-25～-100 ℃, add the butyllithium cyclohexane solution, in the butyllithium cyclohexane solution, the weight content of butyllithium is 0.1～0.2g/ml, reaction 1～5h adds dipropyl disulfide then, and 0～40 ℃ was reacted 12～36 hours, at last, from reaction product, collect logical formula II compound;
The weight ratio of each component is:
The compound of general formula (III): Tetramethyl Ethylene Diamine=1: 1～2;
The compound of general formula (III): Diisopropylamine=1: 20～50;
The compound of general formula (III): butyllithium cyclohexane solution=1: 1～10;
The compound of general formula (III): dipropyl disulfide=1: 0.7～2.5;
In the tetrahydrofuran (THF), the content of the compound of general formula (III) is 10～30g/ml;
(3) will lead to formula II compound and 4-nitrogen, nitrogen-lutidine and difluoroethanol, in solvent, catalyzer exists down, and target product-logical formula I compound is collected in the reaction down 1.5～8 hours that refluxes then from reaction product;
Described catalyzer is selected from more than one in active copper powder, Red copper oxide or the cupric oxide, and catalyst levels is 1～10% of logical formula II compound weight;
Reaction expression is as follows:
R represents CH
3,
Logical formula I compound is preparation 1-(2, the 2-difluoroethoxy)-6-trifluoromethyl-N-([1,2,4] key intermediate of benzsulfamide of triazole [1,5-C] pyrimidine-2-) is a starting raw material with logical formula I compound, prepare the method for penoxsuam, comprise the steps:
Compound I by behind the chloro with 5,8-dimethoxy-[1,2,4] triazolo[1,5-c] the pyrimidin-2-amine reaction generates penoxsuam.
One of tangible characteristics of the present invention are that starting raw material sets out with trifluoromethyl phenol between cheap on the market; at organic bases (as triethylamine; pyridine etc.) there are following and p-methyl benzene sulfonic chloride; trifluoromethanesulfanhydride anhydride; 3; reacting generating compound general formulas (III) such as 5-dinitrophenyl chloride, with this sulphonate that forms not only can be used as protecting group but also can reaction afterwards in do not need again this protecting group of many one-step removals and directly can be used as leavings group.
The present invention is by synthetic 1-(2, the 2-difluoroethoxy)-6-trifluoromethyl-N-([1,2,4] (2-(2 for the intermediate of benzsulfamide of triazole [1,5-C] pyrimidine-2-), the 2-difluoroethoxy)-6-(trifluoromethyl) phenyl propyl thioether), simplify reaction conditions, optimize synthesis technique, improve reaction yield, reduce production costs, thereby improve the synthetic effect of penoxsuam greatly.
Embodiment
Embodiment 1
(1) compound III-1 is synthetic
Get the three-necked bottle of a 250ml, stirrer is equipped with in the inside.Use nitrogen protection, add the triethylamine hydrochloride of 0.1234g, add the triethylamine of 21g, stir, add the methylene dichloride of 100ml.The m-trifluoromethyl phenol that adds 7.86g afterwards again.Claim the Tosyl chloride of 9.13g, join in the reactor, stir that the some plate is followed the tracks of reaction.Stirring is spent the night.After having reacted, add the water of 50ml, stir 2h.Extract with ethyl acetate and water, organic layer is used the salt acid elution of 2N successively, saturated sodium bicarbonate aqueous solution, and water layer is removed in water washing 2 times.Carry out drying, decompression and solvent recovery with anhydrous sodium sulphate afterwards.Get white solid 14.5g.
The solid that previous step obtains is thick product, further uses the petrol ether/ethyl acetate recrystallization purifying.Get white crystal 14g.Productive rate 92%.
1H-NMR(400MHz，CDCl
3)δ：7.72(d，j＝8Hz，1H)，7.52(m，1H)，7.46(m，1H)，7.35(d，j＝8Hz，1H)，7.26(m，1H)，7.26(s，1H)，2.48(s，3H).
13C-NMR(100MHz，CDCl
3)δ：149.7，145.9，132.4，132.0，130.3，129.9，129.8，128.5，127.2，126.0，123.9，123.8，119.7，21.7.
(2) Compound I I-1's is synthetic:
Get 500ml exsiccant three-necked bottle, use nitrogen protection.With 1-(4-Methyl benzenesulfonyl oxygen base)-3-(trifluoromethyl) benzene of 36g, be dissolved in the tetrahydrofuran (THF) of 200ml.Add the Tetramethyl Ethylene Diamine of 22.6g and the Diisopropylamine of 0.94g.Use acetone bath, under the cooling of liquid nitrogen, cool to-80 ℃, this moment, solution colour was faint yellow.Under-80 ℃, slowly drip 11.7g butyllithium cyclohexane solution, the weight content of butyllithium is 0.1g/ml, yellow is deepened, and adds to become red-purple.Under this temperature, insulation reaction 2h.Get the dipropyl disulfide of 29.2g afterwards, slowly be added drop-wise in the reactor at-80 ℃, flavescence gradually becomes pale brown look at last.The point plate is followed the tracks of reaction, stirred overnight at room temperature.With the separating funnel extraction that reaction solution is poured 1000ml into, add the ether of 200ml, saturated aqueous common salt 200mlX3 washing, the ether layer anhydrous magnesium sulfate drying, suction filtration, filtrate decompression reclaims solvent.Separate purifying with silica gel column chromatography, eluent is the product that petrol ether/ethyl acetate (6: 1) obtains 34g, yield 89%.
1H-NMR(400MHz，CDCl
3)δ：7.81(d，j＝8Hz，2H)，?7.60(t，j＝8.8Hz，2H)，7.42(t，j＝8.4Hz，1H)，7.32(d，j＝8Hz，2H)，2.73(t，j＝7.2Hz，2H)，2.45(s，3H)，1.46(m，2H)，0.91(t，j＝7.2Hz，3H).
13C-NMR(100MHz，CDCl
3)δ：152.6，145.6，135.3，132.8，129.7，129.5，129.1，128.6，127.1，126.2，125.0，124.9，124.3，37.9，22.8，21.6，13.1.
(3) Compound I is synthetic:
In the dry reactor of 50ml, the compound ii-1 that adds 2g, the active copper powder that adds 0.28g, 0.12g cupric oxide and the 4-nitrogen of 0.6g, nitrogen-lutidine, the acetonitrile that adds 20ml again stirs 5min, add the 0.42g difluoroethanol at last, reflux 5 hours is cooled to room temperature, adds diatomite filtration, with ethyl acetate washing 2 times, filtrate is used the ethyl acetate water dispenser, and organic phase is water successively, the saturated common salt water washing, anhydrous sodium sulfate drying, decompression and solvent recovery is further used the silicagel column purifying, and petrol ether/ethyl acetate is an eluent.Obtain water white liquid 1.2g.Productive rate is 79%.
1H-NMR(400MHz，CDCl
3)δ：7.39(m，2H)，7.08(m，1H)，6.22(m，1H)，4.30(m，2H)，2.88(t，j＝7.2Hz，2H)，1.55(m，2H)，0.98(t，j＝7.2Hz，3H).
13C-NMR(100MHz，CDCl
3)δ：159.5，135.4，129.1，124.8，124.3，122.1，116.1，113.4，68.4，36.9，22.9，13.2.
Embodiment 2
(1) compound III-2 is synthetic
Get the three-necked bottle of a 250ml, stirrer is equipped with in the inside.Use nitrogen protection.At 0 ℃, the m-trifluoromethyl phenol of 52g is dissolved in the pyridine (this is solvent) of 150ml, then under agitation, slowly drip the trifluoromethanesulfanhydride anhydride of 95.2g.Add the back and stirred 0.5 hour under this temperature, rise to room temperature then, solution deepens.Stirring is spent the night.After having reacted, add the water of 50ml, stir 2h. and distribute with methylene dichloride and water, organic layer is used the salt acid elution of 2N successively, saturated sodium bicarbonate aqueous solution, and water layer is removed in water washing 2 times.Carry out drying, decompression and solvent recovery with anhydrous sodium sulphate afterwards.Get yellow oil 88.5 grams.The thick product that previous step obtains is further used the silicagel column purifying, and petrol ether/ethyl acetate is an eluent.Get faint yellow oily thing 85 grams, purity is 98.5% Compound I I-2, productive rate 92%.
1H-NMR(400MHz，CDCl3)δ：7.70(d，J＝7.7Hz，1H)，7.64(dd，J＝8.0，7.7Hz，1H)，7.57(s，1H)，7.52(d，J＝8.0Hz，1H)；
13C-NMR(100MHz，CDCl3)δ：149.6，133.2，131.1，125.5，125.1，123.0，118.9，118.8.
(2) compound ii-2 is synthetic:
Get 500ml exsiccant three-necked bottle, use nitrogen protection.With 1-(trifluoro-methanesulfonyl oxy)-3-(trifluoromethyl) benzene of 29.4g, be dissolved in the THF of 200ml.Add the Tetramethyl Ethylene Diamine of 22.6g and the Diisopropylamine of 0.94g.Use acetone bath, under the cooling of liquid nitrogen, cool to-80 ℃, this moment, solution colour was faint yellow, dripped 11.7g butyllithium cyclohexane solution, and the weight content of butyllithium is 0.2g/ml, and yellow is deepened, and adds to become red-purple.Under this temperature, insulation reaction 2h.Get the dipropyl disulfide of 30.4ml afterwards, be added drop-wise in the reactor at-80 ℃, flavescence gradually becomes pale brown look at last.The point plate is followed the tracks of reaction, stirred overnight at room temperature.With the separating funnel extraction that reaction solution is poured 1000ml into, add the ether of 200ml, saturated aqueous common salt 200mlX3 washing, the ether layer anhydrous magnesium sulfate drying, suction filtration, filtrate decompression reclaims solvent.Separate purifying with silica gel column chromatography, eluent is the product that petrol ether/ethyl acetate (8: 1) obtains 29.5g, yield 80%.
1H-NMR(400MHz，CDCl3)δ：7.58(d，J＝7.7Hz，1H)，7.44(m，1H)，7.42(d，J＝8.0Hz，1H)，2.70(t，j＝7.2Hz，2H)，1.45(m，2H)，0.94(t，j＝7.2Hz，3H).；
13C-NMR(100MHz，CDCl3)δ：151.4，134.3，132.3，125.8，125.3，123.5，119.6，118.8，37.6，22.9，13.5。
(3) Compound I is synthetic
In the dry reactor of 50ml, the compound ii-2 that adds 3.68g, the active copper powder that adds 0.56g, the 4-nitrogen of the cupric oxide of 0.24g and 1.2g, nitrogen-lutidine, the acetonitrile that adds 20ml again stirs 5min, adds the 0.84g difluoroethanol at last, reflux 5 hours, be cooled to room temperature, add diatomite filtration, with ethyl acetate washing 2 times, filtrate is used the ethyl acetate water dispenser, organic phase is water successively, the saturated common salt water washing, anhydrous sodium sulfate drying, decompression and solvent recovery, further use the silicagel column purifying, petrol ether/ethyl acetate is an eluent.Obtain water white liquid 2.52g.Productive rate is 84%.
1H-NMR(400MHz，CDCl
3)δ：7.39(m，2H)，7.08(m，1H)，6.22(m，1H)，4.30(m，2H)，2.88(t，j＝7.2Hz，2H)，1.55(m，2H)，0.98(t，j＝7.2Hz，3H).
13C-NMR(100MHz，CDCl
3)δ：159.5，135.4，129.1，124.8，124.3，122.1，116.1，113.4，68.4，36.9，22.9，13.2.
Embodiment 3
(1) compound a is synthetic
In the reaction flask of the 2L that is furnished with stirring and thermometer, the Compound I of 130g (0.396moles) is dissolved in 88% the formic acid of 600ml, chlorine under agitation feeds with the speed of 2 gram/minute, reacting liquid temperature is controlled at 37 ℃, the feeding amount of chlorine is 70% of compound (I) molar weight, after reaction will be carried out 1.5 hours, temperature of reaction is reduced to 23 ℃, the aqueous solution of the sodium bisulfite of 63g11% is added reaction solution, the adularescent solid produces, under 5 ℃, the water of 250ml is added in the mixed solution, and fully precipitation is filtered, the white solid solution ethyl acetate that obtains, anhydrous sodium sulfate drying.Evaporating solvent obtains white crystalline powder 135 grams, and productive rate is 95%, and purity is 95%, can be directly used in next step reaction.
1H-NMR(400MHz，CDCl
3)δ：7.83(t，j＝8Hz，1H)，7.64(d，j＝8Hz，1H)，7.43(d，j＝8Hz，1H)，6.29(m，1H)，4.48(m，2H).
13C-NMR(100MHz，CDCl
3)δ：157.9，136.1，132.4，129.9，123.1，120.4，112.8，69.8，30.8.
(2) ([1,2,4] triazole [1,5-C] pyrimidine-2-) benzsulfamide is synthetic for 1-(2, the 2-difluoroethoxy)-6-trifluoromethyl-N-
With 19.5g (0.1moles) compound 5,8-dimethoxy-[1,2,4] triazolo[1,5-c]
Pyrimidin-2-amine and 32.5g (0.1moles) compound a is dissolved in the acetonitrile of 45ml, at room temperature, add 3 of 34g (0.32moles), the 5-lutidine, 18 hats 6 of 1ml and the dimethyl sulfoxide (DMSO) of 0.2g, stirring at room 5 hours, point sample shows compound 5,8-dimethoxy-[1,2,4] triazolo[1,5-c] the pyrimidin-2-amine completely dissolve, the hydrochloric acid 100ml that adds 2N stirred 30 minutes, filter, obtain white crystalline powder 46 grams, purity 98%, yield 90%.
1H-NMR(400MHz，DMSO)δ：11.87(s，1H)，7.78(m，1H)，7.64(m，2H)，7.59(s，1H)，6.52(m，1H)，4.51(m，2H)，4.06(s，3H)，3.86(s，3H).
13C-NMR(100MHz，DMSO)δ：158.4，156.9，148.7，144.4，139.8，134.9，130.0，124.8，121.8，124.6，121.5，120.5，114.5，69.1，57.8，56.3。
Claims (10)
1.2-the preparation method of (2 ', 2 '-difluoroethoxy)-6-trifluoromethyl propyl group thioether is characterized in that, comprises the steps:
(1) in containing the solvent of organic bases, perhaps in the solvent that contains triethylamine hydrochloride and organic bases, under the inert atmosphere, with m-trifluoromethyl phenol and p-methyl benzene sulfonic chloride, trifluoromethanesulfanhydride anhydride or 3, the 5-dinitrophenyl chloride reacts, and collects the compound of general formula (III) then from reaction product;
(2) under the inert atmosphere, the compound with general formula (III) is dissolved in tetrahydrofuran (THF), add Tetramethyl Ethylene Diamine and Diisopropylamine, under-25～-100 ℃, add the reaction of butyllithium cyclohexane solution, add dipropyl disulfide then, logical formula II compound is collected in reaction at last from reaction product;
(3) will lead to formula II compound and 4-nitrogen, nitrogen-lutidine and difluoroethanol, in solvent, catalyzer exists down, and logical formula I compound is collected in the reaction down that refluxes then from reaction product; Reaction expression is as follows:
R represents CH
3,
2. method according to claim 1 is characterized in that, in the step (1), described organic bases is selected from triethylamine, pyridine, N, dinethylformamide or N, accelerine.
3. method according to claim 1 is characterized in that, in the step (1), described solvent is selected from methylene dichloride, trichloromethane, acetonitrile or hexanaphthene.
4. method according to claim 1 is characterized in that, the weight ratio of each component is:
M-trifluoromethyl phenol: p-methyl benzene sulfonic chloride=1: 0.5～1;
M-trifluoromethyl phenol: trifluoromethanesulfanhydride anhydride or 3,5-dinitrophenyl chloride=1: 0.2～0.8;
M-trifluoromethyl phenol: organic bases=1: 0.1～0.7;
The weightmeasurement ratio of triethylamine hydrochloride and organic bases is 4.0～5.0mg/ml;
In the solvent, the volume content of organic bases is 20～50%.
5. method according to claim 1 is characterized in that, in the step (2), in the butyllithium cyclohexane solution, the weight content of butyllithium is 0.1～0.2g/ml.
6. method according to claim 5 is characterized in that, adds butyllithium cyclohexane solution reaction 1～5h, adds dipropyl disulfide then, and 0～40 ℃ was reacted 12～36 hours.
7. method according to claim 1 is characterized in that, the weight ratio of each component is in the step (2):
The compound of general formula (III): Tetramethyl Ethylene Diamine=1: 1～2;
The compound of general formula (III): Diisopropylamine=1: 20～50;
The compound of general formula (III): butyllithium cyclohexane solution=1: 1～10;
The compound of general formula (III): dipropyl disulfide=1: 0.7～2.5;
In the tetrahydrofuran (THF), the content of the compound of general formula (III) is 10～30g/ml.
8. method according to claim 1 is characterized in that, in the step (3), reaction down 1.5～8 hours refluxes.
9. method according to claim 1 is characterized in that, in the step (3), catalyst levels is 1～10% of logical formula II compound weight.
10. according to each described method of claim 1～9, it is characterized in that described catalyzer is selected from more than one in active copper powder, Red copper oxide or the cupric oxide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044431A (en) * | 2012-10-22 | 2013-04-17 | 中国药科大学 | Novel preparation method of penoxsulam |
| 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 |
| CN110590623A (en) * | 2019-09-27 | 2019-12-20 | 江苏好收成韦恩农化股份有限公司 | Method for preparing 6-substituted-2-trifluoromethyl phenyl sulfide in continuous flow microchannel reactor |
| CN110698363A (en) * | 2019-01-28 | 2020-01-17 | 杭州师范大学 | Synthetic method of 2- (2, 2-difluoroethoxy) -6- (trifluoromethyl) benzenesulfonyl chloride |
| CN115703726A (en) * | 2021-08-08 | 2023-02-17 | 上海泰初化工技术有限公司 | Trifluoromethyl phenyl sulfide compound |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103044431A (en) * | 2012-10-22 | 2013-04-17 | 中国药科大学 | Novel preparation method of penoxsulam |
| 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 |
| CN110698363A (en) * | 2019-01-28 | 2020-01-17 | 杭州师范大学 | Synthetic method of 2- (2, 2-difluoroethoxy) -6- (trifluoromethyl) benzenesulfonyl chloride |
| CN110590623A (en) * | 2019-09-27 | 2019-12-20 | 江苏好收成韦恩农化股份有限公司 | Method for preparing 6-substituted-2-trifluoromethyl phenyl sulfide in continuous flow microchannel reactor |
| CN115703726A (en) * | 2021-08-08 | 2023-02-17 | 上海泰初化工技术有限公司 | Trifluoromethyl phenyl sulfide compound |
| CN115703726B (en) * | 2021-08-08 | 2024-04-02 | 上海泰初化工技术有限公司 | Trifluoromethyl phenyl sulfide compound |
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| CN102001979B (en) | 2013-07-31 |
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