CN103664824A - Preparation method of thiadiazole carboxamide compounds - Google Patents
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- CN103664824A CN103664824A CN201310585596.1A CN201310585596A CN103664824A CN 103664824 A CN103664824 A CN 103664824A CN 201310585596 A CN201310585596 A CN 201310585596A CN 103664824 A CN103664824 A CN 103664824A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
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Abstract
The invention discloses a preparation method of thiadiazole carboxamide compounds. Mixed raw materials 2-sulfoxide base-5-trifluoromethyl-1,3,4-thiadiazole (II) and 2-sulfonyl-5-trifluoromethyl-1,3,4-thiadiazole (II') are at a mass ratio of 99:1 to 1:99, and the mixed raw materials react with a compound (III) in the solution of a dissolvent and inorganic alkali at a reaction temperature from minus 20 DEG C to 25 DEG C, so that a compound (I) is obtained. The preparation method of the thiadiazole carboxamide compounds disclosed by the invention is simple in the preparation of the mixed raw materials, simple and convenient to operate, high in reaction speed and yield, less in 'three wastes', and suitable for industrial production.
Description
Technical field
The invention belongs to thiadiazoles acid amides organic synthesis field.More particularly, the present invention relates to the preparation method of thiadiazoles amides.
Background technology
US4708731, US4645525 and US4585471 report thiadiazoles amide derivatives have weeding activity.US4645525 discloses N-methyl-2-[(5-(trifluoromethyl)-1,3 in nineteen eighty-three, 4-thiadiazoles-2-yl)-oxygen base] preparation method of-N-ethanoyl aniline.The method is: N-methyl-2-hydroxy-n-ethanoyl aniline and calcium oxide react at 50 ℃ 1 hour in dimethyl sulfoxide (DMSO), in reaction solution, adds the bromo-2-Trifluoromethyl-1 of 5-, and 3,4-thiadiazoles stirs 40 hours at 50 ℃ of reaction solutions.Mixture is poured into water, and the oily matter dichloromethane extraction of precipitation obtains target product, productive rate approximately 90% after steaming desolventizes.This preparation method is usingd bromine as leavings group, but the bromo-2-Trifluoromethyl-1 of the raw materials used 5-of the method, 3,4-thiadiazoles preparation difficulty, long reaction time, solvent dimethyl sulfoxide (DMSO) is difficult to be reclaimed.
US4708731 discloses a kind of 5-chloro alkyl-1 in 1984,3,4-thiazoldiazolioxo acetamide has weeding activity, and this type of thiadiazoles ethanamide is chloro-1,3 by 2-, and 4-thiadiazoles and hydroxy-n-ethanoyl aniline react preparation under toluene.US4708731 discloses preparation N-ethyl-2-[(5-(trichloromethyl)-1,3,4-thiadiazoles-2-yl)-oxygen base] synthetic schemes of-N-ethanoyl ethamine.Its scheme is: at-10 ℃, toward the chloro-5-of 2-trichloromethyl-1, in the toluene solution of 3,4-thiadiazoles and N-ethyl-2-hydroxy-n-ethanoyl ethamine, drip aqueous sodium hydroxide solution, after dropwising, react 12 hours at 0-5 ℃.Isolate toluene phase, and water washing is extremely neutral, solvent removed in vacuo, resistates is pulled an oar and is separated out solid in sherwood oil, and suction filtration obtains target product, productive rate about 42% after being dried.This preparation method is usingd the alternative bromine of chlorine as leavings group, and raw materials cost is than the bromo-2-Trifluoromethyl-1 of 5-, and 3,4-thiadiazoles technique is low, but long reaction time, end reaction yield only has 42%.
US4585471 discloses preparation 2-[(5-(trifluoromethyl in 1986)-1,3,4-thiadiazoles-2-yl)-oxygen base] method of acetylaminohydroxyphenylarsonic acid 2-ethyl piperidine.This synthetic method is: under sodium tert-butoxide exists, and N-(hydroxyacetyl)-2-ethyl piperidine and the chloro-5-Trifluoromethyl-1 of 2-, 3,4-thiadiazoles reacts 3 hours in the trimethyl carbinol, temperature of reaction 20-30 ℃.Add dichloromethane extraction, dilute hydrochloric acid acidifying, water washing, except desolventizing obtains target product, productive rate approximately 66%.This preparation method adopts the sodium tert-butoxide that price is higher, though reaction yield increase, but still undesirable.
US4968342 discloses 3 '-chloro-N-(sec.-propyl in nineteen ninety)-2-[(5-(trifluoromethyl)-1,3,4-thiadiazoles-2-yl)-oxygen base] synthetic schemes of Acetanilide.This synthetic schemes is: 2-(methylsulfonyl)-5-(trifluoromethyl)-1,3, and 4-thiadiazoles and 3 '-chloro-N-sec.-propyl-2-hydroxyacetanilide is dissolved in acetone soln, slowly drips aqueous sodium hydroxide solution at-20 ℃.At-20 ℃, react 3 hours, reactant is poured into water, the solid that suction filtration obtains separating out, productive rate approximately 85%.Although this preparation method's productive rate than before technique increases (～85%), this process using water-soluble solvent, make raw material 2-(methylsulfonyl)-5-(trifluoromethyl)-1,3,4-thiadiazoles is easily hydrolyzed, and reaction must be carried out at low temperatures, and the difficult recovery of acetone.
US5895818 and US5792872 disclose 4 '-fluoro-N-sec.-propyl-2-[(5-trifluoromethyl-l in 1997,3,4-thiadiazoles-2-yl)-oxygen base] synthetic method of Acetanilide, according to the method, with 2-methylsulfonyl-5-Trifluoromethyl-1,3,4-thiadiazoles and 4 '-fluoro-N-sec.-propyl-2-hydroxyacetanilide is dissolved in toluene solution, at 0-5 ℃, drip sodium hydroxide solution, after dropwising, at 5-10 ℃, continue reaction 2 hours.Dilute hydrochloric acid acidifying pH to 5.0 for reaction mixture, separation of methylbenzene phase, uses toluene aqueous phase extracted, and combining methylbenzene phase obtains target product except after desolventizing, and productive rate is greater than 93%.This preparation method is usingd methylsulfonyl as leavings group, and reaction conditions is gentleer, and productive rate is higher.But methylsulfonyl need to obtain from methylthio group oxidation, wherein sulphur atom, from-be oxidized to+divalent of divalent state state, need to obtain two Sauerstoffatoms from oxygenant, be with oxygenants more than two equivalents, and Atom economy is poor.Meanwhile, the hydrogen peroxide (US5856499) of high density is used in the preparation of raw material methylsulfonyl thiadiazoles.In large production, use high density hydrogen peroxide to there is quite high potential safety hazard.
Recently, CN103113322 discloses a kind of novel method of preparing thiadiazoles acid amides.The method be take sulfoxide group thiadiazoles as the condensation of raw material and 4 '-fluoro-N-sec.-propyl-2-hydroxyacetanilide, reacts to obtain the high-quality target product of high yield.But the weak point of the method is raw material first sulfoxide group thiadiazoles, need prepare through chemo-selective oxidation, thereby make to select to be restricted at oxygenant and reaction conditions.In simultaneous reactions, control requires to improve, and then increases cost.
Technique at synthetic sulfuryl thiadiazoles, as the open technique being oxidized under acetic acid with hydrogen peroxide in US5856499 needs excessive high density hydrogen peroxide, in order to make a small amount of oxidation intermediates sulfoxide thoroughly be converted into sulfone, need reaction for a long time, and in synthetic sulfoxide group thiadiazoles technique, as CN103288776 discloses the technique being oxidized in methanol solvate with potassium hydrogen persulfate, in order to prevent that sulfoxide group thiadiazoles is further oxidized to sulfuryl thiadiazoles, need the strict consumption of controlling oxygenant potassium hydrogen persulfate, need slowly to add oxygenant simultaneously.
Existing, have many problems in preparing thiadiazoles acetamides technology, for example raw material preparation cost is high, productive rate is low, long reaction time, Atom economy are not good, the use of high-risk reagent, and intermediate needs purifying etc.Therefore, develop more economical, safety, the synthetic method of high efficiency thiadiazoles amide compound is significant.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of thiadiazoles amides is provided.
The preparation method of thiadiazoles amides (I) is: mixing raw material 2-sulfoxide group-5-Trifluoromethyl-1,3,4-thiadiazoles (II) and 2-sulfuryl-5-Trifluoromethyl-1,3, the mass ratio of 4-thiadiazoles (II ') be 99:1 to 1:99, mixing raw material and compound (III) react in the solution of solvent and mineral alkali, temperature of reaction is-20-25 ℃ to obtain compound (I);
Wherein, compound (I) general formula is as follows
R
1, R
2, R
3, R
4comprise hydrogen, (C
1-C
6)-alkyl, aryl (C
6-C
14) or nitrogenous, oxygen, sulfur heteroatom aryl,
N is 1-6;
Compound (II) and (II ') general formula are as follows
R comprises (C
1-C
6)-alkyl, aryl (C
6-C
14) or nitrogenous, oxygen, sulfur heteroatom aryl, compound (III) general formula is as follows
R
1, R
2, R
3, R
4, n is as above-mentioned definition,
R
5comprise hydrogen, (C
1-C
4)-alkyloyl or aryl (C
6-C
14) acyl group.
R in described compound (II) and (II ') is (C preferably
1-C
6)-alkyl.Described (C
1-C
6)-alkyl be more preferably methyl.R in described compound (III)
1, R
2, R
3, R
4preferably hydrogen, (C
1-C
6)-alkyl or aryl (C
6-C
14), R
5preferably hydrogen, (C
1-C
4)-alkyloyl.Described R
1, R
2be more preferably hydrogen, R
3be more preferably sec.-propyl, R
4be more preferably 4-fluorophenyl.N preferably 1 in described compound (III).The mol ratio of mixing raw material and compound (III) is 3:1-1:1 preferably, and the mol ratio of mineral alkali and compound (III) is 1:1-3:1. preferably.Described solvent is one or more in normal hexane, sherwood oil, methylene dichloride, dimethylbenzene or toluene preferably.Described mineral alkali is oxyhydroxide or the alkaline earth metal carbonate of alkali metal hydroxide, alkaline carbonate, alkaline-earth metal preferably, described alkali metal hydroxide is more preferably lithium hydroxide, sodium hydroxide or potassium hydroxide, and described inorganic alkali solution concentration is 15%-50% preferably.Described reaction is carried out under catalyzer condition, and described catalyzer is tetrabutyl ammonium halide preferably.
Sulfuryl thiadiazoles of the present invention and sulfoxide group thiadiazoles mixing raw material, can adopt the synthesis technique (can with reference to US5856499) of sulfuryl thiadiazoles, raw material reaction gets final product stopped reaction completely, do not need the distribution of monitoring product for the synthesis of compound (I), can reduce consumption and the reaction times of oxygenant; Can adopt sulfoxide group thiadiazoles technique synthesis technique (can with reference to CN103288776), not need strictly to control amount and the rate of feeding of oxygenant, add after material monitoring raw material and disappear and get final product processing reaction, product is directly used in synthetic compound (I).
The present invention is with mixing raw material 2-sulfoxide group-5-Trifluoromethyl-1,3,4-thiadiazoles (II) and 2-sulfuryl-5-Trifluoromethyl-1,3,4-thiadiazoles (II ') and acid amides (III) they are the synthetic 2-[(5-(trifluoromethyl)-1,3 of initiator, 4-thiadiazoles-2-yl)-oxygen base] and acid amides (I), possess many advantages, be mainly reflected in: mixing raw material prepare simple, easy and simple to handle, reaction fast, yield is high, the three wastes are few, be applicable to industrial production.
Embodiment
The preparation method of thiadiazoles amides (I) is: mixing raw material 2-sulfoxide group-5-Trifluoromethyl-1,3,4-thiadiazoles (II) and 2-sulfuryl-5-Trifluoromethyl-1,3, the mass ratio of 4-thiadiazoles (II ') be 99:1 to 1:99, mixing raw material and compound (III) react in the solution of solvent and mineral alkali, temperature of reaction is-20-25 ℃ to obtain compound (I);
Wherein, compound (I) general formula is as follows
R
1, R
2, R
3, R
4comprise hydrogen, (C
1-C
6)-alkyl, aryl (C
6-C
14) or nitrogenous, oxygen, sulfur heteroatom aryl,
N is 1-6;
Compound (II) and (II ') general formula are as follows
R comprises (C
1-C
6)-alkyl, aryl (C
6-C
14) or nitrogenous, oxygen, sulfur heteroatom aryl, compound (III) general formula is as follows
R
1, R
2, R
3, R
4, n is as above-mentioned definition,
R
5comprise hydrogen, (C
1-C
4)-alkyloyl or aryl (C
6-C
14) acyl group.
R in described compound (II) and (II ') is (C preferably
1-C
6)-alkyl.Described (C
1-C
6)-alkyl be more preferably methyl.R in described compound (III)
1, R
2, R
3, R
4preferably hydrogen, (C
1-C
6)-alkyl or aryl (C
6-C
14), R
5preferably hydrogen, (C
1-C
4)-alkyloyl.Described R
1, R
2be more preferably hydrogen, R
3be more preferably sec.-propyl, R
4be more preferably 4-fluorophenyl.N preferably 1 in described compound (III).The mol ratio of mixing raw material and compound (III) is 3:1-1:1 preferably, and the mol ratio of mineral alkali and compound (III) is 1:1-3:1. preferably.Described solvent is one or more in normal hexane, sherwood oil, methylene dichloride, dimethylbenzene or toluene preferably.Described mineral alkali is oxyhydroxide or the alkaline earth metal carbonate of alkali metal hydroxide, alkaline carbonate, alkaline-earth metal preferably, described alkali metal hydroxide is more preferably lithium hydroxide, sodium hydroxide or potassium hydroxide, and described inorganic alkali solution concentration is 15%-50% preferably.Described reaction is carried out under catalyzer condition, and described catalyzer is tetrabutyl ammonium halide preferably.
The present invention is described further for following examples.
Mixing raw material 2-sulfoxide group-5-Trifluoromethyl-1,3,4-thiadiazoles (II) and 2-sulfuryl-5-Trifluoromethyl-1,3,4-thiadiazoles (II ') synthetic method A:
Toward being furnished with mechanical stirring, in the there-necked flask of the 3000mL of thermometer, add 315g(1.5mol) 2-methylthio group-5-Trifluoromethyl-1, 3, 4-thiadiazoles, add 900mL methyl alcohol and 900mL water, under water-bath, stir, add fast 520g potassium hydrogen persulfate (44%), reinforced complete, continue to stir 5 minutes, filter reaction mixture, filter cake methanol wash, merging filtrate decompression are lower steams except methyl alcohol, the toluene extraction adding, separation of methylbenzene phase, and wash with water twice, separation of methylbenzene phase, except desolventizing obtains 320.6g solid product, yield 95%(2-first sulfoxide group-5-(trifluoromethyl)-1, 3, 4-thiadiazoles content 96%, 2-first sulfoxide group-5-(trifluoromethyl)-1, 3, 4-thiadiazoles content 2.5%).
Mixing raw material 2-sulfoxide group-5-Trifluoromethyl-1,3,4-thiadiazoles (II) and 2-sulfuryl-5-Trifluoromethyl-1,3,4-thiadiazoles (II ') synthetic method B:
Toward being furnished with mechanical stirring, in the there-necked flask of the 3000mL of thermometer, add 315g(1.5mol) 2-methylthio group-5-Trifluoromethyl-1, 3, 4-thiadiazoles, the peroxyboric acid of 30g, the toluene of 1200mL and the Glacial acetic acid of 40g, reaction mixture is heated to 80 ℃, 35% hydrogen peroxide of 2.5mol added in 1 hour, reactant continues minute water reaction 4 hours, after reaction solution cooling, divide water-yielding stratum, wash twice, remove toluene and obtain white solid 333.6g, yield 93%(2-first sulfoxide group-5-(trifluoromethyl)-1, 3, 4-thiadiazoles content 2%, 2-first sulfoxide group-5-(trifluoromethyl)-1, 3, 4-thiadiazoles content 97%).
Embodiment 1
Toward being furnished with in the there-necked flask of 2000mL of mechanical stirring, thermometer and constant pressure funnel, add 219.7g2-methyl sulfoxide base-5-Trifluoromethyl-1,3,4-thiadiazoles and 2-methylsulfonyl-5-Trifluoromethyl-1,3,4-thiadiazoles mixture (mass ratio 96:2.5, be total to 1mol) and 4 '-fluoro-N-sec.-propyl-2-hydroxyacetanilide 215g(1mol), add 1000mL dimethylbenzene, ice-water bath is cooled to below 5 ℃, under agitation in reaction solution, be added dropwise to (containing sodium hydroxide 80g, 2mol) sodium hydroxide solution of 25%.After dropwising, continue stirring reaction 2 hours.Separated organic phase, water washing twice, solvent removes under reduced pressure, obtains 371g white solid, yield 97.5%.
1HNMR(400MHz,CDCl
3),&:7.26(m,2H),7.19(m,2H),4.94(m,1H),4.73(s,2H),1.08(d,J=6.8Hz,6H).
Embodiment 2
Toward being furnished with in the there-necked flask of 500mL of mechanical stirring, thermometer and constant pressure funnel, add 46.82-methyl sulfoxide base-5-Trifluoromethyl-1,3,4-thiadiazoles and 2-methylsulfonyl-5-Trifluoromethyl-1,3, the mixture of 4-thiadiazoles (mass ratio 2:97, be total to 0.2mol) and 4 '-fluoro-N-sec.-propyl-2-hydroxyacetanilide 43g(0.2mol), add 200mL methylene dichloride, ice-water bath is cooled to below 5 ℃, under agitation in reaction solution, be added dropwise to (containing sodium hydroxide 10g, 0.25mol) sodium hydroxide solution of 30%.After dropwising, continue stirring reaction 5 hours.Separated organic phase, water washing twice, solvent removes under reduced pressure, obtains 73.5g white solid, yield 97%.
Embodiment 3
Toward being furnished with mechanical stirring, in the there-necked flask of the 1000mL of thermometer and constant pressure funnel, add 115g2-methyl sulfoxide base-5-Trifluoromethyl-1, 3, 4-thiadiazoles and 2-methylsulfonyl-5-Trifluoromethyl-1, 3, 4-thiadiazoles mixture (mass ratio 2:3, be total to 0.5mol) and 4 '-fluoro-N-sec.-propyl-2-hydroxyacetanilide 108g(0.5mol), add 0.2g Tetrabutyl amonium bromide and 600mL toluene, ice-water bath is cooled to below 5 ℃, under agitation toward be added dropwise in reaction solution 40% (containing sodium hydroxide 20g, 0.5mol) sodium hydroxide solution, after reinforced, continue stirring reaction 0.5 hour.Separation of methylbenzene phase, water washing twice, decompression is lower steams except toluene, obtains 182.8g white solid, yield 98%.
Embodiment 4
Toward being furnished with in the 500mL there-necked flask of mechanical stirring, thermometer and constant pressure funnel, add 22.7g2-methyl sulfoxide base-5-Trifluoromethyl-1,3,4-thiadiazoles and 2-methylsulfonyl-5-Trifluoromethyl-1,3,4-thiadiazoles mixture (mass ratio 1:1, be total to 0.1mol) and 4 '-fluoro-N-sec.-propyl 2-acetoxyl group Acetanilide 26g(0.1mol), add 100mL toluene, ice-water bath is cooled to below 5 ℃, under agitation in reaction solution, be slowly added dropwise to (containing sodium hydroxide 10g, 0.25mol) sodium hydroxide solution of 15%.After dropwising, continue stirring reaction 4 hours.Separation of methylbenzene phase, water washing twice, toluene removes under reduced pressure, obtains 35.1g white solid, yield 91%.
Embodiment 5
Toward being furnished with in the there-necked flask of 250mL of mechanical stirring, thermometer and constant pressure funnel, add 22g2-methyl sulfoxide base-5-Trifluoromethyl-1,3,4-thiadiazoles and 2-methylsulfonyl-5-Trifluoromethyl-1,3,4-thiadiazoles mixture (mass ratio 96:2.5,0.1mol) and 7.2g(0.033mol) 4 '-fluoro-N-sec.-propyl-2-hydroxyacetanilide, add 100mL toluene, at 25 ℃, under agitation in reaction solution, be added dropwise to (containing potassium hydroxide 5.6g, 0.1mol) potassium hydroxide solution of 30%.After dropwising, continue stirring reaction 2 hours.Separated organic phase, water washing twice, solvent removes under reduced pressure, obtains 11.5g white solid, yield 90%.
Embodiment 6
Toward being furnished with in the there-necked flask of 250mL of mechanical stirring, thermometer and constant pressure funnel, add 33g2-methyl sulfoxide base-5-Trifluoromethyl-1,3,4-thiadiazoles and 2-methylsulfonyl-5-Trifluoromethyl-1,3,4-thiadiazoles mixture (mass ratio 96:2.5,0.15mol) and 21.5g(0.1mol) 4 '-fluoro-N-sec.-propyl-2-hydroxyacetanilide, add 150mL toluene, at-20 ℃, under agitation in reaction solution, be added dropwise to (containing lithium hydroxide 3.6g, 0.15mol) lithium hydroxide solution of 35%.After dropwising, continue stirring reaction 2 hours.Separated organic phase, water washing twice, solvent removes under reduced pressure, obtains 35.5g white solid, yield 93%.
Although the present invention has been described in detail and has illustrated; but should be clear; it is only exemplary illustrated object, and the present invention is not limited thereto, and the change that those of ordinary skills carry out the present invention under enlightenment of the present invention and instruction all should drop in protection scope of the present invention.
Claims (10)
1. the preparation method of a thiadiazoles amides (I), it is characterized in that, mixing raw material 2-sulfoxide group-5-Trifluoromethyl-1,3,4-thiadiazoles (II) and 2-sulfuryl-5-Trifluoromethyl-1,3, the mass ratio of 4-thiadiazoles (II ') be 99:1 to 1:99, mixing raw material and compound (III) react in the solution of solvent and mineral alkali, temperature of reaction is-20-25 ℃ to obtain compound (I);
Wherein, compound (I) general formula is as follows
R
1, R
2, R
3, R
4comprise hydrogen, (C
1-C
6)-alkyl, aryl (C
6-C
14) or nitrogenous, oxygen, sulfur heteroatom aryl,
N is 1-6;
Compound (II) and (II ') general formula are as follows
R comprises (C
1-C
6)-alkyl, aryl (C
6-C
14) or nitrogenous, oxygen, sulfur heteroatom aryl, compound (III) general formula is as follows
R
1, R
2, R
3, R
4, n is as above-mentioned definition,
R
5comprise hydrogen, (C
1-C
4)-alkyloyl or aryl (C
6-C
14) acyl group.
2. the preparation method of thiadiazoles amides according to claim 1 (I), is characterized in that, the R in described compound (II) and (II ') is (C
1-C
6)-alkyl.
3. the preparation method of thiadiazoles amides according to claim 2 (I), is characterized in that, described (C
1-C
6)-alkyl be methyl.
4. the preparation method of thiadiazoles amides according to claim 1 (I), is characterized in that, the R in described compound (III)
1, R
2, R
3, R
4hydrogen, (C
1-C
6)-alkyl or aryl (C
6-C
14), R
5hydrogen, (C
1-C
4)-alkyloyl.
5. the preparation method of thiadiazoles amides according to claim 4 (I), is characterized in that, described R
1, R
2hydrogen, R
3sec.-propyl, R
44-fluorophenyl, R
5hydrogen.
6. the preparation method of thiadiazoles amides according to claim 1 (I), is characterized in that, in described compound (III), n is 1.
7. the preparation method of thiadiazoles amides according to claim 1 (I), is characterized in that, the mol ratio of mixing raw material and compound (III) is 3:1-1:1, and the mol ratio of mineral alkali and compound (III) is 1:1-3:1.
8. the preparation method of thiadiazoles amides according to claim 1 (I), is characterized in that, described solvent is one or more in normal hexane, sherwood oil, methylene dichloride, dimethylbenzene or toluene.
9. the preparation method of thiadiazoles amides according to claim 1 (I), it is characterized in that, described mineral alkali is oxyhydroxide or the alkaline earth metal carbonate of alkali metal hydroxide, alkaline carbonate, alkaline-earth metal, described alkali metal hydroxide is lithium hydroxide, sodium hydroxide or potassium hydroxide, and described inorganic alkali solution concentration is 15%-50%.
10. the preparation method of thiadiazoles amides according to claim 1 (I), is characterized in that, described reaction is carried out under catalyzer condition, and described catalyzer is tetrabutyl ammonium halide.
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| CN106866579A (en) * | 2017-02-23 | 2017-06-20 | 西华大学 | The synthetic method of herbicide flufenacet thiadiazoles intermediate |
| CN106905260A (en) * | 2017-03-02 | 2017-06-30 | 西华大学 | Method for preparing herbicide flufenacet Intermediate TDA sulfone |
| WO2021115494A1 (en) * | 2019-12-13 | 2021-06-17 | Jiangsu Rotam Chemistry Co., Ltd | Novel crystalline forms of flufenacet, methods for their preparation and use of the same |
| WO2021115493A3 (en) * | 2019-12-13 | 2021-07-15 | Jiangsu Rotam Chemistry Co., Ltd | Novel crystalline forms of flufenacet, methods for their preparation and use of the same |
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| CN103113322A (en) * | 2013-02-05 | 2013-05-22 | 浙江省诸暨合力化学对外贸易有限公司 | Synthesis method of thiadiazolylamide derivative |
| CN103288776A (en) * | 2013-03-21 | 2013-09-11 | 浙江省诸暨合力化学对外贸易有限公司 | A synthesis method for 2 - sulfinyl -5 - (trifluoromethyl) - 1,3,4 - thiadiazole compounds |
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