CN103113322B - Synthesis method of thiadiazolylamide derivative - Google Patents

Synthesis method of thiadiazolylamide derivative Download PDF

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CN103113322B
CN103113322B CN201310046734.9A CN201310046734A CN103113322B CN 103113322 B CN103113322 B CN 103113322B CN 201310046734 A CN201310046734 A CN 201310046734A CN 103113322 B CN103113322 B CN 103113322B
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thiadiazoles
synthetic method
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trifluoromethyl
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CN103113322A (en
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苏叶华
蔡国平
杨政和
陈邦池
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Oriental Luzhou Agrochemicals Co Ltd
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Zhejiang Zhuji United Chemicals Co Ltd
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Abstract

The invention relates to a synthesis method of 2-[(5-(trifluoromethyl)-1,3,4-thiadiazolyl-2-yl)-oxy]amine derivative (I). The method comprises the following step: in a solvent insoluble with water, 2-sulphinyl-5-trifluoromethyl-1,3,4-thiadiazole (II) and amide (III) react under the action of alkali to obtain the 2-[(5-(trifluoromethyl)-1,3,4-thiadiazolyl-2-yl)-oxy]amine. The reaction can also be performed in the presence of a catalyst. The invention has the advantages of high atomic economical efficiency, safe and simple raw material preparation, simple reaction operation, quick reaction, high yield and fewer three wastes, and is suitable for industrial production.

Description

Thiadiazoles amide derivatives synthetic method
Technical field
The invention belongs to thiadiazoles acid amides organic synthesis field.More particularly, the present invention relates to the synthetic method of thiadiazoles amide derivatives.
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 DEG C 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 DEG C 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 using 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 DEG C, 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 DEG C.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 substitutes bromine as leavings group using chlorine, 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 DEG C.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)-1,3,4-thiadiazoles and 3 '-chloro-N-sec.-propyl-2-hydroxyacetanilide is dissolved in acetone soln, slowly drips aqueous sodium hydroxide solution at-20 DEG C.At-20 DEG C, 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 DEG C, drip sodium hydroxide solution, after dropwising, at 5-10 DEG C, 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 using 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, and with oxygenants more than two equivalents, Atom economy is poor.Meanwhile, the preparation of raw material methylsulfonyl thiadiazoles is used the hydrogen peroxide (US5856499) of high density.In large production, use high density hydrogen peroxide to there is quite high potential safety hazard.
Summary of the invention
Have many problems existing in preparing thiadiazoles acetamides technology, such as raw material is difficult to preparation, cost is high, productive rate is low, long reaction time, Atom economy are not good, the use of high-risk reagent etc.Therefore, the method for the easy synthetic thiadiazoles amides of economic security is needed exploitation badly.
The invention provides the synthetic method of thiadiazoles amides (I), compound (I) general formula is as follows
Wherein
R 1, R 2, R 3, R 4hydrogen, (C 1-C 6)-alkyl, aryl (C 6-C 14) or containing heteroatoms aryl (nitrogen, oxygen, sulphur),
N is 1-6,
Method inclusion compound (II), compound (II) general formula is as follows
R is (C 1-C 6)-alkyl, aryl (C 6-C 14) or containing heteroatoms aryl (nitrogen, oxygen, sulphur), with compound (III), compound (III) general formula is as follows
Wherein
R 1, R 2, R 3, R 4as above-mentioned definition,
N is 1-6,
R 5hydrogen, (C 1-C 4)-alkyloyl, aryl (C 6-C 14) acyl group,
Reaction under solvent neutralization bases exists.This reaction also can be carried out under catalyzer.
Synthetic method of the present invention comprises following concrete steps: 2-sulfoxide group-5-Trifluoromethyl-1,3,4-thiadiazoles (II) and acid amides (III) be dissolved in the immiscible solvent of water in, under alkali effect, react.After finishing, reaction isolates organic phase, washing, precipitation can obtain 2-[(5-(trifluoromethyl)-1,3,4-thiadiazoles-2-yl)-oxygen base] acid amides (I).This reaction also can be carried out under catalyst action.
R in described compound (II) is (C 1-C 6)-alkyl, aryl (C 6-C 14) or containing heteroatoms aryl (nitrogen, oxygen, sulphur), preferably (C 1-C 6)-alkyl, more preferably methyl.
R in described compound (III) 1, R 2, R 3, R 4hydrogen, (C 1-C 6)-alkyl, aryl (C 6-C 14) or containing heteroatoms aryl (nitrogen, oxygen, sulphur).R 1, R 2preferably hydrogen and (C 1-C 6)-alkyl, more preferably hydrogen.R 3preferably hydrogen and (C 1-C 6)-alkyl, more preferably (C 1-C 6)-alkyl, most preferably sec.-propyl.R 4preferably aryl (C 6-C 14) or containing heteroatoms aryl (nitrogen, oxygen, sulphur), more preferably aryl (C 6-C 14), most preferably 4-fluorophenyl.N is 1-6, and preferably 1-3 is most preferably 1.
Described and the immiscible organic solvent of water are normal hexane, sherwood oil, methylene dichloride, dimethylbenzene and toluene.
Described alkali is organic bases and mineral alkali, preferably mineral alkali, the more preferably oxyhydroxide of alkali metal hydroxide, alkaline carbonate, alkaline-earth metal or alkaline earth metal carbonate, most preferably lithium hydroxide, sodium hydroxide and potassium hydroxide.
Described catalyzer be quaternary ammonium salt, season phosphonium salt, crown ether-like and polyethers, preferably quaternary ammonium salt, more preferably tetrabutyl ammonium halide, most preferably Tetrabutyl amonium bromide.
Raw material 2-sulfoxide group-5-Trifluoromethyl-1 of the present invention, 3,4-thiadiazoles (II) can be prepared by multiple method for oxidation, in the prior art can be with reference to disclosed synthetic schemes in US6437189.Another raw material acid amides (III) also can be synthetic by multiple method, in the prior art can be with reference to disclosed synthetic schemes in US5631403 and US4334073.
2-sulfoxide group-5-Trifluoromethyl-1, it is more suitable that 3,4-thiadiazoles (II) and acid amides (III) reaction are carried out at a lower temperature, and preferably temperature of reaction is-20-25 DEG C, and more preferably temperature is-10-15 DEG C, and optimum temperature is 0-10 DEG C.The mol ratio of the solvent adopting in reaction and compound (II) (or III) is preferably 5:1 to 60:1; More excellent ratio be 5:1 to 30:1, optimum ratio is 10:1 to 20:1.
In embodiment of the present invention, the mass content of alkali is 10% to 100%, is preferably 15%-50%.The mol ratio of alkali used and starting compound (II) is preferably 1:1 to 1:2, and preferably mol ratio is that 1:1 is to 1:1.5.
The present invention is with 2-sulfoxide group-5-Trifluoromethyl-1,3,4-thiadiazoles (II) and acid amides (III) are the synthetic 2-[(5-(trifluoromethyl)-1 of raw material, 3,4-thiadiazoles-2-yl)-oxygen base] acid amides (I), possess many advantages, be mainly reflected in: Atom economy is high, raw material prepares that safe and simple, operation is simple, reaction fast, yield is high, the three wastes are few, be applicable to industrial production.
Brief description of the drawings
Fig. 1: be 4 '-fluoro-N-(sec.-propyl)-2-[(5-(trifluoromethyl)-1,3,4-thiadiazoles-2-yl)-oxygen base] Acetanilide 1H-NMR collection of illustrative plates.
Fig. 2: 4 '-fluoro-N-(sec.-propyl)-2-[(5-(trifluoromethyl)-1,3,4-thiadiazoles-2-yl)-oxygen base] Acetanilide high resolution mass spectrum (ESI+) collection of illustrative plates.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described further.
The synthetic 4 '-fluoro-N-(sec.-propyl of embodiment 1)-2-[(5-(trifluoromethyl)-1,3,4-thiadiazoles-2-yl)-oxygen base] Acetanilide
Add 21.9g(0.1mol toward being furnished with in the there-necked flask of 500mL of mechanical stirring, thermometer and 50mL constant pressure funnel) 2-methyl sulfoxide base-5-Trifluoromethyl-1,3,4-thiadiazoles and 21.5g(0.1mol) 4 '-fluoro-N-sec.-propyl-2-hydroxyacetanilide, add 100mL toluene, ice-water bath is cooled to below 5 DEG C, under agitation in reaction solution, drips the aqueous solution that contains 4g sodium hydroxide (0.1mol).After dropwising, continue stirring reaction 1 hour.Separation of methylbenzene phase, washing twice, decompression is lower steams except toluene, obtains 36g white solid, yield 96%.As can be seen from Figure 1, 1h-NMR(CDCl 3) δ 7.28 (m, 2H), 7.20 (m, 2H), 4.95 (m, 1H), 4.73 (s, 1H), 1.10 (s, 3H), 1.08 (s, 3H); As can be seen from Figure 2, high resolution mass spectrum (ESI +) m/z364.0740[C 14h 13f 4n 3o 2s+H requires 364.0737]
The synthetic 4 '-fluoro-N-(sec.-propyl of embodiment 2)-2-[(5-(trifluoromethyl)-1,3,4-thiadiazoles-2-yl)-oxygen base] Acetanilide
Add 21.9g(0.1mol toward being furnished with in the there-necked flask of 1000mL of mechanical stirring, thermometer and 50mL constant pressure funnel) 2-methyl sulfoxide base-5-Trifluoromethyl-1,3,4-thiadiazoles and 21.5g(0.1mol) 4 '-fluoro-N-sec.-propyl-2-hydroxyacetanilide, add 0.1g Tetrabutyl amonium bromide and 500mL toluene, ice-water bath is cooled to below 5 DEG C, under agitation in reaction solution, add 12g(0.3mol in batches) sodium hydroxide, after feeding in raw material, continues stirring reaction 5 hours.Separation of methylbenzene phase, water washing twice, decompression is lower steams except toluene, obtains 35.4g white solid, yield 91.8%.
The synthetic 4 '-fluoro-N-(sec.-propyl of embodiment 3)-2-[(5-(trifluoromethyl)-1,3,4-thiadiazoles-2-yl)-oxygen base] Acetanilide
Add 21.9g(0.1mol toward being furnished with in the there-necked flask of 500mL of mechanical stirring, thermometer and 50mL constant pressure funnel) 2-methyl sulfoxide base-5-Trifluoromethyl-1,3,4-thiadiazoles and 21.5g(0.1mol) 4 '-fluoro-N-sec.-propyl-2-hydroxyacetanilide, add 200mL methylene dichloride, ice-water bath is cooled to below 5 DEG C, under agitation in reaction solution, drips the aqueous solution that contains 4.4g sodium hydroxide (0.11mol).After dropwising, continue stirring reaction 2 hours.Separate organic phase, water washing twice, solvent removes under reduced pressure, obtains 36.5g white solid, yield 98.5%.
The synthetic 4 '-fluoro-N-(sec.-propyl of embodiment 4)-2-[(5-(trifluoromethyl)-1,3,4-thiadiazoles-2-yl)-oxygen base] Acetanilide
Add 21.9g(0.1mol toward being furnished with in the there-necked flask of 500mL of mechanical stirring, thermometer and 50mL constant pressure funnel) 2-methyl sulfoxide base-5-Trifluoromethyl-1,3,4-thiadiazoles and 21.5g(0.1mol) 4 '-fluoro-N-sec.-propyl-2-hydroxyacetanilide, add 200mL methylene dichloride, ice-water bath is cooled to below 5 DEG C, under agitation in reaction solution, drips the aqueous solution that contains 4.4g sodium hydroxide (0.11mol).After dropwising, continue stirring reaction 2 hours.Separate organic phase, water washing twice, solvent removes under reduced pressure, obtains 35.3g white solid, yield 93.5%.
The synthetic 4 '-fluoro-N-(sec.-propyl of embodiment 5)-2-[(5-(trifluoromethyl)-1,3,4-thiadiazoles-2-yl)-oxygen base] Acetanilide
Add 2-methyl sulfoxide base-5-Trifluoromethyl-1 toward being furnished with in the there-necked flask of mechanical stirring, thermometer and constant pressure funnel, 3,4-thiadiazoles and 4 '-fluoro-N-sec.-propyl 2-acetoxyl group Acetanilide, add toluene, ice-water bath is cooled to, below 5 DEG C, under agitation in reaction solution, drip aqueous sodium hydroxide solution.After dropwising, continue stirring reaction 3 hours.Separation of methylbenzene phase, water washing twice, toluene removes under reduced pressure, obtains target product.
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 skill in the art 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. a synthetic method for thiadiazoles amides (I), compound (I) general formula is as follows
Wherein R 1, R 2, R 3, R 4hydrogen, C 1-C 6alkyl, C 6-C 14aryl,
N is 1-6;
Method inclusion compound (II), compound (II) general formula is as follows
R is C 1-C 6alkyl, C 6-C 14aryl,
With compound (III), compound (III) general formula is as follows
Wherein
R 1, R 2, R 3, R 4as above-mentioned definition,
N is 1-6,
R 5hydrogen, C 1-C 4alkyloyl, C 6-C 14aryl-acyl,
Reaction under solvent and alkali existence.
2. the synthetic method of thiadiazoles amides according to claim 1 (I), is characterized in that, the R in described compound (II) is methyl.
3. the synthetic method of thiadiazoles amides according to claim 1 (I), is characterized in that R 1, R 2preferably hydrogen and C 1-C 6alkyl, R 3preferably C 1-C 6alkyl, R 4preferably C 6-C 14aryl.
4. the synthetic method of thiadiazoles amides according to claim 1 (I), is characterized in that R 1, R 2preferably hydrogen, R 3preferably sec.-propyl; R 4preferably 4-fluorophenyl.
5. the synthetic method of thiadiazoles amides according to claim 1 (I), is characterized in that R 5preferably hydrogen.
6. the synthetic method of thiadiazoles amides according to claim 1 (I), is characterized in that, n preferably 1 in described compound (III).
7. the synthetic method of thiadiazoles amides according to claim 1 (I), is characterized in that, described solvent is preferably normal hexane, sherwood oil, methylene dichloride, dimethylbenzene or toluene.
8. the synthetic method of thiadiazoles amides according to claim 1 (I), is characterized in that, described alkali is lithium hydroxide, sodium hydroxide or potassium hydroxide preferably.
9. the synthetic method of thiadiazoles amides according to claim 1 (I), is characterized in that, described reaction is carried out under catalyzer condition.
10. the synthetic method of thiadiazoles amides according to claim 9 (I), is characterized in that, preferably Tetrabutyl amonium bromide of described catalyzer.
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WO2015074180A1 (en) * 2013-11-19 2015-05-28 泸州东方农化有限公司 Method for preparing thiadiazolylamide compounds
CN103664824A (en) * 2013-11-19 2014-03-26 泸州东方农化有限公司 Preparation method of thiadiazole carboxamide compounds

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US4061645A (en) * 1969-12-08 1977-12-06 Schering Aktiengesellschaft 2-Trichloromethyl-5-methylsulfinyl-1,3,4-thiadiazole
DE4415338A1 (en) * 1994-05-02 1995-11-09 Bayer Ag Alkylsulfinyl and alkylsulfonyl-1,2,4-thiadiazolyloxyacetamides
US5792872A (en) * 1997-12-12 1998-08-11 Bayer Corporation Process for producing N-(4-fluorophenyl)-N-(1-methylethyl)-2- (5-trifluoromethyl-1,3,4-thiadiazol-2-yl)oxy!acetamide
US6437189B1 (en) * 1997-12-12 2002-08-20 Bayer Corporation Synthesis of sulfoxides via selective oxidation of sulfides with a perborate or a percarbonate
US5895818A (en) * 1997-12-12 1999-04-20 Bayer Corporation Process for making N-(4-fluorophenyl)-N-(1-methylethyl)-2- (5-trifuloromethyl)-1,3,4-thiadiazol-2-yl)oxy!acetamide using an aprotic, aromatic solvent
ATE401316T1 (en) * 2002-11-08 2008-08-15 Sumitomo Chemical Co 1,2,4-THIADIAZOLE COMPOUNDS AND THEIR APPLICATION

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