阅读说明：本技术 一种具有除草性能的含六氟磺酰胺结构的化合物及其合成方法 (Compound with weeding performance and containing hexafluorosulfonamide structure and synthesis method thereof ) 是由 刘东卫 张彦飞 于 2020-06-30 设计创作，主要内容包括：本发明公开了一种具有除草性能的含六氟磺酰胺结构的化合物,化合物结构如式(Ⅲ)所示。本发明还公开了所述的化合物的合成方法,以2-(2,2-二氟乙氧基)-6-三氟甲基苯磺酰氯、2-氟-N-甲基苯胺为原料,在有机碱、催化剂的催化作用下反应得到目标产物。本发明除草谱广,在防除水稻田禾本科杂草如稗草、千金子,一年生莎草科杂草如异型莎草,阔叶杂草如耳叶水苋具有较好的防效,对水稻类农作物的正常生长无任何不利影响,不需加入安全剂,其使用剂量小,更有利于农业生产中使用。<Image he="634" wi="606" file="DDA0002562771970000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses a compound containing a hexafluorosulfonamide structure and having herbicidal performance, wherein the structure of the compound is shown as a formula (III). The invention also discloses a synthetic method of the compound, which takes 2- (2,2-difluoroethoxy) -6-trifluoromethyl benzene sulfonyl chloride and 2-fluoro-N-methylaniline as raw materials to react under the catalytic action of organic base and catalyst to obtain a target product. The invention has wide weeding spectrum, and has better control effect on preventing and killing gramineous weeds such as barnyard grass and moleplant seed in paddy fields, annual cyperaceae weeds such as cyperus heterophyllus and broadleaf weeds such as amaranthus auritaThe pesticide has no adverse effect on the normal growth of rice crops, does not need to add a safener, has small dosage and is more beneficial to being used in agricultural production.)

1. A compound having the structure shown in formula (III):

2. a method for synthesizing the compound of claim 1, wherein the reaction scheme is as follows:

3. the method for synthesizing the compound according to claim 2, wherein 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride and 2-fluoro-N-methylaniline are used as raw materials and reacted under the catalytic action of organic base and a catalyst to obtain the target product.

4. The method for synthesizing the compound according to claim 3, wherein the molar ratio of 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride to 2-fluoro-N-methylaniline is 1:1 to 1: 1.06.

5. A method of synthesizing a compound according to claim 3, wherein the organic base is triethylamine, N-dimethylaniline, pyridine, 3, 5-lutidine, preferably 3, 5-lutidine.

6. The method of synthesizing the compound according to claim 3 or 4, wherein the molar ratio of the 2-fluoro-N-methylaniline to the organic base is 1:2 to 1:3, preferably 1: 3.

7. A method of synthesizing a compound according to claim 3, wherein the catalyst is DMSO; the mass ratio of the 2-fluoro-N-methylaniline to the catalyst is 100: 2-100: 5, and preferably 100: 4.

8. A process for the synthesis of a compound according to claim 3, characterized in that the reaction solvent is toluene; the molar ratio of the 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride to the toluene is 1: 8-1: 12.

9. Use of the compound according to claim 1 for controlling gramineous weeds, annual sedge weeds and broadleaf weeds.

10. A herbicidal composition, characterized in that it comprises a compound according to claim 1 as an active ingredient or as a main active ingredient, in combination with a pesticidally acceptable adjuvant.

Technical Field

The invention belongs to the field of organic molecule synthesis, relates to a compound with herbicidal performance and a hexafluorosulfonamide structure and a synthesis method thereof, and particularly relates to 2- (2,2-difluoroethoxy) -N- (2-fluorophenyl) -N-methyl-6- (trifluoromethyl) benzenesulfonamide with herbicidal activity and a synthesis method thereof.

Background

Penoxsulam (penoxsulam) is an after-emergence herbicide developed by the american agronomy company (Dow agro sciences), a triazolopyrimidine sulfonamide herbicide that acts by inhibiting acetolactate synthase (ALS).

EPA is officially registered in the United states in 24.9.2004, popularized and applied in the southern rice district of the United states in 2005, and registered in China in 2008. Penoxsulam is concerned by people due to low toxicity, high efficiency and safety, and is further developed in rice application and becomes one of important products. The penoxsulam has a wide herbicidal spectrum, has a good control effect on various common weeds in the paddy field, including barnyard grass, annual sedge and various broad-leaved weeds, has a lasting period of 30-60 days, and can basically control the harm of the weeds in all seasons by one-time application. However, penoxsulam has no obvious weeding effect on moleplant seed, so that a new herbicide needs to be developed to make up for the defects of penoxsulam.

Disclosure of Invention

The invention aims to provide a compound containing a hexafluorosulfonamide structure and having herbicidal properties.

The purpose of the invention is realized by the following technical scheme:

a compound having the structure shown in formula (III):

chemical name of the compound having the structure shown in formula (III): 2- (2,2-Difluoroethoxy) -N- (2-fluorophenyl) -N-methyl-6- (trifluoromethyl) benzenesulfonamide (2- (2,2-difluoroethoxy) -N- (2-fluorophenyl) -N-methyl-6- (trifluoromethyl) benzanesulfonamide).

Another object of the present invention is to provide a method for synthesizing a compound represented by formula (III), wherein the reaction scheme is as follows:

the method comprises the following steps: the method comprises the steps of taking 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride (compound I) and 2-fluoro-N-methylaniline (compound II) as raw materials, and reacting under the catalysis of organic base and a catalyst to obtain a target product.

The molar ratio of the 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride to the 2-fluoro-N-methylaniline is 1: 1-1: 1.06, preferably 1:1.

The organic base is triethylamine, N-dimethylaniline, pyridine and 3, 5-dimethylpyridine, preferably 3, 5-dimethylpyridine; the molar ratio of the 2-fluoro-N-methylaniline to the organic base is 1:2 to 1:3, preferably 1: 3.

The catalyst is DMSO, and the DMSO is easy to form carbanion accelerated reaction process under the alkaline condition; the mass ratio of the 2-fluoro-N-methylaniline to the catalyst is 100: 2-100: 5, and preferably 100: 4.

The reaction solvent is toluene; the molar ratio of the 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride to the toluene is 1: 8-1: 12, and preferably 1: 10.

The method comprises the following specific steps:

(1) dissolving 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride (compound I) in a reaction solvent at the temperature of 60-65 ℃ for later use;

(2) mixing 2-fluoro-N-methylaniline (a compound II), organic base and a catalyst, keeping the temperature at 60-65 ℃, dripping the 2- (2,2-difluoroethoxy) -6-trifluoromethylbenzenesulfonyl chloride solution obtained in the step (1), and reacting for 2 hours at the temperature of 60-65 ℃ after dripping; and after the reaction is finished, cooling to 10 ℃, adding hydrochloric acid with the concentration of 10% to adjust the pH value to 2, layering, performing rotary evaporation on an organic phase to remove the solvent, adding concentrated hydrochloric acid, crystallizing at 0-10 ℃, filtering, washing with water to be neutral, and drying to obtain the target product.

Another object of the present invention is to provide the use of the compound represented by the formula (iii) for controlling grassy weeds, annual sedge weeds and broadleaf weeds, preferably for controlling grassy weeds, annual sedge weeds and broadleaf weeds in paddy fields; the weeds of Gramineae such as barnyard grass and semen Euphorbiae Lathyridis, annual Cyperaceae such as cyperus heterophyllus, and broadleaf weeds such as Amaranthus europaea.

The invention also aims to provide a weeding composition which is prepared into a pesticide acceptable formulation by taking the compound shown in the formula (III) as an active ingredient or a main active ingredient and assisting with a pesticide acceptable auxiliary agent.

The mass content of the active ingredients in the weeding composition can be 2-95%.

The skilled person can prepare the herbicidal composition of the present invention into various dosage forms by known methods, for example, the active ingredients and adjuvants, such as solvents, solid carriers, and if necessary, surfactants can be uniformly mixed and ground together to prepare the desired dosage forms, such as wettable powder, suspending agent, dispersible oil suspending agent, aqueous emulsion, emulsifiable concentrate, water dispersible granules, and the like.

The solvent may be selected from: aromatic hydrocarbons, preferably containing 8 to 12 carbon atoms, such as xylene mixtures or substituted benzenes; phthalate esters, such as dibutyl phthalate or dioctyl phthalate; aliphatic hydrocarbons such as cyclohexane or paraffin; alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl; ketones, such as cyclohexanone; strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide; and vegetable oils, such as soybean oil.

The solid carriers, such as those used for dusts and dispersents, are generally natural mineral fillers, such as talc, kaolin, montmorillonite or attapulgite. To manage the physical properties of the composition, it is also possible to add highly dispersible silicic acid or highly dispersible polymeric adsorbent carriers, for example granular adsorbent carriers or non-adsorbent carriers, suitable granular adsorbent carriers being porous, such as pumice, bentonite or bentonite; suitable non-adsorbent carriers are for example calcite or sand. In addition, a large number of pre-granulated materials of inorganic or organic nature, in particular dolomite, can be used as carriers.

Suitable surfactants, depending on the chemical nature of the active ingredients in the herbicidal compositions according to the invention, are lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, alkaline earth metal or amine salts, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, condensates of sulfonated naphthalene and of naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylaryl polyglycol ether, tributyl benzene polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohol, ethoxylated castor oil, polyoxyethylene alkyl ether, ethylene oxide condensate, ethoxylated polyoxypropylene, lauric acid polyglycol ether acetal, sorbitol ester, lignosulfite waste liquor and methyl cellulose.

Depending on the nature of the herbicidal composition and the purpose and environmental conditions to which the composition is to be applied, the composition may be applied by any method selected from the group consisting of spraying, atomizing, dusting, scattering, pouring, and the like.

Specifically, the application method of the herbicidal composition of the present invention comprises: the herbicidal compositions are applied to the aerial parts, in particular to the foliage or foliar surfaces, where plants grow. The frequency of application and the amount of application depend on the biological and climatic survival conditions of the control subject. The locus of the plant, such as a paddy field, can be drenched with a liquid preparation of the composition, or the composition can be applied to the soil in solid form, such as in granular form (soil application), from where it can enter the plant through the roots of the plant (systemic action).

The invention has the beneficial effects that:

the compound has wide weeding spectrum, can be applied to crop weeding, is particularly used for preventing and removing gramineous weeds (barnyard grass and moleplant seed), cyperaceae weeds and broadleaf weeds in rice fields, can effectively prevent and remove the weeds, and has good weeding effect.

The compound has no adverse effect on the normal growth of rice crops, does not need to add a safener, has small dosage and is more beneficial to being used in agricultural production.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.