Using n-substituted 3-cyano-4,6-dimethyl-5-chloropyridyl-2-sulfonylamides as antidotes of herbicide 2,4-dichlorophenoxyacetic acid in sunflower

FIELD: organic chemistry, antidotes, agriculture.

SUBSTANCE: invention describes using N-substituted 3-cyano-4,6-dimethyl-5-chloropyridyl-2-sulfonylamides of the formula (1-2): wherein in (1) R means benzimidozolyl-1; in (2) R means furfurylamino-group as antidotes of herbicide 2,4-dichlorophenoxyacetic acid in sunflower. Invention provides expanding assortment of biologically active substances prepared by synthetic method for their using in agriculture as antidotes against 2,4-D. Method involves treatment of sunflower seedlings damaged with herbicide by proposed N-substituted 3-cyano-4,6-dimethyl-5-chloropyridyl-2-sulfonylamides.

EFFECT: valuable biological properties of antidotes.

1 tbl, 3 ex

 

The invention relates to biologically active chemical substances pyridine series formula 1-2:

1 R = benzimidazolyl-1;

2 R = furfurylamine;

able to reduce fetotoksicheskoe action of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) on sunflower plants (antidotes). Compound 1 was synthesized for the first time, the previously known compound 2 (Catalog of Chemical Blok Stok Library, Cas Registry No. 698994-57-9, 10.08.2004).

As you know, the sunflower is extremely sensitive culture herbicide group, 2,4-D, and in cases of unintentional contact of herbicide on his crop losses could be, depending on the dose, up to 100% [Diganto, Mesocolon. Herbicide effect of 2,4-D and other halogenosilanes, M.: Nauka, 1973].

Still protecting vegetative plants of sunflower from the damaging effects of 2,4-D remains unresolved.

The closest analogue to the chemical structure of the claimed compounds and, at the same time, with similar properties is known antibacterial drug Sulfalen ["Antidote herbicide hormonal action of 2,4-dichlorophenoxyacetic acid and 4-amino-3,5,6-trichloropicolinic acids." RF patent №2043021 from 10.09.95, application No. 5042089 from 14.05.92] formula 3:

This compound is widely used in ka is este Antibacterials in clinical practice, its synthesis is described in the literature [Wegelius. Pharmaceutical chemistry. - M.: Vysshaya SHKOLA, 1985, p.383, 768]. However Sulfalen has not high enough antidote activity.

The present invention is to expand the Arsenal of biologically active substances obtained synthetically, for use in agriculture as a means of protecting the growth of sunflower plants from the damaging effects of 2,4-D (antidote).

This is achieved by treating the damaged sunflower plants N-substituted 3-cyano-4,6-dimethyl-5-chloropyridin-2-sulfonylamides 1-2.

The synthesis of the claimed compounds 1-2 were carried out in a known manner by the interaction of 3-cyano-4,6-dimethyl-5-chloropyridin-2-sulphonylchloride with amines in the presence of triethylamine at room temperature in the environment of anhydrous benzene [see New sulfonamides: Application 1211567, Japan, MKI407 D 213/74, 241/04 from 24.08.89].

The invention is illustrated by the following examples.

Example 1. 2-[(benzimidazole-1-yl)-sulfonyl]-3-cyano-4,6-dimethyl-5-chloropyridin (connection 1).

To a suspension of 0,43 g (0,0036 mol) benzimidazole and 0.31 g (0,0031 mol) of triethylamine in 15 ml of absolute benzene is poured a solution of 0.8 g (0,0031 mol) of 3-cyano-4,6-dimethyl-5-chloropyridin-2-sulphonylchloride and stirred at room temperature for 8 hours. The reaction mass CTD is collected from the precipitate Et 3N×HCl by filtration, evaporated to dryness, the residue is recrystallized from a mixture of hexane: ethyl acetate =2:1, obtain 0.9 g (84%) of target compound 1 in the form of white crystals with TPL =132-133°C.

Found, %: C at 51.68; N, 3.12; N, 16.41; S 9.44; C15H11ClN4O4S;

Calculated, %: 51.95; N, 3.20; N 16,16; S 9.23.

Mass spectrum, m/z (attributes, intensity): M+346(78); 281(80); 182(22); 165(79); 138(43); 102(74); 90(100).

Example 2. N-furfurylamine-3-cyano-4,6-dimethyl-5-chloropyridin-2-sulfanilamide (compound 2).

To a solution of 0.49 g (0,0050 mol) furfurylamine and 0.45 g (0,0045 mol) of triethylamine in 20 ml of absolute benzene is added dropwise a solution of 1.2 g (0,0045 mol) of 3-cyano-4,6-dimethyl-5-chloropyridin-2-sulphonylchloride in 15 ml of absolute benzene, maintaining the temperature of the reaction mixture in the range of 12-15°C. Upon completion of addition, the temperature slowly raised to room temperature and continue stirring for another 4 hours. The residue is filtered off, rinsed with water and dried. The residue after evaporation of the benzene solution is combined with the precipitate is recrystallized from a mixture of hexane: ethyl acetate =2:1, gain of 1.05 g (70%) of target compound 2 as a white crystalline powder with TPL =138-139°C.

Found, %: C 47,61; N 3,54; N 12,70; S 9,62; C13H12ClN3O3S.

Calculated, %: 47.97; N, 3.72; N, 3.72; S 9.83.

TMR, δ, ppm (group): 2.60 (3H, s, 4-CH3 Ru); to 2.65 (3H, s 6-CH3Ru); 4,27 (2H, s, CH2); 6,20...was 7.45 (3H, m, CH furan ring); cent to 8.85 (1H, s, NH).

Mass spectrum, m/z (attributes, intensity): M+325(3); 261(10); 232(17); 213(15); 166(100); 138(18); 131(22); 102(34); 96(58); 81(45).

Example 3. Evaluation of compounds 1-6 on antidote activity in seedlings of sunflower.

Sprouted sunflower seeds with long embryonic root of 2-4 mm were placed for 1 h in a solution of 2,4-dichlorophenoxyacetic acid (2,4-D) at a concentration of 10-3% get 40-60% inhibition of the growth of the hypocotyl. After herbicide exposure seedlings were rinsed with water and placed in the test solutions on the antidote activity of substances in concentrations of 10-2, 10-3, 10-4, 10-5% (option herbicide + antidote). After 1 h, the seeds were washed with water and spread out on a strip of filter paper (size 10×75 cm) of 20 pieces, which were rolled into rolls and placed in beakers with 50 ml of water. Further germination of seeds was performed in an incubator for 3 days at a temperature of 28°C. the temperature of the solutions and wash water 28°C.

Seeds option "herbicide" (standard) kept for 1 h in a solution of 2,4-D at a concentration of 10-3% and 1 h in water.

Seeds of control variant 2 hours stood in the water.

Experiment was repeated three times. In each replication were used for 20 pieces of seeds.

Protective (anti is now), the effect was determined by increasing the length of hypocotyl and root in the embodiment, the herbicide + antidote regarding the named values in the variant "herbicide" (reference).

Statistical processing of experimental data performed using t-test, Student when P=0,95.

The research results are summarized in the table.

As can be seen from the table, the application on the background of the impact of herbicide offered as antidotes N-substituted 3-cyano-4,6-dimethyl-5-chloropyridin-2-sulfonylamides 1-2 dramatically reduces the toxic effect of the herbicide.

Compounds 1-2 neutralized the negative effect of 2,4-D on the hypocotyl of seedlings, sunflower 24-51% when using three or more concentrations, while the amount of antidote effect Sulfalena (prototype) was 12-22%.

Compounds 1-2 reduced the inhibitory effect of 2,4-D on the roots of seedlings in 28-45% when using three or more concentrations, and Sulfalen (prototype) showed antidote effect on the level of 16-31%.

Thus, the use of the claimed N-substituted 3-cyano-4,6-dimethyl-5-chloropyridin-2-sulfonylamides as antidotes to effectively protect the sunflower from the effects of 2,4-D, as well as to expand the range of known antidotes.

Table

Antidote activity of N-substituted 3-cyano-4,6-dimethyl-5-chloropyridin-2-sulfonylamides and their prototype to 2,4-D on seedlings of sunflower varieties VNIIMK-883.
MedicationConcentrationThe length of the hypocotylRoot length
%mmTo 2,4-D, %mmTo 2,4-D, %
Control07411
2,4-D10-34144
2,4-D + connection 110-2< / br>
10-3< / br>
10-4< / br>
10-5
51

48

52

55
124*

116

128*

133*
59

57

50

61
133*

129*

141*

138*
2,4-D + connection 210-2< / br>
10-3< / br>
10-4< / br>
10-5
50

56

51

62
121

137*

124*

151*
56

59

64

62
128*

134*

145*

142*
2,4-D + connection 3 (prototype)10-2< / br>
10-3< / br>
10-4< / br>
10-5
46

48

50

47
112

118*

122*

115*
58

479

52

51
131*

107

118*

116*
* Different is I between significant at P=0,95

The use of N-substituted 3-cyano-4,6-dimethyl-5-chloropyridin-2-sulfonylamides formula 1-2

1. R = benzimidazolyl-1;

2. R = furfurylamine,

as antidotes of the herbicide 2,4-dichlorophenoxyacetic acid in sunflower.



 

Same patents:

FIELD: agriculture, in particular, suppression of weeds with developed triazine resistance resulted from selection stress acting upon weed population and caused by repeated application of triazines.

SUBSTANCE: method involves introducing into said weed locus combination of mesotrione and triazine, selected from the group consisting of atrazine, cyanazine, propazine, terbutilazine, trietazine, simazine and metribuzine. Mesotrione is introduced in an amount of from 20 to 210 g/hectare, triazine in an amount of from 0.1 to 2 kg/hectare.

EFFECT: increased efficiency of said combination as compared to that of mesotrione in case said combination is used with regard to triazine tolerable weeds.

3 cl, 9 tbl, 6 ex

FIELD: organic chemistry, herbicides.

SUBSTANCE: invention relates to a compound of the general formula [I]: wherein R1 and R2 can be similar or different and each represents (C1-C10)-alkyl group; each among R3 and R4 represents hydrogen atom; R5 and R6 can be similar or different and each represents hydrogen atom or (C1-C10)-alkyl group; Y represents 5-6-membered aromatic heterocyclic group or condensed aromatic heterocyclic group comprising one or some heteroatoms chosen from nitrogen atom, oxygen atom and sulfur atom wherein heterocyclic group can be substituted with 0-6 of similar or different groups chosen from the following group of substitutes α, and so on; n means whole values from 0 to 2; [Group of substitutes α]: hydroxyl group, halogen atoms, (C1-C10)-alkyl groups, (C1-C10)-alkyl groups wherein each group is monosubstituted with group chosen from the following group of substitutes β, (C1-C4)-halogenalkyl groups, (C3-C8)-cycloalkyl groups, (C1-C10)-alkoxy-groups, (C1-C10)-alkoxy-groups wherein each group is monosubstituted with group chosen from the following group of substitutes and so on; [Group of substitutes β]: hydroxyl group, (C3-C8)-cycloalkyl groups that can be substituted with halogen atom or alkyl group, (C1-C10)-alkoxy-group, (C1-C10)-alkylthio-groups, (C1-C10)-alkylsulfonyl groups, (C1-C10)-alkoxycarbonyl groups, amino-group, carbamoyl group (wherein its nitrogen atom can be substituted with similar or different (C1-C10)-alkyl groups), (C1-C6)-acyl groups, (C1-C10)-alkoxyimino-groups, cyano-group, optionally substituted phenyl group; [Group of substitutes γ]: optionally substituted phenyl group, optionally substituted aromatic heterocyclic groups, cyano-group. Also, invention relates to herbicide comprising derivative of isoxazoline of the formula [I] as an active component or its pharmaceutically acceptable salt. Invention provides the development of isoxazoline derivative possessing the herbicide activity with respect to resistant weeds, selectivity for cultural crop and weed.

EFFECT: valuable herbicide properties of substances.

18 cl, 24 tbl, 106 ex

FIELD: agriculture, in particular method for increasing of beet yield and sugar content.

SUBSTANCE: seeds are treated by spraying in leaf clamping step with titanium tetrachloride diluted in dimethylsulfoxide (DMSO). Concentration of DMSO is 0.1-2 %; titanium tetrachloride consumption is up to 50 g per 1 hectare of seeds. Ratio of titanium tetrachloride:dimethylsulfoxide is 100-200 l per 1 hectare. Treatment is carried out twice in vegetation period, namely the first treatment is carried out in leaf clamping step and the second one in 15-20 days before harvesting of root crops.

EFFECT: increased beet yield and sugar content.

1 tbl, 1 ex

FIELD: agriculture, organic chemistry.

SUBSTANCE: invention relates to agent for controlling of plant pathogen fungi containing compound of general formula I as active ingredient, wherein X represents =N-; E represents NO2 or CN; R representsthiazolulmethyl or pyridylmethyl substituted with halogen; A represents hydrogen; Z represents C1-C4-alkylamino group; or A and Z together with atoms bonded thereon form thiazolidine, imidazolidine, hexahydro-1,3,5-triazine, N2- and N5-substituted with two C1-C4-alkyl in alkyl group, 6-membered saturated heterocycle fragment including additionally oxygen and N-(C1-C4)alkyl heterogroup; and fungicide compound selected from group containing cyproconazole, triadimenol, methalaxide, azoxistrobin, kresoximmethyl, etc., in weight ratio compound of formula I/fungicidal agent of 1:(0.1-10). Also disclosed is insecticide agent containing compound of formula I and compound selected from group containing cyproconazole, azoxistrobin, kresoximmethyl, biterthanol, tiram, methalaxide, etc. in ratio of 1:(0.1-10).

EFFECT: enhanced assortment of agents for controlling of plant pathogen fungi and agents for insect controlling.

4 cl, 15 tbl, 15 ex

FIELD: agriculture, organic chemistry.

SUBSTANCE: invention relates to agent for controlling of plant pathogen fungi containing compound of general formula I as active ingredient, wherein X represents =N-; E represents NO2 or CN; R representsthiazolulmethyl or pyridylmethyl substituted with halogen; A represents hydrogen; Z represents C1-C4-alkylamino group; or A and Z together with atoms bonded thereon form thiazolidine, imidazolidine, hexahydro-1,3,5-triazine, N2- and N5-substituted with two C1-C4-alkyl in alkyl group, 6-membered saturated heterocycle fragment including additionally oxygen and N-(C1-C4)alkyl heterogroup; and fungicide compound selected from group containing cyproconazole, triadimenol, methalaxide, azoxistrobin, kresoximmethyl, etc., in weight ratio compound of formula I/fungicidal agent of 1:(0.1-10). Also disclosed is insecticide agent containing compound of formula I and compound selected from group containing cyproconazole, azoxistrobin, kresoximmethyl, biterthanol, tiram, methalaxide, etc. in ratio of 1:(0.1-10).

EFFECT: enhanced assortment of agents for controlling of plant pathogen fungi and agents for insect controlling.

4 cl, 15 tbl, 15 ex

FIELD: agricultural chemistry.

SUBSTANCE: invention relates to herbicidal composition containing (A) mesotrion and (B) the second herbicide selected from amicarbazone, metribuzine, flumetsulfam, trifloxysulfuron, pyriphthalide, prosulfocarb or herbicidically active salts thereof in (A):(B) ratio from 32:1 to 1:3. Disclosed is method for controlling of undesired plants which includes application of herbicidically effective amount of said composition into locus with such plants.

EFFECT: composition of high herbicidal activity.

8 cl, 6 tbl

FIELD: method for controlling of arthropod pests.

SUBSTANCE: claimed method includes application in environments of pests of germinal calls thereof effective amount at least one vicinal diol of formula R(OH)2 selected from group containing diols, wherein R represents aliphatic hydrocarbon chain with the proviso that carbon atom in the chain adjacent to diol functional group is not substituted with ethyl and chain skeleton contains 8-20 carbon atoms. Composition for insecticidal and arachnicidal application containing abovementioned diol of formula R(OH)2 also is disclosed. Methods for controlling of sucking lice, flies, mites, cockroaches, and pests from group comprising Pediculus humanus, Dermatophagoides pteronyssinus, and Musca domestica.

EFFECT: death or non-vitality of pests after treatment.

26 cl, 4 tbl, 4 ex

FIELD: method for controlling of arthropod pests.

SUBSTANCE: claimed method includes application in environments of pests of germinal calls thereof effective amount at least one vicinal diol of formula R(OH)2 selected from group containing diols, wherein R represents aliphatic hydrocarbon chain with the proviso that carbon atom in the chain adjacent to diol functional group is not substituted with ethyl and chain skeleton contains 8-20 carbon atoms. Composition for insecticidal and arachnicidal application containing abovementioned diol of formula R(OH)2 also is disclosed. Methods for controlling of sucking lice, flies, mites, cockroaches, and pests from group comprising Pediculus humanus, Dermatophagoides pteronyssinus, and Musca domestica.

EFFECT: death or non-vitality of pests after treatment.

26 cl, 4 tbl, 4 ex

FIELD: organic chemistry, nematocides.

SUBSTANCE: invention relates to compounds of the formula (I): wherein Ar1 and Ar2 mean independently of one another unsubstituted phenyl or mono- or multi-substituted phenyl with substitutes having independent of one another values and chosen from the group including halogen atom, (C1-C6)-alkyl or halo-(C1-C6)-alkyl; Q1 means -OCH2 or -C(O); Q2 means a direct bond or -C(O); R3 means hydrogen atom; R4, R5 and R6 mean independently of one another hydrogen atom or (C1-C6)-alkyl; W means O or S atom; a means 1, 2, 3 or 4; b means 0; n means 0 or 1. Also, method proposes a method for synthesis of compound of the formula (I) and carriers and/or dispersers also. Also, invention proposes using compound of the formula (I) for control of nematodes. Invention provides preparing derivatives of benzamidoacetonitrile used in control of nematodes.

EFFECT: improved preparing method, valuable properties of compounds.

10 cl, 2 tbl, 19 ex

FIELD: agriculture, herbicides.

SUBSTANCE: invention relates to agent for reducing of toxic action of hormonal herbicidal 2,4-dichlorophenoxyacetic acid on sunflower sprouts. Claimed agent contains 2-(2-furil)-1,3-dioxolane of formula I .

EFFECT: herbicide with decreased toxic action on sunflower.

FIELD: agriculture.

SUBSTANCE: the use of 2-methyl-4-dimethylaminomethyl-5-hydroxybenzoimidazole dihydrochloride as agent for enhancing of grain variety frost and winter resistance is disclosed.

EFFECT: increased winter crop resistance to foul weather conditions.

4 ex, 3 tbl, 2 dwg

FIELD: agriculture.

SUBSTANCE: claimed composition contains (g/t): benzimidasole derivatives (e.g. agrocite, bendan, usgene, fundasol) as protectant not less than 300; and target additives: carbamide 20-25; potassium monosubstituted phosphate 9-12; potassium chloride 7-10; copper sulfate 120-125; zinc sulfate 120-125; magnesium sulfate 120-125; cobalt sulfate 10-12; manganese sulfate 15-17; ammonium molybdate 16-18; and water 1000-1050. Composition for seed pretreatment contains abovementioned components in the same ratio and water soluble film-forming agent in amount of 10-12 g/t.

EFFECT: decreased protectant consumption.

5 cl, 2 ex

The invention relates to compounds of dehalogenation, insecticide/acaricidal agents containing these compounds as active ingredients and intermediates for their production

The invention relates to new fungicidal pyrotechnic composition which may find application in agriculture, food and light industry

The invention relates to new 2-(2,4,5-phenylselenenyl) compounds as their synthesis and intermediate products, as well as to the use of these compounds for weed control

FIELD: organic chemistry, insecticides.

SUBSTANCE: invention relates to compounds of the formula (1) , their N-oxides and salts that can be used in agriculture wherein values A, B, J, R1, R3, R4 and n are given in the invention claim. Also, invention describes a method for control of arthropoda pests to provides high productivity that comprises applying the effective dose of compound of the formula (1) on arthropoda pests and in medium of their habitation, and a the composition with arthropocide activity comprising compounds of the formula (1).

EFFECT: valuable properties of compounds and composition.

23 cl, 34 tbl, 759 ex

Up!