2-dialkylamides and thieno[2,3-b]pyridine-herbicide antidotes hormonal action of 2,4-dichlorophenoxyacetic acid

 

Describes 2-dialkylamides formula I and thieno[2,3-b]pyridine formula IIA, b, which are the antidote to herbicide activity of hormonal action of 2,4-dichlorophenoxyacetic acid in sunflower seedlings. The technical result consists in obtaining the compounds used in agriculture to protect crops from the negative effects of herbicides. 1 PL.

The invention relates to new biologically active chemical substances of some heterocyclic compounds of the formula I and IIA and IIB,

showing property to weaken the toxic effect of the herbicide hormonal action of 2,4-dichlorophenoxyacetic acid (2,4-D) on seedlings of sunflower.

Antidote activity in relation to 2,4-D has a 2-(n-aminobenzoylamino)-5-ethyl-1,3,4-thiadiazole of the formula III as similar properties (patent No. 2040898. The antidote herbicide hormonal action of 2,4-dichlorophenoxyacetic acid // Shooters C. D., Isakov, L. I., Kalita, M. I., L. Litvinov, N., Chubenko T. I. MCI And 01 N 25/32, 43/82, publ. 09.08.95. BI No. 22).

Structure is but[2,3-b]pyridine IV and 6-methyl-4-methoxymethyl-3-cyano-2-(4-nitrobenzyl)-dipyridine V is a structural isomer of compound IV, from which the latter was synthesized from [Ye. A. Kaigorodova, V. K. Vasilin, L. D. Konyushkin, Ye. B. Usova, G. D. Krapivin. Synthesis and Reactions of Substituted 3-amino-2-furyl(benzyl)-thieno[2,3-b]pyridines // Molecules. 2000. No. 5. - R. 1085-1093 //http://www.mdpi.org.

The present invention is to expand the Arsenal of biologically active substances obtained synthetically, for use in agriculture to protect crops from the negative effects of herbicides.

This is achieved by the use of compounds of formula I, IIA and IIIB for processing sprouted sunflower seeds antidote.

The invention is illustrated by the following examples.

Example 1. The way to obtain N1-(3-triptoreline)-2-(6-methyl-4-methoxymethyl-3-cyano-2-pyridylsulfonyl)ndimethylacetamide (I)

Compound I was obtained by interaction of 6-methyl-4-methoxymethyl-3-cyano-2(1H)-pyridinethione VI with N-(3-triptoreline)-2-chloracetamide VII in the presence of equimolar amount of potassium hydroxide in dimethylformamide reaction

The method of obtaining

To a suspension of 1.94 g (0.01 mol) of 6-methyl-4-methoxymethyl-3-cyano-2(1H)-pyridinethione (Tpl.233-234(C) in 20 ml of dimethylformamide (DMF) was added 5.6 ml of 10% aqueous who 3.38 g (0.01 mol) of N-(3-triptoreline)-2-chloroacetamide (Tpl.74-75C) and kept for half an hour. The precipitation was filtered, washed with water, dried. By dilution of the stock solution 15 ml of water was additionally extracted crystals of product I. Product was recrystallized from DMF solution in ethanol (10-15% by volume). The total yield of compound I 3.71 g (94%). TPL= 171-171.5C.

Elemental analysis. Found: 54.63; N, 4.00; N, 10.59. C18H16F3N3O2S. Calculated: 54.68; H 4.08; N, 10.63.

The IR spectrumcm-1(vaseline oil): 3370, 3100 (N-H); 2215 (CN);

1660 (Amide I), 1610 (C=C, C=N); 1125, 1080 (C-O-C).

An NMR spectrum1H (DMSO-d6): 2.55 (3H, s, CH3), 3.45 (3H, s, och3), 4.12 (2H, s, SCH2), 4.55 (2H, s, och2), 7.12 (1H, s, HRu), 7.28...7.96 (4H, m, HAr), 10.27 (1H, ush. s, NH).

Example 2. The way to obtain N2-(2,4-dichlorophenyl)-3-amino-4,6-dimethyl-5-chlorothieno[2,3-b]pyridine IIa

N2-(2,4-dichlorophenyl)-3-amino-4,6-dimethyl-5-chlorothieno[2,3-b]pyridine IIA was obtained by the reaction of

To a suspension of 1.99 g (0.01 mol) of 4,6-dimethyl-5-chloro-3-cyano-2(1H)-pyridinethione in 20 ml of dimethylformamide (DMF) was added 5.6 ml of 10% aqueous solution of potassium hydroxide. To the resulting solution under stirring was made 2.39 g (0.01 N. Then was added 5.6 ml of 10% aqueous potassium hydroxide solution and maintained the reaction mass at a temperature of 75-80With in half an hour and left overnight. Then the reaction mass was diluted with 15-20 ml of water. The precipitate was filtered, washed with water, alcohol, and dried. The product was recrystallized from DMF solution in ethanol (10-15% by volume). The total yield of compound I 3.81 g (95%). Tpl.264-265C.

Elemental analysis. Found: 47.90; N, 2.95; N, 10.46. C16H12Cl3N3OS. Calculated: At 47.96; N, 3.02; N, 10.49.

The IR spectrumcm-1(vaseline oil): 3460, 3380 (N-H); 1660 (Amid), 1590(C=C,C=N).

An NMR spectrum1H (DMSO-d6): 2.65 (3H, s, CH3), 2.78 (3H, s, CH3), 6.87 (2H, ush.s, NH2) 7.31...8.07 (3H, m, HAr), 8.46 (1H, ush. s, NH).

Example 3. Method for the preparation of 3-amino-4,6-dimethyl-5-chlorothieno[2,3-b]pyridine-2-yl-4-brompheniramine IIB

3-Amino-4,6-dimethyl-5-chlorothieno[2,3-b]pyridine-2-yl-4-bromophenyl-methanon IIB was obtained by the reaction of:

To a suspension of 1.99 g (0.01 mol) of 4,6-dimethyl-5-chloro-3-cyano-2(1H)-pyridinethione in 20 ml of dimethylformamide (DMF) was added 5.6 ml of 10% aqueous solution of potassium hydroxide. To the resulting solution under stirring made the 10% aqueous solution of potassium hydroxide and stirred the reaction mass for half an hour, then the precipitate was separated, washed successively with water and ethanol, dried in the air. The filtrate was diluted twice with water. Loose flocculent precipitate was separated, washed with water and then with ethanol, dried in the air. The product was recrystallized from DMF solution in ethanol (10-15% by volume). The total yield of the compound IIB 3.64 g (92%). TPL=234-235C.

Elemental analysis. Found: 48.53; N, 3.01; N, 7.08. C16H12BrClN2OS Calculated: 48.57; N, 3.06; N, 7.08.

The IR spectrumcm-1(vaseline oil): 3440, 3330 (N-H); 1675 (C=O), 1590 (C=C,C=N).

An NMR spectrum1H (DMSO-d6): 2.67 (3H, s, CH3), 2.88 (3H, s, CH3), 7.63 (2H, d, J= 8.5 Hz, H3H5), 7.70 (2H, d, J=8.5 Hz, H2N6), 8.00 (2H, ush. s, NH2).

Example 4. The study of the antidote activity of N1-(3-triptoreline)-2-(6-methyl-4-methoxymethyl-3-cyano-2-pyridylsulfonyl)ndimethylacetamide (I), N2-(2,4-dichlorophenyl)-3-amino-4,6-dimethyl-5-chlorothieno[2,3-b]pyridine-2-carboxamide (IIA), 3-amino-4,6-dimethyl-5-chlorothieno[2,3-b]pyridine-2-yl-4-brompheniramine (IIB)

Antidote activity of N1-(3-triptoreline)-2-(6-methyl-4-methoxymethyl-3-cyano-2-pyridylsulfonyl)ndimethylacetamide (I), N2-(2,4-dichlorophenyl)-3-amino-4,6 dimethyl-5-hartie BP BASFI (GR No. 582313-1) was studied in laboratory conditions on seedlings of sunflower varieties VNIIMK-8883. The inventive compounds I, II, similar in structure IV, V, and similar property III was tested in the form of solutions, the alcohol content in which was 0.2%, the content of the claimed compounds, structural analogs and prototypes was 10-2-10-5% (by weight).

Sprouted sunflower seeds were subjected to exposure to 2,4-D and drugs. Part of the seeds were treated only with the herbicide (standard of comparison). Served as control seeds treated with water. Further germination was carried out at a temperature of 28C for 3 days, measured the length of the hypocotyl and roots of sunflower seedlings.

Antidote activity was evaluated by increasing the length of the root and hypocotyl of seedlings in the embodiment, the herbicide + antidote in comparison with herbicide option (reference).

Statistical processing of experimental data carried out using t-student test at the confidence level P = 0.95. The test results presented in the table.

As follows from the table, the inventive compounds I, IIA and IIB reduce the toxicity of 2,4-D for seedlings of sunflower, surpassing similar III and analogs of structure IV and V. Thus, compound I, acting in the optimal solution of the set concentration of 10-4%, Uwe is rasiii 10-4% increases the length of the hypocotyl by 41.9%, root - 80.6% compared to 2,4-D. Compound IIB, acting in the optimal solution of the set concentration of 10-3% increases the length of the hypocotyl 9.3%, root - to 71.0 per cent in relation to 2,4-D while similar III in optimal concentration of 10-4% increases the length of the hypocotyl 9.3%, root - 32.3% compared to 2,4-D.

Similar in structure IV in optimal concentration of 0.001% increases the length of the hypocotyl 3.3%, root - 16.1% compared to 2,4-D and similar in structure V, operating at an optimal concentration of 10-2% increases the length of the hypocotyl 18.6%, root - 32.3% compared to 2,4-D.

Thus, compounds I, IIA and IIB show the properties of antidotes and can be used in the practice of agriculture to remove toxic effects of the herbicide 2,4-D in plants and activation of their growth.

Claims

N1-(3-Triptoreline)-2-(6-methyl-4-methoxymethyl-3-cyano-2-pyridyl-sulfonyl)ndimethylacetamide formulas I and 3-amino-4,6-dimethyl-5-chlorothieno[2,3-b]-pyridine formula IIA,b, manifesting antidote activity to herbicide hormonal action of 2,4-dichlorophenoxyacetic acid in sunflower seedlings.



 

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< / BR>
where Q is absent or represents-NH-(CH2)5-CO-,

R1denotes X-Arg-Gly-Asp-y,

X - Tripeptide: Gly-Gly-Gly-,

y - dipeptide: -Ser-PrO

or R1denotes A-Cys(R2)-B-U,

R2denotes H, Trt;

And represents Asp or peptide fragment selected from the group consisting of:

Ala-Asp, Thr-Ala-Asp, Lys-Thr-Ala-Asp, Lys-Ala-Ala-Asp,

Arg-Thr-Ala-Asp, Ser-Ala-Asp, Gln-Ser-Ala-Asp,

Gly-Lys-Thr-Ala-Asp, Ile-Ser-Ala-Gly, Arg-Ser-Ala-Gly

Gly-Lys-Thr-Cys (Trt)-Asp

In tstststs or represents Pro or N-methylated derivative of Ala,

moreover, if R1denotes A-Cys(R2)-B-U, only one of the residues a or b may not appear,

U indicates HE or NH2,

or R1means cyclo (Arg-Gly-Asp-Z), Z in the side chain is linked to Q, or if Q is absent, with Biotin,

Z denotes a di - or tripeptides the rest,

moreover, amino acids, independently of one another, are selected from the group consisting of Ala, Val, Tight, Trp, Phe, Cys, Lys, M, these amino acids can be derivatization, and amino acid residues are linked to each other peptidome through N-amino - and = R6- R4< / BR>
where R4= HE

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moreover, if we are talking about the balance of optically active amino acids and amino acid derivatives, are included as D-, L-forms;

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< / BR>
where R3represents (1-6C)alkyl or halogen; m is 0, 1, 2 or 3; R1represents hydroxy, halogen, trifluoromethyl, nitro, amino, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)quinil, (1-6C)alkoxy, (1-6C)alkylamino, di-[(1-6C)alkyl] amino, amino-(2-6C)alkylamino, (1-6C)alkylamino-(2-6C)alkylamino etc

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< / BR>
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< / BR>
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< / BR>
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