Application 1-pyridinyl-2-azolyl-1-phenylethanol as fungicides

 

(57) Abstract:

Describes the use of 1-pyridinyl-2-azolyl-1-phenylethanol formula (I) as fungicides

The presented compounds are effective against certain types of malicious fungi. table 1.

The invention relates to the chemistry of heterocyclic compounds, namely 1-pyridinyl-2-azolyl-1-phenylethanol General formula I

where PY represents 2-pyridinyl, 3-pyridinyl or 4-pyridinyl, X is a nitrogen atom or CH group, which may find application as an agricultural, industrial, medical or veterinary fungicides.

Known 2-thiazoleethanol General formula II, their salts with acids and complexes with metals, where R1means alkyl, cycloalkyl or phenyl, R2means phenyl or benzyl, which possess fungicidal activity [U.S. Patent No. 4623654, class A 01 N 43/653, 1984].

Closest to the claimed structure 1-pyridinyl-2-imidazolidinone General formula III, where R1means a hydrogen atom, alkyl group or halogen atom, R2means substituted or unsubstituted thienyl or substituted or unsubstituted phenyl, R3means a hydrogen atom or a metal is isolani in medicine.

The technical problem solved by this invention is the extension of the range of fungicides for effective action against harmful fungi.

To solve this problem, synthesize 1-pyridinyl-2-azolyl-1-phenylethanol having fungicidal activity.

1-Pyridinyl-2-azolyl-1-phenylethanol can be obtained by the interaction of 1-pyridinyl-2-azollaceae with phenylalkylamine the Grignard [Application Germany No. A, class C 07 D 401/06, 1983]:

They can also be obtained by the interaction of chlorhydrin or oxiranes with azoles [European application No. 0015756 A1, class C 07 D 249/08, 1980]:

Example 1. 2-(2-Phenyl-2-oxiranyl)pyridine.

To the mixture to 9.15 g (0.15 mol) of 2-benzoylpyridine, of 14.28 g (0.07 mol) of iodide trimethylsilane and 31.3 ml of DMSO is added dropwise over 30 min a solution of 4,625 g (0,063 mol) of potassium tert-butylate (31.3 ml of DMSO, cooling the reaction mass of ice, the mixture is stirred for 15 min and added dropwise to 150 ml of water. The product is extracted with chloroform, the extract washed with water and the solvent is distilled off. Get 6,304 g (64%) of 2-(2-phenyl-2-oxiranyl)pyridine in the form of butter.

NMR1N spectrum (DMSO-d6, , M. D.): 3,35 (AB system, 2 H, CH2), 7,40 (m, 7 H, 2 CH pyridine, 5 CH phenyl), 7,80 (m> the solution of 1.65 g (8.3 mmol) of 2-(2-phenyl-2-oxiranyl)pyridine and 0.57 g (8.3 mmol) of imidazole in 5,63 ml of DMF was added 0,033 ml of water, 0.11 g of sodium hydroxide and stirred for 4 h at a temperature of 120C. The reaction mass is then cooled, poured into 40 ml of water. The precipitated crystals filtered off, washed with water and recrystallized from toluene. Obtain 1.2 g (54%) of 1-(pyridinyl-2)-2-(imidazolyl-1)-1-phenylethanol, so pl. 105-S.

NMR1N spectrum (DMSO-d6, , M. D.): 4,85 (AB system, 2 H, CH2), and 6.25 (1H, HE), 6,70 (s, 1 H, CH imidazole), from 7.24 (m, 5 H, 3 CH, phenyl, 1 CH of pyridine, 1 CH imidazole), 7,51 (d, 2 H, CH phenyl), 7,58 (d, 1 H, CH of pyridine), 7,74 (t, 1 H, CH of pyridine), at 8.60 (d, 1 H, CH of pyridine).

Example 3. 1-(Pyridinyl-2)-2-(1,2,4-1H-triazolyl-1)-1-phenylethanol (2).

Yield 54%. So pl. 105-S.

NMR1N spectrum (DMSO-d6, , M. D.): 5,10 (d, AB system, 2 H, CH2), of 6.45 (s, 1 H, HE), 7,27 (m, 3 H, CH phenyl), 7,53 (m, 4 H, 2 CH pyridine, 2 CH phenyl), 7,74 (m, 2 H, CH of pyridine, CH of triazole), 8,18 (s, 1 H, CH of triazole), at 8.60 (m, 1 H, CH of pyridine).

Example 4. 3-(2-Phenyl-2-oxiranyl)pyridine.

Yield 52%. Oil.

NMR1N spectrum (DMSO-d6, , M. D.): 3,36 (AB system, 2 H, CH2), 7,37 (m, 6 H, 1 CH pyridine; 5 CH phenyl), 7,73 (m, 1H, CH of pyridine), 8,55 (m, 2H, CH of pyridine).

Example 5. 1-(> , M. D.): 4,85 (AB system, 2 H, CH2), 6,41 (s, 1 H, HE), and 6.25 (s, 1 H, CH imidazole), PC 6.82 (s, 1 H, CH imidazole), 7,28 (m, 5 H, 3 CH, phenyl, 1 CH, imidazole, 1 CH of pyridine), to 7.50 (d, 2 H, CH phenyl), 7,80 (d, 1 H, CH of pyridine), to 8.40 (s, 1 H, CH of pyridine), 8,65 (s, 1 H, CH of pyridine).

Example 6. 1-(Pyridinyl-3)-2-(1,2,4-1H-triazolyl-1)-1-phenylethanol (4).

Yield 52%. Oil.

NMR1N spectrum (DMSO-d6, , M. D.): 5,10 (AB system, 2 H, CH2), of 6.50 (s, 1 H, HE), 7,30 (m, 4 H, 1 CH pyridine, 3 CH phenyl), 7,52 (d, 2 H, CH phenyl), 7,73 (s, 1 H, CH of triazole), 7,80 (d, 1 H, CH of pyridine), to 8.25 (d, 1H, CH of pyridine), to 8.40 (s, 1 H, CH of pyridine), 8,68 (s, 1 H, CH of triazole).

Example 7. 4-(2-Phenyl-2-oxiranyl)pyridine.

Yield 85%. Oil.

NMR1N spectrum (DMSO-d6, , M. D.): 3,35 (AB system, 2 H, CH2), from 7.24 (m, 2 H, CH phenyl), 7,40 (m, 5 H, 2 CH pyridine, 3 CH phenyl), 8,55 (m, 2 H, CH of pyridine).

Example 8. 1-(Pyridinyl-4)-2-(imidazolyl-1)-1-phenylethanol (5).

Yield 77%. So pl. 87-90.

NMR1N spectrum (DMSO-d6, , M. D.): 4,85 (AB system, 2 H, CH2), to 6.43 (s, 1 H, HE), of 6.65 (s, 1 H, CH imidazole), 6,83 (s, 1 H, CH imidazole), 7,28 (m, 4 H, 3 CH, phenyl, 1 CH, imidazole) to 7.50 (m, 4 H, 2 CH pyridine, 2 CH phenyl), and 8.50 (d, 2 H, CH of pyridine).

Example 9. 1-(Pyridinyl-4)-2-(1,2,4-1H-triazolyl-1)-1-phenylethanol (6).

Yield 65%. So pl. 153-the (a), to 7.50 (m, 4 H, 2 CH pyridine, 2 CH phenyl), of 7.75 (s, 1 H, CH of triazole), of 8.28 (s, 1 H, CH of triazole), to 8.45 (m, 2 H, CH of pyridine).

NMR1H spectra were recorded on the instrument Varian XL-400 (400 MHz).

Example 10. Testing the biological activity of the compounds was performed in vitro. In the molten sacharose-potato agar was added to the test substance in the form of a solution in acetone with a concentration of 3 mg/ml 1 ml per 100 ml of agar. To receive agar medium containing 30 mg/l of the test compound. To the medium control was added with pure acetone in the same amount. So prepared medium was poured into Petri dishes, cooled and the surface of the hardened agar were sown pieces of fungal mycelium, after which the cups were incubated for 3 days at 250,5 S. Inhibition of mycelium growth was calculated in percentage of the untreated control. As a reference used commercial fungicide triadimefon in the same concentration. The test results presented in the table.

Application 1-pyridinyl-2-azolyl-1-phenylethanol General formula I,

where PY represents 2-pyridinyl, 3-pyridinyl or 4-pyridinyl;

X means nitrogen atom or CH group,

as fungicides.

 

Same patents:

The invention relates to the protection of grain crops

The invention relates to new fungicidal compositions intended for the treatment of phytopathogenic diseases of cultivated plants, in particular of diseases caused by phytopathogenic fungi, and to a method of combating phytopathogenic diseases of cultivated plants

The invention relates to agriculture, in particular animal, and can be used for the treatment of arachnocampa

The invention relates to new derivatives of chloropyridinyl formula I where Het is a group of formula a, b, C, d or e, R1is hydrogen, unsubstituted or substituted C1- C6alkyl, and the substituents selected from the group comprising halogen, phenyl, cyano, C1- C4alkoxy, C1- C4alkylthio,1- C4alkylsulphonyl; C2- C4alkenyl, unsubstituted or substituted C1- C4alkoxygroup; phenyl or unsubstituted or substituted 1 or 21- C4alkoxygroup, n = 1 or 2, and their acid additive salts

The invention relates to derivatives of N-sulfanilimide formula I, where R1and R2denote hydrogen, halogen, C1-4alkyl, C1-4alkoxycarbonyl or phenyl which can be substituted one to three times, equal or different residues from the group comprising halogen, C1-4alkyl, trifluoromethyl; R3- halogen, cyano, trifluoromethyl; R4- 4-isoxazolyl, pyrazolyl, which may be substituted with halogen, C1-4the alkyl, amino group, cycloalkyl, as well as their acid-salt additive

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention relates to new substituted benzoylketones of the general formula (I): , all possible tautomeric forms and possible salts that can represent active substance as a component of herbicide agent. In the formula (I) A means (C1-C4)-alkyl; R1 means cyclo-(C3-C6)-alkyl; R2 means hydrogen atom (H), cyano-group (CN); R3 means hydrogen atom (H), halogen atom, CF3, (C1-C4)-alkylsulfonyl; R4 means halogen atom; X means groups: or wherein R5 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, (C1-C4)-alkylthio-group, di-(C1-C6-alkyl)-amino-group; R6 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, cyclo-(C3-C6)-alkyl; n = 0 or 1 including all possible tautomeric forms and possible salts. Compounds of the formula (I) elicit herbicide activity and can be used in herbicide composition.

EFFECT: valuable properties of compounds.

3 cl, 1 sch, 3 tbl, 13 ex

Up!