Pyridine and pyrazine compounds

Abstract

The present invention relates to compounds of formula I ##STR00001##
wherein the variables are defined as given in the description and claims. The invention further relates to uses and composition for compounds of formula I.

Claims

1. A compound of formula I ##STR00507## wherein R.sup.1 is C.sub.1-C.sub.6-alkyl; R.sup.2 is C.sub.1-C.sub.6-alkyl; U is N or CR.sup.3; R.sup.3 is H and C.sub.1-C.sub.6-alkyl; R.sup.4 is selected from H and C.sub.1-C.sub.6-alkyl; Y is O Z is CR.sup.5; R.sup.5 is H; X is halogen; n is 1; Q.sup.1 is selected from C.sub.1-C.sub.6-alkyl and C.sub.1-C.sub.6-halogenalkyl; Q.sup.2 is selected from H and C.sub.1-C.sub.6-alkyl; W is O or NQ.sup.4; Q.sup.3 is selected from substituted C.sub.1-C.sub.15-alkyl, C(═O)C.sub.1-C.sub.15-alkyl, and C(═O)aryl wherein the aliphatic moieties of Q.sup.3 except for substituted C.sub.1-C.sub.15-alkyl moieties are unsubstituted or substituted with identical or different groups Q.sup.3a which independently of one another are selected from: Q.sup.3a halogen, C.sub.1-C.sub.6-alkoxy, and phenyl; and wherein the phenyl groups are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents Q.sup.311a selected from the group consisting of halogen; wherein the aryl moieties of Q.sup.3 are unsubstituted or substituted with 1, 2, 3, 4, 5 or up to the maximum number of identical or different groups Q.sup.3b which independently of one another are selected from: Q.sup.3b halogen and phenyl wherein the phenyl groups are unsubstituted or substituted with 1, 2, 3, 4 or 5 substituents Q.sup.31b selected from the group consisting of halogen Q.sup.4 is hydrogen; with the proviso that if U is CR.sup.3 W cannot be O or S(O).sub.m and of an agriculturally acceptable salt thereof.

2. The compound of claim 1, wherein U is N and W is O.

3. The compound of claim 1, wherein U is N and W is NQ.sup.4.

4. The compound of claim 1, wherein U is CR.sup.3 and W is NQ.sup.4, wherein R.sup.3 is H.

5. A composition comprising one compound of claim 1, an N-oxide or an agriculturally acceptable salt thereof.

6. A method for combating phytopathogenic fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of claim 1.

Description

SYNTHESIS EXAMPLE

(1) With due modification of the starting compounds, the procedures shown in the synthesis examples below were used to obtain further compounds I. The resulting compounds, together with physical data, are listed in Table I below.

(2) HPLC-MS: HPLC-column Kinetex XB C18 1.7μ (50×2.1 mm); eluent: acetonitrile/water+0.1% TFA (5 gradient from 5:95 to 100:0 in 1.5 min at 60° C., flow gradient from 0.8 to 1.0 ml/min in 1.5 min). MS: Quadrupol Electrospray Ionisation, 80 V (positive mode).

1. Synthesis of 2-[2-[(5,6-dimethyl-3-pyridyl)oxy]-6-fluoro-phenyl]-N,2-dimethyl-propanamide (I-1)

(3) To a solution of 2-[2-[(5,6-dimethyl-3-pyridyl)oxy]-6-fluoro-phenyl]propan-2-ol (1.07 g, 3.9 mmol) in acetic acid (15 mL), acetonitrile (3 mL) and sulfuric acid (3 mL) were added at rt. The reaction was stirred for 2 h at 70° C., then ice was added and the reaction mixture was quenchend with NaOH to pH>10. The aqueous phase was extracted with ethyl acetate, the organic phase was washed with water, dried over Na.sub.2SO.sub.4, concentrated. The crude was purified via HPLC (water/acetonitrile) to yield 101 mg (8%) of the title compound as a colorless oil.

(4) .sup.1H-NMR (CDCl.sub.3, δ in ppm): 8.2 (s, 1H); 7.1 (td, 1H); 7.0 (s, 1H); 6.8 (td, 1H); 6.5 (d, 1H); 5.9 (br s, 1H); 2.5 (s, 3H); 2.3 (s, 3H); 1.8 (s, 6H); 1.7 (s, 3H),

2. Synthesis of 5-[2-(1-benzyloxy-1-methyl-ethyl)-3-fluoro-phenoxy]-2,3-dimethyl-pyrazine (I-3)

(5) .sup.1H-NMR (CDCl.sub.3, δ in ppm): 8.0 (s, 1H); 7.4-7.2 (m, 4H); 7.2 (m, 2H); 7.0 (td, 1H); 6.8 (d, 1H); 5.9 (q, 1H); 4.4 (d, 1H), 4.3 (d, 1H), 2.4 (s, 3H); 2.3 (s, 3H); 1.6 (d, 3H).

(6) TABLE-US-00014 TABLE l 06 Mp HPLC-MS (R.sub.t No. U R4 Q1 Q2 W Q3 [° C.]; [min], M.sup.+ + H) I-1 CH H CH.sub.3 CH.sub.3 N COCH.sub.3 0.722 min; M.sup.+ + H = 317 I-2 N H CH.sub.3 H O CH.sub.2Ph 70 1.329 min; M.sup.+ + H = 353.2 I-3 N CH.sub.3 CH.sub.3 H O CH.sub.2Ph 1.62 min; M.sup.+ + H = 367.1 I-4 N CH.sub.3 CF.sub.3 H O CH.sub.2C.sub.6H.sub.4-4-F 1.405 min; M.sup.+ + H = 438.39 I-5 CH H CH.sub.3 CH.sub.3 N COC.sub.6H.sub.4-4-F 0.881 min; M.sup.+ + H = 397 I-6 CH H CH.sub.3 CH.sub.3 N COC.sub.6H.sub.4-4-Cl 0.918 min; M.sup.+ + H = 413 I-7 CH H CH.sub.3 CH.sub.3 N COCH.sub.2OC.sub.6H.sub.4- 0.932 min; 4-F M.sup.+ + H = 427 I-8 CH H CH.sub.3 CH.sub.3 N COCH.sub.2Cl 0.787 min; M.sup.+ + H = 351 I-9 CH H CH.sub.3 CH.sub.3 N CO(CH.sub.2).sub.2CH.sub.3 0.825 min; M.sup.+ + H = 345.1 I-10 CH H CH.sub.3 CH.sub.3 N CO(CH.sub.2).sub.4CH.sub.3 0.945 min; M.sup.+ + H = 373.1 I-11 CH H CH.sub.3 CH.sub.3 N CO(CH.sub.2).sub.3CH.sub.3 0.896 min; M.sup.+ + H = 359.0 I-12 CH H CH.sub.3 CH.sub.3 N COCH.sub.2CH.sub.3 0.789 min; M.sup.+ + H = 331.2 I-13 CH H CH.sub.3 CH.sub.3 N COCH.sub.2- 155 0.665 min; morpholine M.sup.+ + H = 402.2 I-14 N CH.sub.3 CH.sub.3 CH.sub.3 O CH.sub.2Ph 1.381 min; M.sup.+ + H = 381.1 I-15 N CH.sub.3 CF.sub.3 H O CH(CH.sub.3)C.sub.6H.sub.4- 1.420 min 4-F M.sup.+ + H = 453.1

(7) II. Biological Trials

(8) Microtest

(9) The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.

Example 1—Activity Against the Grey Mold Botytis Cinerea in the Microtiterplate Test

(10) The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Botrci cinerea in a DOB medium solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 9 days after the inoculation.

(11) In this test, the samples which had been treated with 31 ppm of the active substance from examples 1-2, I-3, I-5, I-14 and I-15 respectively, showed up to at most 6% growth of the pathogen.

Example 2—Activity Against Fusarium culmorum in the Microtiterplate Test

(12) The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Fusarium culmorum in an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.

(13) In this test, the samples which had been treated with 31 ppm of the active substance from examples 1-2, I-3, I-14 and I-15 respectively, showed up to at most 17% growth of the pathogen.

Example 3—Activity Against Rice Blast Pyricularia oryzae in the Microtiterplate Test

(14) The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Pyricularia oryzae in a DOB medium solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18° C. Using an absorption photometer, the MTPs were measured at 405 nm 9 days after the inoculation.

(15) In this test, the samples which had been treated with 31 ppm of the active substance from examples I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14 and I-15 respectively, showed up to at most 13% growth of the pathogen.

(16) The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.