AMIDE COMPOUND CONTAINING SUBSTITUTED ACETOPHENONE STRUCTURAL FRAGMENTS AND PREPARATION METHOD AND APPLICATION THEREOF

Abstract

The present invention discloses an amide compound containing substituted acetophenone structural fragments, having a structure shown by general formula I:

##STR00001##

The definitions of substituents in the formula are shown in the description. The compound of the present invention has broad-spectrum fungal activity, and has excellent control effects on cucumber downy mildew, wheat powdery mildew, corn rust, cucumber anthracnose, cucumber botrytis and tomato botrytis.

Claims

1. An amide compound containing substituted acetophenone structural fragments, characterized in that: the amide compound containing substituted acetophenone structural fragments is a compound shown by general formula I; ##STR00076## R.sub.1 is selected from hydrogen, halogen, C.sub.1-C.sub.12 alkyl, halogenated C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy or halogenated C.sub.1-C.sub.12 alkoxy; R.sub.2 is selected from hydrogen, C.sub.1-C.sub.12 alkyl, halogenated C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 cycloalkyl, C.sub.2-C.sub.12 alkenyl, C.sub.2-C.sub.12 alkynyl, C.sub.1-C.sub.12 alkoxy C.sub.1-C.sub.12 alkyl, halogenated C.sub.1-C.sub.12 alkoxy C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkylthio C.sub.1-C.sub.12 alkyl, halogenated C.sub.1-C.sub.12 alkylthio C.sub.1-C.sub.12 alkyl, C.sub.4-C.sub.12 cycloalkylalkyl or halogenated C.sub.4-C.sub.12 cycloalkylalkyl; R.sub.3 is selected from hydrogen, C.sub.1-C.sub.12 alkyl, halogenated C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy, halogenated C.sub.1-C.sub.12 alkoxy, C.sub.3-C.sub.12 cycloalkyl, C.sub.1-C.sub.12 alkylthio, halogenated C.sub.1-C.sub.12 alkylthio, C.sub.1-C.sub.12 alkoxy C.sub.1-C.sub.12 alkyl, halogenated C.sub.1-C.sub.12 alkoxy C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkylthio C.sub.1-C.sub.12 alkyl or halogenated C.sub.1-C.sub.12 alkylthio C.sub.1-C.sub.12 alkyl; R.sub.4 is selected from C.sub.1-C.sub.12 alkyl, halogenated C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy, halogenated C.sub.1-C.sub.12 alkoxy, C.sub.3-C.sub.12 cycloalkyl, C.sub.1-C.sub.12 alkylthio, halogenated C.sub.1-C.sub.12 alkylthio, C.sub.1-C.sub.12 alkoxy C.sub.1-C.sub.12 alkyl, halogenated C.sub.1-C.sub.12 alkoxy C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkylthio C.sub.1-C.sub.12 alkyl or halogenated C.sub.1-C.sub.12 alkylthio C.sub.1-C.sub.12 alkyl; B is selected from pyridin-3-yl, 2-difluoromethylpyridin-3-yl, 1-methyl-3-trifluoromethyl-5-fluoro-pyrazol-4-yl, 1-ethyl-3-trifluoromethyl-5-fluoro-pyrazol-4-yl, 1-methyl-3-trifluoromethyl-5-methylthio-pyrazol-4-yl, 1-ethyl-3- trifluoromethyl-5-methylthio-pyrazol-4-yl, 1-methyl-3-trifluoromethyl-5-methylsulfonyl-pyrazol-4-yl, 1-ethyl-3-trifluoromethyl-5-methylsulfonyl-pyrazol-4-yl, 1-methyl-3-methyl-pyrazol-5-yl, 1-ethyl-3-methyl-pyrazol-5-yl, 1-methyl-5-methylpyrazol-3-yl or 1-ethyl-5-methylpyrazol-3-yl, and halogen-substituted isothiazolyl; or pyrazinyl, pyrimidinyl, 4-substituted 2-hydroxythiazol-5-yl, 5-substituted 1-methyl-3-difluoromethylpyrazol-4-yl and 5-substituted 1-ethyl-3-difluoromethylpyrazol-4-yl substituted by 1-2 identical or different following groups; and the following groups are hydrogen, methyl, difluoromethyl, trifluoromethyl, hydroxyl, methoxy, thiol, methylthio, methylsulfonyl or halogen.

2. The amide compound containing substituted acetophenone structural fragments according to claim 1, characterized in that: in the compound of general formula I, R.sub.1 is selected from hydrogen, halogen or C.sub.1-C.sub.8 alkyl; R.sub.2 is selected from hydrogen, C.sub.1-C.sub.8 alkyl, C.sub.3-C.sub.8 cycloalkyl or halogenated C.sub.1-C.sub.8 alkyl; R.sub.3 is selected from hydrogen, C.sub.1-C.sub.8 alkyl or halogenated C.sub.1-C.sub.8 alkyl; R.sub.4 is selected from C.sub.1-C.sub.8 alkyl or halogenated C.sub.1-C.sub.8 alkyl; B is selected from any one of the following B.sub.1-B.sub.30; ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## .

3. The amide compound containing substituted acetophenone structural fragments according to claim 2, characterized in that: in the general formula I, R.sub.1 is selected from hydrogen, halogen or C.sub.1-C.sub.4 alkyl; R.sub.2 is selected from hydrogen, C.sub.1-C.sub.4 alkyl, C.sub.3-C.sub.6 cycloalkyl or halogenated C.sub.1-C.sub.4 alkyl; R.sub.3 is selected from hydrogen, C.sub.1-C.sub.4 alkyl or halogenated C.sub.1-C.sub.4 alkyl; R.sub.4 is selected from C.sub.1-C.sub.4 alkyl or halogenated C.sub.1-C.sub.4 alkyl; B is selected from any one of the following B.sub.1-B.sub.30; ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## .

4. The amide compound containing substituted acetophenone structural fragments according to claim 3, characterized in that: in the general formula I, R.sub.1 is selected from hydrogen, fluorine, chlorine, methyl, ethyl or isopropyl; R.sub.2 is selected from hydrogen, isopropyl, n-propyl, 2-butyl, 2-pentyl, cyclopropyl, cyclopentyl, cyclohexyl, trifluoromethyl or 2,2,2,-trifluoroethyl; R.sub.3 is selected from hydrogen, methyl, ethyl or trifluoromethyl; R.sub.4 is selected from methyl, ethyl or trifluoromethyl; B is selected from B.sub.1, B.sub.2, B.sub.11, B.sub.24, B.sub.25, B.sub.26 or B.sub.27; ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## .

5. The amide compound containing substituted acetophenone structural fragments according to claim 4, characterized in that: in the general formula I, R.sub.1 is selected from hydrogen, chlorine or methyl; R.sub.2 is selected from isopropyl, 2-butyl, 2-pentyl, cyclopropyl or cyclopentyl; R.sub.3 is selected from hydrogen or methyl; R.sub.4 is selected from methyl or ethyl; B is selected from B.sub.2, B.sub.11, B.sub.24, B.sub.25, B.sub.26 or B.sub.27; ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## .

6. An application of the compound of the general formula I of claim 1 for preparing fungal drugs in agriculture or other fields.

7. A fungal composition, comprising the compound of the general formula I of claim 1 as an active ingredient and an acceptable carrier in agriculture, forestry or hygiene; and the weight percentage of the compound of the general formula I as the active ingredient in the composition is 1-99%.

8. A method for disease control, characterized in that: the composition of claim 7 is applied to a disease to be controlled or a growth medium thereof at an effective dose of 10 g to 1000 g per hectare.

Description

DETAILED DESCRIPTION

[0064] The following specific embodiments are used to further illustrate the present invention, but the present invention is not limited to these examples (unless otherwise noted, all raw materials used are commercially available).

Synthesis Embodiment

[0065] Embodiment 1: preparation of intermediate α-amino-4-isopropoxy-2-methylphenyl isobutanone

[0066] 1) Preparation of α-bromo-4-isopropoxy-2-methylphenyl isobutanone

##STR00072##

30 g (0.136 mol) of 4-isopropoxy-2- methylphenyl isobutanone and 50 g (0.224 mol) of copper bromide were put into a three-necked flask containing 250 ml of ethyl acetate, and heated to 70° C. to react for 5-18 hours. After the reaction was monitored by HPLC, the reaction solution was cooled to room temperature and filtered; and a filter cake was washed with ethyl acetate, washed with sodium bicarbonate solution, dried and then subjected to column chromatography to obtain 35 g of light yellow oil, with a yield of 85.9%.

[0067] 2) Preparation of α-azido-4-isopropoxy-2- methylphenyl isobutanone

##STR00073##

35 g (0.117 mol) of α-bromo-4-isopropoxy-2-methylphenyl isobutanone was put into a 500 ml three-necked flask, and heated to 50° C. by using 100 ml of dimethyl sulfoxide as a solvent; and 15.21 g (0.234 mol) of sodium azide was added in batches to react for 4-6 hours. After the reaction was monitored by HPLC, the reaction solution was poured into water after cooling, extracted with ethyl acetate for three times, washed with brine, dried, and then subjected to column chromatography to obtain 25 g of light yellow oil, with a yield of 81.8%.

[0068] 3) Preparation of α-amino-4-isopropoxy-2-methylphenyl isobutanone

##STR00074##

25 g (95.67 mmol) of α-azido-4-isopropoxy-2-methylphenyl isobutanone was put into a 500 ml three-necked flask; 450 ml of tetrahydrofuran was used as a solvent; 50 ml of water was added at 0-15° C.; 12.51 g (0.191 mol) of zinc powder was added; and 7 g (0.131 mol) of saturated ammonium chloride solution was added dropwise to react for 4-16 hours. After the reaction was monitored by HPLC, the reaction solution was filtered, washed twice with saturated brine, dried and then subjected to column chromatography to obtain 17 g of light yellow oil; and white solid or colorless crystals can be precipitated after storage for a long time, with a yield of 75.51%.

[0069] Embodiment 2: preparation of compound 1-2

##STR00075##

0.235 g (1 mmol) of α-amino-4-isopropoxy-2-methylphenyl isobutanone was added into 20 ml of dichloromethane, and 0.230 g (1.2 mmol, 1.2 eqiv) of 2-difluoromethylnicotinyl chloride was added dropwise under an ice bath. 0.121 g (1.2 mmol, 1.2 eqiv) of triethylamine was added dropwise, and the solution was naturally heated to room temperature to react for 2-6 hours. After the reaction was monitored by HPLC, after desolvation, the residues were subjected to column chromatography, with eluents of ethyl acetate and petroleum ether (boiling range of 60-90° C.), and a volume ratio of 0:100 to 20:80 for gradient elution to obtain 0.251 g of yellow solid, with a yield of 64.3%.

[0070] According to the preparation method of the compound of the general formula I described above and the specific process provided in the synthesis embodiments, other compounds shown by the general formula I can be obtained only by replacing the raw material materials (see Table 1).

TABLE-US-00001 Structure and physical properties of some compounds of general formula I Compound No. R.sub.1 R.sub.2 R.sub.3 R.sub.4 B Appearance Melting point (°C) I-1 Me i-Pr Me Me B.sub.1 Yellow wax I-2 Me i-Pr Me Me B.sub.2 Yellow solid 96.9 I-3 Me i-Pr Me Me B.sub.3 Yellow solid 125.5 I-4 Me i-Pr Me Me B.sub.4 I-5 Me i-Pr Me Me B.sub.5 Yellow wax I-6 Me i-Pr Me Me B.sub.6 I-7 Me i-Pr Me Me B.sub.7 I-8 Me i-Pr Me Me B.sub.8 I-9 Me i-Pr Me Me B.sub.9 I-10 Me i-Pr Me Me B.sub.10 I-11 Me i-Pr Me Me B.sub.11 White solid 118.1 I-12 Me i-Pr Me Me B.sub.12 I-13 Me i-Pr Me Me B.sub.13 I-14 Me i-Pr Me Me B.sub.14 I-15 Me i-Pr Me Me B.sub.15 White solid 146.6 I-16 Me i-Pr Me Me B.sub.16 White solid 148.3 I-17 Me i-Pr Me Me B.sub.17 White solid 139.3 I-18 Me i-Pr Me Me B.sub.18 White solid 102.2 I-19 Me i-Pr Me Me B.sub.19 White solid 108.4 I-20 Me i-Pr Me Me B.sub.20 I-21 Me i-Pr Me Me B.sub.21 Colorless glass I-22 Me i-Pr Me Me B.sub.22 Colorless glass I-23 Me i-Pr Me Me B.sub.23 I-24 Me i-Pr Me Me B.sub.24 White solid 84.4 I-25 Me i-Pr Me Me B.sub.25 Yellow wax I-26 Me i-Pr Me Me B.sub.26 White solid 119.4 I-27 Me i-Pr Me Me B.sub.27 Yellow solid 130.5 I-28 Me i-Pr Me Me B.sub.28 I-29 Me i-Pr Me Me B.sub.29 I-30 Me i-Pr Me Me B.sub.30 I-31 Me i-Pr H Me B.sub.1 I-32 Me i-Pr H Me B.sub.2 I-33 Me i-Pr H Me B.sub.3 I-34 Me i-Pr H Me B.sub.4 I-35 Me i-Pr H Me B.sub.5 I-36 Me i-Pr H Me B.sub.6 I-37 Me i-Pr H Me B.sub.7 I-38 Me i-Pr H Me B.sub.8 I-39 Me i-Pr H Me B.sub.9 I-40 Me i-Pr H Me B.sub.10 I-41 Me i-Pr H Me B.sub.11 I-42 Me i-Pr H Me B.sub.12 I-43 Me i-Pr H Me B.sub.13 I-44 Me i-Pr H Me B.sub.14 I-45 Me i-Pr H Me B.sub.15 I-46 Me i-Pr H Me B.sub.16 I-47 Me i-Pr H Me B.sub.17 I-48 Me i-Pr H Me B.sub.18 I-49 Me i-Pr H Me B.sub.19 I-50 Me i-Pr H Me B.sub.20 I-51 Me i-Pr H Me B.sub.21 I-52 Me i-Pr H Me B.sub.22 I-53 Me i-Pr H Me B.sub.23 I-54 Me i-Pr H Me B.sub.24 I-55 Me i-Pr H Me B.sub.25 I-56 Me i-Pr H Me B.sub.26 I-57 Me i-Pr H Me B.sub.27 I-58 Me i-Pr H Me B.sub.28 I-59 Me i-Pr H Me B.sub.29 I-60 Me i-Pr H Me B.sub.30 I-61 H i-Pr Me Me B.sub.1 I-62 H i-Pr Me Me B.sub.2 I-63 H i-Pr Me Me B.sub.3 I-64 H i-Pr Me Me B.sub.4 I-65 H i-Pr Me Me B.sub.5 I-66 H i-Pr Me Me B.sub.6 I-67 H i-Pr Me Me B.sub.7 I-68 H i-Pr Me Me B.sub.8 I-69 H i-Pr Me Me B.sub.9 I-70 H i-Pr Me Me B.sub.10 I-71 H i-Pr Me Me B.sub.11 I-72 H i-Pr Me Me B.sub.12 I-73 H i-Pr Me Me B.sub.13 I-74 H i-Pr Me Me B.sub.14 I-75 H i-Pr Me Me B.sub.15 I-76 H i-Pr Me Me B.sub.16 I-77 H i-Pr Me Me B.sub.17 I-78 H i-Pr Me Me B.sub.18 I-79 H i-Pr Me Me B.sub.19 I-80 H i-Pr Me Me B.sub.20 I-81 H i-Pr Me Me B.sub.21 I-82 H i-Pr Me Me B.sub.22 I-83 H i-Pr Me Me B.sub.23 I-84 H i-Pr Me Me B.sub.24 I-85 H i-Pr Me Me B.sub.25 I-86 H i-Pr Me Me B.sub.26 I-87 H i-Pr Me Me B.sub.27 I-88 H i-Pr Me Me B.sub.28 I-89 H i-Pr Me Me B.sub.29 I-90 H i-Pr Me Me B.sub.30 I-91 Me c-Pr Me Me B.sub.1 I-92 Me c-Pr Me Me B.sub.2 I-93 Me c-Pr Me Me B.sub.11 I-94 Me c-Pr Me Me B.sub.24 I-95 Me c-Pr Me Me B.sub.25 I-96 Me c-Pr Me Me B.sub.26 I-97 Me s-Bu Me Me B.sub.1 I-98 Me s-Bu Me Me B.sub.2 I-99 Me s-Bu Me Me B.sub.11 I-100 Me s-Bu Me Me B.sub.24 I-101 Me s-Bu Me Me B.sub.25 I-102 Me s-Bu Me Me B.sub.26 I-103 Me s-pentyl Me Me B.sub.1 I-104 Me s-pentyl Me Me B.sub.2 I-105 Me s-pentyl Me Me B.sub.11 I-106 Me s-pentyl Me Me B.sub.24 I-107 Me s-pentyl Me Me B.sub.25 I-108 Me s-pentyl Me Me B.sub.26 I-109 Me cyclopentyl Me Me B.sub.1 I-110 Me cyclopentyl Me Me B.sub.2 I-111 Me cyclopentyl Me Me B.sub.11 I-112 Me cyclopentyl Me Me B.sub.24 I-113 Me cyclopentyl Me Me B.sub.25 I-114 Me cyclopentyl Me Me B.sub.26 I-115 Me c-Pr H Me B.sub.1 I-116 Me c-Pr H Me B.sub.2 I-117 Me c-Pr H Me B.sub.11 I-118 Me c-Pr H Me B.sub.24 I-119 Me c-Pr H Me B.sub.25 I-120 Me c-Pr H Me B.sub.26 I-121 Me s-Bu H Me B.sub.1 I-122 Me s-Bu H Me B.sub.2 I-123 Me s-Bu H Me B.sub.11 I-124 Me s-Bu H Me B.sub.24 I-125 Me s-Bu H Me B.sub.25 I-126 Me s-Bu H Me B.sub.26 I-127 Me s-pentyl H Me B.sub.1 I-128 Me s-pentyl H Me B.sub.2 I-129 Me s-pentyl H Me B.sub.11 I-130 Me s-pentyl H Me B.sub.24 I-131 Me s-pentyl H Me B.sub.25 I-132 Me s-pentyl H Me B.sub.26 I-133 Me cyclopentyl H Me B.sub.1 I-134 Me cyclopentyl H Me B.sub.2 I-135 Me cyclopentyl H Me B.sub.11 I-136 Me cyclopentyl H Me B.sub.24 I-137 Me cyclopentyl H Me B.sub.25 I-138 Me cyclopentyl H Me B.sub.26 I-139 Me i-Pr Me Et B.sub.1 I-140 Me i-Pr Me Et B.sub.2 I-141 Me i-Pr Me Et B.sub.11 I-142 Me i-Pr Me Et B.sub.24 I-143 Me i-Pr Me Et B.sub.25 I-144 Me i-Pr Me Et B.sub.26 I-145 Me i-Pr H Et B.sub.1 I-146 Me i-Pr H Et B.sub.2 I-147 Me i-Pr H Et B.sub.11 I-148 Me i-Pr H Et B.sub.24 I-149 Me i-Pr H Et B.sub.25 I-150 Me i-Pr H Et B.sub.26 I-151 H i-Pr H Et B.sub.1 I-152 H i-Pr H Et B.sub.2 I-153 H i-Pr H Et B.sub.11 I-154 H i-Pr H Et B.sub.24 I-155 H i-Pr H Et B.sub.25 I-156 H i-Pr H Et B.sub.26 I-157 H i-Pr H Me B.sub.1 I-158 H i-Pr H Me B.sub.2 I-159 H i-Pr H Me B.sub.11 I-160 H i-Pr H Me B.sub.24 I-161 H i-Pr H Me B.sub.25 I-162 H i-Pr H Me B.sub.26 White paste I-163 Cl i-Pr Me Me B.sub.1 I-164 Cl i-Pr Me Me B.sub.2 I-165 Cl i-Pr Me Me B.sub.11 I-166 Cl i-Pr Me Me B.sub.24 I-167 Cl i-Pr Me Me B.sub.25 I-168 Cl i-Pr Me Me B.sub.26

[0071] Other compounds of the present invention can be prepared with reference to the above embodiments.

[0072] The physical property data and nuclear magnetic data (.sup.1HNMR, 600 MHz, internal standard TMS, ppm) of some compounds are as follows:

[0073] Compound I-1:.sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.14 (s, 1H), 7.42 (d, J = 8.6 Hz, 1H), 6.77 (d, J = 2.4 Hz, 1H), 6.67 (dd, J= 8.6, 2.5 Hz, 1H), 4.59 (hept, J= 6.1 Hz, 1H), 2.33 (s, 3H), 1.82 (s, 6H), 1.34 (d, J= 6.1 Hz, 6H).

[0074] Compound I-2: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.70 (d, J = 4.0 Hz, 1H), 7.67 (d, J = 7.6 Hz, 1H), 7.47 (d, J = 8.6 Hz, 1H), 7.40 (dd, J = 7.6, 4.9 Hz, 1H), 6.97 (s, 1H), 6.79 (d, J = 1.7 Hz, 1H), 6.75 (t, J = 54.5 Hz, 1H), 6.65 (dd, J = 8.6, 2.1 Hz, 1H), 4.73 - 4.47 (m, 1H), 2.38 (s, 3H), 1.78 (s, 6H), 1.34 (d, J = 6.0 Hz, 6H).

[0075] Compound I-3: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.96 (d, J = 1.8 Hz, 1H), 8.71 (dd, J = 4.8, 1.5 Hz, 1H), 8.04 (dt, J = 7.9, 1.9 Hz, 1H), 7.48 (d, J = 8.6 Hz, 1H), 7.38 - 7.31 (m, 2H), 6.76 (d, J = 2.4 Hz, 1H), 6.65 (dd, J = 8.6, 2.5 Hz, 1H), 4.57 (hept, J = 6.1 Hz, 1H), 2.36 (s, 3H), 1.81 (s, 6H), 1.33 (d, J = 6.1 Hz, 6H).

[0076] Compound I-5: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.86 (d, J = 2.3 Hz, 1H), 8.79 (s, 1H), 8.68 (d, J = 2.2 Hz, 1H), 7.75 (t, J= 54.2 Hz, 1H), 7.46 (d, J= 8.6 Hz, 1H), 6.75 (d, J= 2.3 Hz, 1H), 6.59 (dd, J= 8.6, 2.5 Hz, 1H), 4.59 - 4.52 (m, 1H), 2.38 (s, 3H), 1.80 (s, 6H), 1.31 (d, J= 6.1 Hz, 6H).

[0077] Compound I-11: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.43 (d, J = 8.6 Hz, 1H), 7.02 (s, 1H), 6.75 (d, J = 2.2 Hz, 1H), 6.64 (dd, J = 8.6, 2.4 Hz, 1H), 4.66 - 4.48 (m, 1H), 3.81 (s, 3H), 2.33 (s, 3H), 1.76 (s, 6H), 1.33 (d, J= 6.1 Hz, 6H).

[0078] Compound I-15:.sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.67 (s, 1H), 7.44 (d, J = 8.6 Hz, 1H), 6.77 (s, 1H), 6.75 (d, J = 2.3 Hz, 1H), 6.64 (dd, J = 8.6, 2.4 Hz, 1H), 4.57 (hept, J = 6.0 Hz, 1H), 3.82 (s, 3H), 2.44 (s, 3H), 2.33 (s, 3H), 1.76 (s, 6H), 1.33 (d, J= 6.1 Hz, 6H).

[0079] Compound I-16:.sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.44 (d, J = 8.6 Hz, 1H), 6.91 (s, 1H), 6.75 (d, J = 2.3 Hz, 1H), 6.62 (dd, J = 8.6, 2.4 Hz, 1H), 6.28 (s, 1H), 4.56 (hept, J = 6.0 Hz, 1H), 4.34 (q, J = 7.2 Hz, 2H), 2.36 (s, 3H), 2.26 (s, 3H), 1.76 (s, 6H), 1.33 (d, J = 6.1 Hz, 6H), 1.28 (t, J = 7.2 Hz, 3H).

[0080] Compound I-17: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.54 (d, J= 8.6 Hz, 1H), 7.50 (s, 1H), 6.72 (d, J = 2.4 Hz, 1H), 6.59 (dd, J= 8.6, 2.5 Hz, 1H), 6.43 (s, 1H), 4.55 (hept, J= 6.1 Hz, 1H), 3.78 (s, 3H), 2.39 (s, 3H), 2.25 (s, 3H), 1.73 (s, 6H), 1.31 (d, J = 6.1 Hz, 6H).

[0081] Compound I-18:.sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.5 5 (d, J = 8.6 Hz, 1H), 7.51 (s, 1H), 6.72 (d, J = 2.1,1H), 6.59 (dd, J= 8.6, 2.0 Hz, 1H), 6.42 (s, 1H), 4.55 (hept, J = 5.9 Hz, 1H), 4.07 (q, J= 7.3 Hz, 2H), 2.39 (s, 3H), 2.26 (s, 3H), 1.73 (s, 6H), 1.42 (t, J= 7.3 Hz, 3H), 1.31 (d, J = 6.0 Hz, 6H).

[0082] Compound 1-19: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.42 (d, J= 8.6 Hz, 1H), 7.06 (s, 1H), 6.77 (d, J = 2.4 Hz, 1H), 6.67 (dd, J = 8.6, 2.5 Hz, 1H), 4.58 (hept, J = 6.0 Hz, 1H), 2.61 (s, 3H), 2.33 (s, 3H), 1.78 (s, 6H), 1.34 (d, J= 6.1 Hz, 6H).

[0083] Compound 1-21: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.54 (s, 1H), 7.50 (d, J= 8.6 Hz, 1H), 6.78 (t, J = 53.7 Hz, 1H), 6.75 (d, J = 2.3 Hz, 1H), 6.65 (dd, J = 8.5, 2.3 Hz, 1H), 4.57 (hept, J = 6.1 Hz, 1H), 4.22 (s, 3H), 3.39 (s, 3H), 2.35 (s, 4H), 1.73 (s, 6H), 1.33 (d, J= 6.1 Hz, 6H).

[0084] Compound 1-22: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.19 (s, 1H), 7.47 (d, J= 8.6 Hz, 1H), 7.13 (t, J = 54.2 Hz, 1H), 6.74 (d, J = 2.3 Hz, 1H), 6.61 (dd, J = 8.6, 2.5 Hz, 1H), 4.56 (hept, J = 6.0 Hz, 1H), 4.02 (s, 3H), 2.41 (s, 3H), 2.36 (s, 3H), 1.76 (s, 6H), 1.32 (d, J = 6.1 Hz, 6H). MS: [M+1].sup.+ found 440.0, Cal 440.18; [M+Na].sup.+ found 461.9, Cal 462.16.

[0085] Compound 1-24: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.46 (d, J = 8.6 Hz, 1H), 6.99 (t, J = 54.0 Hz, 1H), 6.75 (d, J = 2.3 Hz, 1H), 6.63 (dd, J = 8.6, 2.4 Hz, 1H), 4.60 - 4.53 (m, 1H), 3.89 (s, 3H), 2.35 (s, 3H), 1.76 (s, 6H), 1.33 (d, J= 6.1 Hz, 6H).

[0086] Compound I-25:.sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.45 (d, J = 8.6 Hz, 1H), 7.02 (s, 1H), 6.95 (t, J = 53.9 Hz, 1H), 6.74 (d, J = 2.2 Hz, 1H), 6.63 (dd, J = 8.6, 2.4 Hz, 1H), 4.60 - 4.54 (m, 1H), 3.80 (s, 3H), 2.34 (s, 3H), 1.74 (s, 6H), 1.33 (d, J = 6.0 Hz, 6H).

[0087] Compound 1-26: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.77 (s, 1H), 7.55 (d, J = 8.6 Hz, 1H), 7.05 (s, 1H), 6.84 (t, J = 54.2 Hz, 1H), 6.72 (d, J = 2.4 Hz, 1H), 6.59 (dd, J = 8.6, 2.5 Hz, 1H), 4.55 (hept, J = 6.0 Hz, 1H), 3.86 (s, 3H), 2.39 (s, 3H), 1.72 (s, 6H), 1.31 (d, J = 6.1 Hz, 6H).

[0088] Compound I-27:.sup.1H NMR (600 MHz, CDCl.sub.3) δ 10.72 (s, 1H), 7.70 (s, 1H), 7.25 (d, J = 8.8 Hz, 1H), 6.75 (d, J = 2.0 Hz, 1H), 6.68 (dd, J= 8.6, 2.3 Hz, 1H), 6.41 (t, J= 54.2 Hz, 1H), 4.62 - 4.51 (m, 1H), 3.46 (s, 3H), 2.28 (s, 3H), 1.71 (s, 6H), 1.33 (d, J= 6.0 Hz, 6H).

[0089] Compound 1-162: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.85 (s, 1H), 7.27 (d, J = 8.9 Hz, 2H), 6.99 (t, J = 54.2 Hz, 1H), 6.96 (d, J = 8.7 Hz, 2H), 4.92 (p, J = 6.6 Hz, 1H), 4.61-4.55(m, 1H), 3.94 (s, 3H), 1.36 (dd, J = 6.0, 1.1 Hz, 6H), 1.29 (d, J = 6.7 Hz, 6H).

Embodiments of Determination of Biological Activity

[0090] The compounds of the present invention show good activity against various germs in the agricultural field.

Embodiment 3: Determination of Fungal Activity

[0091] The test of in vivo protection effect is conducted on various fungal diseases of plants through samples of the compounds of the present invention. The determination results of the fungal activity are shown in the following embodiments.

Determination of in Vivo Protection Activity

[0092] The determination method is as follows: the to-be-determined sample of the compound of general formula I obtained above was dissolved with a small amount of solvent (the type of the solvent is, for example, acetone, methanol, DMF, etc., and is selected according to the dissolving ability to the sample; and the volume ratio of the solvent amount to the liquid spray amount is equal to or less than 0.05) by a live pot determination method, and diluted with water containing 0.1% Tween 80 to prepare to-be-determined liquid with required concentration. On a crop sprayer, the to-be-determined liquid was sprayed onto disease host plants (the host plants are standard potted seedlings cultivated in a greenhouse), and the disease was inoculated after 24 hours. According to the characteristics of the disease, the diseased plants that need to be cultivated under temperature control and moisturizing were inoculated and then placed in an artificial climate chamber for cultivation. After the disease completes infection, the disease was transferred into the greenhouse for cultivation, and the diseased plants that do not need moisturizing cultivation were directly inoculated and cultivated in the greenhouse. After full onset through control (usually one week), the disease prevention effect of the compound was evaluated.

[0093] The determination results of in vivo protection activity for some compounds are as follows:

[0094] In vivo protection activity against cucumber downy mildew:

[0095] At a dose of 400 ppm, compounds 1-1, 1-5, 1-19, 1-23 and 1-25 have more than 80% control effects on cucumber downy mildew, and compounds CK1, CK2, CK3 and CK4 have 0 control effects on cucumber downy mildew.

[0096] In vivo protection activity against wheat powdery mildew:

[0097] At a dose of 100 ppm, compounds 1-2 and 1-25 have more than 90% control effects on wheat powdery mildew, and compounds CK1, CK2, CK3 and CK4 have control effects of 85%, 85%, 85% and 75% on wheat powdery mildew at a dose of 400 ppm.

[0098] In vivo protection activity against corn rust:

[0099] At a dose of 400 ppm, compounds 1-21, 1-26 and 1-27 have more than 80% control effects on corn rust, and compounds CK1, CK2, CK3 and CK4 have 0 control effects on corn rust.

[0100] In vivo protection activity against cucumber anthracnose:

[0101] At a dose of 400 ppm, compounds I-1 and 1-26 have control effects of 60% and 40% on cucumber anthracnose, and compounds CK1, CK2, CK3 and CK4 have 0 control effects on cucumber anthracnose.

[0102] In vivo protection activity against cucumber botrytis:

[0103] At a dose of 200 ppm, compound I-11 has more than 80% control effect on cucumber botrytis, and compounds CK1, CK2, CK3 and CK4 have control effects of 0, 0, 60% and 25% on cucumber botrytis.

[0104] In vivo protection activity against tomato botrytis:

[0105] At a dose of 100 ppm, compounds 1-5, 1-15, 1-19, 1-24 and 1-25 have more than 80% control effects on tomato botrytis, and compounds CK2, CK3 and CK4 have control effects of 20%, 35% and 0 on tomato botrytis.

[0106] According to the above method, some compounds of the present invention and known compounds CK1 (self-made, No. 1-20 in patent WO2007069777), CK2 (self-made, No. 1-84 in patent WO2007069777), CK3 (self-made, No. 1-6 in patent JP 2007210924) and CK4 (self-made, No. 1-183 in patent JP 2007210924) were selected for conducting parallel determination of the activity of controlling cucumber downy mildew. Test results are shown in Table 2.

[0107] .sup.1H NMR (600 MHz, CDCl.sub.3) data and physicochemical data of the above obtained compounds CK1-CK4 are as follows:

[0108] CK1: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 8.73 (d, J= 3.9 Hz, 1H), 7.55 (d, J= 7.5 Hz, 1H), 7.48 (dd, J = 7.4, 4.9 Hz, 1H), 7.45 (d, J = 8.5 Hz, 1H), 6.84 (s, 1H), 6.79 (s, 1H), 6.68 (dd, J = 1.4 Hz, J = 8.3 Hz, 1H), 4.64 - 4.57 (m, 1H), 2.36 (s, 3H), 1.80 (s, 6H), 1.35 (d, J = 6.0 Hz, 6H). White solid, m.p. 88.6° C.

[0109] CK2: .sup.1HNMR (600 MHz, CDCl.sub.3) δ 8.48 - 8.31 (m, 1H), 7.79-7.77 (m, 1H), 7.50 (d, J = 8.6 Hz, 1H), 7.29 - 7.25 (m, 2H), 6.77 (d, J = 2.3 Hz, 1H), 6.64 (dd, J = 8.6, 2.4 Hz, 1H), 4.62 - 4.55 (m, 1H), 2.38 (s, 3H), 1.81 (s, 6H), 1.34 (d, J = 6.1 Hz, 6H). White solid, m.p. 124.3° C.

[0110] CK3: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.81 (s, 1H), 7.48 (d, J = 8.6 Hz, 1H), 6.87 (s, 1H), 6.74 (d, J = 2.1 Hz, 1H), 6.61 (dd, J = 8.6, 2.3 Hz, 1H), 4.62 - 4.50 (m, 1H), 3.92 (s, 3H), 2.36 (s, 3H), 1.73 (s, 6H), 1.32 (d, J = 6.0 Hz, 6H). White solid, m.p. 137.4° C.

[0111] CK4: .sup.1H NMR (600 MHz, CDCl.sub.3) δ 7.43 (d, J = 8.6 Hz, 1H), 7.05 (s, 1H), 6.75 (d, J = 2.4 Hz, 1H), 6.64 (dd, J = 8.6, 2.5 Hz, 1H), 4.57 (hept, J = 6.3 Hz, 1H), 3.90 (s, 3H), 2.34 (s, 3H), 1.77 (s, 6H), 1.33 (d, J = 6.1 Hz, 6H). White solid, m.p. 119.0° C.

TABLE-US-00002 Comparison of control effects of some compounds of the present invention and known compounds on cucumber downy mildew Compound Cucumber downy mildew 400 ppm I-1 80 I-2 40 I-3 40 I-5 85 I-16 50 I-18 40 I-19 85 I-21 40 I-22 85 I-25 85 CK1 0 CK2 0 CK3 0 CK4 0

[0112] According to the above method, some compounds of the present invention and known compounds were selected for conducting parallel determination of the activity of controlling wheat powdery mildew. Test results are shown in Table 3.

TABLE-US-00003 Comparison of control effects of some compounds of the present invention and known compounds on wheat powdery mildew Compound Wheat powdery mildew 400 ppm 100 ppm I-1 98 70 I-2 100 100 I-25 100 90 I-27 100 60 I-162 100 20 CK1 85 - CK2 85 - CK3 85 - CK4 75 - Note: “-” represents no test.

[0113] According to the above method, some compounds of the present invention and known compounds were selected for conducting parallel determination of the activity of controlling corn rust. Test results are shown in Table 4.

TABLE-US-00004 Comparison of control effects of some compounds of the present invention and known compounds on corn rust Compound Corn rust 400 ppm I-1 60 I-25 85 I-26 100 I-27 85 I-162 30 CK1 0 CK2 0 CK3 0 CK4 0

[0114] According to the above method, some compounds of the present invention and known compounds were selected for conducting parallel determination of the activity of controlling cucumber botrytis. Test results are shown in Table 5.

TABLE-US-00005 Comparison of control effects of some compounds of the present invention and known compounds on cucumber botrytis Compound Control effects on cucumber botrytis (%) 200 ppm I-11 80 CK1 0 CK2 0 CK4 25

[0115] According to the above method, some compounds of the present invention and known compounds were selected for conducting parallel determination of the activity of controlling tomato botrytis. Test results are shown in Table 6.

TABLE-US-00006 Comparison of control effects of some compounds of the present invention and known compounds on tomato botrytis Compound Control effects on tomato botrytis (%) 100 ppm 25 ppm I-5 80 - I-15 85 60 I-19 80 60 I-24 85 60 I-25 100 98 CK2 20 0 CK3 35 20 CK4 0 0 Note: “-” represents no test.