CN100364955C - 2-(dibasic) methyl acrylic ester compound and its use - Google Patents

2-(dibasic) methyl acrylic ester compound and its use Download PDF

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CN100364955C
CN100364955C CNB2005100989607A CN200510098960A CN100364955C CN 100364955 C CN100364955 C CN 100364955C CN B2005100989607 A CNB2005100989607 A CN B2005100989607A CN 200510098960 A CN200510098960 A CN 200510098960A CN 100364955 C CN100364955 C CN 100364955C
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CN1743304A (en
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于春睿
徐龙鹤
崔东亮
张弘
吐松
李斌
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Dalian University of Technology
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Dalian University of Technology
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Abstract

The present invention belongs to the technical field of herbicide, which particularly relates to a 2-(disubstituted) methacrylate ester type compound and application thereof. The 2-(disubstituted) methacrylate ester type compound is characterized in that the 2-(disubstituted) methacrylate ester type compound is shown in a general formula (I), wherein R1 is selected from phenyl, replaced phenyl and C4 to C6 heterocycle, R2 is selected from H, C1 to C6 alkyl and C3 to C6 alkenyl or C3 to C6 alkynyl, R3 is selected from C1 to C4 alkyl, Q is selected from various aromaticring groups or replaced aromaticring groups, and chiral carbon atoms of a mark <*> and a mark <*>2 are R, S configuration or mixtures with different proportion thereof. The present invention has the effects and the advantages that the compound has herbicidal activity, unifacial leaf weeds can be effectively controlled after the compound is used after seedlings, and the compound is safe for soybeans, paddy rice and wheat, has higher activity for the weeds and performs the good selectivity for crops. The compound of the present invention not only can be singly used but also can be together mixed and used with other known pesticide, germicide, plant growth regulation agents or fertilizer, etc.

Description

A kind of 2-(two replace) methyl acrylic ester compound and application thereof
Technical field
The invention belongs to herbicide technology field, relate to a kind of 2-(two replace) methyl acrylic ester compound and application thereof.
Background technology
Because the succession of weeds population, transition and to the drug-fast generation of chemical pesticide with develop rapidly; People to the reinforcement of ecological environmental protection consciousness and to chemical pesticide pollute, agricultural chemicals is to non-target organism influence and the attention of home to return to problem in the agricultural chemicals ecotope; World cultivated area reduces and the population growth strengthens the grain demand amount; Developing rapidly and reason such as updating of cropping system of agriculture production technology, need constantly invention novel with improved herbicidal compound and composition.
Some acrylic ester compound is as weedicide (EP149034A2, USP6251829, CN1626526) existing report.But as 2-shown in the present (two replace) methyl acrylic ester compound is not seen open.
Summary of the invention
The invention provides a kind of 2-(two replace) methyl acrylic ester compound, shown in general formula (1):
Figure C20051009896000041
Wherein:
R 1Be selected from phenyl, substituted-phenyl, C 4-C 6Heterocycle; Heterocycle is for containing N, S or O;
R 2Be selected from H, C 1-C 6Alkyl;
R 3Be selected from C 1-C 4Alkyl;
Q is selected from one of group as follows:
Mark *With *2 chiral carbon atom is R, S configuration, or the mixture of its different ratios.Comparatively preferred compound is in the general formula (I) among the present invention:
R 1Be selected from phenyl, substituted-phenyl, C 4-C 6Heterocycle; Heterocycle is for containing N, S or O;
R 2Be selected from H, C 1-C 6Alkyl;
R 3Be selected from C 1-C 4Alkyl;
Q is selected from Q1, Q2, Q3, Q4 or Q5;
Mark *Chiral carbon atom be the R configuration.
Mark *2 chiral carbon atom is R, S configuration, or the mixture of its different ratios.Comparatively preferred compound is in the general formula (I) among the present invention:
R 1Be selected from phenyl, substituted-phenyl, C 4-C 6Heterocycle; Heterocycle is for containing N, S or O;
R 2Be selected from H, C 1-C 6Alkyl;
R 3Be selected from methyl;
Q is selected from Q1, Q2, Q5;
Mark *With *2 chiral carbon atom is R, S configuration, or the mixture of its different ratios.Comparatively preferred compound is in the general formula (I) among the present invention:
R 1Be selected from phenyl, substituted-phenyl, C 4-C 6Heterocycle; Heterocycle is for containing N, S or O;
R 2Be selected from H, C 1-C 6Alkyl;
R 3Be selected from methyl;
Q is selected from Q1, Q2, Q5;
Mark *Chiral carbon atom be the R configuration.
Mark *2 chiral carbon atom is R, S configuration, or the mixture of its different ratios.The alkyl of indication comprises the straight or branched alkyl in the general formula (I).
General formula compound I of the present invention can be prepared by following method:
Raw material (II can be buied by market) is dissolved in the The suitable solvent, and joins in the alkaline aqueous solution, temperature is-10 ℃ reacted 0.5-48 hour under boiling point, and again through hydrochloric acid or sulfuric acid acidation, making intermediate acid is compound (II-1).The suitable solvent is selected from chloroform, methylene dichloride, tetracol phenixin, normal hexane, benzene, toluene, ethyl acetate, THF or dioxane etc.; Suitable alkali is selected from sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or sodium bicarbonate etc.
Intermediate acid (II-1) and SOCl 2, oxalyl chloride or PCl 3Be dissolved in The suitable solvent, chloroform for example, methylene dichloride, tetracol phenixin, normal hexane, benzene, toluene, ethyl acetate, in THF or the dioxane etc., and with organic bases, as triethylamine, pyridine or DMF etc. make catalyzer, and temperature is-10 ℃ reacted 0.5-48 hour under boiling point, made intermediate acyl chlorides (II-2).
Intermediate acyl chlorides (II-2) (can obtain mark by corresponding aldehyde and acrylate according to method described in DE2155113, the US3742669 with compound III by the Baylis-Hillman reaction *2 chiral carbon atom is R, S configuration, or the mixture of its different ratios), in The suitable solvent, temperature made product (I) for-10 ℃ in 0.5-48 hour to the following reaction of boiling point.Solvent is selected from chloroform, methylene dichloride, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetone, DMF, THF or dioxane etc.Add alkaloids, as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonates etc. are to reacting favourable.
When intermediate acyl chlorides (II-2) mark *The chiral carbon atom configuration determine, be by R type (or S type), and the compound III mark *When 2 chiral carbon atom is the mixture of R, S configuration different ratios, obtain a pair of different ratios diastereomer Ia (mark C *2 chiral carbon atoms are configured as R or S) and Ib (mark C *2 chiral carbon atoms are configured as S or R) mixture.Isomer Ia, Ib can be by methods such as recrystallization, column chromatography, asymmetric synthesis and are obtained respectively.(absolute configuration of Ia, Ib is not determined).
Figure C20051009896000071
Table 1: the The compounds of this invention (mark of part shown in general formula (I) *Chiral carbon atom be the R configuration, R 3Be methyl)
Table 1:
Compound Ia/Ib Q R 1 R 2 m.p.(℃)
1 1.0 Q1 4-NO 2Ph CH 3 Dope
2 1.6 Q1 4-NO 2Ph C 2H 5 Dope
3 1.0 Q1 4-FPh CH 3 Dope
4 0.2 Q1 2，4-Cl 2Ph CH 3 143～146
5 1.0 Q1 2-thiophen C 2H 5 Dope
6 1.0 Q1 4-ClPh C 2H 5 Dope
7 6.5 Q1 2，4-Cl 2Ph C 2H 5 149～150
8 1.0 Q1 2-furan C 2H 5 Dope
9 Only contain the Ia configuration Q1 2-ClPh CH 3 144～145
10 Only contain the Ia configuration Q1 3-ClPh CH 3 121～122
11 1.0 Q1 2-CH 3OPh CH 3 98～103
12 1.0 Q1 4-CH 3OPh CH 3 111～125
13 1.0 Q1 4-MePh CH 3 Dope
14-1 1.0 Q1 Ph CH 3 Dope
14-2 Only contain the Ia configuration Q1 Ph CH 3 124～126
15-1 Only contain the Ia configuration Q2 2，4-Cl 2Ph CH 3 117～119
15-2 0.3 Q2 2，4-Cl 2Ph CH 3 Dope
16 Only contain the Ia configuration Q2 4-FPh CH 3 105～106
17 1.0 Q2 2，4-Cl 2Ph C 2H 5 88～92
18 1.0 Q2 2-thiophen C 2H 5 Dope
19 1.0 Q2 4-ClPh C 2H 5 Dope
20 1.0 Q2 2-furan CH 3 Dope
21 1.0 Q2 2-furan C 2H 5 Dope
22 1.0 Q2 2-thiophen CH 3 Dope
23 1.0 Q2 4-NO 2Ph CH 3 Dope
24 1.5 Q2 4-NO 2Ph C 2H 5 Dope
25 1.0 Q5 4-NO 2Ph CH 3 Dope
26 1.0 Q5 2，4-Cl 2Ph CH 3 Dope
27 1.0 Q5 4-FPh CH 3 Dope
28 1.0 Q5 2，4-Cl 2Ph C 2H 5 Dope
29 1.0 Q5 2-thiophen C 2H 5 Dope
30 1.0 Q5 4-ClPh C 2H 5 Dope
Annotate: Ia/Ib is the C shown in the general formula (I) *2 configurations (R/S or S/R) ratio, can by 1H NMR analyzes and obtains, but can not judge absolute configuration.
Part of compounds in the table 1 1H NMR (CDCl 3, 300MHz), the IR data are as follows:
Compound 1:(isomer 1a). 1H NMR (CDCl 3, 300MHz) 8.70 (s, 1H), 8.12 (d, J=8.7Hz, 2H), and 8.07-8.05 (m, 1H), 7.67-7.60 (m, 2H), 7.35 (d, J=8.7Hz, 2H), 7.17-7.12 (m, 2H), 6.93-6.87 (m, 2H), 6.76 (s, 1H), 6.49 (s, 1H), 5.90 (s, 1H), 4.91-4.83 (m, 1H), 3.69 (s, 3H), 1.68-1.64 (m, 3H).IRυmax(cm -1)3080，2950，1740，1500，1300，1210。
(isomer 1b). 1H NMR (CDCl 3, 300MHz) 8.68 (s, 1H), 8.22 (d, J=8.7Hz, 2H), and 8.07-8.05 (m, 1H), 7.67-7.60 (m, 2H), 7.57 (d, J=8.7Hz, 2H), 7.17-7.12 (m, 2H), 6.93-6.87 (m, 2H), 6.80 (s, 1H), 6.40 (s, 1H), 5.69 (s, 1H), 4.91-4.83 (m, 1H), 3.74 (s, 3H), 1.68-1.64 (m, 3H).
Compound 2:(isomer 2a). 1H NMR (CDCl 3, 300MHz) 8.70 (s, 1H), 8.11 (d, J=8.7Hz, 2H), 8.06 (m, 1H), 7.64-7.57 (m, 2H), 7.36 (d, J=8.7Hz, 2H), 7.17-7.12 (m, 2H), 6.93-6.87 (m, 2H), 6.76 (s, 1H), 6.49 (s, 1H), 5.90 (s, 1H), 4.91-4.83 (m, 1H), 4.21-4.15 (m, 2H), and 1.68-1.64 (m, 3H), 1.28-1.20 (m, 3H).IRυmax(cm -1)3070，2980，1720，1525，1350。
(isomer 2b). 1H NMR (CDCl 3, 300MHz) 8.68 (s, 1H), 8.21 (d, J=8.7Hz, 2H), 8.06 (m, 1H), 7.64-7.57 (m, 4H), 7.17-7.12 (m, 2H), 6.93-6.87 (m, 2H), 6.80 (s, 1H), 6.40 (s, 1H), 5.69 (s, 1H), 4.91-4.83 (m, 1H), 4.21-4.15 (m, 2H), 1.68-1.64 (m, 3H), 1.28-1.20 (m, 3H).
Compound 3:(isomer 3a). 1H NMR (CDCl 3, 300 MHz) 8.69 (s, 1H), 8.05 (s, 1H), 7.66 (d, J=8.7Hz, 1H), 7.59 (d, J=8.7Hz, 1H), 7.40-6.87 (m, 8H), 6.70 (s, 1H), 6.43 (s, 1H), 5.81 (s, 1H), 4.82 (q, J=6.6Hz, 1H), 3.73 (s, 3H), 1.63 (d, J=6.6Hz, 3H).IRυmax(cm -1)3060，2950，1740，1500，1300，1200。
(isomer 3b). 1H NMR (CDCl 3, 300MHz) 8.67 (s, 1H), 8.05 (s, 1H), 7.66 (d, J=8.7Hz, 1H), 7.59 (d, J=8.7Hz, 1H), 7.40-6.87 (m, 8H), 6.74 (s, 1H), 6.35 (s, 1H), 5.64 (s, 1H), 4.82 (q, J=6.6Hz, 1H), 3.68 (s, 3H), 1.63 (d, J=6.6Hz, 3H).
Compound 4:(isomer 4a). 1H NMR (CDCl 3, 300MHz) 8.70 (s, 1H), 8.06 (d, J=1.8Hz, 1H), 7.69 (d, J=8.7Hz, 1H), 7.61 (dd, J=1.8,8.7Hz, 1H), 7.44-7.25 (m, 3H), 7.16 (d, J=8.7Hz, 2H), 7.04 (s, 1H) .95-6.91 (m, 2H), 6.49 (s, 1H), 5.57 (s, 1H), 4.85 (q, J=6.6Hz, 1H), 3.77 (s, 3H), 1.67 (d, J=6.6Hz, 3H).IRυmax(cm -1)1750，1710，1500，1305，1140。
(isomer 4b). 1H NMR (CDCl 3, 300MHz) 8.69 (s, 1H), 8.06 (d, J=1.8Hz, 1H), 7.69 (d, J=8.7Hz, 1H), 7.61 (dd, J=1.8,8.7Hz, 1H), 7.44-7.25 (m, 3H), 7.16 (d, J=8.7Hz, 2H), 7.04 (s, 1H), 6.95-6.91 (m, 2H), 6.45 (s, 1H), 5.48 (s, 1H), 4.85 (q, J=6.6Hz, 1H), 3.69 (s, 3H), 1.67 (d, J=6.6Hz, 3H)
Compound 5:(isomer 5a). 1H NMR (CDCl 3, 300MHz) 8.67 (s, 1H), 8.05 (d, J=2.1Hz, 1H), 7.68 (d, J=9.0Hz, 1H), 7.60 (dd, J=2.1,9.0Hz, 1H), 7.3 1-7.23 (m, 1H), 7.14-6.87 (m, 7H), 6.46 (s, 1H), 5.96 (s, 1H), 4.82 (q, J=6.6Hz, 1H), 4.25-4.11 (m, 2H), and 1.67-1.63 (m, 3H), 1.27-1.20 (m, 3H).IRυmax(cm -1)3070，2980，1720，1500，1300，1210。
(isomer 5b). 1H NMR (CDCl 3, 300MHz) 8.67 (s, 1H), 8.05 (d, J=2.1Hz, 1H), 7.68 (d, J=9.0Hz, 1H), 7.60 (dd, J=2.1,9.0Hz, 1H), 7.3 1-7.23 (m, 1H), 7.14-6.87 (m, 7H), 6.39 (s, 1H), 5.76 (s, 1H), 4.82 (q, J=6.6Hz, 1H), 4.25-4.11 (m, 2H), and 1.67-1.63 (m, 3H), 1.27-1.20 (m, 3H).
Compound 6:(isomer 6a). 1H NMR (CDCl 3, 300MHz) 8.69 (s, 1H), 8.06-8.05 (m, 1H), 7.67 (d, J=8.7Hz, 1H), 7.60 (dd, J=2.1,8.7Hz, 1H), 7.32-7.12 (m, 6H), 6.88 (dd, J=1.5,9.0Hz, 2H), 6.68 (s, 1H), 6.43 (s, 1H), 5.81 (s, 1H), 4.82 (q, J=6.6Hz, 1H), 4.23-4.07 (m, 2H), 1.64 (d, J=6.6Hz, 3H), 1.27-1.19 (m, 3H).IRυmax(cm -1)3040，2980，1720，1500，1300。
(isomer 6b). 1H NMR (CDCl 3, 300MHz) 8.67 (s, 1H), 8.06-8.05 (m, 1H), 7.67 (d, J=8.7Hz, 1H), 7.60 (dd, J=2.1-8.7Hz, 1H), 7.32-7.12 (m, 6H), 6.88 (dd, J=1.5,9.0Hz, 2H), 6.72 (s, 1H), 6.35 (s, 1H), 5.64 (s, 1H), 4.82 (q, J=6.9Hz, 1H), 4.23-4.07 (m, 2H), 1.64 (d, J=6.6Hz, 3H), 1.27-1.19 (m, 3H).
Compound 7:(isomer 7a). 1H NMR (CDCl 3, 300MHz) 8.70 (s, 1H), 8.07 (d, J=2.1Hz, 1H), 7.68 (d, J=8.7Hz, 1H), 7.61 (dd, J=2.1,8.7Hz, 1H), 7.43-6.90 (m, 8H), 6.48 (s, 1H), 5.58 (s, 1H), 4.84 (q, J=6.9Hz, 1H), 4.27-4.13 (m, 2H), 1.67 (d, J=6.9Hz, 3H), 1.29-1.19 (m, 3H).
(isomer 7b). 1H NMR (CDCl 3, 300MHz) 8.68 (s, 1H), 8.07 (d, J=2.1Hz, 1H), 7.68 (d, J=8.7Hz, 1H), 7.61 (dd, J=2.1,8.7Hz, 1H), 7.43-6.90 (m, 8H), 6.45 (s, 1H), 5.49 (s, 1H), 4.84 (q, J=6.9Hz, 1H), 4.27-4.13 (m, 2H), 1.67 (d, J=6.9Hz, 3H), 1.29-1.19 (m, 3H).
Compound 8:(isomer 8a). 1H NMR (CDCl 3, 300MHz) 8.67 (s, 1H), 8.05 (d, J=2.1Hz, 1H), 7.69 (d, J=9.0Hz, 1H), 7.60 (dd, J=2.1,9.0Hz, 1H), 7.42-7.36 (m, 1H), 7.14 (d, J=9.0Hz,, 2H), 6.93-6.83 (m, 3H), 6.50 (s, 1H), 6.35 (s, 1H), 6.31-6.26 (m, 1H), 5.96 (s, 1H), 4.86-4.79 (m, 1H), 4.26-4.11 (m, 2H), 1.68-1.63 (m, 3H), 1.27-1.21 (m, 3H).
(isomer 8b). 1H NMR (CDCl 3, 300MHz) 8.67 (s, 1H), 8.05 (d, J=2.1Hz, 1H), 7.69 (d, J=9.0Hz, 1H), 7.60 (dd, J=2.1,9.0Hz, 1H), 7.42-7.36 (m, 1H), 7.14 (d J=9.0Hz,, 2H), 6.93-6.83 (m, 3H), 6.43 (s, 1H), 6.35 (s, 1H), 6.31-6.26 (m, 1H), 5.75 (s, 1H), 4.86-4.79 (m, 1H), 4.26-4.11 (m, 2H), 1.68-1.63 (m, 3H), 1.27-1.21 (m, 3H).
Compound 9: 1H NMR (CDCl 3, 300MHz) 8.69 (s, 1H), 8.06 (d, J=2.1Hz, 1H), 7.68 (d, J=9.0Hz, 1H), 7.60 (dd, J=2.1,9.0Hz, 1H), 7.38-7.01 (m, 7H), 6.93 (d, J=9.0Hz, 2H), 6.49 (s, 1H), 5.52 (s, 1H), 4.84 (q, J=6.6,1H), 3.78 (s, 3H), 1.68 (d, J=6.6,3H).
Compound 10: 1H NMR (CDCl 3, 300MHz) 8.68 (s, 1H), 8.06 (s, 1H), 7.67 (d, J=9.0Hz, 1H), 7.60 (d, J=9.0Hz, 1H), 7.37-7.21 (m, 4H), 7.13 (d, J=9.0Hz, 2H), 6.90 (d, J=9.0Hz, 2H), 6.73 (s, 1H), 6.43 (s, 1H), 5.78 (s, 1H), 4.82 (q, J=6.6,1H), 3.73 (s, 3H), 1.64 (d, J=6.6,3H).
Compound 11:(isomer 11a). 1H NMR (CDCl 3, 300MHz) 8.69 (s, 1H), 8.05 (d, J=2.1Hz, 1H), 7.69 (d, J=8.7Hz, 1H), 7.61 (dd, J=2.1,8.7Hz, 1H), 7.37-7.12 (m, 5H), 6.98-6.84 (m, 4H), 6.43 (s, 1H), 5.56 (s, 1H), 4.8 1 (q, J=6.6,1H), 3.83-3.68 (m, 6H), 1.66 (d, J=6.6,3H)
(isomer 11b). 1H NMR (CDCl 3, 300MHz) 8.68 (s, 1H), 8.05 (d, J=2.1Hz, 1H), 7.69 (d, J=8.7Hz, 1H), 7.61 (dd, J=2.1,8.7Hz, 1H), 7.37-7.12 (m, 5H), 6.98-6.84 (m, 4H), 6.40 (s, 1H), 5.47 (s, 1H), 4.81 (q, J=6.6,1H), 3.83-3.68 (m, 6H), 1.66 (d, J=6.6,3H)
Compound 12:(isomer 12a). 1H NMR (CDCl 3, 300MHz) 8.69 (s, 1H), 8.06-8.05 (m, 1H), 7.68 (d, J=8.7Hz, 1H), 7.60 (dd, J=2.1,8.7Hz, 1H), 7.35-6.84 (m, 9H), 6.43 (s, 1H), 5.55 (s, 1H), 4.81 (q, J=6.9,1H), 3.83-3.68 (m, 6H), 1.66 (d, J=6.9,3H)
(isomer 12b). 1H NMR (CDCl 3, 300MHz) 8.67 (s, 1H), 8.06-8.05 (m, 1H), 7.68 (d, J=8.7Hz, 1H), 7.60 (dd, J=2.1,8.7Hz, 1H), 7.35-6.84 (m, 9H), 6.40 (s, 1H), 5.48 (s, 1H), 4.81 (q, J=6.9,1H), 3.83-3.68 (m, 6H), 1.66 (d, J=6.9,3H)
Compound 13:(isomer 13a). 1H NMR (CDCl 3, 300MHz) 8.69 (s, 1H), 8.06 (s, 1H), 7.68 (d, J=8.7Hz, 1H), 7.60 (d, J=8.7Hz, 1H), and 7.29-7.10 (m, 6H), 6.92-6.86 (m, 2H), 6.70 (s, 1H), 6.41 (s, 1H), 5.78 (s, 1H), 4.80 (q, J=6.9,1H), 3.73 (s, 3H), 2.28 (s, 3H), 1.65-1.62 (m, 3H).
(isomer 13b). 1H NMR (CDCl 3, 300MHz) 8.68 (s, 1H), 8.06 (s, 1H), 7.68 (d, J=8.7Hz, 1H), 7.60 (d, J=8.7Hz, 1H), and 7.29-7.10 (m, 6H), 6.92-6.86 (m, 2H), 6.73 (s, 1H), 6.34 (s, 1H), 5.62 (s, 1H), 4.80 (q, J=6.9,1H), 3.67 (s, 3H), 2.32 (s, 3H), 1.65-1.62 (m, 3H).
Compound 14-2:(isomer 14a). 1H NMR (CDCl 3, 300MHz) 8.68 (s, 1 H), 8.06 (d, J=2.1Hz, 1H), 7.67 (d, J=8.7Hz, 1H), 7.60 (dd, J=2.1,8.7Hz, 1H), 7.38-7.20 (m, 5H), 7.13 (d, J=9.0Hz, 2H), 6.90 (d, J=9.0Hz, 2H), 6.73 (s, 1H), 6.43 (s, 1H), 5.78 (s, 1H), 4.82 (q, J=6.6Hz, 1H), 3.73 (s, 3H), 1.64 (d, J=6.6Hz, 3H).
Compound 14-1:(isomer 14b). 1H NMR (CDCl 3, 300MHz) 8.67 (s, 1H), 8.04 (d, J=2.1Hz, 1H), 7.67 (d, J=8.7Hz, 1H), 7.60 (dd, J=2.1,8.7Hz, 1H), 7.38-7.20 (m, 5H), 7.11 (d, J=9.0Hz, 2H), 6.88 (d, J=9.0Hz, 2H), 6.77 (s, 1H), 6.36 (s, 1H), 5.86 (s, 1H), 4.82 (q, J=6.6Hz, 1H), 3.68 (s, 3H), 1.65 (d, J=6.6Hz, 3H).
Compound 15-1:(isomer 15a). 1H NMR (CDCl 3, 300MHz) 7.45-7.42 (m, 2H), 7.38 (d, J=2.1Hz, 1H), and 7.31-7.24 (m, 3H), 7.21 (dd, J=2.1,8.7Hz 1H), 7.01 (s, 1H), 6.92-6.88 (m, 3H), 6.47 (s, 1H), 5.54 (s, 1H), 4.81 (q, J=6.6Hz, 1H), 3.77 (s, 3H), 1.66 (d, J=6.6Hz, 3H).
Compound 15-2:(isomer 15b). 1H NMR (CDCl 3, 300MHz) 7.43-7.38 (m, 3H), 7.31-7.22 (m, 4H), 7.03 (s, 1H), 6.94-6.88 (m, 3H), 6.44 (s, 1H), 5.50 (s, 1H), 4.82 (q, J=6.6Hz, 1H), 3.69 (s, 3H), 1.65 (d, J=6.6Hz, 3H).
Compound 16:(isomer 16a). 1H NMR (CDCl 3, 300MHz) 7.45 (d, 2.1Hz 1H), 7.42 (d, J=8.4Hz, 1H), and 7.28-7.24 (m, 3H), 7.17-7.13 (m, 2H), 7.01-6.95 (m, 2H), 6.87 (d, J=8.7Hz, 2H), 6.68 (s, 1H), 6.42 (s, 1H), 5.79 (s, 1H), 4.78 (q, J=6.6Hz, 1H), 3.73 (s, 3H), 1.61 (d, J=6.6Hz, 3H).
Compound 17:(isomer 17a). 1H NMR (CDCl 3, 300MHz) 7.46-7.37 (m, 3H), 7.31-7.10 (m, 4H), 7.02 (s, 1H), 6.93-6.89 (m, 3H), 6.47 (s, 1H), 5.56 (s, 1H), 4.84-4.77 (m, 1H), and 4.25-4.13 (m, 2H), 1.67-1.64 (m, 3H), 1.29-1.20 (m, 3H).
(isomer 17b). 1H NMR (CDCl 3, 300MHz) 7.46-7.37 (m, 3H), 7.31-7.10 (m, 4H), 7.04 (s, 1H), 6.93-6.89 (m, 3H), 6.43 (s, 1H), 5.50 (s, 1H), 4.84-4.77 (m, 1H), and 4.25-4.13 (m, 2H), 1.67-1.64 (m, 3H), 1.29-1.20 (m, 3H).
Compound 18:(isomer 18a). 1H NMR (CDCl 3, 300MHz) 7.43 (s, 1H), 7.40 (d, J=9.0Hz, 1H), 7.32-7.23 (m, 4H), 7.09-6.86 (m, 5H), 6.46 (s, 1H), 5.95 (s, 1H), 4.82-4.74 (m, 1H), and 4.22-4.15 (m, 2H), 1.65-1.61 (m, 3H), 1.27-1.20 (m, 3H).IRυmax(cm -1)3100，2980，1720，1630，1570，1500，1340。
(isomer 18b). 1H NMR (CDCl 3, 300MHz) 7.43 (s, 1H), 7.40 (d, J=9.0Hz, 1H), 7.32-7.23 (m, 4H), 7.09-6.86 (m, 5H), 6.38 (s, 1H), 5.78 (s, 1H), 4.82-4.74 (m, 1H), and 4.22-4.15 (m, 2H), 1.65-1.61 (m, 3H), 1.27-1.20 (m, 3H).
Compound 19:(isomer 19a). 1H NMR (CDCl 3, 300MHz) 7.45-7.44 (m, 1H), 7.42 (d, J=8.7Hz, 1H), and 7.32-7.09 (m, 7H), 6.87 (m, 2H), 6.67 (s, 1H), 6.42 (s, 1H), 5.79 (s, 1H), 4.82-4.75 (m, 1H), and 4.22-4.11 (m, 2H), 1.62 (d, J=6.6Hz, 3H), 1.28-1.18 (m, 3H).IRυmax(cm -1)3080，2990，1720，1630，1510，1200。
(isomer 19b). 1H NMR (CDCl 3, 300MHz) 7.45-7.44 (m, 1H), 7.42 (d, J=8.7Hz, 1H), and 7.32-7.09 (m, 7H), 6.87 (m, 2H), 6.71 (s, 1H), 6.34 (s, 1H), 5.65 (s, 1H), 4.82-4.75 (m, 1H), and 4.22-4.11 (m, 2H), 1.62 (d, J=6.6Hz, 3H), 1.28-1.18 (m, 3H).
Compound 20:(isomer 20a). 1H NMR (CDCl 3, 300MHz) 7.44-7.36 (m, 3H), 7.30-7.23 (m, 3H), 6.90 (dd, J=2.1,8.7Hz, 2H), 6.83-6.80 (m, 1H), 6.50 (s, 1H), 6.35 (s, 1H), and 6.32-6.25 (m, 1H), 5.96 (s, 1H), 4.79 (q, J=6.6Hz, 1H), 3.76 (s, 3H), 1.66-1.62 (m, 3H).
(isomer 20b). 1H NMR (CDCl 3, 300MHz) 7.44-7.36 (m, 3H), 7.30-7.23 (m, 3H), 6.90 (dd, J=2.1,8.7Hz, 2H), 6.83-6.80 (m, 1H), 6.43 (s, 1H), 6.35 (s, 1H), and 6.32-6.25 (m, 1H), 5.79 (s, 1H), 4.79 (q, J=6.6Hz, 1H), 3.73 (s, 3H), 1.66-1.62 (m, 3H).
Compound 21:(isomer 21a). 1H NMR (CDCl 3, 300MHz) 7.44 (d, J=2.1Hz, 1H), 7.40 (d, J=8.7Hz, 1H), and 7.36-7.23 (m, 4H), 6.90 (dd, J=1.8,8.7Hz, 2H), 6.82 (m, 1H), 6.42 (s, 1H), 6.35 (s, 1H), 6.31-6.25 (m, 1H), 5.95 (s, 1H), 4.79 (q, J=6.6Hz, 1H), 4.26-4.16 (m, 2H), 1.66-1.61 (m, 3H), 1.27-1.21 (3H).
(isomer 21b). 1H NMR (CDCl 3, 300MHz) 7.44 (d, J=2.1Hz, 1H), 7.40 (d, J=8.7Hz, 1H), and 7.36-7.23 (m, 4H), 6.90 (dd, J=1.8,8.7Hz, 2H), 6.82 (m, 1H), 6.49 (s, 1H), 6.35 (s, 1H), 6.31-6.25 (m, 1H), 5.77 (s, 1H), 4.79 (q, J=6.6Hz, 1H), 4.26-4.16 (m, 2H), 1.66-1.61 (m, 3H), 1.27-1.21 (3H).
Compound 22:(isomer 22a). 1H NMR (CDCl 3, 300MHz) 7.44 (d, J=1.8Hz, 1H), 7.41 (d, J=8.4Hz, 1H), 7.32-7.31 (m, 1H), 7.28-7.23 (m, 3H), 7.09-6.93 (m, 3H), 6.91-6.86 (m, 2H), 6.47 (s, 1H), 5.96 (s, 1H), 4.82-4.74 (m, 1H), 3.75 (s, 3H), 1.65-1.61 (m, 3H).
(isomer 22b). 1H NMR (CDCl 3, 300MHz) 7.44 (d, J=1.8Hz, 1H), 7.41 (d, J=8.4Hz, 1H), 7.32-7.31 (m, 1H), 7.28-7.23 (m, 3H), 7.09-6.93 (m, 3H), 6.91-6.86 (m, 2H), 6.39 (s, 1H), 5.79 (s, 1H), 4.82-4.74 (m, 1H), 3.72 (s, 3H), 1.65-1.61 (m, 3H).
Compound 23:(isomer 23a). 1H NMR (CDCl 3, 300MHz) 8.16 (d, J=8.7Hz, 2H), 7.58-7.24 (m, 7H), 6.89 (d, J=8.7Hz, 2H), 6.74 (s, 1H), 6.487 (s, 1H), 5.87 (s, 1H), 4.83 (q, J=6.6Hz, 1H), 3.74 (s, 3H), 1.65 (d, J=6.6Hz, 3H).IRυmax(cm -1)3080，2950，1730，1570，1500，1350，1190。
(isomer 23b). 1H NMR (CDCl 3, 300MHz) 8.22 (d, J=8.7Hz, 2H), 7.58-7.24 (m, 7H), 6.90 (d, J=8.7Hz, 2H), 6.79 (s, 1H), 6.400 (s, 1H), 5.72 (s, 1H), 4.83 (q, J=6.6Hz, 1H), 3.70 (s, 3H), 1.64 (d, J=6.6Hz, 3H).
Compound 24:(isomer 24a). 1H NMR (CDCl 3, 300MHz) 8.16 (d, J=8.4Hz, 2H), 7.52-7.06 (m, 7H), 6.89-6.70 (m, 3H), 6.48 (s, 1H), 5.87 (s, 1H), 4.83 (q, J=6.6Hz, 1H), 4.24-4.14 (m, 2H), 1.65 (d, J=6.6Hz, 3H), 1.28-1.19 (m, 3H).
(isomer 24b). 1H NMR (CDCl 3, 300MHz) 8.26 (d, J=8.4Hz, 2H), 7.52-7.06 (m, 7H), 6.89-6.70 (m, 3H), 6.56 (s, 1H), 5.65 (s, 1H), 4.83 (q, J=6.6Hz, 1H), 4.24-4.14 (m, 2H), 1.65 (d, J=6.6Hz, 3H), 1.28-1.19 (m, 3H).
Compound 25:(isomer 25a). 1H NMR (CDCl 3, 300MHz) 8.30-8.29 (m, 1H), 8.13 (d, J=8.7Hz, 2H), and 7.99-7.97 (m, 1H), 7.31 (d, J=8.7Hz, 2H), 7.05 (d, J=9.0Hz, 2H), 6.87 (d, J=9.0Hz, 2H), 6.74 (s, 1H), 6.47 (s, 1H), 5.86 (s, 1H), 4.84 (q, J=6.6Hz, 1H), 3.74 (s, 3H), 1.64 (m, 3H).IRυmax(cm -1)3070，2950，1750，1610，1500，1325。
(isomer 25b). 1H NMR (CDCl 3, 300MHz) 8.25-8.24 (m, 1H), 8.22 (d, J=8.7Hz, 2H), and 7.99-7.97 (m, 1H), 7.56 (d, J=8.7Hz, 2H), 7.05 (d, J=9.0Hz, 2H), 6.89 (d, J=9.0Hz, 2H), 6.77 (s, 1H), 6.37 (s, 1H), 5.69 (s, H), 4.84 (q, J=6.6Hz, 1H), 3.69 (s, 3H), 1.64 (m, 3H).
Compound 26:(isomer 26a). 1H NMR (CDCl 3, 300MHz) 8.30 (s, 1H), 7.99-7.97 (m, 1H), 7.44-7.37 (m, 1H), 7.17 (dd, J=2.1,8.7Hz, 1H), and 7.07-7.01 (m, 3H), 6.92-6.85 (m, 3H), 6.48 (s, 1H), 5.52 (s, 1H), 4.82 (q, J=6.6Hz, 1H), 3.78 (s, 3H), 1.67-1.63 (m, 3H).IRυmax(cm -1)3050，2950，1730，1500，1320。
(isomer 26b). 1H NMR (CDCl 3, 300MHz) 8.25 (s, 1H), 7.99-7.97 (m, 1H), 7.44-7.37 (m, 1H), 7.17 (dd, J=2.1,8.7Hz, 1H), and 7.07-7.01 (m, 3H), 6.92-6.85 (m, 3H), 6.43 (s, 1H), 5.48 (s, 1H), 4.82 (q, J=6.6Hz, 1H), 3.69 (s, 3H), 1.67-1.63 (m, 3H).
Compound 27:(isomer 27a). 1H NMR (CDCl 3, 300MHz) 8.27-8.26 (m, 1H), 7.98-7.96 (m, 1H), 7.18-7.14 (m, 2H), 7.06-6.93 (m, 4H), 6.86 (dd, J=1.8,9.0Hz, 2H), 6.69 (s, 1H), 6.41 (s, 1H), 5.79 (s, 1H), and 4.82-4.75 (m, 1H), 3.72 (s, 3H), 1.61 (d, J=6.6Hz, 3H).IRυmax(cm -1)3060，2950，1730，1605，1505，1310。
(isomer 27b). 1H NMR (CDCl 3, 300MHz) 8.25-8.24 (m, 1H), 7.98-7.96 (m, 1H), 7.38-7.33 (m, 2H), 7.06-6.93 (m, 4H), 6.86 (dd, J=1.8,9.0Hz, 2H), 6.72 (s, 1H), 6.33 (s, 1H), 5.64 (s, 1H), and 4.82-4.75 (m, 1H), 3.68 (s, 3H), 1.61 (d, J=6.6Hz, 3H).
Compound 28:(isomer 28a). 1H NMR (CDCl 3, 300MHz) 8.31-8.30 (m, 1H), 7.99-7.96 (m, 1H), 7.43-7.37 (m, 1H), 7.27 (s, 1H), 7.18-7.12 (m, 1H), and 7.09-7.03 (m, 3H), 6.89 (d, J=8.7Hz, 2H), 6.47 (s, 1H), 5.54 (s, 1H), 4.85-4.74 (m, 1H), 4.24-4.12 (m, 2H), 1.67-1.63 (m, 3H), 1.29-1.19 (m, 3H).IRυmax(cm -1)3060，2980，1730，1505，1325。
(isomer 28b). 1H NMR (CDCl 3, 300MHz) 8.26-8.25 (m, 1H), 7.99-7.96 (m, 1H), 7.43-7.37 (m, 1H), 7.26 (s, 1H), 7.18-7.12 (m, 1H), and 7.09-7.03 (m, 3H), 6.91 (d, J=8.7Hz, 2H), 6.42 (s, 1H), 5.49 (s, 1H), 4.85-4.74 (m, 1H), 4.24-4.12 (m, 2H), 1.67-1.63 (m, 3H), 1.29-1.19 (m, 3H).
Compound 29:(isomer 29a). 1H NMR (CDCl 3, 300MHz) 8.31-8.30 (m, 1H), 8.25 (s, 1H), 7.96 (s, 1H), 7.70-7.64 (m, 1H), 7.56-7.463 (m, 1H), and 7.32-7.25 (m, 1H), 7.09-6.85 (m, 5H), 6.46 (s, 1H), 5.95 (s, 1H), 4.79 (q, J=6.6Hz, 1H), n4.18 (q, J=6.6Hz, 2H), 1.65-1.61 (m, 3H), 1.27-1.21 (m, 3H).
(isomer 29b). 1H NMR (CDCl 3, 300MHz) 8.31-8.30 (m, 1H), 8.25 (s, 1H), 7.96 (s, 1H), 7.70-7.64 (m, 1H), 7.56-7.463 (m, 1H), and 7.32-7.25 (m, 1H), 7.09-6.85 (m, 5H), 6.37 (s, 1H), 5.76 (s, 1H), 4.79 (q, J=6.6Hz, 1H), 4.18 (q, J=6.6Hz, 2H), 1.65-1.61 (m, 3H), 1.27-1.21 (m, 3H).
Compound 30:(isomer 30a). 1H NMR (CDCl 3, 300MHz) 8.29-8.28 (m, 1H), 7.98-7.96 (m, 1H), 7.32-7.10 (m, 4H), 7.03 (dd, J=1.8,9.0Hz, 2H), 6.86 (dd, J=1.8,9.0Hz, 2H), 6.70 (s, 1H), 6.41 (s, 1H), 5.78 (s, 1H), and 4.83-4.75 (m, 1H), 4.19-4.10 (m, 2H), 1.63 (s, 3H), 1.26-1.19 (m, 3H).
(isomer 30b). 1H NMR (CDCl 3, 300MHz) 8.26-8.25 (m, 1H), 7.98-7.96 (m, 1H), 7.32-7.10 (m, 4H), 7.03 (dd, J=1.8,9.0Hz, 2H), 6.86 (dd, J=1.8,9.0Hz, 2H), 6.69 (s, 1H), 6.33 (s, 1H), 5.64 (s, 1H), and 4.83-4.75 (m, 1H), 4.19-4.10 (m, 2H), 1.60 (s, 3H), 1.26-1.19 (m, 3H).
Effect of the present invention and benefit, general formula of the present invention (I) compound has weeding activity, uses behind seedling and can effectively control monocotyledon weed.To soybean, paddy rice, wheat safety.
The present invention comprises that also with general formula (I) compound be the herbicidal composition of active ingredient.The weight percentage of active ingredient is 1-99% in this herbicidal composition.Comprise also in this herbicidal composition that agricultural goes up acceptable carrier.
Herbicidal composition of the present invention can several formulations form use.Usually with compound dissolution of the present invention or be scattered in and be mixed with preparation in the carrier so that be easier to disperse when using as weedicide.For example: these chemicals can be made into wettable powder or missible oil etc.Therefore, in these compositions, add a kind of liquid or solid carrier at least, and need to add suitable tensio-active agent usually.
Other embodiments of the present invention are method of controlling weeds, and this method comprises herbicidal composition of the present invention is imposed on the surface of the place of described weeds or described weed growth or its growth medium.Usually the comparatively suitable effective dose of selecting is that per hectare 1 restrains 1000 grams, and preferred effective dose is that per hectare 5 restrains 500 grams.Use for some, can in herbicidal composition of the present invention, add one or more other weedicide, can produce additional advantage and effect thus.
Compound of the present invention both can use separately also can be mixed together use with other known sterilant, sterilant, plant-growth regulator or fertilizer etc.
Should be clear and definite be in claim of the present invention institute restricted portion, can carry out various conversion and change.
Embodiment
Following in conjunction with the embodiments with give birth to test and test the result and be described in detail embodiments of the present invention, but do not mean that restriction the present invention.
Synthetic example: compound 1 synthetic:
Figure C20051009896000201
(30.00 grams, 80.40 mmoles are purchased in Jiangsu Fengshan Group Co, mark to add quizalofopPethyl in 500 milliliters reaction flask *Chiral carbon atom be the R configuration, down with) and 80 milliliters of tetrahydrofuran (THF)s, be stirred to moltenly entirely, (3.26 restrain to add sodium hydroxide, 80.68 mmole) and the solution that forms of water (80 milliliters), stirring at room reaction 5 hours, stopped reaction adds 100 milliliters of ethyl acetate extractions, water concentrated hydrochloric acid acidifying, filter, consider the dry white solid that gets of biscuit, i.e. intermediate acid 25.00 grams.
Figure C20051009896000211
In 250 milliliters reaction flask, add above-mentioned intermediate acid (20.00 grams, 58.00 mmole) and 150 milliliters of methylene dichloride, stir and slowly add oxalyl chloride (11.00 grams down, 85.74 mmole), add 3 DMF again, stirring at room reaction 4 hours, afterwards, methylene dichloride is deviate from decompression and excessive oxalyl chloride gets 23.00 gram yellow liquid, i.e. intermediate acyl chlorides.
Figure C20051009896000212
In 50 milliliters reaction flask, add 2-(hydroxyl (4-nitrophenyl) methyl) methyl acrylate (0.71 gram, 3.0 mmole), triethylamine (0.35 gram, 3.43 mmole) and 5 milliliters of methylene dichloride, be added dropwise to above-mentioned intermediate acyl chlorides (1.25 grams under the ice-water bath, 3.40 mmole) and the solution that form of 10 milliliters of methylene dichloride, drip half an hour approximately, reaction is 5 hours under the room temperature, afterwards, in reaction solution, add 100 milliliters of ethyl acetate and 20 ml waters, separatory, ethyl acetate layer is used saturated sodium bicarbonate aqueous solution successively, each 20 milliliters of washing of saturated sodium-chloride water solution, anhydrous magnesium sulfate drying, the decompression precipitation separates (ethyl acetate/petroleum ether=1/10) through silica gel column chromatography, get the brown dope of 1.06 grams, be compound 1.By 1H NMR analyzes its C *2 are configured as the mixture (R/S or S/R=1) of R type and S type, are a pair of diastereomer.
Compound 14-1,14-2's is synthetic:
Figure C20051009896000213
In 50 milliliters reaction flask, add 2-(hydroxyl (phenyl) methyl) methyl acrylate (0.58 gram, 3.00 mmole), triethylamine (0.35 gram, 3.43 mmole) and in 5 milliliters of dichloromethane solutions, be added dropwise to above-mentioned intermediate acyl chlorides (1.25 grams under the ice-water bath, 3.40 mmole) and the solution that form of 10 milliliters of methylene dichloride, drip half an hour approximately, reaction is 8 hours under the room temperature, afterwards, add 100 milliliters of ethyl acetate and 20 ml waters in reaction solution, ethyl acetate layer is used saturated sodium bicarbonate aqueous solution successively, each 20 milliliters of washing of saturated sodium-chloride water solution, anhydrous magnesium sulfate drying, the decompression precipitation, separate (ethyl acetate/petroleum ether=1/5) through silica gel column chromatography, get the light yellow dope of 0.91 gram, be compound 14-1.By 1H NMR analyzes its C *2 are configured as the mixture (R/S or S/R=1) of R type and S type, are a pair of diastereomer.
With top resulting equal proportion diastereomer compound 14-1 benzene recrystallization, separate out white solid earlier, be compound 14-2 (C *2 are configured as R type or S type), m.p.124～126 ℃.
Compound 15-1,15-2's is synthetic:
Figure C20051009896000221
(19.04 grams, 50.0 mmoles are purchased in Shenyang Chemical Engineering Inst, mark to add fenoxaprop in 500 milliliters reaction flask *Chiral carbon atom be the R configuration, down with) and 100 milliliters of tetrahydrofuran (THF)s.Under the room temperature, be added dropwise to the solution that sodium hydroxide (2.30 grams, 55.0 mmoles) and water (100 milliliters) form with 30 fens kinds, stirring at room was reacted 6 hours, stopped reaction.Use hcl acidifying, add ethyl acetate extraction, anhydrous magnesium sulfate drying, precipitation get the light brown solid, i.e. intermediate acid 17.00 grams.
Figure C20051009896000222
In 250 milliliters reaction flask, add above-mentioned intermediate acid (2.67 grams, 8.00 mmole) and 40 milliliters of methylene dichloride, stir and slowly add oxalyl chloride (1.54 grams down, 12.00 mmole), add 2 DMF again, stirring at room reaction 4 hours, afterwards, methylene dichloride is deviate from decompression and excessive oxalyl chloride gets 2.79 gram yellow liquid, i.e. intermediate acyl chlorides.
Figure C20051009896000231
In 50 milliliters reaction flask, add 2-(hydroxyl (2, the 4-dichlorophenyl) methyl acrylate (0.78 gram methyl), 3.00 mmole), triethylamine (0.35 gram, 3.43 mmole) and 5 milliliters of methylene dichloride, be added dropwise to above-mentioned intermediate acyl chlorides (1.19 grams under the ice-water bath, 3.40 mmole) and the solution that form of 10 milliliters of methylene dichloride, drip half an hour approximately, reaction is 5 hours under the room temperature, afterwards, adds 100 milliliters of ethyl acetate and 20 ml waters in reaction solution, separatory, ethyl acetate layer is used saturated sodium bicarbonate aqueous solution successively, each 20 milliliters of washing of saturated sodium-chloride water solution, anhydrous magnesium sulfate drying, decompression precipitation, separate (ethyl acetate/petroleum ether=1/20) through silica gel column chromatography, obtain two compounds respectively.Compound 15-1 and 15-2.Compound 15-1 (C wherein *2 are configured as R type or S type) be white solid (0.32 gram), m.p.117～119 ℃.Compound 15-2 is white dope (0.61 gram), by 1H NMR analyzes its C *2 are configured as the mixture (R/S or S/R=0.3) of R type and S type.
Synthesizing of compound 30:
Figure C20051009896000232
(15.00 grams, 40.0 mmoles are purchased in Shenyang Chemical Engineering Inst, mark to add haloxyfop-r-methyl in 250 milliliters reaction flask *Chiral carbon atom be the R configuration, down with) and 60 milliliters of 2N aqueous sodium hydroxide solutions, be warming up to 70 ℃, stirring reaction 2 hours, stopped reaction.Reduce to room temperature, use the concentrated hydrochloric acid acidifying, add dichloromethane extraction, precipitation gets brown solid, i.e. intermediate acid 13.04 grams.
Figure C20051009896000241
In 250 milliliters reaction flask, add above-mentioned intermediate acid (2.89 grams, 8.00 mmole) and 40 milliliters of methylene dichloride, stir and slowly add oxalyl chloride (1.54 grams down, 12.00 mmole), add 2 DMF again, stirring at room reaction 4 hours, afterwards, methylene dichloride is deviate from decompression and excessive oxalyl chloride gets 2.84 gram yellow liquid, i.e. intermediate acyl chlorides.
Figure C20051009896000242
In 50 milliliters reaction flask, add 2-(hydroxyl (4-chloro-phenyl-) methyl) ethyl propenoate (0.72 gram, 3.00 mmole), triethylamine (0.35 gram, 3.43 mmole) and 5 milliliters of methylene dichloride, be added dropwise to above-mentioned intermediate acyl chlorides (1.29 grams under the ice-water bath, 3.40 mmole) and the solution that form of 10 milliliters of methylene dichloride, drip half an hour approximately, reaction is 5 hours under the room temperature, afterwards, in reaction solution, add 100 milliliters of ethyl acetate and 20 ml waters, separatory, ethyl acetate layer is used saturated sodium bicarbonate aqueous solution successively, each 20 milliliters of washing of saturated sodium-chloride water solution, anhydrous magnesium sulfate drying, the decompression precipitation separates (ethyl acetate/petroleum ether=1/10) through silica gel column chromatography, get 0.92 gram water white transparency dope, be compound 30.By 1H NMR analyzes its C *2 are configured as the mixture (R/S or S/R=1) of R type and S type, are a pair of diastereomer.
Other compounds in the table 1 can make by above similar method.
Give birth to and survey example
With the former medicine of acetone solution, by design dosage, join in the certain water gaging that contains tensio-active agent, make certain density preparation.Spray with mobile belt atomizer.The examination material is put in spraying rolling in the cupboard and is with, and mobile shower nozzle is sprayed onto medicament on the examination material with the covering of the fan Sprayable through examination material top, identical on nozzle and the common field spray device.Roll band and will try material and shift out outside the cupboard, place loft drier dry.
Test behind the seedling, seed germination also grew 10～21 days, made the examination material that has a series of growing stages before the processing, selected size, the consistent examination material of growing stage then, handled, and handled to be placed on the greenhouse and to water.The examination material with compound treatment does not compare.The examination material is monocotyledon weed barnyard grass grass and lady's-grass.
Examination material after the spraying drying places the greenhouse.Test is poured water from the bottom and was kept 48 hours so that water does not touch the blade face behind the seedling.
Handling the back investigated in 4 weeks.Inhibiting rate is total effect of various infringements such as chlorosis, withered spot, retarded growth or the calcination of leaf angle, obtains the result with blank after relatively.Partial test the results are shown in Table 2.
Table 2: the weeding activity (behind the seedling, inhibiting rate %) of compound in the general formula (I)
Compound Dosage ga.i./ha The barnyard grass grass Lady's-grass
1 200 100 100
40 100 98
5 100 *
2 200 100 98
40 100 98
5 100
3 200 100 100
40 100 98
5 40
5 1000 100 100
200 98 90
40 95 80
8 200 100 98
40 100 98
10 100
9 1000 100 98
200 100 95
40 100 90
10 1000 100 100
200 100 100
40 100 98
14-2 1000 100 100
200 100 100
40 100 95
18 200 100 100
40 100 98
5 80
19 1000 100 100
200 95 95
40 90 45
20 1000 100 100
200 100 98
40 100 85
25 200 100 100
40 100 98
5 50
27 200 100 100
40 100 100
20 98 100
30 1000 100 100
200 98 85
40 25 50
*: the space is represented not survey
The present invention has carried out the crop safety test, and partial results sees Table 3.
The security measurement result (behind the seedling) of compound in the table 3 part general formula (I)
Compound Dosage g a.i./ha Suppress or kill %
Wheat Corn Paddy rice Soybean
2 40 0 10 0 0
200 0 30 5 0
1000 15 80 40 0
18 40 0 0 0 0
200 2 20 0 0
1000 4 95 0 0
19 40 0 15 0 0
200 0 55 0 0
1000 5 95 0 0

Claims (6)

1. the 2-of a general formula I (two replace) methyl acrylic ester compound or this compound are marked *With *2 chiral carbon atom is the different ratios mixture of R, S configuration;
Figure C2005100989600002C1
Wherein:
Q is selected from one of group as follows:
Figure C2005100989600002C2
R 1Be selected from phenyl, substituted-phenyl, C 4-C 6Heterocycle; Heterocycle is for containing N, S or O;
R 2Be selected from H, C 1-C 6Alkyl;
R 3Be selected from C 1-C 4Alkyl.
2. compound according to claim 1 or mixture is characterized in that, in the general formula (I):
R 1Be selected from phenyl, substituted-phenyl, C 4-C 6Heterocycle; Heterocycle is for containing N, S or O;
R 2Be selected from H, C 1-C 6Alkyl;
R 3Be selected from C 1-C 4Alkyl;
Q is selected from Q1, Q2, Q3, Q4 or Q5;
Mark *Chiral carbon atom be the R configuration;
Mark *2 chiral carbon atom is R, S configuration, or the mixture of its different ratios.
3. compound according to claim 1 or mixture is characterized in that, in the general formula (I):
R 1Be selected from phenyl, substituted-phenyl, C 4-C 6Heterocycle; Heterocycle is for containing N, S or O;
R 2Be selected from H, C 1-C 6Alkyl;
R 3Be selected from methyl;
Q is selected from Q1, Q2, Q5;
Mark *With *2 chiral carbon atom is R, S configuration, or the mixture of its different ratios.
4. compound according to claim 1 or mixture is characterized in that, in the general formula (I):
R 1Be selected from phenyl, substituted-phenyl, C 4-C 6Heterocycle; Heterocycle is for containing N, S or O;
R 2Be selected from H, C 1-C 6Alkyl;
R 3Be selected from methyl;
Q is selected from Q1, Q2, Q5;
Mark *Chiral carbon atom be the R configuration;
Mark *2 chiral carbon atom is R, S configuration, or the mixture of its different ratios.
5. the described compound of claim 1 is used to control the purposes of weeds, and when it is characterized in that compound and agricultural go up the acceptable carrier mixing, wherein the weight percentage of compound is 1-99%.
6. purposes according to claim 5 is characterized in that imposing on growth medium of weeds, weeds or the growth place of weeds.
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CN1325624A (en) * 2000-05-30 2001-12-12 沈阳化工研究院 Herbicides of benzoyloxy unsaturated carboxylate type
CN1603299A (en) * 2003-09-29 2005-04-06 沈阳化工研究院 Novel carboxylate herbicides
CN1626526A (en) * 2003-12-12 2005-06-15 沈阳化工研究院 Compound of alpha, beta and beta, gamma unsaturation carboxylate class of possessing weeding activity

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6251829B1 (en) * 2000-04-18 2001-06-26 Rohm And Haas Company Herbicidal benzoyloxy carboxylates and carboxamides
CN1325624A (en) * 2000-05-30 2001-12-12 沈阳化工研究院 Herbicides of benzoyloxy unsaturated carboxylate type
CN1603299A (en) * 2003-09-29 2005-04-06 沈阳化工研究院 Novel carboxylate herbicides
CN1626526A (en) * 2003-12-12 2005-06-15 沈阳化工研究院 Compound of alpha, beta and beta, gamma unsaturation carboxylate class of possessing weeding activity

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