CN101362753A - Sulfonyl isoxazole derivates with obvious herbicidal activity - Google Patents
Sulfonyl isoxazole derivates with obvious herbicidal activity Download PDFInfo
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- CN101362753A CN101362753A CNA2008100842201A CN200810084220A CN101362753A CN 101362753 A CN101362753 A CN 101362753A CN A2008100842201 A CNA2008100842201 A CN A2008100842201A CN 200810084220 A CN200810084220 A CN 200810084220A CN 101362753 A CN101362753 A CN 101362753A
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- isoxazole
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- herbicidal activity
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Abstract
The invention relates to a novel sulfonyl isoxazole derivative with obvious herbicidal activity and a preparation method thereof, as well as a composite containing the derivative and a method for weed control by making use of the derivative.
Description
Technical field
The present invention relates to novel sulfonyl isoxazole derivates that has weeding activity and preparation method thereof, contain the composition of this derivative, kill or control method for weed with this derivative.
Background technology
Patent USP6841519, USP7238689, USP7256298 disclose and have contained Isoxazole derivative, and these derivatives have weeding activity.Yet, do not see the report of sulphonyl Isoxazole derivative of the present invention.
Summary of the invention
In order to satisfy the requirement on the agricultural, the invention provides new sulphonyl Isoxazole derivative and the application aspect the controlling weeds and contain the using method of these compound compositions on agricultural.Sulfonyl isoxazole derivates provided by the invention can effectively be controlled the weeds of multiple damage to crops, and good selectivity is arranged between crop and weeds.
Five sulphonyl Isoxazole derivative structural formulas of the present invention are as follows:
Compound among the present invention can be synthetic by several different methods, and for example figure below is depicted as wherein feasible synthetic route.
In the above-mentioned synthetic method, used intermediate is can be by known method synthetic or bought from market, for example:
1) with known method (Liebigs Annalen der Chemie, 1989,10,985-990) synthetic 5,5-dimethyl-3-chlorine dihydro-isoxazole,
2) can be with reference to Tetrahedron Lett.2005,46 (40), the method for 6833-6837 is synthesized following intermediate,
3) can be with reference to European J.Org.Chem.2005, the method for 3680-3676 is synthesized following intermediate,
4) intermediate 3, and 5-dimethyl-4-fluoro-1-trifluoroethyl pyrazoles can synthesize by the following method,
5) (3-methyl-4-X-1-trifluoroethyl pyrazoles-5-yl) methyl thioacetate synthetic method is as follows, and X is identical with definition above,
Weeding active compound of the present invention also comprises their formed salt except that comprising above-mentioned five compounds.
In order to use above-mentioned target compound controlling weeds, need be made into corresponding compositions, contain the described compound of claim 1 of 0.1-99% weight in the said composition.Compound can be applied to soil, plant or seed by making composition such as pulvis, wettable powder, granula (slowly-releasing or quick-release), missible oil, suspension agent, aqua, emulsifiable concentrate, microemulsion, coating agent for seed, smoke substance, may command release dosage form such as the microcapsule granula or the suspension agent etc. of various ways with carrier, emulsifying agent, dispersion agent, auxiliary agent etc.When in soil that is applied to plant or plantation or the water, be scattered in the water during use or in other liquid medium, effectively working concentration is usually at 0.1ppm to 50000ppm, preferred 10ppm to 10000ppm.Concrete consumption will use according to different compounds, target weeds, weed growth situation, envrionment conditions.
These compounds can the single-component pattern use, and also can use with as sterilant, synergistic agent, weedicide, sterilant, plant-growth regulator or fertilizer with suitable one or more biological activities.Other effective ingredient that is suitable for comprises the compound that can enlarge activity profile or prolong the lasting period, can strengthen the compound of the active of target compound or enhancing quick-acting.Other effective ingredient in the mixture, especially wanting can increase the result of use of target compound and will have the different mechanism of action.Target compound can with use with.
Embodiment
Following specific embodiment is used for further specifying the present invention.
Synthetic embodiment
Example 1 compound 1[3-((3-methyl-4-chloro-1-(2,2, the 2-trifluoroethyl)-1H-pyrazoles-5-yl) methyl sulphonyl)-5,5-dimethyl-4,5-dihydro-isoxazole] synthetic
In the 100mL there-necked flask, add 6g (0.06mol) diacetylmethane and 10mL37% concentrated hydrochloric acid, slowly drip 70% hydration trifluoroethyl hydrazine 19.5g (0.12mol) when being cooled to 0-5 ℃ in the ice bath.After dripping off, rise to room temperature reaction 0.5h, the TLC detection reaction is complete.In the aqueous sodium hydroxide solution and hydrochloric acid, separate out white crystal, use CHCl
3Dissolving and extraction, CHCl
3Layer use anhydrous sodium sulfate drying, revolve boil off desolventize after, residuum sherwood oil recrystallization must yellow solid 8.4g, yield 78%.
1H?NMR(CDCl
3)d：2.26(3H，s)，2.42(3H，s)，4.19(2H，m)，6.24(1H，s)ppm。
Get above-mentioned product 1.8g (0.01mol) and 2g (0.015mol) NCS, be dissolved in the 20ml ethyl acetate, stir 20min in the Ultrasonic Cleaners of 25-30 ℃ of water-bath.Organic phase is with 10% hypo solution give a baby a bath on the third day after its birth time (3*20ml).The organic phase anhydrous sodium sulfate drying, decompression steams organic solvent, obtains white solid, and 3,4-dimethyl-4-chloro-1-(2,2, the 2-trifluoroethyl) pyrazoles 1.8g, yield 85%.
1H?NMR(CDCl
3)d：2.05(3H，s)，2.72(3H，s)，4.22(2H，m)ppm。
1.1g3,4-dimethyl-4-chloro-1-(2,2, the 2-trifluoroethyl) pyrazoles (0.005mol), 1gNBS (0.055mol), the benzoyl peroxide of catalytic amount joins in the 50ml flask that contains the 25ml tetracol phenixin backflow 8h, filter, remove most of solvent under reduced pressure, (ethyl acetate: sherwood oil=3:1) purifying obtains faint yellow solid 1g, productive rate 70% with silica gel column chromatography.
1H?NMR(CDCl
3)d：2.04(3H，s)，4.21(2H，m)，4.52(2H，s)ppm。
Get previous step product 1g (0.0035mol), 0.58g thioacetic acid potassium (0.005mol) is dissolved in the 20ml ethanol, stir 3h under the room temperature, filter, steam and remove most of solvent, (ethyl acetate: the purifying of sherwood oil=1:1) obtains colourless liquid 0.6g, productive rate 60% with silica gel column chromatography.
1H?NMR(CDCl
3)d：2.07(3H，s)，2.38(3H，s)，4.23(2H，m)，4.88(2H，s)ppm。
Colourless liquid 0.6g (0.002mol), 0.4g5 that previous step is obtained, 5-dimethyl-3-chlorine isoxzzole (0.003mol) is molten in 10ml ethanol, add 0.42g salt of wormwood (0.003mol), backflow 6h, filter, steam and remove most solutions, silica gel column chromatography (ethyl acetate: the purifying of sherwood oil=1:2), obtain colourless liquid 0.52g, productive rate 76%.
1H?NMR(CDCl
3)d：1.32(6H，s)，1.52(2H，s)，2.05(3H，s)，4.24(2H，m)，4.88(2H，s)ppm。
The product 0.52g (0.0014mol) in last step is dissolved in the 10ml methylene dichloride, and adding 0.6g metachloroperbenzoic acid (0.0035mol), stir under the room temperature and spend the night, steam and remove most of solvent, silica gel column chromatography (ethyl acetate: the purifying of sherwood oil=1:1), obtain weak yellow liquid 0.26g, productive rate 49%.
1H?NMR(CDCl
3)d：1.27(6H，s)，1.51(2H，s)，2.21(3H，s)，4.18(2H，m)，4.69(2H，s)ppm。
Synthesizing of example 2 compounds (2) [3-((3-methyl-4-bromo-1-(2,2, the 2-trifluoroethyl)-1H-pyrazoles-5-yl) methyl sulphonyl)-5,5-dimethyl-4,5-dihydro-isoxazole]
Reaction method is the same, and NCS is changed into NBS.
The compound that obtains at last (2) is a weak yellow liquid,
1H NMR (CDCl
3) d:1.26 (6H, s), 1.51 (2H, s), 2.79 (3H, s), 4.16 (2H, m), 4.69 (2H, s) ppm.
Example of formulations (add-on of active ingredient is metered into after rolling over hundred in the prescription, and all percentage compositions are weight percentage)
Example 3 10% compound (1) missible oil
Compound (1) 10%, farming breast No. 500 2%, farming breast No. 0,201 5%, methyl alcohol 5%, dimethylbenzene complements to 100%.Above-mentioned material mixes, and promptly obtains transparence missible oil.
Example 410% compound (1) wettable powder
Compound (1) 10%, farming breast 500 1%, CMC2%, NNO 6%, and white carbon black complements to 100%.Above-mentioned material thorough mixing after ultrafine crusher is pulverized, promptly obtains converted products,
Example 5 10% compound (2) aqueous emulsions
Compound (2) 10%, polyvinyl alcohol 0.6%, alkylaryl polyoxyethylene poly-oxygen propylene aether 8%, farming breast No. 500 2%, farming breast No. 603 8%, dimethyl formamide 10%, ethylene glycol 5%, under the high-speed stirring, water complements to 100%, obtains the aqueous emulsion of favorable dispersity.
Example 6 50% compound (2) water dispersible granules
Compound (2) 50%, NNO 12%, epoxidized polyether 5%, CMC 15%, and light calcium carbonate complements to 100%.Above-mentioned material mixing after the kneading, adds in the tablets press that the certain specification screen cloth is housed and carries out granulation, and drying, screening obtain granule then.Biological activity determination
Example 7 indoor sprouting activity tests
Barnyard grass grass (Echinochloa crus-galli), Sheathed Monochoria (Monochoria vaginalis (Burm.f.) Presl var.plantaginea Solms), Herba Setariae Viridis (Setaria viridis (L.) Beauv.), firefly Lin (Scirpus trapezoideus Koidz.), pale persicaria (Polygonum lapathifolium L.), lamb's-quarters (Chenopodium album L.), paddy rice (Oryza sativaL.) seed are implanted the growth pipe range, 3 centimetres of implantation depths, upper soll layer sprays processing after 24 hours.
Missible oil of 1-5 compound (EC) and wettable powder (WP) all are diluted with water to 1000ppm, evenly spray to the upper soll layer of the plantation pipe of plantation weeds and paddy rice, detect seedling rate after 20 days, the results are shown in Table 1.
Table 1 suppresses to emerge the activity test result
Activity test behind the example 8 indoor seedlings
Barnyard grass grass (Echinochloa crus-galli), Sheathed Monochoria (Monochoria vaginalis (Burm.f.) Presl var.plantaginea Solms), Herba Setariae Viridis (Setaria viridis (L.) Bea uv.), firefly Lin (Scirpustrapezoideus Koidz.), pale persicaria (Polygonum lapathifolium L.), lamb's-quarters (Chenopodium album L.), paddy rice (Oryza sativaL.) seed are implanted the growth pipe range, 3 centimetres of implantation depths carried out upper soll layer after emerging 7 days and spray processing.
Missible oil of 1-5 compound (EC) and wettable powder (WP) all are diluted with water to 1000ppm, evenly spray to the upper soll layer of the plantation pipe of plantation weeds and paddy rice, detect preventive effect after 10 days, the results are shown in Table 2.
Preventive effect test-results behind table 1 seedling
Claims (5)
1, sulfonyl isoxazole derivates, structural formula is as follows:
2, power is planted the salt that requires 1 described compound formation.
3, the described compound of claim 1 the preparation method, by following trans should making:
4, the application of the described compound of claim 1 aspect management of weeds.
5, a kind of weeding activity composition is characterized in that: contain the described sulfonyl isoxazole derivates of claim 1 in the composition, the weight percentage of active ingredient is 0.1-99%.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008100842201A CN101362753A (en) | 2008-03-26 | 2008-03-26 | Sulfonyl isoxazole derivates with obvious herbicidal activity |
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| CNA2008100842201A CN101362753A (en) | 2008-03-26 | 2008-03-26 | Sulfonyl isoxazole derivates with obvious herbicidal activity |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610249A (en) * | 2014-12-25 | 2015-05-13 | 中国农业科学院植物保护研究所 | Bi-titer sulfonyl isoxazole derivative and application thereof |
| CN104610248A (en) * | 2014-12-25 | 2015-05-13 | 中国农业科学院植物保护研究所 | Multi-titer sulfonyl triazole compounds and application thereof |
| CN117486870A (en) * | 2023-11-03 | 2024-02-02 | 山东德浩化学有限公司 | Topramezone derivative and application thereof |
-
2008
- 2008-03-26 CN CNA2008100842201A patent/CN101362753A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610249A (en) * | 2014-12-25 | 2015-05-13 | 中国农业科学院植物保护研究所 | Bi-titer sulfonyl isoxazole derivative and application thereof |
| CN104610248A (en) * | 2014-12-25 | 2015-05-13 | 中国农业科学院植物保护研究所 | Multi-titer sulfonyl triazole compounds and application thereof |
| CN104610249B (en) * | 2014-12-25 | 2017-09-15 | 中国农业科学院植物保护研究所 | A kind of two potency sulfonyl isoxazole derivates and its application |
| CN104610248B (en) * | 2014-12-25 | 2018-07-20 | 中国农业科学院植物保护研究所 | A kind of multiple-effect valence sulfonyl triazoles class compound and its application |
| CN117486870A (en) * | 2023-11-03 | 2024-02-02 | 山东德浩化学有限公司 | Topramezone derivative and application thereof |
| CN117486870B (en) * | 2023-11-03 | 2024-05-24 | 山东德浩化学有限公司 | Topramezone derivative and application thereof |
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