CN102060747B - Phenyl spirane ketone enol ester compound and application thereof - Google Patents
Phenyl spirane ketone enol ester compound and application thereof Download PDFInfo
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- CN102060747B CN102060747B CN 201010604623 CN201010604623A CN102060747B CN 102060747 B CN102060747 B CN 102060747B CN 201010604623 CN201010604623 CN 201010604623 CN 201010604623 A CN201010604623 A CN 201010604623A CN 102060747 B CN102060747 B CN 102060747B
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Abstract
The invention discloses a phenyl spirane ketone enol ester compound. The compound is characterized in that the structural general formula of the compound is shown as I, wherein R1 is an alkyl group substituted by halogen or a non-substituted alkyl group; and G is a phenylalkyl group substituted by halogen, an alkyl group, an alkoxyl group, a nitro group or an alkyl halide group, or a non-substituted phenylalkyl group or a phenyl alkylene group substituted by halogen, an alkyl group, an alkoxyl group, a nitro group or an alkyl halide group, or a non-substituted phenyl alkylene group, or a heterocyclic alkyl group substituted by halogen, an alkyl group, an alkoxyl group, a nitro group or an alkyl halide group, or a non-substituted heterocyclic alkyl group. The invention also provides application of the phenyl spirane ketone enol ester compound to killing pests or mints.
Description
Technical field
The invention belongs to the Insecticidal and acaricidal agent field, be specifically related to a kind of phenyl spirocyclic ketoenols ester compound with pesticide and miticide actility and uses thereof.
Background technology
Spiral shell worm ethyl ester (formula III compound) is the spirocyclic tetronic acid insecticidal/acaricidal agent of a high-efficiency broad spectrum of Beyer Co., Ltd's exploitation, can effectively prevent and treat various suckings pest, such as aphid, thrips, wood louse, mealybug, aleyrodid and scale insect etc.Applicable staple crop comprises cotton, soybean, oranges and tangerines, tropical fruit tree, nut, grape, hops, potato and vegetables etc.Studies show that it has good selectivity to important beneficial insect such as ladybug, wasp fly and parasitic wasp.Spiral shell worm ethyl ester has unique function Characteristics, is unique modern sterilant with two-way interior suction conductive performance so far.This compound can upwards move down in whole plant materials, arrives at blade face and bark, thereby control is as reaching the corticole insect of fruit on romaine lettuce and the Chinese cabbage internal lobe.The interior absorption of this uniqueness can be protected newborn stem, leaf and root, prevents ovum and the larval growth of insect.Its another characteristics are that the lasting period is long, and the effective control that reached for 8 weeks can be provided.
Wherein, Beyer Co., Ltd also protects the analogue IV of spiral shell worm ethyl ester at patent CN 100374419C.
Active best to aphid in the analogue that these two compounds are spiral shell worm ethyl esters, the spiral shell worm ethyl ester shown in the formula III is 90% to the lethality rate of cotten aphid after 6 days under 20mg/L; The analogue of the spiral shell worm ethyl ester shown in the formula IV is 50% to the lethality rate of knurl aphid after 6 days under 4mg/L.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of phenyl spirocyclic ketoenols ester compound with desinsection, acaricidal activity and uses thereof.
In order to solve the problems of the technologies described above, the invention provides a kind of phenyl spirocyclic ketoenols ester compound, its general structure is shown in I:
Wherein:
R
1Be the alkyl that replaced by halogen or non-substituted alkyl;
G is by the phenylalkyl of halogen, alkyl, alkoxyl group, nitro, haloalkyl replacement, it perhaps is non-substituted phenylalkyl, perhaps be by the phenyl alkylene of halogen, alkyl, alkoxyl group, nitro, haloalkyl replacement, it perhaps is non-substituted phenyl alkylene, perhaps being by the Heterocyclylalkyl of halogen, alkyl, alkoxyl group, nitro, haloalkyl replacement, perhaps is non-substituted Heterocyclylalkyl.
Improvement as phenyl spirocyclic ketoenols ester compound of the present invention:
R
1Be C
1-C
4-alkyl;
G is by fluorine, chlorine, bromine, C
1-C
4-alkyl, C
1-C
3-alkoxyl group, nitro, halo C
1-C
3The phenyl C that-alkyl replaces
1-C
3-alkyl perhaps is non-substituted phenyl C
1-C
3-alkyl perhaps is by fluorine, chlorine, bromine, C
1-C
4-alkyl, C
1-C
3-alkoxyl group, nitro, halo C
1-C
3The phenyl C that-alkyl replaces
2-C
3-alkylene perhaps is non-substituted phenyl C
2-C
3-alkylene perhaps is by fluorine, chlorine, bromine, C
1-C
4-alkyl, C
1-C
3-alkoxyl group, nitro, halo C
1-C
3The heterocycle C that-alkyl replaces
1-C
3-alkyl perhaps is non-substituted heterocycle C
1-C
3-alkyl.
Further improvement as phenyl spirocyclic ketoenols ester compound of the present invention:
R
1Be methyl or ethyl;
G is by fluorine, chlorine, bromine, C
1-C
4-alkyl, C
1-C
3-alkoxyl group, nitro, halo C
1-C
3The phenylmethylene that-alkyl replaces perhaps is non-substituted phenylmethylene, perhaps is by fluorine, chlorine, bromine, C
1-C
4-alkyl, C
1-C
3-alkoxyl group, nitro, halo C
1-C
3The phenyl vinyl that-alkyl replaces perhaps is non-substituted phenyl vinyl.
Further improvement as phenyl spirocyclic ketoenols ester compound of the present invention:
R
1As shown in table 1 below respectively with G:
Table 1
The present invention also provides the purposes of above-mentioned phenyl spirocyclic ketoenols ester compound simultaneously: be used for kill pests or acarid.
The contriver finds on the basis that the analogue of the spiral shell worm ethyl ester shown in the spiral shell worm ethyl ester shown in the formula III and the formula IV is studied: prolong carbochain between 4-position ester group and phenyl ring after, have better activity, and have no bibliographical information.
The above-mentioned synthetic serial new compound that obtains is carried out indoor bioassay with black bean aphid, red spider and the mythimna separata at three initial stages in age respectively, and under 300ppm and 600ppm, all compounds all show good biological activity respectively.Simultaneously further lower concentration screening finds, the activity of black bean aphid is exceeded much than spiral shell worm ethyl ester.
The invention has the advantages that: synthesized series and had no the new compound that is different from III and IV of report, and had better biological activity.
New compound of the present invention, as follows at actual usage and the consumption in field:
Compound 24g, agricultural newborn 500#46g, dimethylbenzene 30g are made into 24% cream preparation.
1, when being used for killing mite:
1), application process: when even spraying, medicament are watered spraying, spray as far as possible evenly, guarantee that liquid sprays application to blade tow sides and fruit surface, brings into play its drug effect to greatest extent.
2), time of application: suggestion is caused harm the evil mite and is used early stage.
3), application program: when the harm of evil mite reaches index for control (every leaf worm ovum number reaches 10 or every leaf nymph 3-4 head); cream preparation (every bottle of 100 milliliters of cream preparations are watered the 800-1000 jin) even spraying after using dilution 4000-5000 doubly, every mu of consumption is 35～50mL cream preparation.
2, when being used for desinsection:
1), application process: when even spraying, medicament are watered spraying, spray as far as possible evenly, guarantee that liquid sprays application to blade tow sides and fruit surface, brings into play its drug effect to greatest extent.
2), time of application: suggestion is caused harm insect and is used early stage.
3), application program: during aphid on being used for the control vegetables, with above-mentioned cream preparation and water according to 1: 4000～5000 volume ratio dilution after, contain the phase of sending out spraying processing wingless aphid, every mu of consumption is 35～50mL cream preparation.
Phenyl spirocyclic ketoenols ester compound of the present invention can use separately, also can be used in combination with remaining bioactive compounds.
Embodiment
Embodiment 1, a kind of synthetic method with phenyl spirocyclic ketoenols ester compound (I-1) of pesticide and miticide actility, its reaction formula is:
Concrete building-up process is as follows:
In reaction flask, add under the ice-water bath 4.5g (15.0mmol) suitable-3-(2, the 5-3,5-dimethylphenyl)-4-hydroxyl-8-methoxyl group-1-azaspiro [4.5]-last of the ten Heavenly stems-3-alkene-2-ketone (structural formula is V), 2.3g (23.0mmol) triethylamine and 60mL methylene dichloride, drip again 2.8g (18.0mmol) phenyllacetyl chloride, (0～30 ℃) stirring reaction 0.5h under the room temperature.Reaction solution is used saturated NaHCO again with the salt acid elution of 1% (mass concentration) three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying concentrates to get the 6.4g solid product, obtains 5.9g Compound I-1 with 95% ethanol 5ml recrystallization.
Compound I-1
1H-NMR (500MHz, CDCl
3, δ ppm): 7.26-7.28 (m, 3H, Ar-H), 7.05-7.06 (m, 4H, Ar-H), 6.87 (s, 1H, Ar-H), 6.50 (s, 1H ,-NH-), 3.62 (s, 2H, Ar-CH
2-), 3.36 (s, 3H ,-O-CH
3), 3.03-3.08 (m, 1H ,-OCH-), 2.25 (s, 3H, Ar-CH
3), 2.13 (s, 3H, Ar-CH
3), 1.32-2.11 (m, 8H, Cyclohexane-H
8).
The synthetic method of compound V prepares with reference to the synthetic method of patent CN 100374419C.
Embodiment 2, a kind of synthetic method with phenyl spirocyclic ketoenols ester compound (I-23) of pesticide and miticide actility, its reaction formula is:
Concrete reaction process is as follows:
In reaction flask, add under the ice-water bath 4.5g (15.0mmol) suitable-3-(2, the 5-3,5-dimethylphenyl)-4-hydroxyl-8-methoxyl group-1-azaspiro [4.5]-last of the ten Heavenly stems-3-alkene-2-ketone (structural formula is V), 2.3g (23.0mmol) triethylamine and 60mL methylene dichloride, drip again 3.5g (18.0mmol) 2,4,6-Three methyl Benzene Acetyl Chloride 98Min., (0～30 ℃) stirring reaction 0.5h under the room temperature.Reaction solution is used saturated NaHCO again with 1% salt acid elution three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying concentrates to get the 7.1g solid product, obtains 6.6g Compound I-23 with 95% ethanol 5ml recrystallization.
Compound I-23
1H-NMR (500MHz, CDCl
3, δ ppm): 7.03-7.05 (m, 2H, Ar-H), 6.82-6.86 (m, 3H, Ar-H), 6.64 (s, 1H ,-NH-), 3.65 (s, 2H, Ar-CH
2-), 3.39 (s, 3H ,-O-CH
3), 3.09-3.05 (m, 1H ,-OCH-), and 2.26,2.27[s, 6H, (Ar-CH
3)
2], 2.09 (s, 3H, Ar-CH
3), 2.04[s, 6H, (Ar-CH
3)
2], 1.34-2.26 (m, 8H, Cyclohexane-H
8).
Embodiment 3, a kind of synthetic method with phenyl spirocyclic ketoenols ester compound (I-27) of pesticide and miticide actility, its reaction formula is:
Concrete reaction process is as follows:
In reaction flask, add under the ice-water bath 4.5g (15.0mmol) suitable-3-(2, the 5-3,5-dimethylphenyl)-4-hydroxyl-8-methoxyl group-1-azaspiro [4.5]-last of the ten Heavenly stems-3-alkene-2-ketone (structural formula is V), 2.3g (23.0mmol) triethylamine and 60mL methylene dichloride, drip again 4.0g (18.0mmol) 2, the 4-dichloro phenyllacetyl chloride, (0～30 ℃) stirring reaction 0.5h under the room temperature.Reaction solution is used saturated NaHCO again with 1% salt acid elution three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying concentrates to get the 7.2g solid product, obtains 6.5g Compound I-27 with 95% ethanol 5ml recrystallization.
Compound I-27
1H-NMR (500MHz, CDCl
3, δ ppm): 7.37 (d, J=2.0Hz, 1H, Ar-H), (7.12-7.14 m, 1H, Ar-H), 7.08 (d, J=7.5Hz, 1H, Ar-H), 7.03-7.04 (m, 1H, Ar-H), (6.91 d, J=8.0Hz, 1H, Ar-H), 6.87 (s, 1H, Ar-H), 6.75 (s, 1H,-NH-), 3.73 (s, 2H, Ar-CH
2-), 3.38 (s, 3H ,-O-CH
3), 3.15-3.20 (m, 1H ,-OCH-), 2.26 (s, 3H, Ar-CH
3), 2.14 (s, 3H, Ar-CH
3), 1.35-2.18 (m, 8H, Cyclohexane-H
8).
Embodiment 4, a kind of synthetic method with phenyl spirocyclic ketoenols ester compound (I-31) of pesticide and miticide actility, its reaction formula is:
Concrete reaction process is as follows:
In reaction flask, add under the ice-water bath 4.5g (15.0mmol) suitable-3-(2, the 5-3,5-dimethylphenyl)-4-hydroxyl-8-methoxyl group-1-azaspiro [4.5]-last of the ten Heavenly stems-3-alkene-2-ketone (structural formula is V), 2.3g (23.0mmol) triethylamine and 60mL methylene dichloride, drip again 3.0g (18.0mmol) cinnamyl chloride, (0～30 ℃) stirring reaction 0.5h under the room temperature.Reaction solution is used saturated NaHCO again with 1% salt acid elution three times
3Solution washing twice washes twice with water, anhydrous Na at last
2SO
4Drying concentrates to get the 6.6g solid product, obtains 6.0g Compound I-31 with 95% ethanol 5ml recrystallization.
Compound I-31
1H-NMR (500MHz, CDCl
3, δ ppm): 7.69 (d, J=16.0Hz, 1H, Ar-CH=CH-), 7.50-7.51 (m, 2H, Ar-H), (7.42-7.44 m, 3H, Ar-H), 6.99-7.08 (m, 3H, Ar-H), 6.63 (s, 1H,-NH-), 6.41 (d, J=16.0Hz, 1H, Ar-CH=CH-), 3.39 (s, 3H ,-O-CH
3), 3.20-3.25 (m, 1H ,-OCH-), 2.26 (s, 3H, Ar-CH
3), 2.24 (s, 3H, Ar-CH
3), 1.43-2.22 (m, 8H, Cyclohexane-H
8).
Embodiment 5,
Two-spotted spider mite and black bean aphid adopt pickling process.To be diluted to the aqueous solution of 300mg/L for after the examination bulk drug DMF dissolution with solvents, in the liquid of every kind of different phenyl spirocyclic ketoenols ester compound, get examination worm dipping afterwards taking-up in 15 seconds about 20, and be placed on the filter paper and naturally dry.Then, putting respectively the glass that bright leaf is housed into supports in the scolite, be placed on temperature and be 25 ℃, atmospheric moisture and be about 65% hot-house culture, use respectively the red spider larva (representative acarid) at three initial stages in age, the black bean aphid at three initial stages in age to carry out indoor bioassay to synthetic new compound, mortality ratio behind the respectively observation statistics 72h, every processing repeats for 3 times.The general sieve of part of compounds the results are shown in Table 2.
Mythimna separata is adopted spray method.Will be for examination bulk drug N, after the dissolving of N solvent dimethylformamide, be diluted to the aqueous solution of 600mg/L, in being lined with the culture dish of filter paper (Φ 90mm), put into the basically identical leaf of Semen Maydis section of size, access again 20 of third-instar larvaes, be put under the Potter spray tower and spray, spray amount 1ml/10 head.Be disposed, be placed on temperature and be 25 ℃, atmospheric moisture and be about 65% hot-house culture.Mortality ratio behind the respectively observation statistics 72h, every processing repeats for 3 times.The general sieve of part of compounds the results are shown in Table 2.
The general sieve measurement result of table 2 compound pesticide and miticide actility
Annotate: III represents the compound (both spiral shell worm ethyl esters) of formula III, and IV represents the spiral shell worm ethyl ester analogue of formula IV
According to above-mentioned biological activity determination method, we choose black bean aphid and further screen, and find that Compound I-1, I-23, I-31 will be higher than spiral shell worm ethyl ester and spiral shell worm ethyl ester analogue to the activity of black bean aphid under 10mg/L, 2.5mg/L, 0.625mg/L.The primary dcreening operation of compound the results are shown in Table 3.
Table 3 compound kills black bean aphid primary dcreening operation determination of activity result
Annotate: III represents the compound (both spiral shell worm ethyl esters) of formula III, and IV represents the spiral shell worm ethyl ester analogue of formula IV
Can be learnt that by above-mentioned table 2 under same dose, the Compound I of gained of the present invention-1, I-23, I-27, I-31 show to have preferably activity to black bean aphid, two-spotted spider mite, mythimna separata.Compound I-1, I-23, I-27, I-31 all are higher than the spiral shell worm ethyl ester analogue of spiral shell worm ethyl ester and formula IV to the activity of black bean aphid, and the virulence rank is the A level; Compound I-1, I-23, I-27 all are higher than the spiral shell worm ethyl ester analogue of spiral shell worm ethyl ester and formula IV to the activity of red spider, and the virulence rank is the A level; Compound I-1, I-27 all are higher than the spiral shell worm ethyl ester analogue of spiral shell worm ethyl ester and formula IV to the activity of mythimna separata, and the virulence rank is the A level.(the evaluated biological activity method: mortality ratio is being the A level more than 90%, is the B level between 70～90%, is the C level between 50～70%, is the D level between 0～50%)
Can be learnt that by above-mentioned table 3 under lower concentration, Compound I-1, I-23 and I-31 have demonstrated superiority of the present invention to the activity of the black bean aphid spiral shell worm ethyl ester analogue apparently higher than spiral shell worm ethyl ester and formula IV.
At last, it is also to be noted that what more than enumerate only is a specific embodiment of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. phenyl spirocyclic ketoenols ester compound is characterized in that general structure is shown in I:
Wherein:
R
1Be C
1-C
4-alkyl;
G is by chlorine, C
1-C
4The phenyl C that-alkyl replaces
1-C
3-alkyl, non-substituted phenyl C
1-C
3-alkyl or non-substituted phenyl C
2-C
3-alkylene.
2. phenyl spirocyclic ketoenols ester compound according to claim 1 is characterized in that structural formula is:
3. the purposes of phenyl spirocyclic ketoenols ester compound as claimed in claim 1 or 2: be used for kill pests.
4. the purposes of phenyl spirocyclic ketoenols ester compound according to claim 3: described insect is acarid.
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| CN 201010604623 CN102060747B (en) | 2010-12-24 | 2010-12-24 | Phenyl spirane ketone enol ester compound and application thereof |
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|---|---|---|---|
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|---|---|
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| CN102060747B true CN102060747B (en) | 2013-01-02 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1692099A (en) * | 2002-07-11 | 2005-11-02 | 拜尔农作物科学股份公司 | Cis-alkoxy-substituted spirocyclic 1-h-pyrrolidine-2,4-dione derivatives serving as pesticides |
| CN101808989A (en) * | 2007-09-25 | 2010-08-18 | 拜尔农作物科学股份公司 | Halogen alkoxy spirocyclic tetramic and tetronic acid derivatives |
-
2010
- 2010-12-24 CN CN 201010604623 patent/CN102060747B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1692099A (en) * | 2002-07-11 | 2005-11-02 | 拜尔农作物科学股份公司 | Cis-alkoxy-substituted spirocyclic 1-h-pyrrolidine-2,4-dione derivatives serving as pesticides |
| CN101808989A (en) * | 2007-09-25 | 2010-08-18 | 拜尔农作物科学股份公司 | Halogen alkoxy spirocyclic tetramic and tetronic acid derivatives |
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