CN101602752A - N-sulfenamide groups-N '-tertiary butyl-N, the fragrant hydrazide compound of N '-two and preparation and application - Google Patents
N-sulfenamide groups-N '-tertiary butyl-N, the fragrant hydrazide compound of N '-two and preparation and application Download PDFInfo
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- CN101602752A CN101602752A CNA200810053461XA CN200810053461A CN101602752A CN 101602752 A CN101602752 A CN 101602752A CN A200810053461X A CNA200810053461X A CN A200810053461XA CN 200810053461 A CN200810053461 A CN 200810053461A CN 101602752 A CN101602752 A CN 101602752A
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Abstract
The present invention relates to N-sulfenamide groups-N '-tertiary butyl-N, the fragrant hydrazide compound of N '-two and preparation and application, its general structure is (wherein the meaning of each group is seen specification sheets) shown in (I).Described compound has excellent insecticidal activity, can be widely used in the pest control of farm crop, is a kind of insect growth regulator(IGR) with broad prospect of application.
Description
Technical field
The present invention relates to as insect growth regulator(IGR), particularly N-sulfenamide groups-N '-tertiary butyl-N the fragrant hydrazide compound of N '-two and preparation and application.
Background technology
US-5,424,333, US 4,814,349, US 5,117,057, EP-228564, EP-236618 and EP-245950 disclose N, N '-two hydrazide kind compound and insecticidal activity thereof, JP8231528, JP8231529, JP 4235177, US5482962 discloses and has contained benzo five-membered heterocyclic two hydrazide derivatives and insecticidal activity thereof, EP496342, EP984009 disclose two hydrazide derivatives and the insecticidal activity thereof that contains the benzo hexa-member heterocycle, and CN 1313276A discloses two hydrazide derivatives and the insecticidal activity thereof that contains benzo five-membered heterocycle and benzo hexa-member heterocycle, EP-395,581 disclose derivative and the insecticidal activity thereof that contains N-sulfo-two hydrazide kind compounds, and CN 1927831A discloses a kind of N-sulfenate group diaromatic hydrazide derivative and preparation and application, and biological activity determination is the result show: this compounds has excellent insecticidal activity, can be widely used in the pest control of farm crop, be a kind of insect growth regulator(IGR) with broad prospect of application.
Summary of the invention
The purpose of this invention is to provide a kind of N-sulfenamide groups-N '-tertiary butyl-N, the fragrant hydrazide compound of N '-two and preparation and application, this compounds has excellent insecticidal activity.
The present invention is that chemical general formula is the N-sulfenamide groups-N '-tertiary butyl-N of (I), the fragrant hydrazide compound of N '-two:
In the formula; A, B represent phenyl, chroman, 2 respectively independently; 3-dihydro-cumarone, cumarone; each group is unsubstituted, or is replaced by one or more following radicals: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxyl group, 1-4 halocarbon substituted alkyl, 1-4 halocarbon are for alkoxyl group, 1-4 carbon alkoxyalkyl, 1-4 carbon alkylthio, 1-4 carbon alkyl sulphinyl, 1-4 carbon alkyl sulphonyl, nitro, cyano group, hydroxyl, carboxyl, 1-4 carbon alkyl-carbonyl or 1-4 carbon alkoxy carbonyl.R
1, R
2Represent 1-6 carbon hydrocarbon carbonyl respectively independently; 1-6 carbon hydrocarbon carbonyl oxygen; carbobenzoxy; carbobenzoxy-(Cbz); 1-4 carbon alkyl; (3-6) carbene base; (3-6) halo carbene base; (3-6) carbyne base; 1-4 halocarbon substituted alkyl; 1-4 carbon alkoxyalkyl; 1-4 carbon alkane sulfane base; phenyl; naphthyl; chroman; 2; 3-dihydro-1; 4-Ben Bing dioxazine; 4H-1; 3-Ben Bing dioxazine; 2; 3-dihydro-cumarone; cumarone; benzothiazole; 1; the 3-benzoxazole; 1; 2-benzoisoxazole or benzoglyoxaline; each group is unsubstituted; or replaced: halogen by one or more following radicals; 1-4 carbon alkyl; 1-4 carbon alkoxyl group; 1-4 halocarbon substituted alkyl; the 1-4 halocarbon is for alkoxyl group; 1-4 carbon alkoxyalkyl; 1-4 carbon alkylthio; 1-4 carbon alkyl sulphinyl; 1-4 carbon alkyl sulphonyl; nitro; cyano group; hydroxyl; carboxyl; 1-4 carbon alkyl-carbonyl; 1-4 carbon alkoxy carbonyl or imido grpup, perhaps R
1R
2N represents morpholinyl, hexahydropyridine base.
N-sulfenamide groups-N ' of the present invention-the tertiary butyl-N, A, B represent phenyl respectively or the phenyl, the benzo five-membered or hexa-member heterocycle that are replaced by one or more 1-4 carbon alkyl independently in the fragrant hydrazide compound of N '-two; R
1, R
2Represent replacement of 1-6 carbon or unsubstituted alkyl, thiazolinyl, alkynyl, replacement or unsubstituted phenyl or imido grpup, perhaps R respectively independently
1R
2N represents morpholinyl, hexahydropyridine base.
The compound of general formula of the present invention (I) can prepare as follows:
With compound (A) and equimolar sulfur dichloride (B) and pyridine in methylene dichloride, reaction is 4-6 hour under the room temperature, methylene dichloride is sloughed in decompression, it is even to add the anhydrous n-hexane jolting, removes by filter pyridine hydrochloride and gets compound (C), and (C) is dissolved in the toluene with compound, ice bath drips the toluene solution of amine and triethylamine down, room temperature reaction 4-6 hour, the precipitation that filters, reduces pressure, recycle silicon glue chromatographic column purifying gets compound (I).
Compd A and B and amine are commercially available or with (referring to the EP-228564, EP-236618 and EP-245950) of currently known methods preparation.
The present invention goes back the compound of listing in the free list 1 and illustrates, but does not limit the present invention.
The compound of general formula of the present invention (I) has excellent insecticidal activity, can be used to prevent and treat lepidopteran class, Coleoptera class, Heteroptera class, Diptera class, Orthoptera class and Homoptera class pest, is particularly suitable for preventing and treating the lepidopteran class pest.
The insecticidal activity of the part of compounds of general formula of the present invention (I) has surpassed the commercialization kind N-tertiary butyl-N '-4-ethylamino benzonitrile acyl group-3, the insecticidal activity of 5-dimethyl benzene formyl hydrazine (rice mite).
The compound of general formula of the present invention (I) can directly use, and can add that also the carrier that agricultural go up to be accepted uses, also can with other sterilant and (or) the composite use of miticide.
Embodiment
Further specify the present invention below in conjunction with embodiment:
Synthesizing of embodiment 1:N-chlorine sulfenyl rice mite
In the 50ml there-necked flask, add 20ml methylene dichloride, 0.008mol sulfur dichloride and 0.008mol pyridine, control reaction temperature is not higher than-10 ℃.Drip off the back and add 0.007mol rice mite, reaction mixture stirring at room 4 hours, steaming vibrating dichloromethane under the decompression adds the 10ml dry toluene then, filters, and obtains yellow solution, can be directly used in next step reaction.
Synthesizing of 2:N-sulphonyl diethylin of embodiment rice mite (I4)
In the 50mL there-necked flask, the toluene solution that contains 3mmol N-chlorine sulfenyl rice mite of step preparation in the adding, cryosel is bathed and is cooled to-10 ℃, slowly drips the toluene solution that 8mL contains 3mmol diethylamine and 3mmol triethylamine, dropwises the back and continues to stir 30min.Filter, filtrate is sloughed solvent, and resistates column chromatography for separation (eluent is the mixed solvent of ethyl acetate and sherwood oil) obtains N-the sulphonyl diethylin rice mite (I4) of colorless solid shape, yield 58.8%.Fusing point is 44-46 ℃.
Equally, can synthesize other compound of the present invention.See Table 1:
Table 1
The present invention has carried out the active mensuration of mythimna separata extremely, and the mensuration program is as follows:
For the examination insect is southern mythimna separata [Mythimna (=Pseudaletia) separata (Walker)], the normal population that indoor leaf of Semen Maydis is raised.Mythimna separata is adopted leaf dipping method, and sample is mixed with the solution of different concns with acetone, and dipping leaf of Semen Maydis in seedling stage is put into the 7cm culture dish after drying, insert 4 instar larvaes, repeats 2-4 time.Contrast acetone soln soaking maize leaf breeding grub.At any time add fresh maize leaf after 24 hours.24 hours, 48 hours, 72 hours, 96 hours viewing test results, normally casting off a skin until control larvae became for 5 ages.Dead fully with armyworm larvae, that promptly touches motionlessly is the death standard of larva.Table 2 is the test result of part of compounds.
The mythimna separata determination of activity result extremely of table 2 portion of product
The present invention has carried out the active mensuration of small cabbage moth extremely, and the mensuration program is as follows:
Shop experiment method: get 240 of field third-instar larvaes, break into the disk of diameter 5cm, respectively at 1125 times of liquid of missible oil of 25% The compounds of this invention with no medicine fresh flower cabbage leaf; Soak in the soup of 1125 times of liquid of 25% meter mite missible oil after 2 minutes, take out airing on thieving paper, put into insect box, insert third-instar larvae, 30 in every box moves in the insectary and raises, and temperature is controlled at about 27 ℃, and humidity is controlled at 80-90%.Test 72 hours dead borer populations of " Invest, Then Investigate ".Calculate virulence.Table 3 is the test result of part of compounds.
Table 3 part of compounds shop experiment is to the prevention effect of small cabbage moth
| Handle | I1 | I2 | I3 | I4 | I5 | I6 |
| Preventive effect (%) | Greater than 85 | Greater than 85 | Greater than 85 | Greater than 85 | Greater than 85 | Greater than 85 |
Claims (3)
1, a kind of N-sulfenamide groups-N '-tertiary butyl-N, the fragrant hydrazide compound of N '-two is characterized in that it has structure shown in the following general formula (I):
In the formula, A, B represent phenyl, chroman, 2 respectively independently, 3-dihydro-cumarone, cumarone, each group is unsubstituted, or is replaced by one or more following radicals: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxyl group, 1-4 halocarbon substituted alkyl, 1-4 halocarbon are for alkoxyl group, 1-4 carbon alkoxyalkyl, 1-4 carbon alkylthio, 1-4 carbon alkyl sulphinyl, 1-4 carbon alkyl sulphonyl, nitro, cyano group, hydroxyl, carboxyl, 1-4 carbon alkyl-carbonyl or 1-4 carbon alkoxy carbonyl;
R
1, R
2Represent 1-6 carbon hydrocarbon carbonyl respectively independently; 1-6 carbon hydrocarbon carbonyl oxygen; carbobenzoxy; carbobenzoxy-(Cbz); 1-4 carbon alkyl; (3-6) carbene base; (3-6) halo carbene base; (3-6) carbyne base; 1-4 halocarbon substituted alkyl; 1-4 carbon alkoxyalkyl; 1-4 carbon alkane sulfane base; phenyl; naphthyl; chroman; 2; 3-dihydro-1; 4-Ben Bing dioxazine; 4H-1; 3-Ben Bing dioxazine; 2; 3-dihydro-cumarone; cumarone; benzothiazole; 1; the 3-benzoxazole; 1; 2-benzoisoxazole or benzoglyoxaline; each group is unsubstituted; or replaced: halogen by one or more following radicals; 1-4 carbon alkyl; 1-4 carbon alkoxyl group; 1-4 halocarbon substituted alkyl; the 1-4 halocarbon is for alkoxyl group; 1-4 carbon alkoxyalkyl; 1-4 carbon alkylthio; 1-4 carbon alkyl sulphinyl; 1-4 carbon alkyl sulphonyl; nitro; cyano group; hydroxyl; carboxyl; 1-4 carbon alkyl-carbonyl; 1-4 carbon alkoxy carbonyl or imido grpup, perhaps R
1R
2N represents morpholinyl, hexahydropyridine base.
2, the N-sulfenamide groups-N ' according to claim 1-tertiary butyl-N, the fragrant hydrazide compound of N '-two is characterized in that A, B represent phenyl respectively independently or the phenyl, the benzo five-membered or hexa-member heterocycle that are replaced by one or more 1-4 carbon alkyl; R
1, R
2Represent replacement of 1-6 carbon or unsubstituted alkyl, thiazolinyl, alkynyl, replacement or unsubstituted phenyl or imido grpup, perhaps R respectively independently
1R
2N represents morpholinyl, hexahydropyridine base.
3, the described N-sulfenamide groups-N ' of the claim 1-tertiary butyl-N, the application of the fragrant hydrazide compound of N '-two, it is characterized in that it is used as insect growth regulator(IGR), control lepidopteran class, Coleoptera class, Heteroptera class, Diptera class, Orthoptera class or Homoptera class insect.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146364A (en) * | 2016-06-28 | 2016-11-23 | 方美兰 | A kind of synthetic method of sulfenamide compounds |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146364A (en) * | 2016-06-28 | 2016-11-23 | 方美兰 | A kind of synthetic method of sulfenamide compounds |
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