CN1177846C - Oxa(thia)diazolylpyridazinone derivative and its preparing process and application - Google Patents
Oxa(thia)diazolylpyridazinone derivative and its preparing process and application Download PDFInfo
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- CN1177846C CN1177846C CNB001163515A CN00116351A CN1177846C CN 1177846 C CN1177846 C CN 1177846C CN B001163515 A CNB001163515 A CN B001163515A CN 00116351 A CN00116351 A CN 00116351A CN 1177846 C CN1177846 C CN 1177846C
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Abstract
The present invention discloses an oxa(thia)diazolyl pyridazinone derivative, a preparing method thereof and applications thereof. The compound can be used as a juvenile hormone type insect growth regulator for inhibiting the growth of pests, and has strong activity for inhibiting the growth of armyworms. IC50 reaches 3 to 8 ppm. The oxa(thia)diazolyl pyridazinone derivative can be extensively applied to the protection of crops, and is an insect growth regulator with extensive application prospects. The preparing process is simple and practical, and the structural general formula of the oxa(thia)diazolyl pyridazinone derivative is shown as the right formula disclosed in the specification.
Description
Technical field
The present invention relates to a kind of insect growth regulator(IGR) and preparation method thereof and application, relate in particular to Yi Zhong oxadiazole radical pyridazine ketone compounds and preparation thereof and application.
Background technology
Conventional pesticides is in pest control, ensure on the agricultural foison and play a significantly greater role, but because frequent, a large amount of use, caused that insect is to organophosphorus, carbamate, pyrethroids etc. produce resistance, being extensive use of of these sterilants pollutes environment again simultaneously, people begin to re-recognize and understand agricultural chemicals, not only require effectively Pest Control of novel pesticide, and more pay attention to the biorational and the environment concordance of agricultural chemicals, pest population is regulated and control (regulation), rather than be purpose only to kill.The insect growth regulator(IGR) of tool juvenile hormone activity can be regulated growing of insect, metamorphosis, and essential characteristics such as reproduction, and sustainable Pest Control population density, but to nontarget organism low toxicity or nontoxic.Therefore the research and development to this type of agricultural chemicals will be the research emphasis and the direction of 21st century novel pesticide.
Pyridazinone is that a class has the active heterogeneous ring compound of good biological, and at agricultural chemicals, aspects such as medicine have a wide range of applications, and has therefore caused investigator's very big concern.Japan Nissan chemical company successively developed new class and has had the active pyridazinone compound NC-170 of JH, NC-184, NC-196 respectively at 1988,1992 in 1994.This compounds novel structure, active high show very high JH activity for control plant hopper, leafhopper class rice grub, but wherein insecticidal spectrum is not very wide.In addition, contain 1,3,4-oxadiazole ring insect growth regulator(IGR) DOW416 has and suppresses chitinous synthetic, disturbs, stops insect cuticle and tissue growth, reduce the activity of the synthesis capability of DNA, yet its solvability in most organic solvents is very limited.Thereby limited its practical application.Therefore, must modify, in the hope of therefrom filtering out the new insect growth regulator(IGR) of tool juvenile hormone activity with potential commercial value to above-mentioned two compounds.
Summary of the invention
It is good that one of the object of the invention is to disclose a class solvability, suppresses insect growth De oxadiazole radical pyridazine ketone derivatives compounds;
Two of the object of the invention is to disclose the preparation method of the described compound of a class;
Three of the object of the invention is to disclose the application of the described compound of a class as insect growth regulator(IGR).
Design of the present invention is such:
Require molecule factor such as molecular length, the amplitude of ring, substituting group size, electrostatic property that the oxadiazole ring is incorporated in the pyridazinone compound according to the molecular biological activity of pyridazinone compound, make two active heterocycles splice the solvability of Gai Bian oxadiazoles, enlarge the insecticidal spectrum of pyridazinone compound.
It is 2-alkyl-4-halo-5-[5-alkyl-2-(1,3,4-oxadiazole base)-hydrocarbon oxygen (sulphur) base that Suo of the present invention is Shuoed De oxadiazole radical pyridazine ketone compounds]-3 (2H) pyridazinone derivative, its general structure is as follows:
In the formula: R
1Be alkyl or aryl, as the tertiary butyl or phenyl etc.; R
2, R
3Be alkyl or hydrogen; R
4Be alkyl or aryl, as phenyl, rubigan, to a fluorophenyl or a fluorophenyl etc.; Y is a chlorine; X is oxygen or sulphur.
The preparation method of said derivative is as described below:
With 2-alkyl-4-halo-5-hydroxyl (mercapto) base-3-(2H) pyridazinone is raw material, with 2-(alpha-halogen alkyl)-5-alkyl-1,3, the 4-oxadiazole is in anhydrous inert solvent, under the condition of alkaline matter and phase-transfer catalyst existence, carry out the alkylated reaction of oxygen (sulphur), its reaction equation is as follows:
In the formula: in the formula: R
1Be alkyl or aryl; R
2, R
3Be alkyl or hydrogen; R
4Be alkyl or aryl; Y is a chlorine; X is oxygen or sulphur; Said 2-(alpha-halogen alkyl)-5-alkyl-1,3, the 4-oxadiazole can preferentially adopt 2-chloromethyl-5-alkyl-1,3,4-oxadiazole.
Said solvent is a kind of in hydro carbons (as toluene or benzene), acetonitrile, dimethyl formamide, the tetrahydrofuran (THF) or their mixture, and preferred solvent is a kind of in acetonitrile, dimethyl formamide or the tetrahydrofuran (THF) or their mixture;
Used alkali is mineral alkali or organic bases, can preferentially adopt a kind of in salt of wormwood, yellow soda ash, potassium hydroxide, sodium hydride or the potassium hydride KH;
Used phase-transfer catalyst is a kind of in Tetrabutyl amonium bromide, triethyl benzyl ammonia chloride, tetrabutylammonium chloride, low polyoxyethylene glycol, crown ether or the methyl three n-octyl chlorination ammoniums.
Temperature of reaction is controlled at 80～110 ℃, and the reaction times is 2-4 hour.
After reaction finishes, adopt conventional method to separate, can obtain target product of the present invention-2-alkyl-4-halo-5-[5-alkyl-2-(1,3,4-oxadiazole base)-hydrocarbon oxygen (sulphur) base]-3 (2H) pyridazinone derivative.
Said 2-alkyl-4-halo-5-[5-alkyl-2-(1,3,4-oxadiazole base)-hydrocarbon oxygen (sulphur) base]-3 (2H) pyridazinone, can adopt USP4,837,217 disclosed technology are prepared.
Said 2-(alpha-halogen alkyl)-5-alkyl-1,3, the 4-oxadiazole can adopt IndianJ.Chem.1973, Vol.11,732. or USP4,328,247 disclosed technology are prepared.
The cited compound of the present invention can be used as the neotonin class insect growth regulator(IGR) that suppresses the insect growth, can adopt ordinary method to use, and the cited compound of the present invention has the activity of strongly inhibited mythimna separata growth, induces to produce overage larva, IC
50Reach 3-8ppm, can be widely used in the protection of farm crop, and preparation process is simple, be a kind of insect growth regulator(IGR) with broad prospect of application.
Bioactive test:
Press down the active mensuration of worm:
1. giving birth to the test worm chooses:
Larva with 2 ages of corn armyworm Pseudaletia separata (Walker) is a tested object.
2. give birth to the survey method
Get an amount of former medicine and be dissolved in few organic solvent of trying one's best, wiring solution-forming, the aqueous solution that adds the emulsifying agent of a little is made into certain density soup, and the corn of newly cutting is immersed in the soup, waits to soak into complete back and takes out airing.
Put into 10 of corn armyworm 2 instar larvaes in the beaker, the above-mentioned corn that soaks medicine is put into beaker, get hospital gauze and seal.The soup of each concentration is placed three and is repeated to observe, and feeds continuously 7 days with soaking the jobstears leaf, measures the inhibiting rate to the larva individuality.
Growth inhibition ratio (%)=(control larvae body weight-processing larva body weight)/(control larvae body weight) * 100%
Specific implementation method
Further illustrate content of the present invention below in conjunction with embodiment, but these embodiment do not limit protection scope of the present invention.
Embodiment 1
The 2-tertiary butyl-4-chloro-5-[5-phenyl-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone synthetic, reaction equation is as follows:
With the 2-tertiary butyl-4-chloro-5-hydroxyl-3 (2H) pyridazinone 0.5g (2.47mmol), dry DMF 5mL, Anhydrous potassium carbonate 1.115g (8.08mmol), Tetrabutyl amonium bromide 0.16g (0.5mmol) places flask at the bottom of the garden, drip 0.48g (2.47mmol) 2-chloromethyl-5-phenyl-1 down at 85 ℃, 3, the 5mL anhydrous DMF solution of 4-oxadiazole was 85 ℃ of following stirring reactions 2 hours.Reaction finishes, the most of DMF of pressure reducing and steaming, residue is poured in the 20mL water, with chloroform extraction (3 * 10mL), be washed to neutrality, the organic layer anhydrous magnesium sulfate drying, concentrated solution, residue separate through silica gel column chromatography, eluent is a sherwood oil: ethyl acetate=5: 1 (V/V) at last white crystals, productive rate 70.6%, m.p.187～188 ℃.
1H?NMR，δ(ppm)：8.08～7.26(5H，m)，7.97(1H，s)，5.55(2H，s)，1.65(9H，s)。
MS，361(M
+，12.7)，325(20.0)，305(40.5)，268(36.9)，159(70.9)，105(100.0)，77(54.9)，57(56.0)。
Ultimate analysis:
C％ H％ N％
Theoretical value: 56.59 4.75 15.52
Measured value: 56.46 4.72 15.66
Suppress the mythimna separata activity: 62.5ppm 70%, IC
50=31ppm.
Embodiment 2
The 2-tertiary butyl-4-chloro-5-[5-(4-chloro-phenyl-)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone synthetic, reaction equation is as follows:
The preparation method is with embodiment 1, and wherein raw material is 2-chloromethyl-5-(4-chloro-phenyl-)-1,3,4-oxadiazole, productive rate 67.8%, m.p:149～150 ℃.
1H?NMR，δ(ppm)：8.03～7.51(4H，m)，7.97(1H，s)，5.55(2H，s)，1.65(9H，s)。
MS，395(M
+，9.6)，336(15.3)，193(32.7)，137(15.4)，140(100.0)，57(38.3)。
Ultimate analysis:
C％ H％ N％
Theoretical value: 51.66 4.08 14.18
Measured value: 51.50 3.95 14.18
Suppress the mythimna separata activity: 5ppm 57%, IC
50=3ppm, IC
90=31ppm.
Embodiment 3
The 2-tertiary butyl-4-chloro-5-[5-(4-fluorophenyl)-2-(1,3,4-oxadiazole base) methoxyl group]-3 (2H) pyridazinone synthetic, reaction equation is as follows:
The preparation method is with embodiment 1, and wherein raw material is 2-chloromethyl-5-(4-fluorophenyl)-1,3,4-oxadiazole, productive rate 75.6%, m.p:159～160 ℃.
1H?NMR，δ(ppm)：8.12～7.22(4H，m)7.99(1H，s)，5.55(2H，s)，1.65(9H，s).
MS，379(M
++1，4.4)，323(7.2)，287(6.5)，177(25.2)，123(100.0)，95(18.5)，57(33.5).
Ultimate analysis:
C％ H％ N％
Theoretical value: 53.90 4.26 14.79
Measured value: 53.88 4.15 14.89
Suppress the mythimna separata activity: 5ppm 57%, IC
50=4ppm, IC
90=36ppm.
Embodiment 4
The 2-tertiary butyl-4-chloro-5-[5-(3-fluorophenyl)-2-(1,3, the 4-oxadiazole)-methoxyl group]-3-(2H) pyridazinone synthetic, reaction equation is as follows:
The preparation method is with embodiment 1, and wherein raw material is 2-chloromethyl-5-(3-fluorophenyl)-1,3,4-oxadiazole, productive rate 60.1%, m.p:149～150 ℃.
1H?NMR，δ(ppm)：7.97(1H，s)，7.90～7.29(4H，m)，5.56(2H，s)，1.66(9H，s)。
MS，378(M
+，34.6)，321(57.6)，286(32.1)，176(66.0)，123(100.0)，56(45.5)。
Ultimate analysis:
C％ H％ N％
Theoretical value: 53.90 4.26 14.79
Measured value: 53.70 4.26 15.00
Suppress the mythimna separata activity: 10ppm 57%, IC
50=8ppm.
Embodiment 5
The 2-tertiary butyl-4-chloro-5-[5-(4-p-methoxy-phenyl)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone synthetic as follows:
The preparation method is with embodiment 1, and wherein raw material is 2-chloromethyl-5-(4-p-methoxy-phenyl)-1,3, the 4-oxadiazole,
Productive rate 78.3%, m.p:165～167 ℃.
1H?NMR，δ(ppm)：8.03～8.00(4H，m)，7.99(1H，s)，5.54(2H，s)，2.09(3H，s)，1.65(9H，s)。
MS，370(M
+，8.3)，298(8.4)，189(26.4)，135(100.0)，56(11.9)。
Ultimate analysis
C％ H％ N％
Theoretical value: 55.32 4.90 14.34
Measured value: 55.18 5.04 14.38
Suppress the mythimna separata activity: 10ppm 41%, IC
50=11ppm.
Embodiment 6
The 2-tertiary butyl-4-chloro-5-[5-(2-fluorophenyl)-2-(1,3, the 4-oxadiazole)-methoxyl group]-3 (2H) pyridazinone synthetic, reaction equation is as follows:
The preparation method is with embodiment 1, and wherein raw material is 2-chloromethyl-5-(2-fluorophenyl)-1,3,4-oxadiazole, productive rate 61.2%, m.p:167～168 ℃.
1H?NMR，δ(ppm)：8.09～7.26(4H，m)，7.98(1H，s)，5.58(2H，s)，1.65(9H，s)。
Suppress the mythimna separata activity: 10ppm 38%, IC
50=19ppm.
Embodiment 7
The 2-tertiary butyl-4-chloro-5-[5-(4-ethylphenyl)-2-(1,3, the 4-oxadiazole)-methoxyl group]-3 (2H) pyridazinone synthetic, reaction equation is as follows:
The preparation method is with embodiment 1, and wherein raw material is 2-chloromethyl-5-(4-ethylphenyl)-1,3,4-oxadiazole, productive rate 68.3%, m.p:159～160 ℃.
1HNMR，δ(ppm)：8.00～7.35(4H，m)，7.98(1H，s)，5.54(2H，s)，2.74(2H，q)，1.64(9H，s)，1.28(3H，t)
Suppress the mythimna separata activity: 10ppm 42%, IC
50=12ppm.
Can prepare following compound easily with similar approach:
The 2-tertiary butyl-4-chloro-5-[5-(4-nitrophenyl)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone, m.p.215～216 ℃;
The 2-tertiary butyl-4-chloro-5-[5-(4-aminomethyl phenyl)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone, m.p.177～178 ℃;
The 2-tertiary butyl-4-chloro-5-[5-(3-aminomethyl phenyl)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone, m.p.146～147 ℃;
The 2-tertiary butyl-4-chloro-5-[5-(3, the 5-3,5-dimethylphenyl)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone, m.p.189～190 ℃;
The 2-tertiary butyl-4-chloro-5-[5-(2,4-two chloro-5-fluorophenyls)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone, m.p.161～162 ℃;
2-phenyl-4-chloro-5-[5-(4-chloro-phenyl-)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone, m.p.150～151 ℃;
2-phenyl-4-chloro-5-[5-(4-fluorophenyl)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone, m.p.172～173 ℃;
2-phenyl-4-chloro-5-[5-(3-fluorophenyl)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone, m.p.181～182 ℃;
2-phenyl-4-chloro-5-[5-(4-ethylphenyl)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone, m.p.137～138 ℃;
2-phenyl-4-chloro-5-[5-phenyl-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone, m.p.142～143 ℃:
2-phenyl-4-chloro-5-[5-(4-p-methoxy-phenyl)-2-(1,3,4-oxadiazole base)-methoxyl group]-3 (2H) pyridazinone, m.p.145～146 ℃;
The 2-tertiary butyl-4-chloro-5-[5-(4-chloro-phenyl-)-2-(1,3,4-oxadiazole base)-methylthio group]-3 (2H) pyridazinone, m.p.156～157 ℃;
The 2-tertiary butyl-4-chloro-5-[5-(4-fluorophenyl)-2-(1,3,4-oxadiazole base)-methylthio group]-3 (2H) pyridazinone, m.p.175～176 ℃.
Claims (8)
1. Yi Zhong oxadiazole radical pyridazine ketone derivatives, its general structure is as follows:
In the formula: R
1Be alkyl or aryl; R
2, R
3Be alkyl or hydrogen; R
4Be alkyl or aryl; Y is a chlorine; X is oxygen or sulphur.
2. derivative as claimed in claim 1 is characterized in that R
1Be the tertiary butyl or phenyl, R
2, R
3Be hydrogen, R
4For phenyl, rubigan, to a fluorophenyl or a fluorophenyl.
3. the preparation method of derivative as claimed in claim 1, it is characterized in that, with 2-alkyl-4-halo-5-hydroxyl or sulfydryl-3-(2H) pyridazinone is raw material, with 2-[alpha-halogen alkyl]-5-alkyl-(1,3,4)-oxadiazoles are in anhydrous inert solvent, under the condition of alkaline matter and phase-transfer catalyst existence, carry out the alkylated reaction of oxygen or sulphur, its reaction equation is as follows:
In the formula: R
1Be alkyl or aryl; R
2, R
3Be alkyl or hydrogen; R
4Be alkyl or aryl; Y is a chlorine; X is oxygen or sulphur;
Said solvent is a kind of in hydro carbons, acetonitrile, dimethyl formamide or the tetrahydrofuran (THF), or their mixture; Used alkali is mineral alkali or organic bases; Used phase-transfer catalyst is a kind of in Tetrabutyl amonium bromide, triethyl benzyl ammonia chloride, tetrabutylammonium chloride, low polyoxyethylene glycol, crown ether or the methyl three n-octyl chlorination ammoniums; Temperature of reaction is 80～110 ℃, and the reaction times is 2～4 hours; Reaction finishes can obtain target product of the present invention after separating---2-alkyl-4-halo-5-[5-alkyl-2-(1,3,4-oxadiazole base)-hydrocarbon oxygen or sulfenyl] and-3 (2H) pyridazinone derivative.
4. preparation method as claimed in claim 3 is characterized in that, wherein said solvent is toluene or benzene.
5. preparation method as claimed in claim 3 is characterized in that, wherein said 2-(alpha-halogen alkyl)-5-alkyl-(1,3,4)-oxadiazoles are 2-chloromethyl-5-alkyl-1,3, the 4-oxadiazole.
6, preparation method as claimed in claim 3 is characterized in that, wherein said alkali is salt of wormwood, yellow soda ash, potassium hydroxide, sodium hydride or potassium hydride KH.
7, preparation method as claimed in claim 3 is characterized in that, wherein said solvent is a kind of in acetonitrile, dimethyl formamide or the tetrahydrofuran (THF), or their mixture.
8, the application of derivative according to claim 1 is characterized in that, described derivative can be used as the neotonin class insect growth regulator(IGR) that suppresses the insect growth.
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| CNB001163515A CN1177846C (en) | 2000-06-06 | 2000-06-06 | Oxa(thia)diazolylpyridazinone derivative and its preparing process and application |
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|---|---|---|---|
| CNB001163515A CN1177846C (en) | 2000-06-06 | 2000-06-06 | Oxa(thia)diazolylpyridazinone derivative and its preparing process and application |
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| CN1177846C true CN1177846C (en) | 2004-12-01 |
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| CN102532126B (en) * | 2012-02-10 | 2014-06-18 | 贵州大学 | 2-substituted-4-chloro-5-[5-subtsituted amino-2-(1,3,4-thiadiazole)-sulfydryl]-3(2H)- pyridazinone derivatives, and preparation method and application thereof |
| CN103980268B (en) * | 2014-04-29 | 2016-08-24 | 上海工程技术大学 | A kind of thiadiazole compound and synthetic method thereof |
| CN105924432B (en) * | 2016-07-13 | 2018-08-24 | 青岛农业大学 | Pyridazinone derivative and its preparation method and application |
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