CN102225931B - Amino acid ester-containing bivalent cis-neonicotinoid compound and its preparation method and application - Google Patents
Amino acid ester-containing bivalent cis-neonicotinoid compound and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to the field of pesticides and relates to an amino acid ester-containing bivalent cis-neonicotinoid compound and its preparation method and application. Because the prior arts have the defects of optical instability and poor hydrophobicity, nicotinic pesticides can not be used widely. A structural general formula of the neonicotinoid compound is shown in the formula (I). The preparation method of the neonicotinoid compound comprises the following steps that thionyl chloride is added dropwisely into an ethanol solvent or a methanol solvent and a temperature of the mixed liquid is controlled below -5 DEG C; the mixture obtained from the previous step is heated to room temperature when the above adding process is finished; amino acid is added into the resulting products obtained from the previous step and excess ethanol is removed through a backflow and decompression process to obtain an amino-acid ester hydrochloride; and the amino-acid ester hydrochloride obtained from the previous step, nitenpyram, formaldehyde, triethylamine as an acid binding agent undergo a microwave reaction. The amino acid ester-containing bivalent cis-neonicotinoid compound has the advantages of high insecticidal activity, good insecticidal effects, low toxicity, no damage on human and animals, growth promoting effects on crops, simple and convenient use way, short reaction time and simple preparation method.
Description
Technical field
The invention belongs to agricultural chemical insecticide, specifically a class contains two of amino acid ester tire cis-neonicotine compounds and preparation method and as the application of sterilant.
Background technology
Anabasine insecticide be after organic phosphates, amino formate, pyrethroid insecticides the 4th generation sterilant.The anabasine material is as nAChR (nAChRs) agonist, neural system (nAChRs) to insect optionally works, it has not only shown high-affinity to (nAChRs), but also has shown unionized and the medium characteristic such as water-soluble.Because it has unique insecticidal mechanism and the performance of high-efficiency low-toxicity, become rapidly the higher effective and lower toxic pesticide new variety that modern agriculture needs.
Ti304 is that a class is efficient, the first-generation anabasine insecticide of wide spectrum, is one of last word of nicotinoids Agrochemicals so far.Due to long-term and use frequently, more insect develops immunity to drugs to it, and in addition, its photo-labile and relatively poor hydrophobicity have also limited being widely used of it.
The example of duster compound successful Application has appearred in prior art in the medical research field, but the report of also relevant cluster effect not being used in novel pesticide research both at home and abroad.The present invention is used for novel pesticide with cluster effect, synthesized take amino acid, glycol, formaldehyde and Ti304 as raw material first a series of contain amino acid ester have two of an insecticidal activity cis-neonicotine compounds of tiring, and it is active to have measured the efficient insecticide of this sterilant.
The present invention synthesized both has the efficient insecticide activity, have again promote the crop growth function contain two of the amino acid ester cis anabasine insecticide of tiring, have advantages of good disinsection effect, low to the person poultry toxicity, production technique is simple, output is high, cost is low.
Summary of the invention
The purpose of this invention is to provide a class and contain two of the amino acid ester cis-neonicotine compounds of tiring, good disinsection effect, low to the person poultry toxicity, production technique is simple, output is high, cost is low, can be used as sterilant.
Another object of the present invention is to provide this method for producing insecticide.
Purpose of the present invention is achieved through the following technical solutions.
One class contains two of the amino acid ester cis-neonicotine compounds of tiring, and general formula is (I):
Wherein, Z is selected from (CH
2)
2, (CH
2)
3, (CH
2)
4, (CH
2)
5, (CH
2)
6Or
During n=0, R
1Be H, CH
3, CH (CH
3) CH
2CH
3, CH
2CH (CH
3)
2, CH (CH
3)
2, CH
2CH
2SCH
3Or CH
2C
6H
5
N=1 or 2 o'clock, R
1Be H.
Contain two of the amino acid ester cis-neonicotine compounds of tiring, the preparation method is as follows:
(1) Preparation of amino acid ester hydrochloride, general formula (II):
Wherein, Z is selected from (CH
2)
2, (CH
2)
3, (CH
2)
4, (CH
2)
5, (CH
2)
6Or
During n=0, R
1Be H, CH
3, CH (CH
3) CH
2CH
3, CH
2CH (CH
3)
2, CH (CH
3)
2, CH
2CH
2SCH
3, CH
2C
6H
5
N=1 or 2 o'clock, R
1Be H.
Thionyl chloride is added drop-wise in glycol, controls below temperature-5 ℃; Dropwise, rise to room temperature; Add amino acid, heating, unnecessary alcohol is removed in decompression, obtains amino acid ester hydrochloride (II); Amino acid is preferably glycine, L-Ala or aminobutyric acid;
(2) the preparation general formula contains two of the amino acid ester cis-neonicotine compounds of tiring for (I):
A. amino acid ester hydrochloride (II) and Ti304, formaldehyde, the acid binding agent triethylamine with step (1) preparation mixes; Preferably, the mol ratio of amino acid ester hydrochloride (II), Ti304 is 1: 1.2～1: 1.5;
B. mentioned solution is put into microwave reactor, control 65～70 ℃ of temperature, microwave reaction 20～30 minutes makes general formula and is the cis that contains amino acid ester two of (I) anabasine compound of tiring.
The preparation feedback formula is: step (1):
Step (2):
Contain two of the amino acid ester cis-neonicotine compounds of tiring, can be made into emulsion, aqueous suspension and water emulsion pesticide sterilant, be used for killing crop pests.
Main points of the present invention are:
Take amino acid as raw material, both had the efficient insecticide activity with the anabasine insecticide Ti304 is synthetic, have again promote the crop growth function contain two of the amino acid ester cis anabasine insecticide of tiring.
The inventive method is divided into two steps: first make the hydrochloride (II) of amino acid ester, then make and contain two of the amino acid ester cis-neonicotine compounds (I) of tiring.
The present invention adopts novel microwave process for synthesizing to improve productive rate and greatly shortened the reaction times; For example adopt heating reflux method usually to need 6 hours, the present invention adopts microwave process for synthesizing only to need 25 minutes.
With general formula (I) expression contain two of the amino acid ester cis-neonicotine compounds of tiring, have good insecticidal activity, the effective active composition of useful as pesticides is made the various pesticide formulation.Example emulsion, aqueous suspension and aqueous emulsion etc.
The present invention has synthesized first series and has contained two of the amino acid ester cis-neonicotine compounds of tiring take amino acid as raw material, the effective active composition of useful as pesticides, make the various pesticide formulation such as emulsion, aqueous suspension and aqueous emulsion, kill various crop pests, have practicality widely.
Advantage of the present invention is:
1, have efficient insecticide activity, good disinsection effect.
2, toxicity is low, the person poultry safety.
3, promote crop growth.
4, using method is easy.
5, the preparation method is simple.
6, the reaction times is short.
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with specific embodiment.
The tire embodiment of cis-neonicotine compounds of two of amino acid ester that contains of the present invention preparation is:
(Ia) 2,2 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-diacetate glycol ester;
(Ib) 3,3 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-the dipropionic acid glycol ester;
(Ic) 4,4 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-two butyric acid glycol esters;
(Id) 2,2 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-the dipropionic acid glycol ester;
(Ie) 3,3 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-dipropionic acid-1,3-PD ester;
(If) 4,4 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-two butyric acid-1,3-PD ester.
Embodiment 1
Preparation (Ia) 2,2 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-diacetate glycol ester.
Add 20mL ethylene glycol in 100mL three-necked bottle (being with dry alkali liquor absorption device), cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under magnetic agitation, controlling rate of addition makes temperature of reaction be no more than-5 ℃, react and naturally be warming up to room temperature after 1 hour, obtain sulfur oxychloride-ethylene glycol solution.Add the 1.60g glycine in sulfur oxychloride-ethylene glycol solution, 80 ℃ were heated 12 hours, removal of solvent under reduced pressure and excessive sulfur oxychloride, obtain white solid, white solid gets white needle-like crystals with dehydrated alcohol-ether recrystallization, namely 2,2 '-diamino-diacetate glycol ester hydrochloride (IIa), productive rate is 96.54%.
With 2.707g Ti304,2.998g 2,2 '-diamino-diacetate glycol ester hydrochloride, 1.8mL triethylamine and 2.0mL concentration are that 37% formaldehyde solution is dissolved in 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed in microwave reactor, be heated to 65 ℃ in 5 minutes, and keep 65 ℃ of reactions after 20 minutes decompression steam solvent, add 10mL water dissolution and divide three extractions with the 60mL ethyl acetate.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains yellow oil.With ethyl acetate: ethanol=column chromatography got faint yellow oily thing in 6: 1, and productive rate is 74.23%.
Ultimate analysis: measured value C%50.18 H%5.55 N%18.32
Calculated value C%50.20 H%5.53 N%18.29
IR(KBr，cm
-1)v
max?2951，1744，1660，1410
1H?NMR(CDCl
3，400MHz)δ8.32(d，J＝2.4Hz，2H，Pyridine)，7.72(dd，J＝8.2，2.5Hz，2H，Pyridine)，7.34(d，J＝8.2Hz，2H，Pyridine)，4.53(d，J＝15.0Hz，2H，Pyridine-CH
2)，4.29(dd，J＝5.4，3.9Hz，4H，OCH
2CH
2O)，4.18(d，J＝15.0Hz，2H，Pyridine-CH
2)，3.84-3.75(m，8H)，3.48(s，4H)，3.27(dd，J＝14.1，7.1Hz，2H)，3.06(s，6H，NCH
3)，2.94(dd，J＝14.1，7.1Hz，2H)，1.19(t，J＝7.1Hz，6H，NCH
2CH
3)。
Embodiment 2
Preparation (Ib) 3,3 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-the dipropionic acid glycol ester.
Add 20mL ethylene glycol in 100mL three-necked bottle (being with dry alkali liquor absorption device), cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under magnetic agitation, controlling rate of addition makes temperature of reaction be no more than-5 ℃, react and naturally be warming up to room temperature after 1 hour, obtain sulfur oxychloride-ethylene glycol solution.Add the 1.85g Beta-alanine in sulfur oxychloride-ethylene glycol solution, 80 ℃ were heated 12 hours, removal of solvent under reduced pressure and excessive sulfur oxychloride, obtain white solid, white solid gets white needle-like crystals with dehydrated alcohol-ether recrystallization, namely 3,3 '-diamino-dipropionic acid glycol ester hydrochloride (IIb), productive rate is 98.50%.
With 2.707g Ti304,3.324g 3,3 '-diamino-dipropionic acid glycol ester hydrochloride, 1.8mL triethylamine and 2.0mL concentration are that 37% formaldehyde solution is dissolved in 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed in microwave reactor, be heated to 65 ℃ in 5 minutes, and keep 65 ℃ of reactions after 20 minutes decompression steam solvent, add 10mL water dissolution and divide three extractions with the 60mL ethyl acetate.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains yellow oil.With ethyl acetate: ethanol=column chromatography got faint yellow oily thing in 6: 1, and productive rate is 79.45%.
Ultimate analysis: measured value C%51.48 H%5.80 N%17.68
Calculated value C%51.45 H%5.84 N%17.65
IR(KBr，cm
-1)v
max?2955，1746，1671，1414
1H?NMR(CDCl
3，400MHz)δ8.29(d，J＝2.5Hz，2H，Pyridine)，7.68(dd，J＝8.2，2.4Hz，2H，Pyridine)，7.32(d，J＝8.2Hz，2H，Pyridine)，4.50(d，J＝15.0Hz，2H，Pyridine-CH
2)，4.39-4.33(m，4H，OCH
2CH
2O)，4.17(d，J＝15.0Hz，2H，Pyridine-CH
2)，3.67-3.57(m，8H)，3.25(dd，J＝14.0，7.1Hz，2H)，2.97(s，6H，NCH
3)，2.93(dd，J＝14.1，7.1Hz，2H)，2.83(m，J＝11.9，5.8Hz，4H)，2.60(t，J＝6.7Hz，4H)，1.17(t，J＝7.1Hz，6H，NCH
2CH
3)。
Embodiment 3
Preparation (Ic) 4,4 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-two butyric acid glycol esters.
Add 20mL ethylene glycol in 100mL three-necked bottle (being with dry alkali liquor absorption device), cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under magnetic agitation, controlling rate of addition makes temperature of reaction be no more than-5 ℃, react and naturally be warming up to room temperature after 1 hour, obtain sulfur oxychloride-ethylene glycol solution.Add the 4.70g γ-aminobutyric acid in sulfur oxychloride-ethylene glycol solution, 80 ℃ were heated 12 hours, removal of solvent under reduced pressure and excessive sulfur oxychloride, obtain white solid, white solid gets white needle-like crystals with dehydrated alcohol-ether recrystallization, namely 4,4 '-diamino-two butyric acid glycol ester hydrochloride (IIc), productive rate are 98.35%.
With 2.707g Ti304,3.66g 4,4 '-diamino-two butyric acid glycol ester hydrochloride, 1.8mL triethylamine and 2.0mL concentration are that 37% formaldehyde solution is dissolved in 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed in microwave reactor, be heated to 65 ℃ in 5 minutes, and keep 65 ℃ of reactions after 20 minutes decompression steam solvent, add 10mL water dissolution and divide three extractions with the 60mL ethyl acetate.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains yellow oil.With ethyl acetate: ethanol=column chromatography got faint yellow oily thing in 6: 1, and productive rate is 80.23%.
Ultimate analysis: measured value C%52.60 H%6.15 N%17.03
Calculated value C%52.62 H%6.13 N%17.04
IR(KBr，cm
-1)v
max?2956，1748，1675，1418
1H?NMR(CDCl
3，400MHz)δ8.31(d，J＝2.4Hz，2H，Pyridine)，7.70(dd，J＝8.2，2.5Hz，2H，Pyridine)，7.33(d，J＝8.2Hz，2H，Pyridine)，4.51(d，J＝14.9Hz，2H，Pyridine-CH
2)，4.35(dd，J＝6.1，5.1Hz，4H，OCH
2CH
2O)，4.19(d，J＝15.0Hz，2H，Pyridine-CH
2)，3.68-3.55(m，8H)，3.27(dd，J＝14.1，7.1Hz，2H)，3.00(s，6H，NCH
3)，2.95(dd，J＝14.1，7.1Hz，2H)，2.54(dd，J＝13.6，6.4Hz，4H)，2.48(t，J＝7.2Hz，4H)，1.89(m，J＝7.1Hz，4H)，1.20(t，J＝7.1Hz，6H，NCH
2CH
3)。
Embodiment 4
Preparation (Id) 2,2 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-the dipropionic acid glycol ester.
Add 20mL ethylene glycol in 100mL three-necked bottle (being with dry alkali liquor absorption device), cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under magnetic agitation, controlling rate of addition makes temperature of reaction be no more than-5 ℃, react and naturally be warming up to room temperature after 1 hour, obtain sulfur oxychloride-ethylene glycol solution.Add 1.85g L-α-alanine in sulfur oxychloride-ethylene glycol solution, 80 ℃ were heated 12 hours, removal of solvent under reduced pressure and excessive sulfur oxychloride, obtain white solid, white solid gets white needle-like crystals with dehydrated alcohol-ether recrystallization, namely 2,2 '-diamino-dipropionic acid glycol ester hydrochloride (IId), productive rate is 95.60%.
With 2.707g Ti304,3.66g 2,2 '-diamino-dipropionic acid glycol ester hydrochloride, 1.8mL triethylamine and 2.0mL concentration are that 37% formaldehyde solution is dissolved in 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed in microwave reactor, be heated to 65 ℃ in 5 minutes, and keep 65 ℃ of reactions after 20 minutes decompression steam solvent, add 10mL water dissolution and divide three extractions with the 60mL ethyl acetate.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains yellow oil.With ethyl acetate: ethanol=column chromatography got faint yellow oily thing in 6: 1, and productive rate is 78.46%.
Ultimate analysis: measured value C%51.43 H%5.82 N%17.68
Calculated value C%51.45 H%5.84 N%17.65
IR(KBr，cm
-1)v
max?2953，1745，1668，1415
1H?NMR(CDCl
3，400MHz)δ8.31(d，J＝2.5Hz，2H，Pyridine)，7.73(dd，J＝8.2Hz，2H，Pyridine)，7.33(d，J＝8.2Hz，2H，Pyridine)，4.62-4.47(m，2H，Pyridine-CH
2)，4.28(m，4H，OCH
2CH
2O)，4.19(dd，J＝21.2，6.1Hz，2H，Pyridine-CH
2)，3.84-3.68(m，8H)，3.63(m，2H)，3.26(m，2H)，2.98(d，J＝5.8Hz，6H，NCH
3)，2.96-2.85(m，2H)，1.43(dd，J＝7.1，3.5Hz，6H，CHCH
3)，1.22-1.11(m，6H，NCH
2CH
3)。
Embodiment 5
Preparation (Ie) 3,3 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-dipropionic acid-1,3-PD ester.
Add 20mL1 in 100mL three-necked bottle (being with dry alkali liquor absorption device), 3 propylene glycol, cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under magnetic agitation, controlling rate of addition makes temperature of reaction be no more than-5 ℃, react and naturally be warming up to room temperature after 1 hour, obtain sulfur oxychloride-1,3 propylene glycol solution.To sulfur oxychloride-1, add the 1.85g Beta-alanine in 3 propylene glycol solutions, 80 ℃ were heated 12 hours, removal of solvent under reduced pressure and excessive sulfur oxychloride obtain white solid, and white solid gets white needle-like crystals with dehydrated alcohol-ether recrystallization, namely 3,3 '-diamino-dipropionic acid-1,3 butylene glycol ester hydrochloride (IIe), productive rate is 95.89%.
With 2.707g Ti304,3.492g3,3 '-diamino-dipropionic acid-1, ammediol ester hydrochloride, 1.8mL triethylamine and 2.0mL concentration are that 37% formaldehyde solution is dissolved in 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed in microwave reactor, be heated to 65 ℃ in 5 minutes, and keep 65 ℃ of reactions after 20 minutes decompression steam solvent, add 10mL water dissolution and divide three extractions with the 60mL ethyl acetate.Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains yellow oil.With ethyl acetate: ethanol=column chromatography got faint yellow oily thing in 6: 1, and productive rate is 77.76%.
Ultimate analysis: measured value C%52.08 H%5.96 N%17.29
Calculated value C%52.04 H%5.99 N%17.34
IR(KBr，cm
-1)v
max?2955，1749，1678，1419
1H?NMR(CDCl
3，400MHz)δ8.30(d，J＝2.3Hz，2H，Pyridine)，7.70(dd，J＝8.2，2.5Hz，2H，Pyridine)，7.32(d，J＝8.1Hz，2H，Pyridine)，4.49(d，J＝15.0Hz，2H，Pyridine-CH
2)，4.32(dd，J＝11.7，5.6Hz，2H，OCH
2)，4.29-4.22(m，2H，OCH
2)，4.19(d，J＝14.8Hz，2H，Pyridine-CH
2)，3.66-3.60(m，8H)，3.27(dd，J＝14.1，7.1Hz，2H)，2.97(s，6H，NCH
3)，2.96-2.89(m，2H)，2.82(m，4H，NCH
2)，2.57(t，J＝6.7Hz，4H，CH
2CO)，1.91-1.87(m，2H)，1.19(t，J＝7.1Hz，6H，NCH
2CH
3)。
Embodiment 6
Preparation (If) 4,4 '-2,6-dihydro-4[N-(6-chloro-3-pyridylmethyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-two butyric acid-1,3-PD ester.
Add 20mL1 in 100mL three-necked bottle (being with dry alkali liquor absorption device), 3 propylene glycol, cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under magnetic agitation, controlling rate of addition makes temperature of reaction be no more than-5 ℃, react and naturally be warming up to room temperature after 1 hour, obtain sulfur oxychloride-1,3 propylene glycol solution.To sulfur oxychloride-1, add the 4.70g γ-aminobutyric acid in 3 propylene glycol solutions, 80 ℃ were heated 12 hours, removal of solvent under reduced pressure and excessive sulfur oxychloride obtain white solid, and white solid gets white needle-like crystals with dehydrated alcohol-ether recrystallization, namely 4,4 '-diamino-two butyric acid-1,3-PD ester hydrochloride (IIf), productive rate is 96.10%.
With 2.707g Ti304,3.828g 4,4 '-diamino-two butyric acid-1, ammediol ester hydrochloride, 1.8mL triethylamine and 2.0mL concentration are that 37% formaldehyde solution is dissolved in 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed in microwave reactor, be heated to 65 ℃ in 5 minutes, and keep 65 ℃ of reactions after 20 minutes decompression steam solvent, add 10mL water dissolution and divide three extractions with the 60mL ethyl acetate.
Combining extraction liquid spends the night with anhydrous magnesium sulfate drying, steams solvent, obtains yellow oil.With ethyl acetate: ethanol=column chromatography got faint yellow oily thing in 6: 1, and productive rate is 78.17%.
Ultimate analysis: measured value C%53.15 H%6.30 N%16.78
Calculated value C%53.17 H%6.27 N%16.76
IR(KBr，cm
-1)v
max?2958，1751，1680，1417
1H?NMR(CDCl
3，400MHz)δ8.30(d，J＝2.2Hz，2H，Pyridine)，7.69(dd，J＝8.2，2.5Hz，2H，Pyridine)，7.32(d，J＝8.2Hz，2H，Pyridine)，4.49(d，J＝15.0Hz，2H，Pyridine-CH
2)，4.23(d，J＝6.0Hz，2H，Pyridine-CH
2)，4.19(dd，J＝16.3，3.9Hz，4H，OCH
2)，3.67-3.53(m，8H)，3.25(dd，J＝14.1，7.1Hz，2H)，3.00(s，6H，NCH
3)，2.94(dd，J＝14.1，7.1Hz，2H)，2.56-2.44(m，4H，NCH
2)，2.40(t，J＝7.1Hz，4H，CH
2CO)，1.89-1.83(m，6H)，1.18(t，J＝7.1Hz，6H，NCH
2CH
3)。
Embodiment 7 insecticidal activity tests
1. test target
Black peach aphid (Myxus persicae), carmine spider mite (Tetranychus cinnabarnus).
2. plant and instrument
Culture dish, electronic analytical balance, Potter spray tower, liquid-transfering gun, writing brush etc.
3. chemicals treatment
Take the medicament of a certain amount of target compound with analytical balance (0.0001g), add the solvent that contains 0.1% tween-80, be mixed with 1～5% preparation.Take the preparation of certain mass, the adding distil water dilution is mixed with the liquid of measuring desired concn.General sieve concentration is generally 500mg/L.
4. test method
A. aphis craccivora screening---soak the seedling feeding method:
Broad Bean Leaves is broken into the leaf dish, and the back side is placed on the fritter cotton up, is placed in plastic culture dish, adds a small amount of water, if connect aphis craccivora aphid mixed population.Wait trying worm after stablizing on blade, blade is fully infiltrated 10s in liquid after, again be placed on cotton, naturally dry to be placed on and observe indoor feeding and observation.Check result after 48h.Take 0.1% tween water as blank.
B. carmine spider mite screening---pickling process
Broad Bean Leaves is cut off two ends, and the back side is placed on the fritter cotton up, is placed in culture dish, adds a small amount of water, connects carmine spider mite and becomes 30～40 of mites on blade.After becoming mite stable, blade is connected worm band leaf fully infiltrate 5s in liquid, take out rapidly and suck the blade surface water droplet with thieving paper, again be placed on cotton, be treated to contrast with Provado.Carry out mark and be placed in observation ward, check result after 48h.
Test statistics and advance the sieve standard:
Add up the dead borer population of each processing and the borer population of living, the calculating mortality ratio (Abbott ' the s formula).
Embodiment Compound I a～If desinsection test result:
The insecticidal activity of target compound Ia～If to aphis craccivora (Myxus persicae) and carmine spider mite (Tetranychus cinnabarnus), (Imidacloprid) does contrast with Provado, and activity data sees Table 1.
Table 1 embodiment compound (Ia-Ig) and the Provado inhibiting rate to mythimna separata and carmine spider mite
Above-described embodiment is only preference of the present invention, is not used for limiting the present invention, and all within principle of the present invention, any modifications and variations of doing are all within protection scope of the present invention.
Claims (7)
1. one kind contains two of the amino acid ester cis-neonicotine compounds of tiring, and it is characterized in that, structural formula is as shown in general formula (I):
Wherein, Z is selected from (CH
2)
2Or (CH
2)
3
During n=0, R
1Be H or CH
3
N=1 or 2 o'clock, R
1Be H.
2. described the tire preparation method of cis-neonicotine compounds of two of amino acid ester that contains of claim 1, is characterized in that, comprises the steps:
(1) thionyl chloride is added drop-wise in glycol, controls Wen Du – below 5 ℃; Dropwise, rise to room temperature; Add amino acid, heating, unnecessary alcohol is removed in decompression, the amino acid ester hydrochloride of (II) structure that obtains having general formula;
Wherein, Z is selected from (CH
2)
2, (CH
2)
3
During n=0, R
1Be H or CH
3
N=1 or 2 o'clock, R
1Be H;
(2) amino acid ester hydrochloride and Ti304, formaldehyde, acid binding agent triethylamine are mixed, microwave reaction is 20～30 minutes under 60～70 ℃ of conditions.
3. described the tire preparation method of cis-neonicotine compounds of two of amino acid ester that contains of claim 2, is characterized in that, the mol ratio of amino acid ester hydrochloride, Ti304 and formaldehyde is 1:1.2～1:1.5.
4. described the tire preparation method of cis-neonicotine compounds of two of amino acid ester that contains of claim 2, is characterized in that, the temperature of described microwave reaction is 65～70 ℃, and the time is 20～30 minutes.
5. described the tire preparation method of cis-neonicotine compounds of two of amino acid ester that contains of claim 4, is characterized in that, described amino acid is selected from glycine, L-Ala or aminobutyric acid.
6. described two of the amino acid ester that contains of claim 1 is tired cis-neonicotine compounds in the application of preparation aspect sterilant.
7. a sterilant, is characterized in that, contains described two of the amino acid ester cis-neonicotine compounds of tiring that contains of claim 1, is emulsion or aqueous suspension agricultural chemicals.
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Non-Patent Citations (4)
| Title |
|---|
| 利用簇合效应发现和创制高效新农药的设想;梅向东 等;《农药学学报》;20061231;第8卷(第3期);203-208 * |
| 新烟碱类簇合物的合成及其生物活性;杨国权 等;《农药学学报》;20081231;第10卷(第3期);367-370 * |
| 杨国权 等.新烟碱类簇合物的合成及其生物活性.《农药学学报》.2008,第10卷(第3期),367-370. |
| 梅向东 等.利用簇合效应发现和创制高效新农药的设想.《农药学学报》.2006,第8卷(第3期),203-208. |
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