CN102225931A - 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 anabasine compound 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 medium characteristic such as water-soluble.Because it has the unique insecticidal mechanism and the performance of high-efficiency low-toxicity, become the higher effective and lower toxic pesticide new variety that modern agriculture needs rapidly.
Ti304 is that a class is efficient, the first-generation anabasine insecticide of wide spectrum, is one of last word of nicotinoids agricultural chemicals development so far.Because long-term and frequent use, more insect develops immunity to drugs to it, and in addition, its photo-labile and relatively poor hydrophobicity have also limited being extensive use of 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, first with amino acid, glycol, formaldehyde and Ti304 be raw material synthesized a series of contain amino acid ester have two of an insecticidal activity cis anabasine compound of tiring, and measured the efficient insecticide activity of this sterilant.
Institute of the present invention synthetic had both had the efficient insecticide activity, have again promote the crop growth function contain two of the amino acid ester cis anabasine insecticide of tiring, have good disinsection effect,, production technique simple, output high, cost low advantage low to the person poultry toxicity.
Summary of the invention
The purpose of this invention is to provide a class and contain two of the amino acid ester cis anabasine compound 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 provides 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 anabasine compound 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 anabasine compound of tiring, the preparation method is as follows:
(1) preparation 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 the glycol, below the controlled 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 anabasine compound 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. above-mentioned solution is put into microwave reactor, 65～70 ℃ of controlled 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 anabasine compound of tiring, can be made into emulsion, aqueous suspension and water emulsion pesticide sterilant, be used to kill crop pests.
Main points of the present invention are:
With amino acid is raw material, has 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: make the hydrochloride (II) of amino acid ester earlier, make and contain two of the amino acid ester cis anabasine compound (I) of tiring.
The present invention adopts novel microwave process for synthesizing to improve productive rate and has greatly shortened the reaction times; For example adopt heating reflux method to need 6 hours usually, 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 anabasine compound 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 is that raw material has synthesized series first and contains two of the amino acid ester cis anabasine compound of tiring with amino acid, 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, has 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 anabasine compound 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-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-diacetate glycol ester;
(Ib) 3,3 '-2,6-dihydro-4[N-(6-chloro-3-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-the dipropionic acid glycol ester;
(Ic) 4,4 '-2,6-dihydro-4[N-(6-chloro-3-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-two butyric acid glycol esters;
(Id) 2,2 '-2,6-dihydro-4[N-(6-chloro-3-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-the dipropionic acid glycol ester;
(Ie) 3,3 '-2,6-dihydro-4[N-(6-chloro-3-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-dipropionic acid-1, the ammediol ester;
(If) 4,4 '-2,6-dihydro-4[N-(6-chloro-3-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-two butyric acid-1, the ammediol ester.
Embodiment 1
Preparation (Ia) 2,2 '-2,6-dihydro-4[N-(6-chloro-3-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-diacetate glycol ester.
In 100mL three-necked bottle (being with dry alkali lye absorption unit), add 20mL ethylene glycol, cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under the magnetic agitation, the control rate of addition makes temperature of reaction be no more than-5 ℃, react and be warming up to room temperature naturally after 1 hour, obtain sulfur oxychloride-ethylene glycol solution.In sulfur oxychloride-ethylene glycol solution, add the 1.60g glycine, 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, promptly 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 the 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed microwave reactor, 5 minutes internal heating to 65 ℃, 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-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-the dipropionic acid glycol ester.
In 100mL three-necked bottle (being with dry alkali lye absorption unit), add 20mL ethylene glycol, cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under the magnetic agitation, the control rate of addition makes temperature of reaction be no more than-5 ℃, react and be warming up to room temperature naturally after 1 hour, obtain sulfur oxychloride-ethylene glycol solution.In sulfur oxychloride-ethylene glycol solution, add the 1.85g Beta-alanine, 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, promptly 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 the 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed microwave reactor, 5 minutes internal heating to 65 ℃, 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-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-two butyric acid glycol esters.
In 100mL three-necked bottle (being with dry alkali lye absorption unit), add 20mL ethylene glycol, cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under the magnetic agitation, the control rate of addition makes temperature of reaction be no more than-5 ℃, react and be warming up to room temperature naturally after 1 hour, obtain sulfur oxychloride-ethylene glycol solution.In sulfur oxychloride-ethylene glycol solution, add the 4.70g γ-An Jidingsuan, 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, promptly 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 the 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed microwave reactor, 5 minutes internal heating to 65 ℃, 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-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-the dipropionic acid glycol ester.
In 100mL three-necked bottle (being with dry alkali lye absorption unit), add 20mL ethylene glycol, cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under the magnetic agitation, the control rate of addition makes temperature of reaction be no more than-5 ℃, react and be warming up to room temperature naturally after 1 hour, obtain sulfur oxychloride-ethylene glycol solution.In sulfur oxychloride-ethylene glycol solution, add 1.85g L-α-Bing Ansuan, 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, promptly 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 the 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed microwave reactor, 5 minutes internal heating to 65 ℃, 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-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-dipropionic acid-1, the ammediol ester.
In 100mL three-necked bottle (being with dry alkali lye absorption unit), add 20mL1,3 propylene glycol, cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under the magnetic agitation, the control rate of addition makes temperature of reaction be no more than-5 ℃, react and be warming up to room temperature naturally 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, promptly 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 the 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed microwave reactor, 5 minutes internal heating to 65 ℃, 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-picolyl) ethylamino-3-methyl-5-nitro]-the 1-pyrimidyl }-two butyric acid-1, the ammediol ester.
In 100mL three-necked bottle (being with dry alkali lye absorption unit), add 20mL1,3 propylene glycol, cryosel is bathed and is cooled to-10 ℃～-15 ℃, drip the new sulfur oxychloride that steams of 3.60mL under the magnetic agitation, the control rate of addition makes temperature of reaction be no more than-5 ℃, react and be warming up to room temperature naturally after 1 hour, obtain sulfur oxychloride-1,3 propylene glycol solution.To sulfur oxychloride-1, add the 4.70g γ-An Jidingsuan 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, promptly 4,4 '-diamino-two butyric acid-1, ammediol ester hydrochloride (IIf), productive rate are 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 the 30mL ethanol together, the three-necked flask that mixed reaction solution is housed is placed microwave reactor, 5 minutes internal heating to 65 ℃, 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)。
The test of embodiment 7 insecticidal activities
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 by weighing 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 by weighing the preparation of certain mass, the adding distil water dilution is mixed with the soup of measuring desired concn.General sieve concentration is generally 500mg/L.
4. test method
A. aphis craccivora screening---soak the seedling feeding method:
If the broad bean blade is broken into the leaf dish, and the back side is placed on the fritter cotton up, places in the plastic culture dish, adds less water, connects aphis craccivora the aphid mixed population.Wait to try worm after stablizing on the blade, blade behind the abundant infiltration 10s, is placed on the cotton in soup again, dry naturally to be placed on and observe indoor feeding and observation.Check result behind the 48h.With 0.1% tween water is blank.
B. carmine spider mite screening---pickling process
The broad bean blade is cut off two ends, and the back side is placed on the fritter cotton up, places in the culture dish, adds less water, connects carmine spider mite and becomes 30～40 of mites on blade.Treat into mite stable after, blade is connected worm band leaf in soup, fully soaks into 5s, take out rapidly with thieving paper and inhale defoliation sheet surface water droplet, place again on the cotton, be treated to contrast with Provado.Carry out mark and place observation ward, check result behind the 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:
Target compound Ia～If is to the insecticidal activity of aphis craccivora (Myxus persicae) and carmine spider mite (Tetranychus cinnabarnus), and (Imidacloprid) does contrast with Provado, and activity data sees Table 1.
Table 1 embodiment compound (Ia-Ig) and Provado are to the inhibiting rate of mythimna separata and carmine spider mite
The foregoing description only is a 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 being done are all within protection scope of the present invention.
Claims (7)
1. one kind contains two of the amino acid ester cis anabasine compound of tiring, and it is characterized in that structural formula is shown in general formula (I):
Wherein, Z is selected from (CH
2)
2, (CH
2)
3, (CH
2)
4, (CH
2)
5, (C
H2
)6 or
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.
2. described the tire preparation method of cis anabasine compound 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 the glycol, below the controlled temperature-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, (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.
(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 anabasine compound 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 anabasine compound 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 anabasine compound 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 the cis anabasine compound in the application of preparation aspect the sterilant.
7. a sterilant is characterized in that, contains described two of the amino acid ester cis anabasine compound of tiring that contains of claim 1, is emulsion, aqueous suspension and water emulsion pesticide.
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| CN 201110104403 CN102225931B (en) | 2011-01-30 | 2011-04-15 | Amino acid ester-containing bivalent cis-neonicotinoid compound and its preparation method and application |
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| CN107778446A (en) * | 2017-10-18 | 2018-03-09 | 圆容生物医药无锡有限公司 | Degradation time is controllable, the adjustable medical degradable polyurethane of elongation at break |
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| CN101558758A (en) * | 2009-05-26 | 2009-10-21 | 上海师范大学 | L-alpha-amino acid ester contained Z-configuration anabasine pesticide and preparation method thereof |
| CN101792430A (en) * | 2010-03-02 | 2010-08-04 | 上海师范大学 | (Z) type tetrahydro-pyrimidine carboxylic ester derivative and preparation method thereof |
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2011
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| CN101558758A (en) * | 2009-05-26 | 2009-10-21 | 上海师范大学 | L-alpha-amino acid ester contained Z-configuration anabasine pesticide and preparation method thereof |
| CN101792430A (en) * | 2010-03-02 | 2010-08-04 | 上海师范大学 | (Z) type tetrahydro-pyrimidine carboxylic ester derivative and preparation method thereof |
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| CN107778446A (en) * | 2017-10-18 | 2018-03-09 | 圆容生物医药无锡有限公司 | Degradation time is controllable, the adjustable medical degradable polyurethane of elongation at break |
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