CN102241676A - Tetrahydropyridone 1,3-diazacyclo cis-neonicotine compounds as well as preparation method and applications thereof - Google Patents
Tetrahydropyridone 1,3-diazacyclo cis-neonicotine compounds as well as preparation method and applications thereof Download PDFInfo
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Abstract
The invention belongs to a pesticide and discloses tetrahydropyridone 1,3-diazacyclo cis-neonicotine compounds shown in a general formula (I) as well as a preparation method and applications thereof. The preparation method comprises the following steps: using ethanol as solvent, and adding neonicotine compounds, aldehyde and Meldrum's acid; and adding piperidine used as a catalyst, and refluxing to react. In the method, a tetrahydropyridone structure is introduced in the neonicotine compounds for the first time. The tetrahydropyridone 1,3-diazacyclo cis-neonicotine compounds have the following advantages: the preparation process is simple, and the yield is high; the preparation process has no pollution; and the compounds have good insecticidal effects and are safe for human and livestock.
Description
Technical field
The invention belongs to agricultural chemical insecticide, relate to a class tetrahydropyridone and 1 particularly, 3-diazacyclo cis anabasine compound.
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 physics-chem characteristic such as water-soluble.Because it has the unique insecticidal mechanism and the performance of high-efficiency low-toxicity, becomes modern agriculture higher effective and lower toxic pesticide new variety rapidly.
Because the comparatively serious resistance problem that causes of the excessive frequent use of neonicotine sterilant and because the cross resistance between the neonicotine sterilant that structural similarity is brought, limit such application of compound, become the major issue of this compounds development of restriction.The present invention holds in the nitro cis-configuration enhancing light stability by tetrahydropyridone environmental protection of introducing on the neonicotine structure, increase conjugation with twin nuclei, reach the effect that improves drug effect in the hope of the interaction that can strengthen anabasine compound and nAChRs.
The present invention is that raw material has synthesized a series of tetrahydropyridones and 1 with Michaelis acid, aldehyde and anabasine compound first, 3-diazacyclo cis neonicotine analogue, and measured the efficient insecticide activity of this sterilant.
Summary of the invention
The purpose of this invention is to provide a kind of tetrahydropyridone and 1, the cis anabasine compound of 3-diazacyclo.
Second purpose of the present invention provides above-mentioned tetrahydropyridone and 1, the preparation method of the cis anabasine compound of 3-diazacyclo.
The 3rd purpose of the present invention provides above-mentioned tetrahydropyridone and 1, the application of the cis anabasine compound of 3-diazacyclo.
Purpose of the present invention is achieved through the following technical solutions.
A kind of tetrahydropyridone and 1,3-diazacyclo cis anabasine compound, represent with general formula (I):
Wherein: n=0 or 1;
R
2Be alkyl, cycloalkyl, aryl, benzyl or heterocyclic substituent, be preferably phenyl, chloro-phenyl-or p-methoxy-phenyl.
Above-mentioned tetrahydropyridone and 1, the preparation method of 3-diazacyclo cis anabasine compound may further comprise the steps: make solvent with ethanol, adding mol ratio is 1: (1～1.5): the aldehyde of the anabasine compound of the formula of (1～1.5) (II) structure, formula (III) structure and the Michaelis acid of formula (IV) structure; With the piperidines is catalyzer; 10～the 15h that refluxes under 78～80 ℃ of temperature makes general formula (I) tetrahydropyridone and 1,3-diazacyclo cis anabasine compound.
Preferably, the Michaelis of the aldehyde of the anabasine compound of formula (II) structure, formula (III) structure and formula (IV) structure acid mol ratio is 1: 1.5: 1.5; 78 ℃ of following backflow 12h.
Wherein: n=0 or 1;
R
2Be alkyl, cycloalkyl, aryl, benzyl or heterocyclic substituent, be preferably phenyl, chloro-phenyl-or p-methoxy-phenyl.
Reaction formula is:
The tetrahydropyridone with insecticidal activity and 1 with general formula (I) expression, the effective active components of 3-diazacyclo cis anabasine compound useful as pesticides is made emulsion, aqueous suspension and water emulsion pesticide, and carmine spider mite, planthopper, aphid and mythimna separata are had the efficient insecticide activity.
Main points of the present invention are:
The inventive method is utilized Michaelis acid good reaction activity, introduces the tetrahydropyridone structure first in anabasine compound.
The tetrahydropyridone with insecticidal activity and 1 with general formula (I) expression, 3-diazacyclo cis anabasine compound has good insecticidal activity, the effective active composition of useful as pesticides according to the prior art pesticide production technology, is made the various pesticide formulation; Example emulsion, aqueous suspension and aqueous emulsion etc.
The present invention is that raw material has synthesized a series of tetrahydropyridones and 1 with insecticidal activity with the anabasine compound of formula (II) structure, the aldehyde of formula (III) structure, the Michaelis acid of formula (IV) structure first, 3-diazacyclo cis anabasine compound, after measured, this compound has the efficient insecticide activity, has significant practicality in modern agriculture production.
Advantage of the present invention is:
1. preparation technology is simple, the productive rate height.
2. preparation process is pollution-free.
3. good disinsection effect is to the person poultry safety.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.The catalyzer that uses is piperidines, and catalyst consumption is 0.2～0.3mL.
Have the tetrahydropyridone and 1 of insecticidal activity, the embodiment of 3-diazacyclo cis anabasine compound is:
(Ia), cis-1-(6-chloro-3-picolyl)-7-phenyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] and pyridine-5-ketone;
(Ib), cis-1-(6-chloro-3-picolyl)-7-(4-chloro-phenyl-)-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] and pyridine-5-ketone;
(Ic), cis-1-(6-chloro-3-picolyl)-7-(3-chloro-phenyl-)-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] and pyridine-5-ketone;
(Id), cis-1-(6-chloro-3-picolyl)-7-(4-p-methoxy-phenyl)-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] and pyridine-5-ketone;
(Ie), cis-1-(2-chloro-5-thiazole methyl)-7-phenyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] and pyridine-5-ketone;
(If), cis-1-(2-chloro-5-thiazole methyl)-7-(4-chloro-phenyl-)-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] and pyridine-5-ketone;
Embodiment 1
Preparation cis-1-(6-chloro-3-picolyl)-7-phenyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] and pyridine-5-ketone;
The synthetic of raw material 2-chloro-5-(2-Nitromethylene-1-imidazolyl methyl)-pyridine synthesized according to literature method: (a) Zhong Li; Wenwen Zhang; Zewen Liu; J.Agric.Food.Chem.2010.58.6296-6299; (b) Xusheng Shao, Zhong Li, XuHong, Qian, and Xiaoyong Xu.J.Agric.Food.Chem.2009.57.951-957.
Concrete step is:
(1) synthetic N '-(6-chloro-3 picolyls)-1:
Get 16.1g (100mmol) 2-chloro-5-chloromethylpyridine and be dissolved in the 100ml acetonitrile, under the condition of ice bath, slowly be added drop-wise in the mixed solution of forming by 30.30g (500mmol) quadrol and 80ml acetonitrile, drip two and one-half-hours time.Continue to react stopped reaction after 8 hours, revolve to steam and remove the part acetonitrile.Add 100ml water in reaction solution, with dichloromethane extraction repeatedly, combining extraction liquid is used anhydrous sodium sulfate drying, obtains the 16.7g weak yellow liquid after the filtering and concentrating, productive rate 90%, content 91%.
GC-MS (m/s) 185 (5) M
+, 155 (49), 126 (100), 99 (9), 90 (12). and with literature value GC-MS (m/s) 185 (5) M
+, 155 (49), 126 (100), 99 (9), 90 (12) conform to.
(2) Synthetic 2-chloro-5-(2-Nitromethylene-1-imidazolyl methyl)-pyridine:
Get 16.5g (100mmol) 1, the N ' of 1-two thiomethyls-2-nitroethylene, 18.5g (100mmol)-(6-chloro-3 picolyls)-1, the ethanol of adding 100ml, temperature refluxed 4 hours for 80 ℃～90 ℃.Cooling, solid to be separated out, filtration, drying make 20.4g pale yellow powder shape solid, and productive rate is 81%, and content 92%, conforms to literature value 159-161 ℃ by fusing point 161-162 ℃.。
(3) cis-1-(6-chloro-3-picolyl)-7-phenyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] and pyridine-5-ketone synthetic
With 2-chloro-5-(2-Nitromethylene-1-imidazolyl methyl)-pyridine of 10mmol, the phenyl aldehyde of 15mmol, the Michaelis acid of 15mmol, the ethanol of 0.3mL piperidines and 30ml places the round-bottomed flask of 100ml, and 78 ℃ of reflux finish behind the reaction 12h.Revolve and desolvate, with ethyl acetate extraction 3 times, column chromatography again after the extraction with ethyl acetate and 1: 1 eluent of sherwood oil, obtains faint yellow solid, and productive rate is 76.1%.
Ultimate analysis: measured value C%60.70 H%5.55 N%13.55
Calculated value C%60.79 H%5.59 N%13.50
IR(KBr，cm
-1)v
max?2968，2357，1683，1648，1485，1413，1648，1557，1226，1097，889.
1H?NMR(CDCl
3，400MHz)δ8.27(s，1H，Pyridine)，7.49(dd，J＝2.5，8.3Hz，1H)，7.26-7.28(m，3H)，7.18(d，J＝8.2Hz，1H)，7.07-7.10(m，2H)，4.88(t，J＝4.3Hz，1H)，4.85(d，J＝3.9Hz，2H)，3.64-4.45(m，4H)，3.05(d，J＝4.5Hz，2H).
The product that present embodiment makes is made insecticide emulsion, converts water spray, to vegetable aphid killing rate 100%, has the efficient insecticide activity, the person poultry safety.
Embodiment 2
Preparation cis-1-(6-chloro-3-picolyl)-7-(4-chloro phenyl)-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] pyridine-5-ketone.
With the phenyl aldehyde among the 4-chlorobenzaldehyde replacement embodiment 1, all the other conditions are identical with embodiment 1, obtain yellow solid, productive rate 90.2%.
Ultimate analysis: measured value C%54.40 H%3.85 N%13.35
Calculated value C%54.43 H%3.85 N%13.36
IR(KBr，cm
-1)v
max?2978，2359，1685，1650，1481，1423，1418，1257，1226，1095，892.
1H?NMR(CDCl
3，400MHz)δ8.29(s，1H，Pyridine)，7.51(dd，J＝2.5，8.5Hz，1H)，7.22-7.28(m，2H)，7.22(d，J＝8.2Hz，1H)，7.07-7.13(m，2H)，4.89(t，J＝4.4Hz，1H)，4.95(d，J＝3.9Hz，2H)，3.64-4.46(m，4H)，3.12(d，J＝4.5Hz，2H).
The product that present embodiment makes is made aqueous suspension, converts water spray, and the red spider killing rate more than 95%, is had the efficient insecticide activity, the person poultry safety.
Embodiment 3
Preparation cis-1-(6-chloro-3-picolyl)-7-(3-chloro-phenyl-)-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] pyridine-5-ketone.
With the phenyl aldehyde among the m chlorobenzaldehyde replacement embodiment 1, all the other conditions are identical with embodiment 1, obtain yellow solid, productive rate 83.5%.
Ultimate analysis: measured value C%54.41 H%3.82 N%13.33
Calculated value C%54.43 H%3.85 N%13.36
IR(KBr，cm
-1)v
max?2998，2367，1783，1648，1485，1313，1248，1227，1216，1007，880.
1H?NMR(CDCl
3，400MHz)δ8.20(s，1H，Pyridine)，7.28-7.38(m，3H)，7.20(d，J＝8.2Hz，1H)，7.08-7.16(m，2H)，4.97(t，J＝4.3Hz，1H)，4.79(d，J＝3.9Hz，2H)，?3.72-4.45(m，4H)，3.10(d，J＝4.5Hz，2H).
The product that present embodiment makes is made the water and milk sterilant, converts water spray, and the rice flying lice killing rate more than 90%, is had the efficient insecticide activity, the person poultry safety.
Embodiment 4
Preparation cis-1-(6-chloro-3-picolyl)-7-(4-p-methoxy-phenyl)-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] pyridine-5-ketone.
With the phenyl aldehyde among the aubepine replacement embodiment 1, all the other conditions are identical with embodiment 1, obtain yellow solid, productive rate 70.2%.
Ultimate analysis: measured value C%57.92 H%4.61 N%13.55
Calculated value C%57.90 H%4.62 N%13.51
IR(KBr，cm
-1)v
max?2975，2867，2362，1697，1644，1595，1513，1508，1257，1226，1017，983.
1H?NMR(CDCl
3，400MHz)δ8.17(s，1H，Pyridine)，7.59(dd，J＝2.5，8.3Hz，1H)，7.26-7.30(m，2H)，7.09(d，J＝8.2Hz，1H)，7.00-7.04(m，2H)，4.65(t，J＝4.3Hz，1H)，4.45(d，J＝3.9Hz，2H)，3.64-4.40(m，4H)，3.59(s，3H)，3.05(d，J＝4.5Hz，2H).
The product that present embodiment makes is made the water and milk sterilant, converts water spray, and wheat mythimna separata killing rate more than 95%, is had the efficient insecticide activity, the person poultry safety.
Embodiment 5
Preparation cis-1-(2-chloro-5-thiazole methyl)-7-phenyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] and pyridine-5-ketone.
(1) Synthetic 2-chloro-5-(2-Nitromethylene-1-imidazolyl methyl)-thiazole.
Press embodiment 1 described method, replace 2-chloro-5-picoline to prepare 2-chloro-5-(2-Nitromethylene-1-imidazolyl methyl)-thiazole with 2-chloro-5-5-chloromethyl thiazole as starting raw material, productive rate 54%, content 90%, GCMS (m/s) 226 (24), 132 (100), 77 (9), with literature value GC MS (m/s) 226 (24), 132 (100), 77 (9) values conform to.
(2) synthesizing cis-1-(2-chloro-5-thiazole methyl)-7-phenyl-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] and pyridine-5-ketone.
With 2-chloro-5-(2-Nitromethylene-1-imidazolyl methyl)-thiazole of 10mmol, the phenyl aldehyde of 15mmol, the Michaelis acid of 15mmol, the ethanol of 0.3mL piperidines and 30ml places the round-bottomed flask of 100ml, 78 ℃ of reflux, behind the reaction 12h, reaction finishes.Revolve and desolvate, with ethyl acetate extraction 3 times, column chromatography again after the extraction with ethyl acetate and 1: 1 eluent of sherwood oil, obtains faint yellow solid, and productive rate is 71.3%.
Ultimate analysis: measured value C%54.23 H%5.02 N%13.35
Calculated value C%54.22 H%5.03 N%13.31
IR(KBr，cm
-1)v
max?3015，2987，2345，1683，1648，1485，1413，1408，1357，1226，1097，897.
1H?NMR(CDCl
3，400MHz)δ8.57(s，1H)，7.26-7.28(m，3H)，7.07-7.10(m，2H)，4.76(t，J＝4.3Hz，1H)，4.85(d，J＝3.9Hz，2H)，3.64-4.45(m，4H)，3.12(d，J＝4.5Hz，2H).
The product that present embodiment makes is made the water and milk sterilant, converts water spray, and wheat mythimna separata killing rate more than 96%, is had the efficient insecticide activity, the person poultry safety.
Embodiment 6
Cis-1-(2-chloro-5-thiazole methyl)-7-(4-chloro-phenyl-)-8-nitro-1,2,3,5,6,7-six hydrogen imidazoles [1,2-a] and pyridine-5-ketone;
With the phenyl aldehyde among the 4-chlorobenzaldehyde replacement embodiment 5, all the other conditions are identical with embodiment 5, obtain yellow solid, productive rate 84.0%.
Ultimate analysis: measured value C%48.03 H%3.30 N%13.75
Calculated value C%48.01 H%3.32 N%13.71
IR(KBr，cm
-1)v
max?3201，2997，2645，1693，1688，1495，1413，1365，1356，1228，1097，997.
1H?NMR(CDCl
3，400MHz)δ8.67(s，1H)，7.30-7.38(m，2H)，7.22-7.28(m，2H)，4.93(t，J＝4.3Hz，1H)，4.87(d，J＝3.9Hz，2H)，3.69-4.55(m，4H)，3.00(d，J＝4.5Hz，2H).
The product that present embodiment makes is made insecticide emulsion, converts water spray, and the rice flying lice killing rate more than 90%, is had the efficient insecticide activity, the person poultry safety.
The test of embodiment 7 insecticidal activities:
1. test target
Mythimna separata (Mythima separate), carmine spider mite (Tetranychus cinnabarnus), aphis craccivora (Aphis medicaginis), paddy rice brown paddy plant hopper (Nilaparvata legen)
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.
Test method
A. mythimna separata screening---soak the seedling feeding method:
Leaf of Semen Maydis is fully soaked into the back dry in the shade naturally in soup, put into culture dish, connect 3 mid-term in age larva, add a cover mark and be placed in the observation ward.Check result behind the 72h.
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 on the cotton again.Carry out mark and place observation ward, check result behind the 48h.
C. aphis craccivora screening---pickling process
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.
D. brown paddy plant hopper screening---spray method
Adopt the Potter spray method.(being about 3～4cm) is fixed in the culture dish of Ф 7cm with white quartz sand to be about to the rice seedling of 4～6 2 leaf 1 hearts, after paddy rice brown paddy plant hopper nymph in 3 mid-term in age is anaesthetized with CO2, every ware connects 30～40, place under the Potter spray tower quantitatively (2.5mL) spraying to handle that (pressure is 5Ib/iW2, sinkability is 4.35mg/cm2), the tween water that the organic solvent that contains maximum concentration is established in test is blank, the spraying back covers with the transparent plastics cup, place 27 ℃, the observation indoor cultivation of 14h illumination, 3d " Invest, Then Investigate " result.Touch polypide with writing brush, reactionlessly be considered as dead worm.
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 mythimna separata (Mythima separate), carmine spider mite (Tetranychus cinnabarnus), aphis craccivora (Aphis medicaginis), paddy rice brown paddy plant hopper (Nilaparvata legen), (Imidacloprid) does contrast with Provado, and activity data sees Table 1.
Table 1 embodiment compound (Ia-If) 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 (5)
1. a tetrahydropyridone and 1,3-diazacyclo cis anabasine compound, with general formula (I) expression:
Wherein: n=0 or 1;
R
2Be alkyl, cycloalkyl, aryl, benzyl or heterocyclic substituent, be preferably phenyl, chloro-phenyl-or p-methoxy-phenyl.
2. the described tetrahydropyridone of claim 1 and 1,3-diazacyclo cis anabasine compound is characterized in that described R
2Be phenyl, chloro-phenyl-or p-methoxy-phenyl.
3. claim 1 or 2 described tetrahydropyridones and 1, the preparation method of 3-diazacyclo cis anabasine compound, it is characterized in that, may further comprise the steps: be solvent with ethanol, add mol ratio and be anabasine compound, the aldehyde of formula (III) structure and the Michaelis acid of formula (IV) structure of 1: 1～1.5: 1～1.5 formula (II) structure; With the piperidines is catalyzer, and 10～15h refluxes under 78～80 ℃ of temperature;
Wherein: n=0 or 1;
R
2Be alkyl, cycloalkyl, aryl, benzyl or heterocyclic substituent.。
4. claim 1 or 2 described tetrahydropyridones and 1, the application of 3-diazacyclo cis anabasine compound aspect the preparation sterilant.
5. a sterilant is characterized in that, with claim 1 or 2 described tetrahydropyridones and 1,3-diazacyclo cis anabasine compound is an effective active components, and formulation is emulsion, aqueous suspension or aqueous emulsion.
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| CN109369618A (en) * | 2018-12-04 | 2019-02-22 | 上海生农生化制品股份有限公司 | Cook different foods in one pot and prepare the chloro- 5-((2-(Nitromethylene of 2-) imidazoline -1- base) methyl) and pyridine method |
| CN109369618B (en) * | 2018-12-04 | 2021-05-11 | 上海生农生化制品股份有限公司 | Method for preparing 2-chloro-5- ((2- (nitromethylene) imidazoline-1-yl) methyl) pyridine in one pot |
| CN111662282A (en) * | 2019-03-07 | 2020-09-15 | 湖南化工研究院有限公司 | Aza-and pyridine compounds and intermediates thereof |
| CN111662282B (en) * | 2019-03-07 | 2021-07-06 | 湖南化工研究院有限公司 | Aza-and pyridine compounds and intermediates thereof |
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Application publication date: 20111116 |