CN102067838A - Amide fragment-containing (Z) type nitenpyram analogue pesticide and preparation method thereof - Google Patents
Amide fragment-containing (Z) type nitenpyram analogue pesticide and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to pesticides, and discloses an amide fragment-containing (Z) type nitenpyram analogue pesticide and a preparation method thereof. The amide fragment-containing (Z) type nitenpyram analogue pesticide has the structure which is shown by a general formula (I). The preparation method of the pesticide comprises the following steps of: adding amino-containing amide, formaldehyde and nitenpyram into a three-neck flask; controlling the temperature to be 78 DEG C; and refluxing to react for 3 hours to prepare the amide fragment-containing (Z) type nitenpyram analogue pesticide which is shown by the general formula (I). The pesticide has the advantages of efficient pesticide activity, high pesticide effect, low toxicity, safety for human and animals, simple and convenient using method, simple preparation method and short reaction time, and can be easily prepared into various formulations such as missible oil, a suspending agent, wettable powder and the like. In the formula, n is equal to 1, 2, 3, 4, 5 or 6; and -R represents H, a C1 to C10 alkyl group, an aryl group or a substituted aromatic group, or a heterocyclic ring or a substituted heterocyclic ring which contains O, S, N and the like.
Description
Technical field
The invention belongs to insecticide, specifically class amide containing fragment (Z) type Nitenpyram analog insecticide and preparation method thereof.
Background technology
After having experienced organic phosphates, carbamates, pyrethroid insecticides, people researched and developed the 4th generation insecticide---anabasine insecticide.Because this insecticides has unique mechanism of action, it optionally works to the nervous system nAChR (nAChRs) of insect, not only has high-affinity, but also has shown good physicochemical characteristics.Anabasine insecticide and common insecticides do not have cross resistance, and absorption in efficient, wide spectrum and the good root is not only arranged, tag and stomach poison function, and also low to mammalian toxicity, environmentally safe.These features all meet the requirement of people to modern agricultural chemicals.But up to this point, still kind is few for anabasine insecticide; And complex manufacturing, yield poorly, the cost height, can't replace on a large scale before the long-term pesticide that uses.So invention good disinsection effect,, production technology simple, output high, cost low anabasine insecticide new varieties low to the person poultry toxicity are for the development of pesticide industry and promote that the agricultural progress is crucial.
Nitenpyram is a kind of nicotimine insecticides of exploitation after Imidacloprid, and nineteen ninety-five registered in Japan by the initiative exploitation of Japanese Wu Tian company in 1989, in China's protection that patents, is one of present up-to-date nicotinic insecticide subsequently.It has super-high-efficient, wide spectrum, consumption is few, toxicity is low, lasting medicine, crop is not had poisoning, advantage such as safe in utilization, is the new varieties of the malicious organophosphorous pesticide of a kind of alternative height of domestic new popularization in recent years.But its long-term use makes that specifically insect develops immunity to drugs to it, and in addition, its photo-labile and hydrophobicity in vivo are relatively poor and limit that it is widely-used.
Amides compound is that extremely agricultural chemicals circle is paid close attention to always, thereby improves biologically active because the formation of the peptide bond in acid amides bond energy and organism hydrogen bond is easily absorbed by organism.
The present invention introduces the photo-labile that the tetrahydropyrimidine ring improves Nitenpyram by Mannich reaction on the structure of Nitenpyram, and the introducing of amide segments has also solved the relatively poor problem of Nitenpyram hydrophobicity in vivo.
Summary of the invention
The purpose of this invention is to provide class amide containing fragment (Z) type Nitenpyram analog insecticide.
Second purpose of the present invention provides amide containing fragment (Z) type Nitenpyram analog method for producing insecticide.
The 3rd purpose of the present invention provides the insecticidal activity of (Z) type Nitenpyram analog insecticide of general formula (I) amide containing fragment.
The 4th purpose of the present invention provides the preparation type of (Z) type Nitenpyram analog insecticide of general formula (I) amide containing fragment.
The object of the present invention is achieved like this:
One class amide containing fragment (Z) type Nitenpyram analog insecticide, represent with general formula (I):
n＝1，2，3，4，5，6
-R=H contains C
1-C
10Alkyl, aryl and substituted aryl contain heterocycle and the substituted heterocycle of O, S, N etc.
One class amide containing fragment (Z) type Nitenpyram analog insecticide, the preparation method is:
(1) get ethylenediamine and add in the anhydrous ethanol solvent, stirring at normal temperature drips Ester, reaction 12h, and the centrifugation solvent makes intermediate (II);
(2) successively intermediate (II), absolute ethyl alcohol, Nitenpyram, formaldehyde are joined in the container, heating reflux reaction 3h makes (Z) type Nitenpyram analog insecticide of the amide containing fragment of general formula (I);
Reaction equation is: step 1:
Step 2:
n＝1，2，3，4，5，6
-R=H contains C
1-C
10Alkyl, aryl and substituted aryl contain heterocycle and the substituted heterocycle of O, S, N etc.
The ester class is in the step (1): a kind of in Ethyl formate, ethyl acetate, o-fluorobenzoic acid methyl esters, Methyl Salicylate, parachlorobenzoic-acid methyl esters, ethyl benzoate, ethyl hexanoate, the methylfuroate.
During described step (1) preparation intermediate (II), the mol ratio of ester and diamines is 1: 1.
During described step (2) preparation (I), the mol ratio of intermediate (II), Nitenpyram and formaldehyde is 1: 1: 2.
During described step (2) preparation (I), various raw materials are all dropped in the still, adopt the method preparation for the treatment of different things alike.
Amide containing fragment (Z) the type Nitenpyram analog insecticide of general formula (I) is a raw material, makes the agricultural chemicals of formulations such as missible oil, suspending agent, wetting powder.
Main points of the present invention are:
At first diamines and various ester are made intermediate list replacement amine (II).Then Nitenpyram, intermediate (II), formaldehyde and ethanol are dropped in the reactor, after 3 hours, column chromatography for separation obtains the end product of general formula for (I) 78 ℃ of left and right sides back flow reaction.What the present invention prepared is class series of products, and this series products can be made into the agricultural chemicals of formulations such as missible oil, suspending agent, wetting powder as pesticide material.Have wide spectrum, characteristics of high efficiency.
During preparation intermediate (II), temperature is a normal temperature, and solvent is an absolute ethyl alcohol; The mol ratio of ester and diamines is 1: 1,12 hours time.Solvent is an absolute ethyl alcohol during preparation (I); The mol ratio of intermediate (II), Nitenpyram and formaldehyde is 1: 1: 2; The method that employing is treated different things alike prepares general formula (I) product.
During preparation end product (I), according to the reactivity difference of ester, the mol ratio that also can regulate diamines and ester is 1: 1～1.3: 1.The sequencing that reactant feeds intake during reaction is all influential to the generation and the productive rate of accessory substance, after the parallel test relatively, selects various raw materials are all dropped in the still, and promptly adopting the reaction for the treatment of different things alike is preferred plan.
General formula (I) amide containing fragment (Z) the type Nitenpyram analog insecticide of the present invention's preparation can be made multiple formulation agricultural chemicals such as suspending agent, missible oil, wetting powder for the raw material of preparation agricultural chemicals.
General formula (I) amide containing fragment (Z) the type Nitenpyram analog insecticide of the present invention's preparation has the efficient insecticide activity to various crop insects such as mythimna separata, brown rice fulgorid, aphids, to the person poultry safety.
Advantage of the present invention is:
1, (Z) type Nitenpyram analog insecticide of amide containing fragment of the present invention can be made multiple formulation agricultural chemicals, and is easy to use, good disinsection effect, low, environmentally friendly to the person poultry toxicity.
2, preparation technology of the present invention is simple, production is easy.
3, product cost of the present invention cheap, be easy to large-scale popularization.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.
(Z) type Nitenpyram analog insecticide of amide containing fragment, represent with general formula (I):
n＝1，2，3，4，5，6
-R=H contains C
1-C
10Alkyl, aryl and substituted aryl contain heterocycle and the substituted heterocycle of O, S, N etc.
The example of (Z) type Nitenpyram analog insecticide of the amide containing fragment of the present invention's preparation is:
(Ia), (Z)-2H, 6H-3-methyl isophthalic acid-(2-formamido) ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine;
(Ib), (Z)-2H, 6H-3-methyl isophthalic acid-(2-acetamido) ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine;
(Ic), (Z)-2H, 6H-3-methyl isophthalic acid-[2-(2-fluorobenzoyl amido)] ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine;
(Id), (Z)-2H, 6H-3-methyl isophthalic acid-[2-(2-(2-hydroxybenzoyl) amido)] ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine;
(Ie), (Z)-2H, 6H-3-methyl isophthalic acid-[2-(4-chloro-benzoyl amino)] ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine;
(If), (Z)-2H, 6H-3-methyl isophthalic acid-(2-benzamide base) ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine;
(Ig), (Z)-2H, 6H-3-methyl isophthalic acid-(2-hexanoyl amido) ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine;
(Ih), (Z)-2H, 6H-3-methyl isophthalic acid-[2-(furans-2-formamido)] ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine.
Embodiment 1:
Preparation (Ia): (Z)-2H, 6H-3-methyl isophthalic acid-(2-formamido) ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine.
Get ethylenediamine 6.7mL (0.1mol), the absolute ethyl alcohol of 30mL is made solvent, under the stirring at normal temperature, to wherein dripping Ethyl formate 7.4g (0.1mol), reacts 12h, and after stopping to react, the centrifugation solvent obtains N-(2-amino-ethyl) formamide.
Successively N-(2-amino-ethyl) formamide 2.2g (0.025mol), absolute ethyl alcohol 30mL, Nitenpyram 6.75g (0.025mol) and formaldehyde 3mL (0.5mol) are added in the three-necked round bottom flask, be heated to 78 ℃, after the stirring and refluxing 3 hours, cross column chromatography, obtain faint yellow oily thing 4.15g, productive rate is 50.5%.
Elementary analysis: measured value C%50.20 H%6.06 N%21.95
Calculated value C%50.23 H%6.16 N%22.00
IR (KBr compressing tablet cm
-1): 3300,1670,1591,1546.
1HNMR(δ，ppm，CDCl
3)：8.311-8.305(d，J＝2.4Hz，1H，Py-H)，8.238(s，1H，HC＝O)，7.702-7.675(d×d，J
1＝2Hz，J
2＝8Hz，1H，Py-H)，7.349-7.329(d，J＝8Hz，1H，Py-H)，6.130(s，1H，N-H)，4.523-4.203(d，J＝14.8Hz，2H，Py-CH
2)，3.755-3.585(m，4H)，3.511-3.467(q，2H)，3.337-3.249(m，1H)，3.028(s，3H，NCH
3)，3.009-2.939(m，1H)，2.715-2.594(m，2H)，1.237-1.201(t，J＝7.2Hz，3H，CH
2CH
3)
The product that present embodiment makes is made the suspending agent disinfestation agent, to aphid killing rate 100%, has the efficient insecticide activity, to the person poultry safety.
Embodiment 2:
Preparation (Ib): (Z)-2H, 6H-3-methyl isophthalic acid-(2-acetamido) ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine.
Get ethylenediamine 6.7mL (0.1mol), the absolute ethyl alcohol of 30mL is made solvent, under the stirring at normal temperature, to wherein dripping ethyl acetate 8.8g (0.1mol), reacts 12h, and after stopping to react, the centrifugation solvent obtains N-(2-amino-ethyl) acetamide.
Successively N-(2-amino-ethyl) acetamide 2.55g (0.025mol), absolute ethyl alcohol 30mL, Nitenpyram 6.75g (0.025mol) and formaldehyde 3mL (0.5mol) are added in the three-necked round bottom flask, be heated to 78 ℃, after the stirring and refluxing 3 hours, cross column chromatography, obtain brown oil 6.01g, productive rate is 60.5%.
Elementary analysis: measured value C%51.45 H%6.35 N%21.18
Calculated value C%51.50 H%6.55 N%21.13
IR (KBr compressing tablet cm
-1): 3306,1680,1585,1550
1HNMR(δ，ppm，CDCl
3)：8.292-8.286(d，J＝2.4Hz，1H，Py-H)，7.685-7.659(d×d，J
1＝2.4Hz，J
2＝8Hz，1H，Py-H)，7.329-7.309(d，J＝8Hz，1H，Py-H)，5.984(s，1H，N-H)，4.502-4.188(d，J＝14.8Hz，2H，Py-CH
2)，3.708-3.557(m，4H)，3.426-3.381(q，2H)，3.297-3.226(m，1H)，3.007(s，3H，NCH
3)，2.974-2.902(m，1H)，2.628-2.561(m，2H)，2.012(s，3H，CH
3C＝O)，1.218-1.182(t，J＝7.2Hz，3H，CH
2CH
3)。
The product that present embodiment makes is made the suspending agent disinfestation agent, and the rice flying lice killing rate more than 100%, is had the efficient insecticide activity, to the person poultry safety.
Embodiment 3:
Preparation (Ic): (Z)-2H, 6H-3-methyl isophthalic acid-[2-(2-fluorobenzoyl amido)] ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine.
Get ethylenediamine 6.7mL (0.1mol), the absolute ethyl alcohol of 30mL is made solvent, under the stirring at normal temperature, to wherein dripping o-fluorobenzoic acid methyl esters 15.4g (0.1mol), reaction 12h is after stopping to react, the centrifugation solvent obtains N-(2-amino-ethyl)-2-fluoro-benzamide.
Successively N-(2-amino-ethyl)-2-fluoro-benzamide 4.55g (0.025mol), absolute ethyl alcohol 30mL, Nitenpyram 6.75g (0.025mol) and formaldehyde 3mL (0.5mol) are added in the three-necked round bottom flask, be heated to 78 ℃, after the stirring and refluxing 3 hours, cross column chromatography, obtain faint yellow oily thing 7.5g, productive rate is 63.0%.
Elementary analysis: measured value C%55.40 H%5.49 N%17.62
Calculated value C%55.48 H%5.50 N%17.63
IR (KBr compressing tablet cm
-1): 3295,1680,1590,1550,745.
1HNMR(δ，ppm，CDCl
3)：8.317-8.311(d，J＝2.4Hz，1H，Py-H)，8.118-8.074(m，1H，ph-H)，7.703-7.676(d×d，J
1＝2.4Hz，J
2＝8.4Hz，1H，Py-H)，7.524-7.467(m，1H，ph-H)，7.331-7.310(d，J＝8.4Hz，1H，Py-H)，7.284-7.263(m，1H，ph-H)，7.176-7.123(m，1H，ph-H)，5.970(s，1H，N-H)，4.531-4.179(d，J＝14.8Hz，2H，Py-CH
2)，3.742-3.649(m，6H)，3.307-3.254(m，1H)，3.014(s，3H，NCH
3)，2.991-2.938(m，1H)，2.797-2.749(m，2H)，1.223-1.189(t，J＝7.2Hz，3H，CH
2CH
3)。
The product that present embodiment makes is made, and the suspending agent disinfestation agent to rice flying lice killing rate 100%, has the efficient insecticide activity, fruit noresidue, people's edible safety.
Embodiment 4:
Preparation (Id): (Z)-2H, 6H-3-methyl isophthalic acid-[2-(2-(2-hydroxybenzoyl) amido)] ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine.
Get ethylenediamine 6.7mL (0.1mol), the absolute ethyl alcohol of 30mL is made solvent, under the stirring at normal temperature, to wherein dripping Methyl Salicylate 15.2g (0.1mol), reaction 12h is after stopping to react, the centrifugation solvent obtains N-(2-amino-ethyl)-2-hydroxyl-benzamide.
Successively N-(2-amino-ethyl)-2-hydroxyl-benzamide 4.5g (0.025mol), absolute ethyl alcohol 30mL, Nitenpyram 6.75g (0.025mol) and formaldehyde 3mL (0.5mol) are added in the three-necked round bottom flask, be heated to 78 ℃, after the stirring and refluxing 3 hours, cross column chromatography, obtain salmon pink grease 6.8g, productive rate is 57.3%.
Elementary analysis: measured value C%55.64 H%5.73 N%17.69
Calculated value C%55.60 H%5.80 N%17.66
IR (KBr compressing tablet cm
-1): 3220,1677,1582,1550,750.
1HNMR(δ，ppm，CDCl
3)：12.298(s，1H，OH)，8.268-8.281(d，J＝2Hz，1H，Py-H)，7.672-7.646(d×d，J
1＝2.4Hz，J
2＝8Hz，1H，Py-H)，7.542-7.522(d，J＝8Hz?1H，ph-H)，7.417-7.378(t，J＝3.2Hz，1H，ph-H)，7.312-7.291(d，J＝8.4Hz，1H，Py-H)，7.001-6.980(d，J＝8.4Hz，1H，ph-H)，6.884-6.846(t，J＝7.2Hz，1H，ph-H)，6.102(s，1H，N-H)，4.499-4.220(d，J＝14.8Hz，2H，Py-CH
2)，3.797-3.596(m，6H)，3.310-3.257(m，1H)，3.011(s，3H，NCH
3)，2.990-2.937(m，1H)，2.798-2.707(m，2H)，1.228-1.193(t，J＝7.2Hz，3H，CH
2CH
3)。
The product that present embodiment makes is made, and the suspending agent disinfestation agent to aphid killing rate 100%, has the efficient insecticide activity, to the person poultry safety.
Embodiment 5:
Preparation (Ie): (Z)-2H, 6H-3-methyl isophthalic acid-[2-(4-chloro-benzoyl amino)] ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine.
Get ethylenediamine 6.7mL (0.1mol), the absolute ethyl alcohol of 30mL is made solvent, under the stirring at normal temperature, to wherein dripping parachlorobenzoic-acid methyl esters 18.9g (0.1mol), reaction 12h is after stopping to react, the centrifugation solvent obtains N-(2-amino-ethyl)-4-chloro-benzamide.
Successively N-(2-amino-ethyl)-4-chloro-benzamide 5.0g (0.025mol), absolute ethyl alcohol 30mL, Nitenpyram 6.75g (0.025mol) and formaldehyde 3mL (0.5mol) are added in the three-necked round bottom flask, be heated to 78 ℃, after the stirring and refluxing 3 hours, cross column chromatography, obtain faint yellow oily thing 7.3g, productive rate is 59.2%.
Elementary analysis: measured value C%53.56 H%5.31 N%17.03
Calculated value C%53.60 H%5.50 N%17.00
IR (KBr compressing tablet cm
-1): 3290,1675,1599,1540,810.
1HNMR(δ，ppm，CDCl
3)：8.296-8.290(d，J＝2.4Hz，1H，Py-H)，7.788-7.767(d，J＝8.4Hz，2H，ph-H)，7.683-7.656(d×d，J
1＝2.4Hz，J
2＝8.4Hz，1H，Py-H)，7.445-7.423(d，J＝8.8Hz，2H，ph-H)，7.325-7.305(d，J＝8Hz，1H，Py-H)，6.792(s，1H，N-H)，4.508-4.207(d，J＝14.8Hz，2H，Py-CH
2)，3.805-3.582(m，6H)，3.327-3.239(m，1H)，3.014(s，3H，NCH
3)，2.991-2.956(m，1H)，2.765-2.708(m，2H)，1.232-1.197(t，J＝7.2Hz，3H，CH
2CH
3)。
Get present embodiment and make product, make suspending agent.To aphid killing rate 100%, has the efficient insecticide activity, to the person poultry safety.
Embodiment 6:
Preparation (If): (Z)-2H, 6H-3-methyl isophthalic acid-(2-benzamide base) ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine.
Get ethylenediamine 6.7mL (0.1mol), the absolute ethyl alcohol of 30mL is made solvent, under the stirring at normal temperature, to wherein dripping ethyl benzoate 15.0g (0.1mol), reacts 12h, and after stopping to react, the centrifugation solvent obtains N-(2-amino-ethyl) benzamide.
Successively N-(2-amino-ethyl) benzamide 4.1g (0.025mol), absolute ethyl alcohol 30mL, Nitenpyram 6.75g (0.025mol) and formaldehyde 3mL (0.5mol) are added in the three-necked round bottom flask, be heated to 78 ℃, after the stirring and refluxing 3 hours, cross column chromatography, obtain brownish black grease 6.8g, productive rate is 59.3%.
Elementary analysis: measured value C%57.58 H%5.93 N%18.31
Calculated value C%57.60 H%5.90 N%18.38
IR (KBr compressing tablet cm
-1): 3303,1665,1590,1544,720.
1HNMR(δ，ppm，CDCl
3)：8.296-8.290(d，J＝2.4Hz，1H，Py-H)，7.817-7.795(m，2H，ph-H)，7.684-7.657(d?×d，J
1＝2.4Hz，J
2＝8Hz，1H，Py-H)，7.559-7.493(m，1H，ph-H)，7.460-7.423(t，J＝7.6Hz，2H，ph-H)，7.304-7.284(d，J＝8Hz，1H，Py-H)，6.841(s，1H，N-H)，?4.506-4.181(d，J＝14.8Hz，2H，Py-CH
2)，3.799-3.610(m，6H)，3.306-3.210(m，1H)，3.010(s，3H，NCH
3)，2.984-2.931(m，1H)，2.787-2.721(m，2H)，1.212-1.177(t，J＝6.8Hz，3H，CH
2CH
3)。
The product that present embodiment makes is made the wettable insecticide, to aphid killing rate 100%, has the efficient insecticide activity.Noresidue, the person poultry safety.
Embodiment 7:
Preparation (Ig): (Z)-2H, 6H-3-methyl isophthalic acid-(2-hexanoyl amido) ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine.
Get ethylenediamine 6.7mL (0.1mol), the absolute ethyl alcohol of 30mL is made solvent, under the stirring at normal temperature, to wherein dripping ethyl hexanoate 14.4g (0.1mol), reacts 12h, and after stopping to react, the centrifugation solvent obtains N-(2-amino-ethyl) caproamide.
Successively N-(2-amino-ethyl) caproamide 3.95g (0.025mol), absolute ethyl alcohol 30mL, Nitenpyram 6.75g (0.025mol) and formaldehyde 3mL (0.5mol) are added in the three-necked round bottom flask, be heated to 78 ℃, after the stirring and refluxing 3 hours, cross column chromatography, obtain khaki grease 4.0g, productive rate is 35.3%.
Elementary analysis: measured value C%55.68 H%7.34 N%18.55
Calculated value C%55.70 H%7.38 N%18.50
IR (KBr compressing tablet cm
-1): 3290,1663,1585,1540.
1HNMR(δ，ppm，CDCl
3)：8.235-8.186(d×d，J
1＝2Hz，J
2＝17.2Hz，1H，Py-H)，7.667-7.617(m，1H，Py-H)，7.327-7.292(d×d，J
1＝6Hz，J
2＝8Hz，1H，Py-H)，7.178(s，1H，N-H)，4.483-4.257(m，4H)，3.957-3.286(m，8H)，3.132-3.097(m，1H)，3.074-3.037(d，J＝14.8Hz，3H，NCH
3)，3.029-2.976(m，1H)，2.730-2.613(m，2H)，2.201-2.176(m，2H)，1.482-1.446(t，J＝7.2Hz，3H，CH
2CH
2CH
3)，1.281-1.197(m，5H)。
The product that present embodiment makes is made the missible oil suspending agent, to mythimna separata killing rate 〉=90%, and the insecticidal activity height.
Embodiment 8:
Preparation (Ih): (Z)-2H, 6H-3-methyl isophthalic acid-[2-(furans-2-formamido)] ethyl-4-[N-ethyl-N-(6-chloro-3-pyridine) methyl] amino-5-nitro-pyrimidine.
Get ethylenediamine 6.7mL (0.1mol), the absolute ethyl alcohol of 30mL is made solvent, under the stirring at normal temperature, to wherein dripping methylfuroate 12.6g (0.1mol), reacts 12h, and after stopping to react, the centrifugation solvent obtains N-(2-amino-ethyl)-2-furoylamide.
Successively N-(2-amino-ethyl)-2-furoylamide 3.85g (0.025mol), absolute ethyl alcohol 30mL, Nitenpyram 6.75g (0.025mol) and formaldehyde 3mL (0.5mol) are added in the three-necked round bottom flask, be heated to 78 ℃, after the stirring and refluxing 3 hours, cross column chromatography, obtain yellow oil 5.2g, productive rate is 46.4%.
Elementary analysis: measured value C%53.51 H%5.61 N%18.72
Calculated value C%53.48 H%5.57 N%18.75
IR (KBr compressing tablet cm
-1): 3306,1650,1600,1540.
1HNMR(δ，ppm，CDCl
3)：8.309-8.303(d，J＝2.4Hz，1H，Py-H)，7.701-7.674(d×d，J
1＝2.4Hz，J
2＝8.4Hz，1H，Py-H)，7.476(s，1H，furan-H)，7.325-7.305(d，J＝8Hz，1H，Py-H)，7.129-7.120(d，J＝3.6Hz，1H，furan-H)，6.841(s，1H，N-H)，6.519-6.507(t，1H，furan-H)，4.515-4.217(d，J＝14.8Hz，2H，Py-CH
2)，3.750-3.591(m，6H)，3.309-3.221(m，1H)，3.007(s，3H，NCH
3)，2.983-2.948(m，1H)，2.787-2.659(m，2H)，1.214-1.179(t，J＝2.8Hz，3H，CH
2CH
3)。
The product that present embodiment makes is made cream pesticide, to mythimna separata killing rate 100%, has the efficient insecticide activity, noresidue, person poultry safety.
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 (8)
1. class amide containing fragment (Z) type Nitenpyram analog insecticide, with general formula (I) expression:
n＝1，2，3，4，5，6
-R=H contains C
1-C
10Alkyl, aryl and substituted aryl contain 0, heterocycle and the substituted heterocycle of S, N etc.
2. class amide containing fragment (Z) type Nitenpyram analog insecticide, the preparation method is:
(1) get ethylenediamine and add in the anhydrous ethanol solvent, stirring at normal temperature drips Ester, reaction 12h, and the centrifugation solvent makes intermediate (II);
(2) successively intermediate (II), absolute ethyl alcohol, Nitenpyram, formaldehyde are joined in the container, heating reflux reaction 3h makes (Z) type Nitenpyram analog insecticide of the amide containing fragment of general formula (I);
Reaction equation is: step 1:
Step 2:
n＝1，2，3，4，5，6
-R=H contains C
1-C
10Alkyl, aryl and substituted aryl contain 0, heterocycle and the substituted heterocycle of S, N etc.
3. amide containing fragment according to claim 2 (Z) type Nitenpyram analog insecticide preparation method is characterized in that: the ester class is in the step (1): a kind of in Ethyl formate, ethyl acetate, o-fluorobenzoic acid methyl esters, Methyl Salicylate, parachlorobenzoic-acid methyl esters, ethyl benzoate, ethyl hexanoate, the methylfuroate.
4. amide containing fragment according to claim 2 (Z) type Nitenpyram analog insecticide preparation method is characterized in that: during described step (1) preparation intermediate (II), the mol ratio of ester and diamines is 1: 1.
5. amide containing fragment according to claim 2 (Z) type Nitenpyram analog insecticide preparation method is characterized in that: during described step (2) preparation (I), the mol ratio of intermediate (II), Nitenpyram and formaldehyde is 1: 1: 2.
6. amide containing fragment according to claim 2 (Z) type Nitenpyram analog insecticide preparation method is characterized in that: during described step (2) preparation (I), various raw materials are all dropped in the still, adopt the method preparation for the treatment of different things alike.
7. amide containing fragment (Z) the type Nitenpyram analog insecticide of general formula (I) is a raw material, makes the agricultural chemicals of formulations such as aqueous suspension, emulsifiable concentrate and wetting powder.
8. the agricultural chemicals made of amide containing fragment (Z) type Nitenpyram analog insecticide is in the application of killing on grain, vegetables, the fruit tree crop insect.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102344446A (en) * | 2011-08-19 | 2012-02-08 | 上海师范大学 | Cis-nitenpyram analog containing carboxylic acid-substituted methyl ester and preparation method and application thereof |
| CN102838587A (en) * | 2012-07-12 | 2012-12-26 | 上海师范大学 | Peptide bond containing cis nitenpyram analogue, and preparation and application thereof |
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| CN102718755B (en) * | 2012-07-12 | 2014-06-25 | 上海师范大学 | Cis nitenpyram compound with amide flexible bond and preparation method and application thereof |
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| DE4401635A1 (en) * | 1994-01-21 | 1995-07-27 | Bayer Ag | Substituted 1,2,3,4-tetrahydro-5-nitro-pyrimidines |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344446A (en) * | 2011-08-19 | 2012-02-08 | 上海师范大学 | Cis-nitenpyram analog containing carboxylic acid-substituted methyl ester and preparation method and application thereof |
| CN102344446B (en) * | 2011-08-19 | 2014-04-09 | 上海师范大学 | Cis-nitenpyram analog containing carboxylic acid-substituted methyl ester and preparation method and application thereof |
| CN102838587A (en) * | 2012-07-12 | 2012-12-26 | 上海师范大学 | Peptide bond containing cis nitenpyram analogue, and preparation and application thereof |
| CN102838587B (en) * | 2012-07-12 | 2015-07-29 | 上海师范大学 | Containing cis-nitenpyram analogue and the Synthesis and applications thereof of peptide bond |
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