CN102070613A - Analogue of (Z) type bivalent nitenpyram and preparation method thereof - Google Patents
Analogue of (Z) type bivalent nitenpyram and preparation method thereof Download PDFInfo
- Publication number
- CN102070613A CN102070613A CN2010106083029A CN201010608302A CN102070613A CN 102070613 A CN102070613 A CN 102070613A CN 2010106083029 A CN2010106083029 A CN 2010106083029A CN 201010608302 A CN201010608302 A CN 201010608302A CN 102070613 A CN102070613 A CN 102070613A
- Authority
- CN
- China
- Prior art keywords
- analogue
- type
- nitenpyram
- preparation
- pyridine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 CCN(Cc(cc1)cnc1Cl)C(N(C)CN(*N(C1)CN(C)C(N(CC)Cc(cc2)cnc2Cl)=C1[N+]([O-])=O)C1)=C1[N+]([O-])=O Chemical compound CCN(Cc(cc1)cnc1Cl)C(N(C)CN(*N(C1)CN(C)C(N(CC)Cc(cc2)cnc2Cl)=C1[N+]([O-])=O)C1)=C1[N+]([O-])=O 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an analogue of a (Z) type bivalent neonicotinoid insecticide, namely nitenpyram and a preparation method thereof. The analogue of the (Z) type bivalent nitenpyram has a structure shown as a general formula (I). The method for preparing the analogue of the (Z) type bivalent nitenpyram comprises the steps of: adding aliphatic diamine, 37 percent formaldehyde and the nitenpyram into a three-neck flask, controlling the temperature to be 45 DEG C or so, and stirring the mixture for 2h to obtain the analogue of the (Z) type bivalent nitenpyram shown as the general formula (I). The analogue has the advantages of efficient insecticidal activity, good insecticidal effect, low toxicity, no harm to people and livestock, promotion of crop growth, simple and convenient using method, and simple preparation method.
Description
Technical field
The invention belongs to agricultural chemical insecticide, specifically two of a class (Z) the formula configuration analogues of neonicotine sterilant Ti304 and preparation method thereof of tiring.
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, become the higher effective and lower toxic pesticide new variety that modern agriculture needs rapidly.
Ti304 is a kind of first-generation anabasine insecticide of efficient, 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.
Have in recent years and morely significantly improve the bioactive report of compound by the multiple-effect valence effect about medicine.Reports such as Kagabu are linker synthetic Provado two compound of tiring with the methylene radical of different chain length, thiazolinyl, alkynyl etc., show biological activity preferably.And two compounds of tiring of Ti304 do not have report.Institute of the present invention synthetic new compound has 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 two of a class (Z) the type analogue of Ti304 and preparation method thereof of tiring.
Purpose of the present invention can be achieved through the following technical solutions.
The tire analogue of Ti304 of above-mentioned (Z) type two, available general formula (I) expression:
Wherein:
With the tire analogue of anabasine insecticide Ti304 of (Z) type two of general formula (I) expression, the preparation method is as follows: Ti304,37% formaldehyde, aliphatic diamine are dropped in the three-necked flask, and solvent is a dehydrated alcohol; The mol ratio of Ti304, formaldehyde and aliphatic diamine 2: 4.6～5.0: 1.2～1.5; 45 ℃ of temperature, reaction 2h makes general formula and is the tire analogue of anabasine insecticide Ti304 of (Z) type two of (I).
Can be made into emulsion, aqueous suspension and water emulsion pesticide in order to (Z) type two of general formula (I) expression Ti304 analogue of tiring.Red spider, planthopper, aphid and mythimna separata all had higher inhibition activity.
The reaction formula of above-mentioned preparation process is:
Wherein:
In the described reaction, solvent is an ethanolic soln; The mol ratio of Ti304 and formaldehyde is 1: 2.3～1: 2.5; The mol ratio of Ti304 and aliphatic diamine is 2: 1.2～2: 1.5.
In the described reaction, adopt various raw materials are put into the method preparation that the reaction vessel three-necked flask is treated different things alike.
The analogue that the present invention (Z) type two is tired Ti304 is that a class has identical (Z) word configuration and the different Ti304 class material of molecular formula.
Advantage of the present invention is:
1, has efficient insecticide activity, good disinsection effect.
2, toxicity is low, the person poultry safety.
3, the preparation method is simple.
4, cost of the present invention cheap, be convenient to large-scale popularization.
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with specific embodiment.
One class has the tire analogue of Ti304 of efficient insecticide active (Z) type two, with general formula (I) expression:
In the formula,
The tire embodiment of analogue of Ti304 of (Z) type two of the present invention preparation is:
(Ia) 1,2 pair-[(4Z)-(and 2H, 6H)-3-methyl-4-(N-ethyl-N-6-chloro-3-picolyl) amino-5-nitro-1-pyrimidyl] ethane;
(Ib) 1,2-pair-[(4Z)-(and 2H, 6H)-3-methyl-4-(N-ethyl-N-6-chloro-3-picolyl) amino-5-nitro-1-pyrimidyl] propane;
(Ic) 1,3-pair-[(4Z)-(and 2H, 6H)-3-methyl-4-(N-ethyl-N-6-chloro-3-picolyl) amino-5-nitro-1-pyrimidyl] propane;
(Id) 1,4-pair-[(4Z)-and 2H, 6H-3-methyl-4-(N-ethyl-N-6-chloro-3-picolyl) amino-5-nitro-1-pyrimidyl] butane;
(Ie) 1,6-pair-[(4Z)-(and 2H, 6H)-3-methyl-4-(N-ethyl-N-6-chloro-3-picolyl) amino-5-nitro-1-pyrimidyl] hexane;
(If) suitable-1,2-is two-and [(4Z)-(2H, 6H)-3-methyl-4-(N-ethyl-N-6-chloro-3-picolyl) amino-5-nitro-1-pyrimidyl] hexanaphthene;
(Ig) anti--1,2-is two-and [(4Z)-(2H, 6H)-3-methyl-4-(N-ethyl-N-6-chloro-3-picolyl) amino-5-nitro-1-pyrimidyl] hexanaphthene.
Embodiment 1: preparation (Ia).
With 2.707g Ti304,0.360g quadrol and 1.875g concentration is that 37% formaldehyde solution is dissolved in the 30mL ethanol together, places the three-necked flask of 250mL, and mixed reaction solution was heated to 45 ℃ of reactions after 3 hours, separate out faint yellow solid, filter, use washing with alcohol, oven dry.Productive rate is 81.23%.Fusing point: 169-171 ℃.
Ultimate analysis: measured value C% 51.76 H% 5.95 N%21.61
Calculated value C% 51.77 H% 5.90 N%21.56
IR(KBr，cm
-1)v
max?1640，1535，1333，1293。
1H?NMR(CDCl
3，400MHz)δ8.306-8.301(d，J＝2.1Hz，2H，Pyridine)，7.711-7.685(dd，J
1＝2.4Hz，J
2＝8.2Hz，2H，Pyridine)，7.353-7.332(d，J＝8.2Hz，2H，Pyridine)，4.526-4.489(d，J＝15.0Hz，2H，Pyridine-CH
2)，4.259-4.211(dd，J
1＝3.8Hz，J
2＝15.0Hz，2H，Pyridine-CH
2)，3.749-3.606(m，8H)，3.295-3.265(m，2H)，3.032(s，6H)，2.980-2.945(m，2H)，2.699(s，4H)，1.239-1.203(t，J＝7.1Hz，6H)。
The product that present embodiment makes is made insecticide emulsion, converts water spray, to vegetable aphid killing rate 100%, has the efficient insecticide activity, to the person poultry safety.
Embodiment 2: preparation (Ib).
With 2.707g Ti304,0.444g 1,2-propylene diamine and 1.875g concentration are that 37% formaldehyde solution is dissolved in the 30mL ethanol together, place the three-necked flask of 250mL, mixed reaction solution was heated to 45 ℃ of reactions after 3 hours, separates out faint yellow solid, filter, use washing with alcohol, oven dry.Productive rate is 85.21%.Fusing point: 126～128 ℃.
Ultimate analysis: measured value C% 52.41 H% 6.10 N% 21.13
Calculated value C% 52.49 H% 6.08 N% 21.11
IR(KBr，cm
-1)v
max?1645，1526，1340，1271。
1H?NMR(CDCl
3，400MHz)δ8.30-8.27(d，J＝8.7Hz，2H，Pyridine)，7.76-7.63(m，2H，Pyridine)，7.34-7.31(m，2H，Pyridine)，4.57-4.46(q，2H，Pyridine-CH
2)，4.27-4.12(t，2H，Pyridine-CH
2)，3.79-3.58(m，8H)，3.35-3.28(m，2H)，3.00-2.97(t，6H，N-CH
3)，2.95(s，2H，N-CH
2)，2.74-2.64(m，1H)，2.44-2.31(m，1H)，1.26-1.24(d，1H)，1.22-1.16(m，6H)，1.12-1.09(m，3H)。
The product that present embodiment makes is made insecticide emulsion, converts water spray, to rice flying lice killing rate 100%, has the efficient insecticide activity, to the person poultry safety.
Embodiment 3: preparation (Ic).
With 2.707g Ti304,0.444g 1,3-propylene diamine and 1.875g concentration are that 37% formaldehyde solution is dissolved in the 30mL ethanol together, place the three-necked flask of 250mL, mixed reaction solution is heated to 45 ℃ of reactions after 3 hours, concentrates ethyl acetate extraction, the organic layer drying, column chromatography gets yellow oil, and productive rate is 45.00%.
Ultimate analysis: measured value C% 52.46 H% 6.11 N% 21.15
Calculated value C% 52.49 H% 6.08 N% 21.11
IR(KBr，cm-1)v
max?1620，1540，1396，1251。
1H?NMR(CDCl
3，400MHz)δ8.312(s，2H，Pyridine)，7.713-7.686(d，J＝10.6Hz，2H，Pyridine)，7.352-7.332(d，J＝8.3Hz，2H，Pyridine)，4.533-4.495(d，J＝15.0Hz，2H，Pyridine-CH
2)，4.249-4.211(d，J＝14.9Hz，2H，Pyridine-CH
2)，3.751-3.520(m，8H)，3.370-3.227(m，2H)，3.071-3.000(m，6H，N-CH
3)，2.997-2.921(m，2H)，2.631-2.464(m，4H)，1.792-1.640(m，2H)，1.215-1.205(d，J＝4.2Hz，6H)。
The product that present embodiment makes is made insecticide emulsion, converts water spray, and the red spider killing rate more than 95%, is had the efficient insecticide activity, to the person poultry safety.
Embodiment 4: preparation (Id).
With 2.707g Ti304,0.572g butanediamine and 1.875g concentration is that 37% formaldehyde solution is dissolved in the 30mL ethanol together, places the three-necked flask of 250mL, and mixed reaction solution was heated to 45 ℃ of reactions after 3 hours, separate out faint yellow solid, filter, use washing with alcohol, oven dry.Productive rate is 82.00%.Fusing point: 174～176 ℃.
Ultimate analysis: measured value C% 53.22 H% 6.23 N% 20.65
Calculated value C% 53.17 H% 6.25 N% 20.67
IR(KBr，cm
-1)v
max?1681，1539，1343，1222。
1H?NMR(CDCl
3，400MHz)δ8.303-8.298(d，J＝2.1Hz，2H，Pyridine)，7.709-7.682(dd，J
1＝8.2，J
2＝2.5Hz，2H，Pyridine)，7.339-7.319(d，J＝8.0Hz，2H，Pyridine)，4.520-4.483(d，J＝15.0Hz，2H)，4.223-4.186(d，J＝15.0Hz，2H)，3.663-3.582(m，8H)，3.309-3.256(m，2H)，3.010(s，6H)，2.988-3.935(q，2H)，2.482-2.468(d，J＝5.5Hz，4H)，1.601(s，4H)，1.219-1.184(t，J＝7.1Hz，6H)。
The product that present embodiment makes is made aqueous suspension, converts water spray, and wheat mythimna separata killing rate more than 98%, is had the efficient insecticide activity, to the person poultry safety.
Embodiment 5: preparation (Ie).
With 2.707g Ti304,0.731g hexanediamine and 1.875g concentration is that 37% formaldehyde solution is dissolved in the 30mL ethanol together, places the three-necked flask of 250mL, and mixed reaction solution was heated to 45 ℃ of reactions after 3 hours, separate out faint yellow solid, filter, use washing with alcohol, oven dry.Productive rate is 79.52%.Fusing point: 168～170 ℃
Ultimate analysis: measured value C% 54.51 H% 6.55 N% 19.82
Calculated value C% 54.46 H% 6.57 N% 19.85
IR(KBr，cm
-1)v
max?1660，1517，1460，1262.
1H?NMR(CDCl
3，400MHz)δ8.303-8.298(d，J＝2.3Hz，2H，Pyridine)，7.704-7.677(dd，J
1＝8.2Hz，J
2＝2.5Hz，2H，Pyridine)，7.332-7.311(d，J＝8.2Hz，2H，Pyridine)，4.517-4.479(d，J＝15.2Hz，2H)，4.217-4.179(d，J＝15.2Hz，2H)，3.626-3.588(m，8H)，3.300-3.247(q，2H)，3.002(s，6H)，2.468-2.416(q，4H)，1.563-1.530(m，4H)，1.365(s，4H)，1.256-1.175(m，6H).
The product that present embodiment makes is made the water and milk sterilant, converts water spray, to wheat mythimna separata killing rate 100%, has the efficient insecticide activity, to the person poultry safety.
Embodiment 6: preparation (If).
With 2.707g Ti304,0.741g cis 1,2-cyclohexanediamine and 1.875g concentration are that 37% formaldehyde solution is dissolved in the 30mL ethanol together, place the three-necked flask of 250mL, mixed reaction solution was heated to 45 ℃ of reactions after 3 hours, concentrate ethyl acetate extraction, organic layer drying, column chromatography, get yellow oil, productive rate is 45%.Fusing point: 119-121 ℃.
(C＝0.01g/mL?CH
3CH
2OH)。
Ultimate analysis: measured value C% 54.57 H% 6.31 N% 19.86
Calculated value C% 54.62 H% 6.30 N% 19.91
IR(KBr，cm
-1)v
max?1685，1546，1382，1382。
1H?NMR(CDCl
3，400MHz)δ8.261-8.213(d，J＝2.0Hz，2H，Pyridine)，7.732-7.573(m，2H?Pyridine)，7.338-7.281(m，2H，Pyridine)，4.622-4.463(q，2H)，4.334-4.224(m，2H)，3.840-3.581(m，8H)，3.354-3.268(m，2H)，3.079-2.970(m，5H)，2.913-2.905(d，J＝3.2Hz，3H)，2.817-2.738(m，2H)，1.834-1.743(m，4H)，1.281-1.125(m，10H)。
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 95%, is had the efficient insecticide activity, to the person poultry safety.
Embodiment 7: preparation (Ig).
With 2.707g Ti304,0.741g trans 1,2-cyclohexanediamine and 1.875g concentration are that 37% formaldehyde solution is dissolved in the 30mL ethanol together, place the three-necked flask of 250mL, mixed reaction solution is heated to 45 ℃ of reactions after 3 hours, concentrates ethyl acetate extraction, the organic layer drying, column chromatography gets yellow oil, and productive rate is 45.00%.Fusing point: 127-130 ℃.
(C＝0.01g/mL?CH
3CH
2OH)
Ultimate analysis: measured value C% 54.63 H% 6.36 N% 19.86
Calculated value C% 54.62 H% 6.30 N% 19.91
IR(KBr，cm
-1)v
max?1683，1557，1339，1301.
1H?NMR(CDCl
3，400MHz)δ8.258-8.209(d，J＝8.4Hz，2H，Pyridine)，7.715-7.573(m，2H，Pyridine)，7.327-7.347(m，2H，Pyridine)，4.618-4.458(q，2H，COOCH)，4.329-4.222(m，2H)，3.793-3.598(m，8H)，.352-3.266(m，2H)，3.075-3.004(m，5H)，2.904(s，3H)，2.814-2.739(q，2H)，1.832-1.756(m，4H)，1.277-1.174(m，10H)。
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, to the 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 (4)
1. (Z) type two analogue of anabasine insecticide Ti304 of tiring, general formula is (I):
Wherein:
2. (Z) type two analogue of anabasine insecticide Ti304 of tiring, the preparation method is as follows: Ti304,37% formaldehyde, aliphatic diamine are dropped in the three-necked flask, and solvent is a dehydrated alcohol; The mol ratio 2 of Ti304, formaldehyde and aliphatic diamine: 4.6-5.0: 1.2-1.5; 45 ℃ of temperature, reaction 2h makes general formula and is the tire analogue of anabasine insecticide Ti304 of (Z) type two of (I).
3. (Z) type two analogue of anabasine insecticide Ti304 of tiring, the effective active components of useful as pesticides is made emulsion, aqueous suspension and water emulsion pesticide.
4. (Z) type two analogue of anabasine insecticide Ti304 of tiring has higher inhibition activity to red spider, planthopper, aphid and mythimna separata.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106083029A CN102070613A (en) | 2010-12-28 | 2010-12-28 | Analogue of (Z) type bivalent nitenpyram and preparation method thereof |
| CN 201110104410 CN102225932B (en) | 2010-12-28 | 2011-04-15 | (Z) type divalent nitenpyram derivatives as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106083029A CN102070613A (en) | 2010-12-28 | 2010-12-28 | Analogue of (Z) type bivalent nitenpyram and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102070613A true CN102070613A (en) | 2011-05-25 |
Family
ID=44029393
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010106083029A Pending CN102070613A (en) | 2010-12-28 | 2010-12-28 | Analogue of (Z) type bivalent nitenpyram and preparation method thereof |
| CN 201110104410 Expired - Fee Related CN102225932B (en) | 2010-12-28 | 2011-04-15 | (Z) type divalent nitenpyram derivatives as well as preparation method and application thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110104410 Expired - Fee Related CN102225932B (en) | 2010-12-28 | 2011-04-15 | (Z) type divalent nitenpyram derivatives as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN102070613A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4401635A1 (en) * | 1994-01-21 | 1995-07-27 | Bayer Ag | Substituted 1,2,3,4-tetrahydro-5-nitro-pyrimidines |
| 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 |
-
2010
- 2010-12-28 CN CN2010106083029A patent/CN102070613A/en active Pending
-
2011
- 2011-04-15 CN CN 201110104410 patent/CN102225932B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102225932B (en) | 2013-04-17 |
| CN102225932A (en) | 2011-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW200847924A (en) | Fungicides | |
| CN104540824A (en) | Solid forms of a pyrido-pyrimidinium inner salt | |
| CN111253400B (en) | Halogenated pyrazole matrine derivative with insecticidal activity and preparation method and application thereof | |
| CN109090123A (en) | Application of the new cryptolepine derivative in prevention and treatment plant source germ | |
| CN112457288B (en) | Piperine acid derivative and application thereof | |
| CN106117064B (en) | A kind of (anti-)-β-farnesene analog of acid groups containing jasmine and its preparation and application | |
| CN103214461A (en) | Quinoline derivative and application thereof | |
| CN107474021B (en) | Oxadiazine derivatives, preparation method and application thereof | |
| CN110372622A (en) | Phenyl acetanides containing chiral oxazoline and the purposes as disinfectant use in agriculture | |
| Daneshvari et al. | Controlled-release formulations of trifluralin herbicide by interfacial polymerization as a tool for environmental hazards | |
| CN102070613A (en) | Analogue of (Z) type bivalent nitenpyram and preparation method thereof | |
| CN102070610A (en) | 1,4-dihydropyridine ring-containing cis-neonicotinoid compounds and preparation thereof | |
| CN103641795B (en) | One class contains acetophenone derivs of 1,2,3-thiadiazoles and its production and use | |
| CN101921244A (en) | Derivative of 4-methyl-1,2,3-thiadiazole containing 4-(1,1,2,2-tetrafluoroethoxy)-3,5-dichlorobenzene amino and synthesis method and application thereof | |
| CN106749288B (en) | N- (substituted-phenyl) Bi Zuo Bing fraxinellones analog derivative, preparation method and application | |
| CN102067838A (en) | Amide fragment-containing (Z) type nitenpyram analogue pesticide and preparation method thereof | |
| CN100447129C (en) | Oximated ginger phenol and its synthesis and use | |
| CN113024379A (en) | Carbonyl-containing compound and preparation method and application thereof | |
| CN107857791B (en) | Oleanolic acid derivative, preparation method and application | |
| CN1060008A (en) | The 4-Quinoxalinyloxy pheroxyalkylnitrile herbicides | |
| CN110642791B (en) | Sulfonylurea compound, preparation method thereof and application thereof in preparing herbicide | |
| CN113651760B (en) | Pyrimidine selenobenzoic acid derivative, preparation method thereof and application of pyrimidine selenobenzoic acid derivative as herbicide | |
| CN102070609A (en) | Cis nitenpyram analog containing 1,4-dihydropyridine ring and preparation method thereof | |
| CN103214475A (en) | Alpha-(substituted)oxyamide derivatives containing 4-methyl-1,2,3-thiadiazole and preparation methods and application thereof | |
| CN102229560B (en) | Cis-nitenpyram compound including 1,3-dicarbonyl, preparation method and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20110525 |