CN102225932B - (Z) type divalent nitenpyram derivatives as well as preparation method and application thereof - Google Patents
(Z) type divalent nitenpyram derivatives as well as preparation method and application thereof Download PDFInfo
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- CN102225932B CN102225932B CN 201110104410 CN201110104410A CN102225932B CN 102225932 B CN102225932 B CN 102225932B CN 201110104410 CN201110104410 CN 201110104410 CN 201110104410 A CN201110104410 A CN 201110104410A CN 102225932 B CN102225932 B CN 102225932B
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Abstract
The invention discloses (Z) type divalent nitenpyram derivatives as well as a preparation method and application thereof. The structure of the (Z) type divalent nitenpyram derivatives is as shown in a general formula (I), wherein Z is selected from C2-C6 alkyl or naphthenic base. The preparation method comprises the following steps: reacting aliphatic diamine, formaldehyde and nitenpyram so as to prepare (Z) type divalent nitenpyram analogues as shown in the general formula (I). The derivatives have the advantages of efficient insecticidal property, good insecticidal effect and low toxicity, can ensure people and livestock to be safe, and can promote growth of crops; the use method is simple; and the preparation method is simple.
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 its preparation method and application 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 the medium physics-chem characteristic such as water-soluble.Because it has unique insecticidal mechanism and the performance of high-efficiency low-toxicity, become rapidly the higher effective and lower toxic pesticide new variety that modern agriculture needs.
Ti304 is a kind of first-generation anabasine insecticide of efficient, wide spectrum, is one of last word of so far nicotinoids Agrochemicals.Because long-term and frequently use, more insect develops immunity to drugs to it, and in addition, its photo-labile and relatively poor hydrophobicity have also limited being widely used of it.
Have in recent years and morely significantly improve the bioactive report of compound about medicine by the multiple-effect valence effect.The reports such as Kagabu are synthetic Provado two compound of tiring take the methylene radical of different chain length, thiazolinyl, alkynyl etc. as linker, shows preferably biological activity.And two compounds of tiring of Ti304 do not have report.The new compound that the present invention synthesized 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 a class (Z) type two nitenpyram derivatives of tiring.
Its preparation method that the present invention also provides above-mentioned (Z) type two to tire nitenpyram derivatives.
The present invention tires nitenpyram derivatives for the preparation of sterilant with above-mentioned (Z) type two.
Purpose of the present invention can be achieved through the following technical solutions.
Above-mentioned (Z) type two nitenpyram derivatives of tiring, available general formula (I) expression:
Wherein: Z is selected from C2～C6 alkyl or cycloalkyl, is preferably-CH
2CH
2-,-CH
2(CHCH
3) CH
2-,-CH
2CH
2CH
2-,-CH
2(CH
2)
2CH
2-,-CH
2(CH
2)
3CH
2-,-CH
2(CH
2)
4CH
2-, cis or trans 1, the 2-cyclohexyl.
That is:
With (Z) type two of general formula (I) expression nitenpyram derivatives of tiring, the preparation method is as follows: Ti304, formaldehyde, C1～C6 aliphatic diamine are mixed, and take dehydrated alcohol as solvent, 42～48 ℃ of lower reaction 2～4h of temperature; The mol ratio of Ti304, formaldehyde and aliphatic diamine 2: 4.6～5.0: 1.2～1.5.
Preferable reaction temperature is 45 ℃, reaction times 2h.
The reaction formula of above-mentioned preparation process is:
Wherein:: Z is selected from C2～C6 alkyl or cycloalkyl, is preferably-CH
2CH
2-,-CH
2(CHCH
3) CH
2-,-CH
2CH
2CH
2-,-CH
2(CH
2)
2CH
2-,-CH
2(CH
2)
3CH
2-,-CH
2(CH
2)
4CH
2-, cis or trans 1, the 2-cyclohexyl.That is:
Can be made into emulsion, aqueous suspension and water emulsion pesticide sterilant in order to (Z) type two of general formula (I) expression nitenpyram derivatives of tiring.Red spider, planthopper, aphid and mythimna separata all had higher inhibition activity.
In the described reaction, adopt various raw materials are put into the method preparation that reaction vessel is treated different things alike.
The present invention (Z) type two nitenpyram compound of tiring 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, have the efficient insecticide activity, good disinsection effect has higher inhibition activity to red spider, planthopper, aphid and mythimna separata.
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.
(Z) the tire embodiment of nitenpyram derivatives of type two is:
(Ia) 1,2 pair-[(4Z)-(2H, 6H)-and 3-methyl-4-(N-ethyl-N-6-chloro-3-pyridylmethyl) amino-5-nitro-1-pyrimidyl] ethane;
(Ib) 1,2-pair-[(4Z)-(2H, 6H)-and 3-methyl-4-(N-ethyl-N-6-chloro-3-pyridylmethyl) amino-5-nitro-1-pyrimidyl] propane;
(Ic) 1,3-pair-[(4Z)-(2H, 6H)-and 3-methyl-4-(N-ethyl-N-6-chloro-3-pyridylmethyl) amino-5-nitro-1-pyrimidyl] propane;
(Id) Isosorbide-5-Nitrae-two-[(4Z)-2H, 6H-3-methyl-4-(N-ethyl-N-6-chloro-3-pyridylmethyl) amino-5-nitro-1-pyrimidyl] butane;
(Ie) 1,6-pair-[(4Z)-(2H, 6H)-and 3-methyl-4-(N-ethyl-N-6-chloro-3-pyridylmethyl) amino-5-nitro-1-pyrimidyl] hexane;
(If) suitable-1,2-is two-[(4Z)-(2H, 6H)-and 3-methyl-4-(N-ethyl-N-6-chloro-3-pyridylmethyl) amino-5-nitro-1-pyrimidyl] hexanaphthene;
(Ig) anti--1,2-is two-[(4Z)-(2H, 6H)-and 3-methyl-4-(N-ethyl-N-6-chloro-3-pyridylmethyl) amino-5-nitro-1-pyrimidyl] hexanaphthene.
Embodiment 1 preparation (Ia)
Be that 37% formaldehyde solution is dissolved in the 30mL ethanol together with 2.707g (0.010mol) Ti304,0.360g (0.006mol) quadrol and 1.875g concentration, place the three-necked flask of 250mL, 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
max1640，1535，1333，1293.
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)。
Embodiment 2 preparations (Ib)
With 2.707g (0.010mol) Ti304,0.444g 1,2-propylene diamine (0.006mol) 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, separate 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)。
Embodiment 3 preparations (Ic)
With 2.707g (0.010mol) Ti304,0.444g (0.006mol) 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 was heated to 45 ℃ of reactions after 3 hours, concentrated, ethyl acetate extraction, organic layer is dry, 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)。
Embodiment 4 preparations (Id)
Be that 37% formaldehyde solution is dissolved in the 30mL ethanol together with 2.707g (0.010mol) Ti304,0.572g (0.006mol) butanediamine and 1.875g concentration, place the three-necked flask of 250mL, 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)。
Embodiment 5 preparations (Ie)
Be that 37% formaldehyde solution is dissolved in the 30mL ethanol together with 2.707g (0.010mol) Ti304,0.731g (0.006mol) hexanediamine and 1.875g concentration, place the three-necked flask of 250mL, 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)。
Embodiment 6 preparations (If)
With 2.707g (0.010mol) Ti304,0.741g (0.006mol) 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, concentrated, ethyl acetate extraction, organic layer is dry, column chromatography gets yellow oil, and productive rate is 45.00%.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)。
Embodiment 7 preparations (Ig)
With 2.707g (0.010mol) Ti304,0.741g (0.006mol) 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 was heated to 45 ℃ of reactions after 3 hours, concentrated, ethyl acetate extraction, organic layer is dry, 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 test of embodiment 8 insecticidal activities:
1. test target: Nilaparvata lugen (brown planthopper).
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 (such as acetone) 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 liquid of measuring desired concn.General sieve concentration is generally 500mg/L.
4. test method
Brown Planthopper screening---the quantitative spray method of culture dish seedling worm:
Rice seedlings is fixed in the culture dish with white quartz sand; Use CO
2Anaesthetize 3 mid-term in age nymph, place under the POTTER spray tower and spray.Cover with the transparent plastics cup after the spraying, be put in the observation ward behind the mark.Check result behind the 72h.
5. 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～Ig desinsection test result:
Target compound Ia-Ig does contrast to the insecticidal activity of Nilaparvata lugen (brown planthopper) with Ti304, and activity data sees Table 1.
Table 1
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have change and change.Within the spirit and principles in the present invention all, any modification of doing, improvement etc. all should be included within protection scope of the present invention.
Claims (3)
1. (Z) type two nitenpyram derivatives of tiring is characterized in that having the structure of general formula (I):
Wherein: Z is selected from-CH
2CH
2-,-CH
2(CH
3) CH-,-CH
2CH
2CH
2-,-CH
2(CH
2)
2CH
2-,-CH
2(CH
2)
4CH
2-, cis or trans 1, the 2-cyclohexyl.
2. claim 1 described (Z) type two is tired nitenpyram derivatives in the application of preparation aspect the sterilant.
3. a sterilant is characterized in that, contains claim 1 described (Z) type two nitenpyram derivatives of tiring, and formulation is emulsion or aqueous suspension.
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|---|---|---|---|
| CN2010106083029A CN102070613A (en) | 2010-12-28 | 2010-12-28 | Analogue of (Z) type bivalent nitenpyram and preparation method thereof |
| CN201010608302.9 | 2010-12-28 | ||
| CN 201110104410 CN102225932B (en) | 2010-12-28 | 2011-04-15 | (Z) type divalent nitenpyram derivatives as well as preparation method and application thereof |
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| 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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