CN104892577B - Pymetrozine derivative and preparation method thereof and the application in terms of desinsection - Google Patents

Pymetrozine derivative and preparation method thereof and the application in terms of desinsection Download PDF

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CN104892577B
CN104892577B CN201510353096.4A CN201510353096A CN104892577B CN 104892577 B CN104892577 B CN 104892577B CN 201510353096 A CN201510353096 A CN 201510353096A CN 104892577 B CN104892577 B CN 104892577B
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pymetrozine
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CN104892577A (en
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汪清民
杨岩
刘玉秀
王兹稳
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Nankai University
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    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines

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Abstract

Application the present invention relates to pymetrozine derivative (I) and preparation method thereof and in terms of desinsection, the meaning of each group is shown in specification in formula.The pymetrozine derivative of this patent shows good killing aphids activity, while also shows insecticidal activity to mosquito larvae, bollworm, corn borer and mythimna separata.

Description

Pymetrozine derivative and preparation method thereof and the application in terms of desinsection
Technical field
Application the present invention relates to pymetrozine derivative and preparation method thereof and in terms of desinsection belongs to technical field of pesticide.
Background technology
Pymetrozine (Pymetrozine) be by the new pyridine heterocyclic insecticides of the exploitation of Ciba-Geigy companies 1988, The insecticides with unique effect mode are represented, it is to sucking pest particularly aphid, trialeurodes vaporariorum, black tail leaf Cicada has unique control effect (Hunan chemical industry, 2000,30 (10), 25-26).This compound is right because of the selectivity of its height The hypotoxicity of mammal, to birds, fish, non-target arthropod safety and shown in integrated control (IPM) Good development prospect.As environmental protection is increasingly paid attention in the whole world, for exploitation pymetrozine as efficiently, low toxicity, Environmental-friendly insecticide has positive effect to agricultural sustainable development.
Invention content
Application the object of the present invention is to provide pymetrozine derivative and preparation method thereof and in terms of desinsection.This patent Pymetrozine derivative shows good killing aphids activity, while also mosquito larvae, bollworm, corn borer and mythimna separata is shown to kill Worm activity.
The pymetrozine derivative of the present invention is the compound for having structure shown in below formula (I)：
The pymetrozine derivative compound I-1 of the present invention can be prepared as follows (route one)：6- chlorine cigarette aldehyde (2) with Phenol reactant generates ether compound 3, then obtains compound I-1 using the condensation reaction with amino triazine ketone 1；
The acid binding agent of the first step can be sodium carbonate, potassium carbonate, cesium carbonate；Ketone catalyst can be stannous chloride, bromination Cuprous, cuprous iodide；Solvent can be n,N-Dimethylformamide, dimethyl sulfoxide (DMSO)；Reaction temperature is at 100 DEG C to 150 DEG C It carries out；The catalyst of second step can be p-methyl benzenesulfonic acid, trifluoroacetic acid；Solvent can be methanol, toluene, dimethylbenzene；Instead Temperature is answered to be carried out at 50 DEG C to 150 DEG C.
The pymetrozine derivative compound I-2-I-5 of the present invention can be prepared as follows (route two)：Difference substitution The pyridone 4a-4d of base generates ether compound 5a-5d with phenol reactant, then anti-using the condensation with amino triazine ketone 1 It should obtain compounds I-2-I-5；
The acid binding agent of the first step can be sodium hydride, sodium carbonate, potassium carbonate, cesium carbonate；Ketone catalyst can be protochloride Copper, cuprous bromide, cuprous iodide；Solvent can be n,N-Dimethylformamide, dimethyl sulfoxide (DMSO)；Reaction temperature at 100 DEG C extremely It is carried out at 160 DEG C；The catalyst of second step can be p-methyl benzenesulfonic acid, trifluoroacetic acid；Solvent can be methanol, toluene, two Toluene；Reaction temperature carries out at 50 DEG C to 150 DEG C.
The pymetrozine derivative compound I-6-I-22 of the present invention can be prepared as follows (route three)：Difference substitution Pyridyl ethers compound 6a-6s and the condensation reaction of amino triazine ketone 1 obtain compounds I-6-I-22；
Catalyst can be p-methyl benzenesulfonic acid, trifluoroacetic acid；Solvent can be methanol, toluene, dimethylbenzene；Reaction temperature It is carried out at 50 DEG C to 150 DEG C.
In above each general formula,
R1Hydrogen, hydroxyl, halogen atom, cyano, ester group, amide groups, 1-10 carbon alkyl, 1-6 carbon alkoxy, 1- are represented respectively 4 carbon alkyl carbonyl oxies, 1-4 carbon alkoxies carbonyloxy group, 1-10 carbon nitrogen heterocyclic ring, 1-10 carbon oxygen heterocycle, 1-10 carbon sulfur heterocyclic rings；
R2Hydrogen, hydroxyl, 1-6 carbon alkoxy 1-10 carbon alkylamino radical, halogen atom, cyano, aldehyde radical, 1-6 carbon alkane are represented respectively Carbonyl, 1-10 carbon alkoxy carbonyl group, 1-10 carbon alkanamines carbonyl, 1-6 carbon alkyl oxy carbonyl oxygen, 1-6 carbon alkanamine carbonyloxy groups；And contain simultaneously There is 2-3 R2Representative substituent group.
Pymetrozine derivative (I) of the present invention preferably following compound：
(E) -6- methyl -4- (1- (6- (2- methylphenoxies) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydro -1, 2,4- triazine -3 (2H) -one (I-6)；
(E) -6- methyl -4- (1- (6- (2- ethoxy phenoxies) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros - 1,2,4- triazine -3 (2H) -one (I-7)；
(E) -6- methyl -4- (1- (6- (4- ethyls phenoxy group) pyridine -3- acyl groups) ethyleneimino) -4,5- bis- chloro- 1, 2,4- triazine -3 (2H) -one (I-11)；
(E) -6- methyl -4- (1- (6- (4- cumenes oxygroup) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros - 1,2,4- triazine -3 (2H) -one (I-12)；
(E) -6- methyl -4- (1- (6- (4- tert-butyl benzenes oxygroup) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros - 1,2,4- triazine -3 (2H) -one (I-13)；
(E) -6- methyl -4- (1- (6- (4- bromobenzenes oxygroup) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros -1,2, 4- triazines -3 (2H) -one (I-14)；
(E) -6- methyl -4- (1- (6- (4- (benzyloxy) phenoxy group) pyridine -3- acyl groups) ethyleneimino) -4,5- bis- Hydrogen -1,2,4- triazines -3 (2H) -one (I-16)；
(E) -6- methyl -4- (1- (6- (4- isopropyl -3- methylphenoxies) pyridine -3- acyl groups) ethyleneimino) -4, 5- dihydros -1,2,4- triazines -3 (2H) -one (I-18)；
(E) -6- methyl -4- (1- (6- (2- isopropyl -5- methylphenoxies) pyridine -3- acyl groups) ethyleneimino) -4, 5- dihydros -1,2,4- triazines -3 (2H) -one (I-19)；
(E) -6- methyl -4- (1- (6- (4- pi-allyl -2- methoxyphenoxies) pyridine -3- acyl groups) ethyleneimino) - 4,5- dihydros -1,2,4- triazines -3 (2H) -one (I-20).
The pymetrozine derivative of the present invention shows good killing aphids activity, while also to mosquito larvae, bollworm, corn Snout moth's larva and mythimna separata show certain activity.
Specific embodiment
Following embodiments and raw test result can be used to further illustrate the present invention, but be not intended to limit this hair It is bright.
Embodiment 1：(E) -6- methyl -4- (6- phenoxypyridines -3- acyl groups) ethyleneimino) -4,5- dihydros -1,2,4- The synthesis of triazine -3 (2H) -one (I-1)
The synthesis of 6- phenoxypyridines -3- formaldehyde (3)
6- chloropyridine -3- formaldehyde (2) (0.28g, 2mmol), phenol (0.19g, 2mmol) are dissolved in DMF (30mL), Zhi Houjia Enter Cs2CO3(0.78g, 2.4mmol) and CuCl (0.24g, 2.4mmol), is heated to reflux 10 hours later.Add in ethyl acetate and Moisture liquid, saturated common salt washing organic phase, anhydrous sodium sulfate drying, precipitation obtain white solid 0.36g with recrystallizing methanol. Yield 92%, 91-93 DEG C of fusing point；1H NMR (400MHz, CDCl3)：δ 9.98 (s, 1H, CHO), 8.63 (s, 1H, Py-H), 8.19 (d, J=8.4Hz, 1H, Py-H), 7.46 (t, J=7.6Hz, 2H, Ar-H), 7.30 (d, J=7.6Hz, 1H, Ar-H), 7.17 (d, J=7.6Hz, 2H, Ar-H), 7.16 (d, J=8.4Hz, 1H, Py-H)；13C NMR (100MHz, CDCl3) δ 189.4, 167.3,153.0,152.8,138.7,129.9,127.7,125.8,121.6,112.1.ESI-HRMS (m/z)： Calcd.forC12H10NO2[M+H]+200.0706；found 200.0708.
(E) -6- methyl -4- (6- phenoxypyridines -3- acyl groups) ethyleneimino) -4,5- dihydros -1,2,4- triazines -3 The synthesis of (2H) -one (I-1)
In 250mL single port bottles, add in amino triazine ketone (1) (0.51g, 4mmol), p-methyl benzenesulfonic acid (0.14g, 0.8mmol), methanol (120mL) stirring and dissolving adds in 6- phenoxypyridines -3- formaldehyde (3) (0.80g, 4mmol), heating later Flow back 6h, and TLC monitoring reactions finish.After reaction solution is depressurized precipitation, white solid 0.80g, yield are obtained with recrystallizing methanol 65%, 200-201 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 10.10 (s, 1H, NH), 8.37 (s, 1H, N=CH), 8.20 (d, J=8.8Hz, 1H, Py-H), 7.89 (s, 1H, Py-H), 7.44 (t, J=7.6Hz, 2H, Ar-H), 7.24 (t, J= 7.6Hz, 1H, Ar-H), 7.17 (d, J=7.6Hz, 2H, Ar-H), 7.11 (d, J=8.8Hz, 1H, Py-H), 4.35 (s, 2H, CH2), 1.94 (s, 3H, CH3)；13C NMR (100MHz, DMSO-d6) δ 163.6,153.6,147.3,146.9,144.0, 137.8,136.8,129.8,126.7,124.9,121.4,111.9,47.7,20.2.ESI-HRMS (m/z)：Calcd.for C16H16N5O2[M+H]+310.1299；found 310.1300.
Embodiment 2：The synthesis of compound I-2-I-5
The synthesis of 1- (6- phenoxypyridines -3- acyl groups) ethyl ketone (5a)
Under room temperature, NaH (0.12g, 3mmol, 60%) is dissolved in DMSO (10ml), adds in phenol (0.19g, 2mmol), Stirring 30 minutes adds in 6- chloropyridine -3- ethyl ketones (4a) (0.31g, 2mmol), is heated to reflux later 12 hours later.Add water quenching It goes out reaction, adds in ethyl acetate liquid separation, saturated common salt washing organic phase, anhydrous sodium sulfate drying, precipitation, with petroleum ether/acetic acid Ethyl ester (10: 1) carries out normal pressure column chromatography and obtains white solid 0.29g.Yield 68%, 202-204 DEG C of fusing point；1H NMR (400MHz, CDCl3)：δ 8.77 (s, 1H, Py-H), 8.27 (d, J=8.8Hz, 1H, Py-H), 7.45 (t, J=7.6Hz, 2H, Ar-H), 7.28 (t, J=7.6Hz, 1H, Ar-H), 7.16 (d, J=7.6Hz, 2H, Ar-H), 6.97 (d, J=8.8Hz, 1H, Py-H), 2.57 (s, 3H, CH3)；13C NMR (100MHz, CDCl3) δ 195.5,166.6,153.4,149.8,139.4,130.0, 128.4,125.7,121.7,111.4,26.6.ESI-HRMS (m/z)：Calcd.for C13H12NO2[M+H]+214.0836； found 214.0864.
Compound 5b-5d is completed by repeating the above steps.
The synthesis of 1- (6- phenoxypyridines -3- acyl groups) acetone (5b)
White solid, yield 74%, 64-66 DEG C of fusing point；1H NMR (400MHz, CDCl3)：δ 8.78 (s, 1H, Py-H), 8.27 (d, J=8.8Hz, 1H, Py-H), 7.44 (t, J=7.6Hz, 2H, Ar-H), 7.26 (t, J=7.6Hz, 1H, Ar-H), 7.16 (d, J=7.6Hz, 2H, Ar-H), 6.97 (d, J=8.8Hz, 1H, Py-H), 2.94 (q, J=7.6Hz, 2H, CH2CH3), 1.22 (t, J=7.6Hz, 3H, CH2CH3)；13C NMR (100MHz, CDCl3) δ 198.4,166.4,153.4,149.3,139.3, 129.9,128.0,125.6,121.6,111.4,31.9,8.17.ESI-HRMS (m/z)：Calcd.for C14H14NO2[M+H]+ 228.1019；found 228.1023.
The synthesis of 2- methyl-1s-(6- phenoxypyridines -3- acyl groups) acetone (5c)
White solid, yield 63%, 42-44 DEG C of fusing point；1H NMR (400MHz, CDCl3)：δ 8.78 (s, 1H, Py-H), 8.27 (d, J=8.8Hz, 1H, Py-H), 7.44 (t, J=7.6Hz, 2H, Ar-H), 7.26 (t, J=7.6Hz, 1H, Ar-H), 7.16 (d, J=7.6Hz, 2H, Ar-H), 6.97 (d, J=8.8Hz, 1H, Py-H), 3.40-3.47 (m, 1H, CH (CH3)2), 1.22 (d, J=6.4Hz, 6H, CH (CH3)2)；13C NMR (100MHz, CDCl3) δ 202.1,166.4,153.4,149.4, 139.8,130.0,125.6,121.7,115.5,111.5,35.8,19.1.ESI-HRMS (m/z)：Calcd.for C15H16NO2 [M+H]+242.1176；found 242.1180.
The synthesis of 2,2,2- tri- fluoro- 1- (6- phenoxypyridines -3- acyl groups) ethyl ketones (5d)
Yellow liquid, yield 75%；1H NMR (400MHz, CDCl3)：δ 8.91 (s, 1H, Py-H), 8.37 (d, J= 8.8Hz, 1H, Py-H), 7.49 (t, J=7.6Hz, 2H, Ar-H), 7.33 (t, J=7.6Hz, 1H, Ar-H), 7.20 (d, J= 7.6Hz, 2H, Ar-H), 7.10 (d, J=8.8Hz, 1H, Py-H)；13C NMR (100MHz, CDCl3) δ 178.6 (q, J= 37Hz), 167.7,152.8,152.0,151.9,140.8,130.0,126.1,121.7,121.5,116.6 (q, J= 289Hz), 112.1.ESI-HRMS (m/z)：Calcd.for C13H9F3NO2[M+H]+268.0580；found 268.0580.
(E) -6- methyl -4- (1- (6- phenoxy groups) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros -1,2,4- tri- Piperazine -3 (2H) -one (I-2)；
In 250mL single port bottles, add in amino triazine ketone (1) (0.51g, 4mmol), p-methyl benzenesulfonic acid (0.14g, 0.8mmol), methanol (80mL) stirring and dissolving adds in 6- phenoxypyridines -3- ethyl ketones (5a) (0.85g, 4mmol), heating later Flow back 8h.Add in ethyl acetate and moisture liquid, saturated common salt washing organic phase, anhydrous sodium sulfate drying, precipitation, with petroleum ether/ Ethyl acetate (10: 1) carries out normal pressure column chromatography and obtains white solid 0.88g.Yield 68%, 202-204 DEG C of fusing point；1H NMR (400MHz, CDCl3)：δ 8.62 (s, 1H, NH), 8.27 (d, J=8.8Hz, 1H, Py-H), 7.75 (s, 1H, Py-H), 7.44 (t, J=7.6Hz, 2H, Ar-H), 7.25 (t, J=7.6Hz, 1H, Ar-H), 7.17 (d, J=7.6Hz, 2H, Ar-H), 6.94 (d, J=8.8Hz, 1H, Py-H), 4.21 (s, 2H, CH2), 2.31 (s, 3H, CH3), 2.06 (s, 3H, CH3)；13C NMR (100MHz, CDCl3) δ 168.2,165.4,153.9,149.0,147.3,145.7,138.3,129.9,128.0,125.2, 121.4,111.2,51.9,20.6,17.4.ESI-HRMS (m/z)：Calcd.for C17H18N5O2[M+H]+324.1455； found 324.1459.
Compound I-3-I-5 is completed by repeating the above steps.
(E) -6- methyl -4- (1- (6- phenoxy groups) pyridine -3- acyl groups) propylidene amino) -4,5- dihydros -1,2,4- tri- Piperazine -3 (2H) -one (I-3)；
White solid, yield 46%, 124-126 DEG C of fusing point；1H NMR (400MHz, CDCl3)：δ 8.55 (s, 1H, NH), 8.19 (d, J=8.8Hz, 1H, Py-H), 7.75 (s, 1H, Py-H), 7.42 (t, J=8.0Hz, 2H, Ar-H), 7.23 (t, J= 7.6Hz, 1H, Ar-H), 7.15 (d, J=8.0Hz, 2H, Ar-H), 6.93 (d, J=8.8Hz, 1H, Py-H), 4.13 (s, 2H, CH2), 2.72 (q, J=7.6Hz, 2H, CH2CH3), 2.04 (s, 3H, CH3), 1.12 (t, J=7.6Hz, 3H, CH2CH3)；13C NMR (100MHz, CDCl3) δ 174.8,165.3,153.8,149.4,147.6,145.4,139.0,129.9,126.6, 125.2,121.5,111.3,51.8,23.6,20.7,11.7.ESI-HRMS (m/z)：Calcd.for C18H20N5O2[M+H]+ 338.1612；found 338.1611.
(E) -6- methyl -4- (2- methyl-1s-(6- phenoxy groups) pyridine -3- acyl groups) propylidene amino) -4,5- dihydro -1, 2,4- triazine -3 (2H) -one (I-4)；
White solid, yield 42%, 40-42 DEG C of fusing point；1H NMR (400MHz, CDCl3)：δ 7.94 (s, 1H, NH), 7.65 (d, J=8.4Hz, 1H, Py-H), 7.46 (s, 1H, Py-H), 7.41 (t, J=7.6Hz, 2H, Ar-H), 7.22 (t, J= 7.2Hz, 1H, Ar-H), 7.16 (d, J=7.6Hz, 2H, Ar-H), 6.88 (d, J=8.4Hz, 1H, Py-H), 3.97 (s, 2H, CH2), 2.89-2.99 (m, CH (CH3)2), 1.89 (s, 3H, CH3), 1.19 (d, J=6.8Hz, 6H, CH (CH3)2)；13C NMR (100MHz, CDCl3) δ 180.4,163.8,153.7,148.4,144.6,144.4,138.5,129.9,127.2,125.2, 121.6,110.9,51.5,37.2,20.5,20.1.ESI-HRMS (m/z)：Calcd.for C19H22N5O2[M+H]+ 352.1768；found 352.1772.
(E) -6- methyl -4- (2,2,2- tri- fluoro- 1- (6- phenoxy groups) pyridine -3- acyl groups) ethyleneimino) -4,5- bis- Hydrogen -1,2,4- triazines -3 (2H) -one (I-5)；
White solid, yield 41%, 150-151 DEG C of fusing point；1H NMR (400MHz, CDCl3)：δ 8.16 (s, 1H, NH), 8.13 (s, 1H, Py-H), 7.82 (d, J=8.0Hz, 1H, Py-H), 7.45 (t, J=7.6Hz, 2H, Ar-H), 7.28 (d, J= 7.2Hz, 1H, Ar-H), 7.19 (d, J=8.0Hz, 2H, Ar-H), 7.00 (d, J=8.0Hz, 1H, Py-H), 4.19 (s, 2H, CH2), 2.00 (s, 3H, CH3)；13C NMR (100MHz, CDCl3) δ 164.5,153.2 (q, J=33Hz), 153.1,146.8, 146.2,146.0,139.1,129.8,125.5,121.6,120.1 (q, J=257Hz), 111.5,52.3,20.5.ESI- HRMS(m/z)：Calcd.for C17H15F3N5O2[M+H]+378.1172；found 378.1181.
Embodiment 3：The synthesis of compound I-6-I-22
The step of compound I-6-I-22 is by repeating I-1 is completed.
(E) -6- methyl -4- (1- (6- (2- methylphenoxies) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydro -1, 2,4- triazine -3 (2H) -one (I-6)
White solid, yield 56%, 166-167 DEG C of fusing point；1H NMR (400MHz, DMSO-d6) δ 9.97 (s, 1H, NH), 8.55 (s, 1H, Py-H), 8.31 (d, J=8.8Hz, 1H, Py-H), 7.34 (d, J=7.6Hz, 1H, Ar-H), 7.27 (t, J= 7.6Hz, 1H, Ar-H), 7.19 (t, J=7.6Hz, 1H, Ar-H), 7.09 (t, J=8.8Hz, 2H, Py-H, Ar-H), 4.15 (s, 2H, CH2), 2.19 (s, 3H, CH3), 2.09 (s, 3H, CH3), 1.95 (s, 3H, CH3)；13C NMR (100MHz, DMSO-d6)δ 167.3,164.8,152.1,149.3,147.2,145.9,138.8,131.7,130.7,128.1,127.8,125.8, 122.5,110.8,51.4,20.6,17.4,16.4.ESI-HRMS (m/z)：Calcd.for C18H20N5O2[M+H]+ 338.1612；found338.1616.
(E) -6- methyl -4- (1- (6- (2- ethoxy phenoxies) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros - The synthesis of 1,2,4- triazine -3 (2H) -one (I-7)
Yellow solid, yield 80%, 167-168 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.96 (s, 1H, NH), 8.52 (s, 1H, Py-H), 8.27 (d, J=8.8Hz, 1H, Py-H), 7.12-7.23 (m, 3H, Ar-H), 6.96-7.04 (m, 2H, Py-H, Ar-H), 4.15 (s, 2H, CH2), 3.96 (q, J=6.8Hz, 2H, CH2CH3), 2.18 (s, 3H, CH3), 1.93 (s, 3H, CH3), 1.05 (t, J=6.8Hz, 3H, CH2CH3)；13C NMR (100MHz, DMSO-d6) δ 166.9,164.5,150.6, 148.8,146.4,145.3,142.1,137.9,127.5,126.2,122.9,120.9,114.3,110.0,63.7,50.9, 20.1,16.9,14.4.ESI-HRMS (m/z)：Calcd.for C19H22N5O3[M+H]+368.1717；found 368.1722.
(E) -6- methyl -4- (1- (6- (2- tert-butyl benzenes oxygroup) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros - The synthesis of 1,2,4- triazine -3 (2H) -one (I-8)
White solid, yield 69%, 122-123 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.97 (s, 1H, NH), 8.59 (s, 1H, Py-H), 8.30 (d, J=8.8Hz, 1H, Py-H), 7.43 (d, J=7.6Hz, 1H, Ar-H), 7.25 (t, J= 6.8Hz, 1H, Ar-H), 7.18 (t, J=7.6Hz, 1H, Ar-H), 7.07 (d, J=8.8Hz, 1H, Py-H), 6.99 (d, J= 7.6Hz, 1H, Ar-H), 4.15 (s, 2H, CH2), 2.19 (s, 3H, CH3), 1.94 (s, 3H, CH3), 1.31 (s, 9H, CH3)；13C NMR (100MHz, DMSO-d6) δ 166.9,164.6,152.1,148.8,146.8,145.4,140.8,138.3,127.7, 127.2,124.9,123.5,111.1,50.9,34.3,30.1,20.2,16.9.ESI-HRMS (m/z)：Calcd.for C21H26N5O2[M+H]+380.2081；found 380.2086.
(E) -6- methyl -4- (1- (6- (3- nitro-phenoxies) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydro -1, The synthesis of 2,4- triazine -3 (2H) -one (I-9)
White solid, yield 63%, 171-172 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.98 (s, 1H.NH), 8.60 (s, 1H, Py-H), 8.38 (d, J=8.8Hz, 1H, Py-H), 8.12 (d, J=8.0Hz, 1H, Ar-H), 8.06 (t, J= 2.0Hz, 1H, Ar-H), 7.69-7.77 (m, 2H, Ar-H), 7.25 (d, J=8.8Hz, 1H, Py-H), 4.16 (s, 2H, CH2), 2.20 (s, 3H, CH3), 1.95 (s, 3H, CH3)；13C NMR (100MHz, DMSO-d6) δ 166.6,163.5,153.8,148.7, 148.6,146.4,145.4,138.7,131.0,128.8,128.4,119.8,116.5,111.7,50.9,20.1, 17.1.ESI-HRMS(m/z)：Calcd.for C17H17N6O4[M+H]+369.1306；found 369.1311.
(E) -4- (1- (6- (3- amino-benzene oxygens) pyridine -3- acyl groups) ethyleneimino) -6- methyl -4,5- dihydro -1, The synthesis of 2,4- triazine -3 (2H) -one (I-10)
White solid, yield 27%, 187-188 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.97 (s, 1H, NH), 8.60 (s, 1H, Py-H), 8.27 (d, J=8.8Hz, 1H, Py-H), 7.04 (t, J=7.2Hz, 1H, Ar-H), 6.96 (d, J= 8.8Hz, 1H, Py-H), 6.42 (d, J=7.2Hz, 1H, Ar-H), 6.29 (s, 1H, Ar-H), 6.24 (d, J=7.2Hz, 1H, Ar-H), 5.27 (s, 2H, NH2), 4.15 (s, 2H, CH2), 2.19 (s, 3H, CH3), 1.94 (s, 3H, CH3)；13C NMR (100MHz, DMSO-d6) δ 166.6,164.5,154.4,150.2,148.6,146.6,145.2,138.0,129.7,127.5, 110.6,110.3,107.6,105.9,50.7,19.9,16.8.ESI-HRMS (m/z)：Calcd.for C17H19N6O2[M+H]+ 339.1564；found339.1569.
(E) -6- methyl -4- (1- (6- (4- ethyls phenoxy group) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydro -1, The synthesis of 2,4- triazine -3 (2H) -one (I-11)
White solid, yield 59%, 131-132 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.96 (s, 1H, NH), 8.56 (s, 1H, Py-H), 8.29 (d, J=8.8Hz, 1H, Py-H), 7.27 (d, J=7.2Hz, 2H, Ar-H), 7.06 (t, J= 7.2Hz, 3H, Ar-H, Py-H), 4.15 (s, 2H, CH2), 2.63 (q, J=6.8Hz, 2H, CH2CH3), 2.18 (s, 3H, CH3), 1.94 (s, 3H, CH3), 1.21 (t, J=7.6Hz, 3H, CH2CH3)；13C NMR (100MHz, DMSO-d6) δ 166.8,164.6, 151.3,148.8,146.6,145.4,140.4,138.3,129.0,127.8,121.2,110.9,50.9,27.6,20.1, 17.0,15.7.ESI-HRMS (m/z)：Calcd.for C19H22N5O2[M+H]+352.1768；found 352.1772.
(E) -6- methyl -4- (1- (6- (4- cumenes oxygroup) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros - The synthesis of 1,2,4- triazine -3 (2H) -one (I-12)
White solid, yield 53%, 128-129 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.96 (s, 1H, NH), 8.57 (s, 1H, Py-H), 8.29 (d, J=8.8Hz, 1H, Py-H), 7.30 (d, J=8.4Hz, 2H, Ar-H), 7.07 (t, J= 6.8Hz, 3H, Ar-H, Py-H), 4.15 (s, 2H, CH2), 2.89-2.96 (m, 1H, CH (CH3)2), 2.18 (s, 3H, CH3), 1.94 (s, 3H, CH3), 1.22 (d, J=6.8Hz, 6H, CH (CH3)2)；13C NMR (100MHz, DMSO-d6) δ 166.8, 164.6,151.4,148.8,146.6,145.4,145.0,138.3,127.8,127.5,121.2,110.9,50.9,32.9, 24.0,20.1,17.0.ESI-HRMS (m/z)：Calcd.for C20H24N5O2[M+H]+366.1925；found 366.1930.
(E) -6- methyl -4- (1- (6- (4- tert-butyl benzenes oxygroup) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros - The synthesis of 1,2,4- triazine -3 (2H) -one (I-13)
White solid, yield 86%, 183-184 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.97 (s, 1H, NH), 8.57 (s, 1H, Py-H), 8.30 (d, J=8.8Hz, 1H, Py-H), 7.45 (d, J=8.8Hz, 2H, Ar-H), 7.08 (t, J= 6.4Hz, 3H, Ar-H, Py-H), 4.15 (s, 2H, CH2), 2.19 (s, 3H, CH3), 1.94 (s, 3H, CH3), 1.31 (s, 9H, C (CH3)3)；13C NMR (100MHz, DMSO-d6) δ 166.8,164.6,151.1,148.8,147.2,146.6,145.4, 138.3,127.8,126.5,120.8,110.9,50.9,34.2,31.3,20.1,17.0, ESI-HRMS (m/z)： Calcd.for C21H26N5O2[M+H]+380.2081；found 380.2089.
(E) -6- methyl -4- (1- (6- (4- bromobenzenes oxygroup) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros -1,2, The synthesis of 4- triazines -3 (2H) -one (I-14)
White solid, yield 50%, 204-205 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.98 (s, 1H, NH), 8.58 (s, 1H, Py-H), 8.32 (d, J=8.8Hz, 1H, Py-H), 7.62 (d, J=8.8Hz, 2H, Ar-H), 7.16 (t, J= 8.8Hz, 3H, Ar-H, Py-H), 4.15 (s, 2H, CH2), 2.19 (s, 3H, CH3), 1.94 (s, 3H, CH3)；13C NMR (100MHz, DMSO-d6) δ 166.7,164.0,152.8,148.8,146.5,145.4,138.5,132.6,128.3,123.7, 117.0,111.3,50.9,20.1,17.0.ESI-HRMS (m/z)：Calcd.for C17H17BrN5O2[M+H]+402.0560； found 402.0566.
(E) -6- methyl -4- (1- (6- (4- iodobenzenes oxygroup) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros -1,2, The synthesis of 4- triazines -3 (2H) -one (I-15)
White solid, yield 46%, 180-181 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.97 (s, 1H, NH), 8.57 (s, 1H, Py-H), 8.31 (d, J=8.8Hz, 1H, Py-H), 7.77 (d, J=7.6Hz, 2H, Ar-H), 7.13 (d, J= 8.8Hz, 1H, Py-H), 7.02 (d, J=7.6Hz, 2H, Ar-H), 4.15 (s, 2H, CH2), 2.19 (s, 3H, CH3), 1.94 (s, 3H, CH3)；13C NMR (100MHz, DMSO-d6) δ 166.7,163.9,153.4,148.7,146.5,145.3,138.4, 128.3,123.9,111.3,89.1,50.9,20.1,17.0.ESI-HRMS (m/z)：Calcd.for C17H17IN5O2[M+H]+ 450.0421；found 450.0416.
(E) -6- methyl -4- (1- (6- (4- (benzyloxy) phenoxy group) pyridine -3- acyl groups) ethyleneimino) -4,5- bis- Hydrogen -1,2, the synthesis of 4- triazines -3 (2H) -one (I-16)
White solid, yield 50%, 149-150 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.96 (s, 1H, NH), 8.55 (s, 1H, Py-H), 8.27 (d, J=8.8Hz, 1H, Py-H), 7.47 (d, J=7.6Hz, 2H, Ar-H), 7.41 (t, J= 8.8Hz, 2H, Ar-H), 7.34 (t, J=7.2Hz, 1H, Py-H), 7.02-7.11 (m, 5H, Ar-H), 5.12 (s, 2H, OCH2), 4.14 (s, 2H, CH2), 2.18 (s, 3H, CH3), 1.94 (s, 3H, CH3)；13C NMR (100MHz, DMSO-d6) δ 166.8, 164.8,155.4,148.8,146.8,146.6,145.3,138.2,137.1,128.4,127.8,127.7,122.5, 115.6,110.6,69.6,50.9,20.1,16.9.ESI-HRMS (m/z)：Calcd.for C24H24IN5O3[M+H]+ 430.1874；found 430.1881.
(E) -6- methyl -4- (1- (6- (4- benzophenones oxygroup) pyridine -3- acyl groups) ethyleneimino) -4,5- dihydros - The synthesis of 1,2,4- triazine -3 (2H) -one (I-17)
White solid, yield 21%, 173-174 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.97 (s, 1H, NH), 8.64 (s, 1H, Py-H), 8.37 (d, J=8.8Hz, 1H, Py-H), 7.84 (d, J=8.8Hz, 2H, Ar-H), 7.76 (d, J= 7.2Hz, 2H, Ar-H), 7.69 (t, J=7.6Hz, 1H, Ar-H), 7.58 (t, J=7.6Hz, 1H, Ar-H), 7.35 (d, J= 8.8Hz, 2H, Ar-H), 7.23 (d, J=8.8Hz, 1H, Py-H), 4.16 (s, 2H, CH2), 2.21 (s, 3H, CH3), 1.95 (s, 3H, CH3)；13C NMR (100MHz, DMSO-d6) δ 194.6,166.7,163.4,157.3,146.7,145.4,138.7, 137.2,133.3,132.5,131.8,129.5,128.6,120.9,111.9,50.9,20.1,17.1.ESI-HRMS (m/z)： Calcd.for C24H22IN5O3[M+H]+428.1717；found 428.1720.
(E) -6- methyl -4- (1- (6- (4- isopropyl -3- methylphenoxies) pyridine -3- acyl groups) ethyleneimino) -4, 5- dihydros -1,2, the synthesis of 4- triazines -3 (2H) -one (I-18)
White solid, yield 50%, 164-165 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.96 (s, 1H, NH), 8.57 (s, 1H, Py-H), 8.28 (d, J=8.8Hz, 1H, Py-H), 7.28 (d, J=8.0Hz, 1H, Ar-H), 7.04 (d, J= 8.4Hz, 1H, Ar-H), 6.95 (d, J=8.4Hz, 2H, Ar-H, Py-H), 4.15 (s, 2H, CH2), 3.07-3.13 (m, 1H, CH (CH3)2), 2.30 (s, 3H, CH3), 2.19 (s, 3H, CH3), 1.94 (s, 3H, CH3), 1.20 (d, J=6.0Hz, 6H, CH (CH3)2)；13C NMR (100MHz, DMSO-d6) δ 166.8,164.7,150.9,148.8,146.7,145.4,143.0, 138.2,136.4,127.7,125.8,122.6,118.9,110.9,50.9,28.3,23.2,20.1,18.9,17.0.ESI- HRMS(m/z)：Calcd.for C21H26IN5O2[M+H]+380.2081；found 380.2087.
(E) -6- methyl -4- (1- (6- (2- isopropyl -5- methylphenoxies) pyridine -3- acyl groups) ethyleneimino) -4, 5- dihydros -1,2, the synthesis of 4- triazines -3 (2H) -one (I-19)
White solid, yield 53%, 165-166 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.96 (s, 1H, NH), 8.56 (s, 1H, Py-H), 8.28 (d, J=8.8Hz, 1H, Py-H), 7.28 (d, J=8.0Hz, 1H, Ar-H), 7.04 (d, J= 8.4Hz, 2H, Ar-H, Py-H), 6.85 (s, 1H, Ar-H), 4.14 (s, 2H, CH2), 2.90-2.97 (m, 1H, CH (CH3)2), 2.26 (s, 3H, CH3), 2.17 (s, 3H, CH3), 1.94 (s, 3H, CH3), 1.09 (d, J=6.8Hz, 6H, CH (CH3)2)；13C NMR (100MHz, DMSO-d6) δ 166.8,164.9,150.3,148.8,146.7,145.3,138.3,137.1,136.4, 127.6,126.7,126.3,122.6,110.4,50.9,26.5,22.9,20.4,20.1,16.9.ESI-HRMS (m/z)： Calcd.for C21H26IN5O2[M+H]+380.2081；found 380.2087.
(E) -6- methyl -4- (1- (6- (4- pi-allyl -2- methoxyphenoxies) pyridine -3- acyl groups) ethyleneimino) - 4,5- dihydros -1,2, the synthesis of 4- triazines -3 (2H) -one (I-20)
White solid, yield 49%, 127-128 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.94 (s, 1H, NH), 8.51 (s, 1H, Py-H), 8.25 (d, J=8.4Hz, 1H, Py-H), 7.08 (d, J=8.0Hz, 1H, Ar-H), 7.00 (d, J= 8.4Hz, 1H, Py-H), 6.97 (s, 1H, Ar-H), 6.81 (d, J=8.0Hz, 1H, Ar-H), 5.96-6.06 (m, 1H ,=CH), 5.14 (d, J=17.2Hz, 1H ,=CH), 5.08 (d, J=10.0Hz, 1H ,=CH), 4.14 (s, 2H, CH2), 3.66 (s, 3H, OCH3), 3.40 (d, J=6.8Hz, 2H, CH2), 2.17 (s, 3H, CH3), 1.94 (s, 3H, CH3)；13C NMR (100MHz, DMSO-d6) δ 166.9,164.5,151.2,148.8,146.5,145.3,139.8,138.2,138.0,137.5,127.4, 122.7,120.5,116.0,113.2,109.9,55.6,50.9,20.1,16.9.ESI-HRMS (m/z)：Calcd.for C21H24IN5O3[M+H]+394.1874；found 394.1880.
(E) -4- (1- (6- (2- benzoyl -4- methoxyphenoxies) pyridine -3- acyl groups) ethyleneimino) -6- methyl - 4,5- dihydros -1,2, the synthesis of 4- triazines -3 (2H) -one (I-21)
White solid, yield 35%, 85-87 DEG C of fusing point；1H NMR (400MHz, DMSO-d6)：δ 9.95 (s, 1H, NH), 8.42 (s, 1H, Py-H), 8.13 (d, J=8.8Hz, 1H, Py-H), 7.52-7.59 (m, 4H, Ar-H), 7.41 (t, J= 8.0Hz, 1H, Ar-H), 6.98 (d, J=8.8Hz, 1H, Py-H), 6.91 (d, J=2.4Hz, 1H, Ar-H), 6.71 (d, J= 8.8Hz, 1H, Ar-H), 4.12 (s, 2H, CH2), 3.85 (s, 3H, OCH3), 2.12 (s, 3H, CH3), 1.93 (s, 3H, CH3)；13C NMR (100MHz, DMSO-d6) δ 193.4,166.6,163.7,162.8,152.7,148.7,146.0,145.3,138.1, 137.7,132.7,132.1,129.1,128.2,127.9,124.1,111.0,110.6,108.6,55.8,50.9,20.1, 16.9.ESI-HRMS(m/z)：Calcd.for C25H24IN5O4[M+H]+458.1823；found 458.1830.
(E) -4- (1- (6- (5- amino-2-methyls phenoxy group) pyridine -3- acyl groups) ethyleneimino) -6- methyl -4,5- Dihydro -1,2, the synthesis of 4- triazines -3 (2H) -one (I-22)
White solid, yield 41%, 84-85 DEG C of fusing point；1H NMR (300MHz, DMSO-d6)：δ 9.95 (s, 1H, NH), 8.57 (s, 1H, Py-H), 8.27 (d, J=8.7Hz, 1H, Py-H), 6.94 (t, J=8.7Hz, 2H, Ar-H, Py-H), 6.39 (d, J=7.8Hz, 1H, Ar-H), 6.26 (s, 1H, Ar-H), 5.04 (s, 2H, NH2), 4.14 (s, 2H, CH2), 2.18 (s, 3H, CH3), 1.94 (s, 3H, CH3), 1.88 (s, 3H, CH3)；13C NMR (100MHz, DMSO-d6) δ 166.9,164.6,152.2,148.8, 148.2,146.8,145.3,138.2,131.3,127.3,116.0,111.3,110.0,107.1,50.9,29.0,20.1,16.9, 15.0.ESI-HRMS(m/z)：Calcd.for C18H21IN6O2[M+H]+353.1721；found 353.1728.
Embodiment 4：The measure of killing aphids, mensuration program are as follows：
The active testing of aphid
Killing aphids determination of activity step is as follows：Test worm be aphid (Aphis laburni Kaltenbach), laboratory silkworm The normal population of beans leaf raising.Drug is weighed, 1mL DMF is added to dissolve, adds two drop Tween-20 emulsifiers, adds in a certain amount of steaming Distilled water stirs evenly, and is made into the liquid of required concentration.It will immerse in medicament 5 seconds, take out with aphid (about 60) Broad Bean Leaves It gently dries, blots extra medicament with filter paper, then enter broad bean stem cutting in water-absorbing sponge, and branch is covered with cloche, use Gauze seals, and 96 hours inspection results, each compound is repeated 3 times.Control only adds in emulsifier and solvent into distilled water, stirs It mixes uniformly.
The killing aphids active testing result of 1 pymetrozine of table and its derivative (I)：
aIs not surveyed
It can be seen in table 1 that in 100mg/kg concentration, most pymetrozine derivatives show good killing aphids and live Property.In 5mg/kg concentration, I-6, I-11, I-12, I-14, I-16, I-18, I-19 shows and the comparable killing aphids of pymetrozine Activity.Especially compound I-7, I-13 show the killing aphids activity higher than pymetrozine in 5mg/kg concentration；In 2.5mg/ Compound I-7 during kg concentration, I-13 still show killing aphids activity, and pymetrozine does not have killing aphids activity.
Embodiment 5：Mosquitocidal larva, bollworm, corn borer, mythimna separata activity measure, mensuration program is as follows：
The active testing of mosquito larvae
The experimental method of mosquito larvae：Culex pipiens pallens, the normal population of indoor raising.Weigh test compound about 5mg adds 5mL acetone (or suitable solvent), as oscillation dissolving, 1000ppm mother liquors in penicillin medicine bottle.Pipette 0.5mL Mother liquor is added in the 100mL beakers for filling 89.9mL water, and larvae at the beginning of choosing 10 4 ages falls together together with 10mL feeding liquids Enter in beaker, the concentration of liquid is 5ppm.It is put into standard process chamber, for 24 hours inspection result.It is molten to contain 0.5mL experiments The aqueous solution of agent is blank control.
The active testing of bollworm
The experimental method of bollworm：Feed mixes medicine method, and the firm configuration that 3mL adds in about 27g is pipetted from the solution being configured In good feed, so as to obtain the required concentration of ten times of dilution.It equably pours into 24 clean orifice plates, dries in the air cool after medicament mixing 24 three age bollworms, inspection result after observation 3-4 days are accessed afterwards.
The active testing of corn borer
The test method of corn borer：The blade that diameter is about 5-6cm after required concentration is postponed, is immersed medicine by leaf dipping method It 5-6 seconds in liquid, takes out, is placed on blotting paper and dries, be placed in the culture dish specified, access 10 3 instar larvaes, be put into 27 ± 1 DEG C insectary in observe 3-4 days after inspection result.
The active testing of mythimna separata
The experimental method of mythimna separata：The blade that diameter is about 5-6cm after required concentration is postponed, is immersed liquid by leaf dipping method It is 5-6 seconds middle, it takes out, is placed on blotting paper and dries, be placed in the culture dish specified, access 10 3 instar larvaes, be put into 27 ± 1 DEG C Insectary in observe 3-4 days after inspection result.
The mosquito-larvicidal activity test result of 2 pymetrozine of table and its derivative (I)：
aIs not surveyed
3 pymetrozine of table and its derivative (I) kill bollworm, corn borer, mythimna separata active testing result：
The mosquitocidal larva of 4 pymetrozine of table and its derivative (I), bollworm, corn borer, mythimna separata active testing result：
As it can be seen that most of pymetrozine derivatives show activity to mosquito larvae from table 2 and table 4.Especially compound I-13 and I-20 shows mosquito larvae very high activity, and in 0.5mg/kg, I-13 shows 40% insecticidal activity, During 0.01mg/kg, I-20 shows 20% insecticidal activity.
As it can be seen that most of pymetrozine derivatives show activity to bollworm, corn borer and mythimna separata from table 3 and table 4. In 100mg/kg, 30%, 20% and 60% is shown to bollworm, corn borer and mythimna separata respectively by especially compound I-20 Insecticidal activity.

Claims (2)

1. compound is selected from：
2. application of the pymetrozine class compound described in claim 1 in terms of desinsection, wherein pest be selected from aphid, mosquito larvae, Bollworm, corn borer and mythimna separata.
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