CN1663384A - Pesticide and its preparing method - Google Patents
Pesticide and its preparing method Download PDFInfo
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- CN1663384A CN1663384A CN 200510045998 CN200510045998A CN1663384A CN 1663384 A CN1663384 A CN 1663384A CN 200510045998 CN200510045998 CN 200510045998 CN 200510045998 A CN200510045998 A CN 200510045998A CN 1663384 A CN1663384 A CN 1663384A
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Abstract
Disclosed is a pesticide having insecticidal activity, its preparation. and compounds containing the active constituent with general formula disclosed in t he specification, wherein R1 is trifluoromethyl or hydrogen substituent group, R2 is trifluoromethyl, trifluoro methoxyl or hydrogen substituent group. The preparation process comprises the synthesis of intermediate compound 3-(5-chlorin-2-carboxyl phenyl) propionic acid, synthesis of 5-chlorin-1-carbonyl-1,3-dihydrogen-2-indenyl methyl formate, synthesis of 5-chlorin-1-carbonyl-1-carbonyl-1,3-dihydrogen-2-indenyl methyl formate.
Description
Technical field
The invention belongs to the insecticide technical field, insecticide of specifically a kind of fused-ring derivatives with insecticidal activity and preparation method thereof.
Background technology
Because human attention to environmental issue is had higher requirement to the toxicity of agricultural chemicals and to the influence of environment, high malicious organophosphorous pesticide is because toxicity and environmental problem and be eliminated gradually.In recent decades, the insecticide of having researched and developed many new and effective, low toxicities is to substitute high malicious organophosphorous pesticide, and the condensed ring insecticides is a class wherein.Its mechanism of action is the sodium-ion channel in the blocking-up insect nerve cell, thereby makes the nerve cell loss of function, thereby causes target pest paralysis, inaccurate coordination, and is final dead.The indoxacarb (WO 92/11249) of E.I.Du Pont Company's exploitation is one of them, and it is new that it has structure, mechanism of action uniqueness, and consumption is low, and is all effective to nearly all lepidoptera pest, and to characteristics such as the mankind, environment, crop and non-target organism safety.In addition, indoxacarb medication binding hours before crop harvesting is short, is fit to the pest management integrated system, is to substitute one of desirable kind of organic phosphorous insecticide, has become present research focus and the product that is subjected to extensive concern.In addition, E.I.Du Pont Company has also reported many similar compounds, and structure comprises thick two rings, thick three rings, and the compound of being reported mostly has activity.
Summary of the invention
Purpose of the present invention is exactly on the basis of above-mentioned research, keeps the active part of compound, changes other variable group, develops insecticide with efficient insecticide effect of a class new construction and preparation method thereof.
The object of the present invention is achieved like this: be the condensed ring insecticides, comprise two rings, tricyclic structure, wherein have chlorine and replace on phenyl ring, have the structure of urea at the remainder of molecule, structural formula of the present invention is the following general formula compound that contains as active component:
R in the formula
1Be trifluoromethyl or hydrogen bond substituting group.
The present invention also comprises the following general formula compound that contains as active component:
R in the formula
2Be trifluoromethyl, trifluoromethoxy or hydrogen bond substituting group.
Five kinds of concrete structural formulas of the present invention are as follows:
Their preparation is to be raw material with the 4-Chlorophenylacetic acid, finishes through steps such as closed loop, oxidation, condensation, hydrogenation deprotection, acidylates, and concrete synthetic route is as follows.
Reaction equation according to above-mentioned the present invention includes following steps:
3-(5-chloro-2-carboxyl phenyl) propionic acid synthetic (a, b, c):
In fact this operation comprises three-step reaction: at first, change 4-Chlorophenylacetic acid into acyl chlorides, used chlorination reagent is thionyl chloride, phosphorus trichloride etc., with chlorobenzene acetic acid amount of substance proportioning be 1: 1～4: 1, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, reaction temperature from room temperature to the solvent refluxing temperature, reaction time 3～10h; Then under alchlor catalysis, with ethene addition and further closed loop, the consumption of alchlor is 50%～300%, reaction temperature-15～25 ℃; Use Peracetic acid oxidation open loop again, obtain intermediate 3-(5-chloro-2-carboxyl phenyl) propionic acid, used Peracetic acid content is from 10%～30%, 0～50 ℃ of reaction temperature, reaction time 10h～5 day.
5-chloro-1-carbonyl-1, synthetic (d) of 3-dihydro-2-indenyl methyl formate:
This operation in fact also comprises two-step reaction: at first, with 3-(5-chloro-2-carboxyl phenyl) propionic acid esterification, generate corresponding diester, esterifying agent is dimethyl carbonate, dimethyl suflfate, methyl benzene sulfonate etc., be reflected under the catalysis such as sulfuric acid, acetate, p-methyl benzenesulfonic acid, hydrogen chloride, under reflux state, carry out 10～24h; Then, closed loop under the highly basic effect obtains product, and used alkali is sodium methoxide, caustic alcohol, potassium ethoxide etc., 10～80 ℃ of reaction temperatures, reaction time 0.5～15h.
5-chloro-2-hydroxyl-1-carbonyl-1, synthetic (e) of 3-dihydro-2-indenyl methyl formate:
Reaction adopts peroxide to make oxidant, used oxidant comprises TBHP, Peracetic acid, m-chloro-benzoic acid peroxide etc., solvent comprises ester class (as ethyl acetate, isopropyl acetate etc.), halogenated hydrocarbons (as carrene, chloroform etc.) etc., and oxidant and substrate proportioning are 1: 1～6: 1.Reaction is generally at room temperature carried out, and the different condition of basis of time did not wait from 1h to 30 day.
Synthetic (f) of [5-chloro-2-hydroxyl-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate:
5-chloro-2-hydroxyl-1-carbonyl-1,3-dihydro-2-indenyl methyl formate and hydrazino benzyl formate condensation under acid catalysis promptly obtain product.Be reflected in methyl alcohol, ethanol, dichloroethane, chloroform, the acetate equal solvent and carry out, used acid catalyst is that (consumption is 5-chloro-2-hydroxyl-1-carbonyl-1 for sulfonic acid, sulfuric acid, acetate etc., 1%～20% (w/w) of 3-dihydro-2-indenyl methyl formate), 5-chloro-2-hydroxyl-1-carbonyl-1, the proportioning of 3-dihydro-2-indenyl methyl formate and hydrazino benzyl formate is 1: 0.9～1: 1.8.Several hours to several days time is generally carried out in reaction under reflux state.
2-benzyl-7-chlorine [1,2-e] indeno [1,3,4] oxadiazines-2,4a (3H, 5H)-synthetic (g) of dioctyl phthalate methyl esters and [5-chloro-2-methoxymethoxy-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate:
[5-chloro-2-hydroxyl-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate and formaldehyde and analog reaction thereof can obtain closed loop or alkylate.The formaldehyde analog that the present invention adopts is a dimethoxymethane, and reaction dissolvent is chlorohydrocarbon (as carrene, dichloroethane, a chloroform etc.), and catalyzer is the phosphorus pentoxide of diatomite adsorption, and reaction temperature is a room temperature to 80 ℃.Reaction mechanism mechanism of reaction reality is at first sloughed a part methyl alcohol, generates the O-alkylate; Then, slough a part methyl alcohol again, generate the closed loop product.Therefore, in the control reaction time, can obtain different products: reaction 10～20h mainly obtains alkylate [5-chloro-2-methoxymethoxy-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate; Reacted 1～3 day, mainly obtain closed loop product 2-benzyl-7-chlorine [1,2-e] indeno [1,3,4] oxadiazines-2,4a (3H, 5H)-the dioctyl phthalate methyl esters.
Synthetic (h, the i of the object of the invention compound; H ', i '):
2-benzyl-7-chlorine [1 that the front is synthetic; 2-e] indeno [1; 3; 4] oxadiazines-2; 4a (3H; 5H)-dioctyl phthalate methyl esters or [5-chloro-2-methoxymethoxy-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate molecule in benzyl ester protecting group on the nitrogen remove, connect different side chains with acyl chloride reaction again, can obtain the purpose compound of claim.
This step comprises two-step reaction, catalytic hydrogenation deprotection and N-acylation reaction.The catalytic hydrogenation deprotection carries out in ethyl acetate, methyl acetate, methyl alcohol, ethanol equal solvent, and catalyzer is palladium or activated carbon loaded palladium load capacity (0..8%～10%), and Hydrogen Vapor Pressure is normal pressure or 1.0 * 10
5The low pressure that Pa is following also should add catalyst such as small amount of acetic acid, sodium acetate, sodium dihydrogen phosphate in the reaction system, and reaction temperature is a room temperature to 45 ℃, time 1～40h.The resulting product of catalytic hydrogenation deprotection both can be separated, and also can not separate elimination catalyzer, the directly use of washing back.The N-acylation reaction is carried out in ethyl acetate, methyl acetate, acetone, carrene, dichloroethane, chloroform, benzene, toluene equal solvent; add alkali (as potash, sodium carbonate, sodium bicarbonate etc.) and make acid binding agent; reaction temperature from 0 ℃ to refluxing, the time ask 2～20h.The separation of product is purified, and (solvent is methyl alcohol, ethanol, propyl alcohol, ethyl acetate, methyl acetate, benzinum, benzene,toluene,xylene, chloroform, carrene etc. to the method that both can adopt recrystallization, or its mixture), the method that also can adopt column chromatography to separate.
According to the method described above, synthesized the compound of claim of the present invention, their analysis data are as shown in table 1.
Each compound analysis data of table 1
| Compound | ? ?mp/℃ | ? 1H?NMR，δ(CDCl 3，400M) | ????QTOF-MS(ES，positive)，m/z | |
| Calculated value | Measured value | |||
| ? ? ??PC-1 ? ? | ? ? ?138～140 ? ? | 12.76(s，1H)，7.75(d，1H，J＝8.8Hz)， 7.69(d，2H，J＝8.0Hz)，7.35(d，2H，J＝8.4 Hz)，7.27(d，2H，J＝8.4Hz)，5.05(q，2H)， 3.77(s，3H)，3.73(s，3H)，3.67(q，2H)， 3.51(s，3H) | ? ? ????[M+H] +， ????544.1098 ? | ? ? ??[M+H] +， ??544.1101 ? |
| ? ??PC-2 ? | ? ?150～156 ? | 12.75(s，1H)，7.75(d，1H，J＝8.8Hz)， 7.2～7.5(m，7H)，5.04(q，2H)，3.75(s，3H)， 3.73(s，3H)，3.65(q，2H)，3.51(s，3H) | ? ????[M+K] +， ????514.0783 | ? ??[M+K] +， ??514.0778 |
| ? ??PC-3 ? ? | ? ?134～137 ? ? | 12.75(s，1H)，7.75(d，1H，J＝8.8Hz)， 7.2～7.4(m，6H)，5.06(d，1H，J＝7.6Hz)， 5.03(d，1H，J＝7.6Hz)，3.77(s，3H)， | ? ????[M+K] +， ????598.0606 ? | ? ??[M+K] +， ??598.0591 ? |
| ? ? ? ? ? PC-4 ? ? ? | ? ? ? ? ? ??118～126 ? ? ? | 3.73(s，3H)，3.70(d，1H，J＝17.2Hz)， 3.61(d，1H，J＝17.2Hz)，3.51(s，3H) 7.64(d，2H，J＝8.4Hz)，7.50(d，1H，J＝8.0 Hz)，7.45(d，2H，J＝8.0Hz)，7.33(d，1H， J＝8.0Hz)，7.32(s，1H)，5.73(d，1H，J＝9.6 ? .Hz)，5.24(d，1H，J＝9.6Hz)，3.75(s，3H)， 3.72(s，3H)，3.50(d，1H，J＝16Hz)，3.27(d， 1H，J＝16Hz) | ? ? ? ? ??[M+H] +， ? ??512.0836 ? ? | ? ? ? ? ????[M+H] +， ? ????512.0852 ? ? |
| ? ? PC-5 ? ? | ? ? ??137～139 ? ? | 7.53(d，2H，J＝8.4Hz)，7.2～7.4(m，7H)， 5.70(d，1H，J＝9.6Hz)，5.22(d，1H，J＝9.6 ? Hz)，3.72(s，3H)，3.70(s，3H)，3.48(d，1H， J＝16Hz)，3.25(d，lH，J＝16Hz) | ? ??MS(ES，positive)，m/z： ? ??494([M+H] +) ? | |
The compound that is synthesized is carried out the insecticidal activity test, the insect of test is: mythimna separata, diamond-back moth, cotten aphid, Tetranychus cinnabarinus, Culex pipiens pallens, test compounds concentration is except that being the 10mg/L to Culex pipiens pallens, all the other insects are 600mg/L, not dispenser is a blank, and control drug and concentration thereof are fluorine worm nitrile 150mg/L, Imidacloprid 10mg/L, efficient chlorine cyanogen 10mg/L.Dispenser is calculated insecticidal activity in the dead ratio of insect two days later, and test result is shown in Table 2.
Table 2 insecticidal activity test result
| Compound | Insecticidal activity/% | ||||
| Mythimna separata | Diamond-back moth | Cotten aphid | Tetranychus cinnabarinus | Culex pipiens pallens | |
| The efficient chlorine cyanogen of PC-1 PC-3 PC-4 PC-5 ethiprole 150mg/L Imidacloprid 10mg/L 10mg/L CK | ????100 ????60 ????100 ????20 ????20 ????0 ????100 ????0 | ????40 ????40 ????100 ????80 ????100 ????0 ????0 ????0 | ????20 ????70 ????0 ????0 ????80 ????100 ????100 ????0 | ????0 ????0 ????0 ????0 ????0 ????0 ????20 ????0 | ????100 ????0 ????50 ????0 ????100 ????100 ????100 ????0 |
Compound of the present invention is used to prevent and treat various agricultural insect, especially lepidoptera pest.
Insecticide of the present invention belongs to sodium channel blocking-up type insecticide, and its dominant mechanism is by the sodium-ion channel in the blocking-up insect nerve cell, makes the nerve cell loss of function, causes target pest paralysis, inaccurate coordination, and is final dead.It has mechanism of action uniqueness, and consumption is low, and is safe and efficient, all effective to each instar larvae, does not have the characteristics of cross resistance with agricultural chemicals such as chrysanthemum ester class, carbamatess.They have efficient to various lepidoptera pests (as cotton bollworm, cabbage caterpillar, oriental tobacco budworm, diamond-back moth, beet armyworm, prodenia litura, tomato moth, rape three-spotted plusia, the emerald green line of cotton spark, Lee's Grapholita spp, cotton cotton leafroller, codling moth, grape berry moth, potato tuberworm), and to the mankind, environment, crop and non-target organism safety.
The present invention can be widely used in preventing and treating various lepidoptera pests on the crops such as wild cabbage, cucumber, capsicum, cotton, apple, grape, potato, pears, rape, sweet corn, lettuce.Medicament enters in the pest body by contacting or get food, and insect promptly stops feed in 0～4 hour, and paralysis is to death immediately.Therefore, can prevent the harm of insect effectively, and crop is not damaged the blade of crop, bud, fruit etc.These insecticides are very low to people's toxicity, and are very little to user's threat, are a kind of agricultural chemicals that can relieved use.These insecticides residence time in crop is short, and the medication binding hours is short before the results, is fit to the pest integrated management.In addition, the solvability of these insecticides in water is very little, is not easy to be advanced rivers,lakes and seas by rain drop erosion.Simultaneously, their vapour pressure is lower, is not easy volatilization and causes air pollution.Therefore, these insecticides are to substitute organophosphorus insecticide, are used for the integrated control of insect and the desirable medicament of resistance management.
Insecticide of the present invention can be configured to various formulations (as missible oil, pulvis etc.), also can be made into various concentration by demand and use.Simultaneously, they can also with the pesticide compositional of other type after use, can strengthen control efficiency to insect.In a word, these insecticides have excellent application performance energy and application prospects.
To be described in further detail the present invention by example below, but following example only is the present invention's example wherein, the rights protection scope of not representing the present invention and being limited, the scope of the present invention is as the criterion with claims.
Embodiment
Embodiment 1
Synthetic (step a, b, the c) of 3-(5-chloro-2-carboxyl phenyl) propionic acid
In the 500mL there-necked flask, add 4-Chlorophenylacetic acid 40g, dichloroethane 140mL is warming up to backflow, dripping thionyl chloride 30mL, and back flow reaction 3h steams the intact thionyl chloride of dichloroethane and unreacted.Be cooled to below 0 ℃, add dichloroethane 100mL, alchlor 45g.The control temperature slowly feeds ethene below 5 ℃ under liquid level, rise to room temperature reaction and spend the night.Then, reactant liquor is poured in the hydrochloric frozen water, separatory, water layer extracts with dichloroethane.Merge organic layer, washing, the 1mol/L sodium hydroxide solution is washed, washing.Put into the 1L there-necked flask, add sodium acetate 19g, drip 20% Peracetic acid 240mL, reaction 3d.Reactant liquor is poured in the 300mL 1mol/L watery hydrochloric acid, filtered, dichloroethane is washed, and drying gets white solid 10～20g.
1H?NMR，δ(CDCl
3，400M)：7.84(d，1H，J＝8.0Hz)，7.32(s，1H)，7.26(d，1H，J＝8.0Hz)，3.17(t，2H，J＝7.2Hz)，2.52(t，2H，J＝7.2Hz)。
5-chloro-1-carbonyl-1, the synthetic (step d) of 3-dihydro-2-indenyl methyl formate
In the 500mL there-necked flask, add 3-(5-chloro-2-carboxyl phenyl) propionic acid 24g, dimethyl carbonate 90mL, methyl alcohol 4.8mL, sulfuric acid 2.4mL, back flow reaction 15h.Steam dimethyl carbonate, add methyl alcohol 150mL, 25% sodium methoxide/methanol solution 75mL, back flow reaction 5h separates out white solid gradually.Reduce to room temperature, add acetate to solid molten entirely (about 50mL), pour in the water, filter, drying gets white solid 21g.
1H?NMR，δ(CDCl
3，400M)：10.2～10.4(br，～0.24H)，7.70(d，1H，J＝8Hz)，7.56(d，～0.33H)，7.50(s，1H)，～7.46(～0.29H)，7.37(d，1H，J＝8.0Hz)，7.26(s，～0.33H)，3.86(s，～0.84H)，3.79(s，3H)，3.74(dd，1H，J＝8.4×4.0Hz)，3.54(dd，1H，J＝17.6×4.0Hz)，3.50(s，～0.8H)，3.34(dd，1H，J＝17.6×8.4Hz)。
5-chloro-2-hydroxyl-1-carbonyl-1, the synthetic (step e) of 3-dihydro-2-indenyl methyl formate
In the 250mL flask, add 5-chloro-1-carbonyl-1,3-dihydro-2-indenyl methyl formate 15g, isopropyl acetate 150mL, cinchonine 0.45g, TBHP 15mL, room temperature reaction 10d.Add triethylamine 4mL, react 10d again.Saturated solution of sodium bisulfite is washed, the pickling of 1mol/L salt, and washing, drying steams isopropyl acetate, and ethyl alcohol recrystallization gets faint yellow solid 9g.
Synthetic (the step f) of [5-chloro-2-hydroxyl-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate
In the 100mL there-necked flask, add 5-chloro-2-hydroxyl-1-carbonyl-1,3-dihydro-2-indenyl methyl formate 10g, hydrazino benzyl formate 8.3g, p-methyl benzenesulfonic acid 0.3g, methyl alcohol 50mL, back flow reaction 4h.White solid is separated out in cooling, filters, and methyl alcohol is washed, and drying gets white solid 12g.
1H?NMR，δ(CDCl
3，400M)：9.47(s，1H)，7.76(d，1H，J＝8.0Hz)，7.1～7.4(m，7H)，7.19(s，2H)，4.38(s，1H)，3.72(s，3H)，3.49(d，1H，J＝17.2Hz)，3.27(d，1H，J＝17.2Hz)。
Synthetic (the step g) of [5-chloro-2-methoxymethoxy-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate
In the 500mL there-necked flask, add diatomite 20g, dichloroethane 80mL, dimethoxymethane 15mL, add phosphorus pentoxide 10g under stirring in batches, stir 20min.Add [5-chloro-2-hydroxyl-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate 10g and be dissolved in 150mL dichloroethane hot solution, room temperature reaction 15h.Filter, dichloroethane filter wash cake merges organic layer, washing, and drying steams dichloroethane, and ethyl alcohol recrystallization gets white solid 4g.
1H?NMR，δ(CDCl
3，400M)：9.63(s，1H)，7.71(d，1H，J＝8.0Hz)，7.2～7.5(m，7H)，5.29(d，1H，J＝12.0Hz)，5.24(d，1H，J＝12.0Hz)，4.87(d，1H，J＝7.2Hz)，4.84(d，1H，J＝7.2Hz)，3.70(s，1H)，3.66(d，1H，J＝16.8Hz)，3.56(d，1H，J＝16.8Hz)，3.41(s，1H)。
1-(N-amino) imino group-5-chloro-2-methoxymethoxy-1, synthetic (the step h ') of 3-dihydro indenes-2-base methyl formate
In the 100mL flask, add 5%Pd/C 0.1g, [5-chloro-2-methoxymethoxy-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate 1g, ethyl acetate 30mL, acetate 3mL, with the air in the hydrogen exchange flask, logical hydrogen under the stirring at room, TLC detection reaction terminal point, reaction need 12～20h approximately.After reacting end, filter, ethyl acetate filter wash cake merges organic solvent, and the 1mol/L sodium hydroxide solution is washed, washing, and drying steams solvent, gets white solid 0.45g.
1H?NMR，δ(CDCl
3，400M)：7.47(d，1H，J＝8.0Hz)，7.22(d，1H，J＝8.0Hz)，7.21(s，1H)，6.22(s，2H)，4.87(q，2H)，3.74(s，3H)，3.57(q，2H)，3.42(s，3H)。
1-[N-[N '-[[N "-methoxycarbonyl group-N "-(4 '-trifluoromethyl) phenyl] amino carbonyl] amino]] imino group-5-chloro-2-methoxymethoxy-1, synthetic (step I ') of 3-dihydro indenes-2-base methyl formate (Compound P C-1)
In the 20mL there-necked flask; add 1-(N-amino) imino group-5-chloro-2-methoxymethoxy-1; 3-dihydro indenes-2-base methyl formate 100mg, N-chloroformyl-N-(4-trifluoromethyl) methyl carbamate 80mg, ethyl acetate 10mL, Anhydrous potassium carbonate 0.66g; stirring at room reaction 15h; washing, drying steams solvent; add the small amount of ethanol recrystallization, get white solid 110mg.Product structure is confirmed correct through mass spectrum, nuclear magnetic resonance spectrum.
Embodiment 2
1-[N-[N '-[(N "-methoxycarbonyl group-N "-phenyl) amino carbonyl] amino]] imino group-5-chloro-2-methoxymethoxy-1,3-dihydro indenes-2-base methyl formate (Compound P C-2) synthetic
In the 20mL there-necked flask; add 1-(N-amino) imino group-5-chloro-2-methoxymethoxy-1; 3-dihydro indenes-2-base methyl formate 100mg, N-chloroformyl-N-phenylcarbamic acid methyl esters 72mg, ethyl acetate 10mL, Anhydrous potassium carbonate 0.66g; stirring at room reaction 15h; washing, drying steams solvent; add the small amount of ethanol recrystallization, get white solid 120mg.Product structure is confirmed correct through mass spectrum, nuclear magnetic resonance spectrum.
Embodiment 3
1-[N-[N '-[[N "-methoxycarbonyl group-N "-(4 '-trifluoromethoxy) phenyl] amino carbonyl] amino]] imino group-5-chloro-2-methoxymethoxy-1,3-dihydro indenes-2-base methyl formate (Compound P C-3) synthetic
In the 20mL there-necked flask; add 1-(N-amino) imino group-5-chloro-2-methoxymethoxy-1; 3-dihydro indenes-2-base methyl formate 100mg, N-chloroformyl-N-(4-Trifluoromethoxyphen-l) methyl carbamate 85mg, ethyl acetate 10mL, Anhydrous potassium carbonate 0.66g; stirring at room reaction 15h; washing, drying steams solvent; add the small amount of ethanol recrystallization, get white solid 130mg.Product structure is confirmed correct through mass spectrum, nuclear magnetic resonance spectrum.
Embodiment 4
2-benzyl-7-chlorine [1,2-e] indeno [1,3,4] oxadiazines-2, and 4a (3H, 5H)-synthetic (step g) of dihydro methyl formate
In the 500mL there-necked flask, add diatomite 20g, dichloroethane 80mL, dimethoxymethane 15mL, add phosphorus pentoxide 10g under stirring in batches, stir 20min.Add [5-chloro-2-hydroxyl-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate 10g and be dissolved in 150mL dichloroethane hot solution, room temperature reaction 2d.Filter, dichloroethane filter wash cake merges organic layer, washing, and drying steams dichloroethane, and ethyl alcohol recrystallization gets white solid 6g.
1H?NMR，δ(CDCl
3，400M)：7.69(d，1H，J＝8.4Hz)，7.2～7.5(m，7H)，7.56(br?d，J＝7.6Hz)，5.34(d，1H，J＝12.0Hz)，5.29(d，1H，J＝12.0Hz)，5.15(d，1H，J＝9.6Hz)，3.66(s?3H)，3.45(d，1H，J＝16.0Hz)，3.23(d，1H，J＝16.0Hz)。
7-chloro-2,3,4a, 5-tetrahydrochysene-2-[methoxycarbonyl group (4-trifluoromethyl) carbamoyl] indenes penta [1,2-e] [synthetic (step h, the i) of 1,3,4] oxadiazines-4a-methyl formate (Compound P C-4)
In the 20mL flask, add 2-benzyl-7-chlorine [1,2-e] indeno [1,3,4] oxadiazines-2,4a (3H, 5H)-dioctyl phthalate methyl esters 350mg, 5%Pd/C 35mg, methyl acetate 8mL, sodium acetate 4mg, with the air in the hydrogen exchange flask, logical hydrogen under the stirring at room, TLC detection reaction terminal point, reaction needs 2～6h approximately.After reaction finishes, filter, filter cake is washed with methyl acetate.Merge organic layer, saturated sodium bicarbonate solution is washed, washing, and organic layer is put into the 20mL flask.Add N-chloroformyl-N-(4-trifluoromethyl) methyl carbamate 200mg, saturated sodium bicarbonate solution 5mL again, under the nitrogen protection, room temperature reaction 3h.Add water, stirring makes solid molten entirely, separatory, and the washing organic layer, drying, solvent flashing gets grease.Ethyl alcohol recrystallization or column chromatography are separated, and get product 20～40mg.Product structure is confirmed correct through mass spectrum, nuclear magnetic resonance spectrum.
Embodiment 5
7-chloro-2,3,4a, 5-tetrahydrochysene-2-[methoxycarbonyl group (phenyl) carbamoyl] indenes penta [1,2-e] [synthesizing of 1,3,4] oxadiazines-4a-methyl formate (Compound P C-5)
In the 20mL flask, add 2-benzyl-7-chlorine [1,2-e] indeno [1,3,4] oxadiazines-2,4a (3H, 5H)-dioctyl phthalate methyl esters 350mg, 5%Pd/C 35mg, methyl acetate 8mL, sodium acetate 4mg, with the air in the hydrogen exchange flask, logical hydrogen under the stirring at room, TLC detection reaction terminal point, reaction needs 2～6h approximately.After reaction finishes, filter, filter cake is washed with methyl acetate.Merge organic layer, saturated sodium bicarbonate solution is washed, washing, and organic layer is put into the 20mL flask.Add N-chloroformyl-N-phenylcarbamic acid methyl esters 180mg, saturated sodium bicarbonate solution 5mL again, under the nitrogen protection, room temperature reaction 3h.Add water, stirring makes solid molten entirely, separatory, and the washing organic layer, drying, solvent flashing gets grease.Ethyl alcohol recrystallization or column chromatography are separated, and get product 20～40mg.Product structure is confirmed correct through mass spectrum, nuclear magnetic resonance spectrum.
Embodiment 6
Synthesizing of 4-Trifluoromethoxyphen-l methyl carbamate
In the 100mL there-necked flask, add 4-trifluoro-methoxyaniline 10mL, ethyl acetate 40mL, pyridine 8.3mL, the ice-water bath cooling drips methylchloroformate 8mL down, reaction 8h.Add water, separatory is used 1mol/L hydrochloric acid, 1mol/L sodium hydroxide solution, water successively, washes twice, and drying steams solvent, and the benzinum recrystallization gets white solid 16.5g.
Embodiment 7
Synthesizing of N-chloroformyl-N-(4-Trifluoromethoxyphen-l) methyl carbamate
In the 100mL there-necked flask, add 4-Trifluoromethoxyphen-l methyl carbamate 4g, toluene 40mL, glycol dimethyl ether 10mL, 50% sodium hydride 2g, stirring at room 8h gets suspension.In another there-necked flask, triphosgene 5g is dissolved in 20mL toluene, and ice-water bath is cooled to below 5 ℃, and above-mentioned suspension is splashed into, and about 1h drips off, and continues reaction 2h.Frozen water is washed, and drying steams solvent, and chloroform/carbon tetrachloride recrystallization gets white solid 1.7g.
Embodiment 8
Synthesizing of N-chloroformyl-N-(4-trifluoromethyl) methyl carbamate
In the 100mL there-necked flask, add 4-trifluoromethyl methyl carbamate 4g, toluene 40mL, glycol dimethyl ether 10mL, 50% sodium hydride 2g, stirring at room 8h gets suspension.In another there-necked flask, triphosgene 5g is dissolved in 20mL toluene, and ice-water bath is cooled to below 5 ℃, and above-mentioned suspension is splashed into, and about 1h drips off, and continues reaction 2h.Frozen water is washed, and drying steams solvent, and chloroform/carbon tetrachloride recrystallization gets white solid 2.5g.
Embodiment 9
Synthesizing of N-chloroformyl-N-phenylcarbamic acid methyl esters
In the 100mL there-necked flask, add phenylcarbamic acid methyl esters 4g, toluene 40mL, glycol dimethyl ether 10mL, 50% sodium hydride 2.5g, stirring at room 8h gets suspension.In another there-necked flask, triphosgene 6g is dissolved in 20mL toluene, and ice-water bath is cooled to below 5 ℃, and above-mentioned suspension is splashed into, and about 1h drips off, and continues reaction 2h.Frozen water is washed, and drying steams solvent, and chloroform/carbon tetrachloride recrystallization gets white solid 2.7g.
Test examples 1
The insecticidal activity test
The mixed solvent of getting 2.5ml acetone/methanol (1: 1) joins in the measuring cup that fills the 3mg noval chemical compound, stirs it is fully dissolved, and adds the running water that leaves standstill that 2.5ml contains 1 ‰ Tween 80s, obtains the noval chemical compound solution 5ml of 600mg/L after stirring.The processing method of the former medicine of standard medicament is all identical with noval chemical compound.Be treated to blank with acetone/methanol/water (1: 1: 2, contain 1 ‰ Tween 80s).
Mythimna separata, diamond-back moth, cotten aphid and Tetranychus cinnabarinus adopt the airbrush spray-on process to handle, and atomisation pressure is 0.7kg/cm
2, spouting liquid 0.3ml, 2 repetitions are established in every processing.Mythimna separata and diamond-back moth are at first sprayed and handle blade (mythimna separata is used maize leaves, and diamond-back moth is used cabbage leaves), connect 5 larvas after blade dries in the shade.For cotten aphid and Tetranychus cinnabarinus, then directly cucumber leaves and the Kidney bean blade that target is arranged infected in the spraying processing.Culex pipiens pallens adopts immersion method to handle, and being about to soup has in the beaker of 20 larvas direct the adding.
Examination material after the processing moves to that (23～25 ℃, 40～60%R.H., L/D are 13h: 11h) in the standard observation ward.Lepidopterous larvae is handled the lethality of back 3 days investigation examination worms, and black peach aphid, Tetranychus cinnabarinus and Culex pipiens pallens write down (the results are shown in Table shown in 2) in the lethality of processing investigation examination in back 2 days worm according to trying the insecticidal activity of worm lethality to compound.
Claims (4)
1, a kind of insecticide with insecticidal activity, contain the following general formula compound as active component:
R in the formula
1Be trifluoromethyl or hydrogen bond substituting group.
2, preparation method according to claim 1 may further comprise the steps: the first step, change 4-Chlorophenylacetic acid into acyl chlorides, and by ethene addition and further closed loop, use Peracetic acid oxidation open loop again, obtain intermediate 3-(5-chloro-2-carboxyl phenyl) propionic acid; The 5-chloro-1-carbonyl-1 in second step, 3-dihydro-2-indenyl methyl formate synthetic; The 5-chloro-2-hydroxyl-1-carbonyl-1 in the 3rd step, 3-dihydro-2-indenyl methyl formate synthetic; Synthesizing of [5-chloro-2-hydroxyl-2-(the methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate in the 4th step; 2-benzyl-7-chlorine [1,2-e] indeno in the 5th step [1,3,4] oxadiazines-2, and 4a (3H, 5H)-the dioctyl phthalate methyl esters is synthetic with [5-chloro-2-methoxymethoxy-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate; At last; 2-benzyl-7-chlorine [1 that the front is synthetic; 2-e] indeno [1; 3; 4] oxadiazines-2,4a (3H, 5H)-dioctyl phthalate methyl esters or [5-chloro-2-methoxymethoxy-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate molecule in benzyl ester protecting group on the nitrogen remove; connect different side chains with acyl chloride reaction again, can obtain the purpose compound.
3, a kind of insecticide with insecticidal activity, contain the following general formula compound as active component:
R in the formula
2Be trifluoromethyl, trifluoromethoxy or hydrogen bond substituting group.
4, preparation method according to claim 1 may further comprise the steps: the first step, change 4-Chlorophenylacetic acid into acyl chlorides, and by ethene addition and further closed loop, use Peracetic acid oxidation open loop again, obtain intermediate 3-(5-chloro-2-carboxyl phenyl) propionic acid; The 5-chloro-1-carbonyl-1 in second step, 3-dihydro-2-indenyl methyl formate synthetic; The 5-chloro-2-hydroxyl-1-carbonyl-1 in the 3rd step, 3-dihydro-2-indenyl methyl formate synthetic; Synthesizing of [5-chloro-2-hydroxyl-2-(the methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate in the 4th step; 2-benzyl-7-chlorine [1,2-e] indeno in the 5th step [1,3,4] oxadiazines-2, and 4a (3H, 5H)-the dioctyl phthalate methyl esters is synthetic with [5-chloro-2-methoxymethoxy-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate; At last; 2-benzyl-7-chlorine [1 that the front is synthetic; 2-e] indeno [1; 3; 4] oxadiazines-2,4a (3H, 5H)-dioctyl phthalate methyl esters or [5-chloro-2-methoxymethoxy-2-(methoxycarbonyl)-1-indenes imido grpup] benzyq carbamate molecule in benzyl ester protecting group on the nitrogen remove; connect different side chains with acyl chloride reaction again, can obtain the purpose compound.
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Cited By (7)
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|---|---|---|---|---|
| CN102391261A (en) * | 2011-10-14 | 2012-03-28 | 上海交通大学 | N-substituted dioxazine compound as well as preparation method and application thereof |
| CN101723913B (en) * | 2009-12-03 | 2012-04-11 | 湖南化工研究院 | O-substituted dioxazine compound with bactericidal activity, preparation method thereof and application thereof |
| CN104151260A (en) * | 2014-08-26 | 2014-11-19 | 常州大学 | Preparation method of novel oxadiazine pesticide SIOC-Y-047 |
| CN107986991A (en) * | 2017-12-18 | 2018-05-04 | 湖南国发精细化工科技有限公司 | The synthetic method of N- chloroformyls-N [(4- trifluoromethoxies) phenyl] methyl carbamate |
| CN109627161A (en) * | 2018-11-09 | 2019-04-16 | 新乡医学院 | A method of synthesizing Alpha-hydroxy-beta-dicarbonyl class compound using water as solvent |
| CN111116507A (en) * | 2019-12-30 | 2020-05-08 | 江苏腾龙生物药业有限公司 | Synthetic process of indoxacarb |
| CN115974808A (en) * | 2022-12-21 | 2023-04-18 | 大连奇凯医药科技有限公司 | Preparation method of 2-benzyl-7-chlorine [1,2-e ] indeno [1,3,4] oxadiazine methyl diformate |
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- 2005-03-11 CN CN 200510045998 patent/CN1663384A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723913B (en) * | 2009-12-03 | 2012-04-11 | 湖南化工研究院 | O-substituted dioxazine compound with bactericidal activity, preparation method thereof and application thereof |
| CN102391261A (en) * | 2011-10-14 | 2012-03-28 | 上海交通大学 | N-substituted dioxazine compound as well as preparation method and application thereof |
| CN104151260A (en) * | 2014-08-26 | 2014-11-19 | 常州大学 | Preparation method of novel oxadiazine pesticide SIOC-Y-047 |
| CN107986991A (en) * | 2017-12-18 | 2018-05-04 | 湖南国发精细化工科技有限公司 | The synthetic method of N- chloroformyls-N [(4- trifluoromethoxies) phenyl] methyl carbamate |
| CN109627161A (en) * | 2018-11-09 | 2019-04-16 | 新乡医学院 | A method of synthesizing Alpha-hydroxy-beta-dicarbonyl class compound using water as solvent |
| CN109627161B (en) * | 2018-11-09 | 2021-04-16 | 新乡医学院 | Method for synthesizing alpha-hydroxy-beta-dicarbonyl compound by using water as solvent |
| CN111116507A (en) * | 2019-12-30 | 2020-05-08 | 江苏腾龙生物药业有限公司 | Synthetic process of indoxacarb |
| CN115974808A (en) * | 2022-12-21 | 2023-04-18 | 大连奇凯医药科技有限公司 | Preparation method of 2-benzyl-7-chlorine [1,2-e ] indeno [1,3,4] oxadiazine methyl diformate |
| CN115974808B (en) * | 2022-12-21 | 2024-03-12 | 大连奇凯医药科技有限公司 | Preparation method of 2-benzyl-7-chloro [1,2-e ] indeno [1,3,4] oxadiazine dimethyl ester |
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