CN105712946A - Quaternary ammonium compound and application thereof - Google Patents
Quaternary ammonium compound and application thereof Download PDFInfo
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- CN105712946A CN105712946A CN201410722388.6A CN201410722388A CN105712946A CN 105712946 A CN105712946 A CN 105712946A CN 201410722388 A CN201410722388 A CN 201410722388A CN 105712946 A CN105712946 A CN 105712946A
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Abstract
The present invention belongs to the field of herbicides, and particularly relates to a quaternary ammonium salt compound and application thereof. The compound is as shown in a general formula (I), and substituent groups in the general formula are defined in the specification. The compound of the general formula I has excellent herbicidal activity and can be used for controlling weeds.
Description
Technical field
The invention belongs to herbicide field.Specifically a kind of quaternary ammonium compound and application thereof.
Background technology
Due to the succession of weed population, transition and to the drug-fast generation of chemical pesticide with develop rapidly; the continuous reinforcement that ecological environmental protection is realized by people, chemical pesticide is polluted, understanding that non-target organism is affected by pesticide and in pesticide ecological environment the attention of home to return to problem improve constantly.Along with the gradually decreasing of world's cultivated area, constantly the increasing and increase to grain demand amount of population, force people to develop agriculture production technology rapidly, improve and improve cropping system and it needs to constantly invention herbicides compounds that is novel and that improve and compositions.
Tradition pesticide based on cream, wettable powder, powder and granule, generally requires a large amount of organic solvents of addition, surfactant, auxiliary agent and penetrating agent to increase the water solublity of medicine in dosage form selection when preparation processing.But this also brings the problems such as production cost increase, environmental pollution.Just can reduce even do not use organic solvent, surfactant, auxiliary agent and penetrating agent if drug molecule itself can have good fat-soluble and water solublity.Quaternary compound has good fat-soluble and water solublity, this patent is according to this feature, pesticide molecule carries out transformation modify, wish so that drug molecule has good biological pharmacy characteristic, the Cytoplasm that also can be efficiently entering inside through biomembranous lipid layer can be dissolved in Cell sap, and then arrival target, finally play biological activity.
JP54088229 reports some 2,4-D class quaternary compound can as herbicide, for instance No. 1 compound K C therein:
A kind of quaternary ammonium compound involved in the present invention and preparation thereof are not disclosed with activity of weeding.
Summary of the invention
It is an object of the invention to provide a kind of quaternary ammonium compound and application thereof.
For achieving the above object, technical scheme is as follows:
A kind of quaternary ammonium compound, as shown in formula I:
In formula:
N is selected from 0-10；
R1Selected from C1-C12Alkyl, C1-C12Haloalkyl or the phenyl replaced by least one substituent group following: halogen, nitro, CN, C1-C6Alkyl or C1-C6Haloalkyl；
R2Selected from C1-C12Alkyl, C1-C12Haloalkyl or the phenyl replaced by least one substituent group following: halogen, nitro, CN, C1-C6Alkyl or C1-C6Haloalkyl；
Or R1And R2Collectively form with the nitrogen connected:
R3Selected from C1-C12Alkyl；
Y-is selected from fluorion, chloride ion, bromide ion, iodide ion, acetate, p-methyl benzenesulfonic acid root or bisulfate ion；
X is selected from NH, O or S；
Q is selected from structure:
Currently preferred structural formula of compound is as follows:
In formula:
N is selected from 1,2,3 or 4；
R1Selected from C1-C4Alkyl, C1-C4Haloalkyl or the phenyl replaced by least one substituent group following: halogen, nitro, CN, C1-C6Alkyl or C1-C6Haloalkyl；
R2Selected from C1-C4Alkyl, C1-C4Haloalkyl or the phenyl replaced by least one substituent group following: halogen, nitro, CN, C1-C6Alkyl or C1-C6Haloalkyl；
Or R1And R2Collectively form with the nitrogen connected:
R3Selected from C1-C4Alkyl；
Y-is selected from fluorion, chloride ion, bromide ion or iodide ion；
X is selected from NH or O；
Q is selected from Q1、Q2、Q3、Q4Or Q5。
The present invention it is preferred that structural formula of compound as follows:
N=1；
R1Selected from methyl or ethyl；
R2Selected from methyl or ethyl；
R3Selected from methyl；
Y-is selected from iodide ion；
X is selected from NH or O；
Q is selected from Q1、Q3Or Q5。
Formula of the present invention (I) compound can be prepared by the following method, as defined above except as otherwise dated other each groups outer in reaction equation:
Compound of Formula I can by Compounds of formula II and compound of formula III in suitable solvent, and temperature is-10 DEG C and within 0.5-48 hour, prepares to reaction between suitable solvent boiling point.Suitable solvent selected from chloroform, dichloromethane, carbon tetrachloride, normal hexane, benzene, toluene, ethyl acetate, THF or dioxane etc..R3Y is commercially available, such as iodomethane etc..
General formula compound II preparation method is as follows:
General formula compound (IV) and acyl halide reagent are in suitable solvent, and temperature is-10 DEG C and reacts 0.5-48 hour prepared intermediate acid chloride V between suitable solvent boiling point.Suitable acyl halide reagent is selected from oxalyl chloride, thionyl chloride, Phosphorous chloride., phosphorus tribromide, phosphorus pentachloride or phosphorus pentabromide.Solvent selected from chloroform, dichloromethane, carbon tetrachloride, normal hexane, benzene, toluene, ethyl acetate, THF or the dioxane etc. being suitable for.
Intermediate acid chloride V and compound of formula VI are in suitable solvent, and temperature is-10 DEG C and reacts 0.5-48 hour prepared product II between suitable solvent boiling point.Solvent selected from chloroform, dichloromethane, carbon tetrachloride, normal hexane, benzene, toluene, ethyl acetate, THF or the dioxane etc. being suitable for.Add suitable alkaline matter, as pyridine, triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate etc. are favourable to reaction.
Compound of formula VI is commercially available.
General formula compound IV preparation method is as follows:
General formula compound VII is dissolved in suitable solvent, and adds alkaline aqueous solution, and temperature is-10 DEG C and reacts 0.5-48 hour between suitable solvent boiling point, prepares compound IV.Solvent selected from chloroform, dichloromethane, carbon tetrachloride, normal hexane, benzene, toluene, ethyl acetate, methanol, ethanol, THF or the dioxane etc. being suitable for；Suitable alkali is selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium bicarbonate etc..General formula compound VII is commercially available.
Compound of Formula I contains chiral centre, there is R, S isomer, and R, S mixture of its single optical voidness R or S or different proportion can be that initiation material prepares by the corresponding optical voidness of formula VII or optics mixture.The single optical voidness R of formula I or S compound adopt the methods such as column chromatography, recrystallization, chiral material fractionation to separate also by the optics mixture of mutual-through type I and obtain.
The structure of partial Formula I and physical property are in Table 1
Table 1
Part of compounds1HNMR(300MHz,CDCl3, δ) and data are as follows:
Compound 13:7.51 7.31 (m, 2H), 7.10 6.82 (m, 5H), 4.89 (d, J=6.9Hz, 1H), 4.69 (s, 2H), 4.17 (d, J=4.7Hz, 2H), 3.42 (s, 9H), 1.67 1.62 (m, 3H).
Compound 37:7.44 (d, J=2.5Hz, 1H), 7.19 (dd, J=8.8,2.5Hz, 1H), 6.89 (p, J=8.9Hz, 4H), 4.86 (d, J=6.8Hz, 1H), 4.67 (s, 2H), 4.17 (s, 2H), 3.41 (s, 9H), 1.64 (d, J=6.8Hz, 3H).
Compound 47:1HNMR(300MHz,CDCl3) δ 7.50 7.35 (m, 2H), 7.16 (dd, J=8.8,2.5Hz, 1H), 7.07 6.76 (m, 5H), 4.76 (d, J=6.7Hz, 1H), 3.79 3.51 (m, 2H), 3.51 3.39 (m, 2H), 3.31 (s, 9H), 2.18 2.01 (m, 2H), 1.56 (d, J=6.7Hz, 3H).
Compound 49:1HNMR(300MHz,CDCl3) δ 7.43 (s, 1H), 7.36 7.26 (m, 4H), 6.99 (d, J=9.0Hz, 2H), 4.92 (d, J=6.8Hz, 1H), 4.69 (s, 2H), 4.14 (s, 2H), 3.35 (s, 9H), 1.67 (d, J=6.9Hz, 3H).
A kind of described formula (I) compound is for preparing the herbicide controlling weeds.
A kind of Herbicidal combinations, using described formula (I) compound as active component and its agriculturally acceptable carrier；In compositions, the weight percentage of active component is 5-90%.
A kind of method controlling weeds, uses the per hectare 1 gram described Herbicidal combinations to 1000 grams of effective doses on the somatomedin or place of weeds or weeds.
Specifically, the compound of Formula I of the present invention has activity of weeding, can be used for agriculturally preventing and treating multiple weeds.As: using after Seedling and can effectively control weeds, the quaternary ammonium compound of the present invention has the weeding ability of excellence.Therefore technical scheme also includes formula (I) compound for controlling the purposes of weeds.
Present invention additionally comprises the Herbicidal combinations being active component with compound of Formula I.In this Herbicidal combinations, the weight percentage of active component is 5-90%.This Herbicidal combinations also includes agriculturally acceptable carrier.As the compound of Formula I of active component, both can be single optical voidness R or S compound, it is also possible to be the mixture of two kinds of optical pure compounds.
The Herbicidal combinations of the present invention can the form of several formulations be used.Generally using the compound dissolution of the present invention or be scattered in carrier to be configured to preparation so as herbicide use time more readily dispersible.Such as: these chemicals can be made into wettable powder or cream etc..Therefore, in these compositionss, at least add a kind of liquid or solid carrier, and typically require the surfactant that addition is suitable.
Present invention also offers the implementation of controlling weeds, the method includes on the surface of place or its somatomedin that the Herbicidal combinations of the present invention of herbicidally effective amount imposes on described weeds or described weed growth.Comparatively suitable effective dose is per hectare 1 gram to 1000 grams, it is preferable that effective dose is per hectare 10 grams to 500 grams.For some application, one or more other herbicide can be added in the Herbicidal combinations of the present invention, thus can produce advantage and the effect added.
The compound of the present invention both can be used alone can also be known with other insecticide, antibacterial, plant growth regulator or fertilizer etc. mixes together.
It should be appreciated that, in the claim limited range of the present invention, various conversion and change can be carried out.
Detailed description of the invention
The following example and raw result of the test of surveying can be used to further illustrate the present invention, but are not intended to limit the present invention.
Embodiment 1, compound 49 synthesis:
(1) synthesis of intermediate (IV-1)
(R)-2-[4-(6-chloro-2-benzothiazole oxygen base) phenoxy group] ethyl propionate (36.18 grams is added in the reaction bulbs of 500 milliliters, 100 mMs) and 80 milliliters of oxolanes, stirring is to entirely molten, sodium hydroxide (4.17 grams is dripped under condition of ice bath, 100 mMs, 100 milliliters of water) aqueous solution, then rise to room temperature and continue stirring reaction 5-6h.Thin layer chromatography is monitored after completion of the reaction, adds 100 milliliters of extraction into ethyl acetate, separate in reactant liquor.Aqueous phase concentrated hydrochloric acid acidifying, regulates pH value to 1, has a large amount of solid to precipitate out, filter, dry to obtain 25.00 grams of intermediate acid IV-1, yield 75%.
(2) synthesis of intermediate (II-1)
Adding intermediate acid IV-1 (0.5 gram, 1.48 mMs), thionyl chloride 20 milliliters, heating reflux reaction 3h, cooling in reaction bulb, decompression boils off excessive thionyl chloride, dissolves standby by obtained acyl chlorides with 10 milliliters of dichloromethane.By N, N-dimethyl-2 hydroxy ethylamine (0.13 gram, 1.48 mMs) it is dissolved in 20 milliliters of dichloromethane, add 5 milliliters of triethylamines, the dichloromethane solution of acyl chlorides it is slowly added dropwise under condition of ice bath, drip to finish and be slowly increased to room temperature, continue stirring reaction, thin layer chromatography (ethyl acetate petroleum ether=1 1, (V/V) triethylamine that adds 1%) monitoring, after question response completes, removal of solvent under reduced pressure, through column chromatography, (eluant is made in ethyl acetate petroleum ether=1 2 to residue, (V/V) triethylamine that adds 1%, 100～140 order silica gel that subsidiary factory of Qingdao Haiyang bioid factory produces) weak yellow liquid (II-1) 0.41g, yield: 68.3%.
(3) product (49) synthesis
Intermediate II-1 (0.3 gram, 1.01 mMs), 5 milliliters of ethanol are added, after sample dissolves in reaction bulb, add ether 30 milliliters, drip iodomethane (0.71 gram, 6.07 mMs) under stirring, be stirred at room temperature, react about 30min, white solid occur, filtered by reactant mixture, filter cake absolute ether washs, obtain white solid 0.40g (49), yield 72.7%.
Other compound of table 1 is all referred to said method and prepares.
Embodiment 2, compound K C synthesis:
(1) synthesis of intermediate II-2
2-(2 is added in single port bottle, 4-Dichlorophenoxy) acetic acid (1.00 grams, 4.52 mMs), thionyl chloride 20 milliliters, heating reflux reaction 3h, cooling, decompression boils off excessive thionyl chloride, obtained acyl chlorides is dissolved standby with 10 milliliters of dichloromethane, by N, N-dimethyl-2 hydroxy ethylamine (0.41 gram, 4.60 mMs) it is dissolved in 20 milliliters of dichloromethane, add 5 milliliters of triethylamines, the dichloromethane solution of acyl chlorides it is slowly added dropwise under condition of ice bath, drip to finish and be slowly increased to room temperature, continue stirring reaction, thin layer chromatography (ethyl acetate: petroleum ether=1:1, (V/V) triethylamine that adds 1%) monitoring, after question response completes, remove solvent under reduced pressure, residue column chromatography (ethyl acetate: petroleum ether=1:2 makes eluant, (V/V) triethylamine that adds 1%, 100～140 order silica gel that subsidiary factory of Qingdao Haiyang bioid factory produces) purification obtains II-2, pale yellow oily liquid body 0.94 gram, yield is 38.52%, HPLC normalizing purity 95%.
(2) synthesis of compound K C
II-2 (0.70 gram is added in single port bottle, 2.40 mMs), 20 milliliters of ether, drip iodomethane (2.04 grams, 13.38 mMs) under stirring, thin layer chromatography (ethyl acetate: petroleum ether=1:2, add 1% (V/V) triethylamine) monitoring.It is stirred at room temperature, solution turned cloudy after about 10 minutes, continues stirring 6h.Filtering, filter cake absolute ether washs, and obtains white solid 0.60 gram, and m.p.125-126 DEG C, yield is 57.59%.
Compound K C:(300MHz, D2O)δ8.33(s,1H),7.52(s,1H),7.30(d,1H),6.97(d,1H),4.71(s,2H),3.77(s,2H),3.50(t,2H),3.14(s,9H).
Raw survey example
Embodiment 3: the mensuration of activity of weeding
Adopt the stem and leaf in the pot-culture method to mechanism of action sensitivity to process the compound to the present invention and carry out Preliminary activation test respectively.
Quantitative grassy weed (barnyard grass, Setaria glauca) seed is sowed at respectively diameter be 7cm equipped with in the dixie cup of Nutrition Soil, broadcast rear earthing 1cm, cultivate according to a conventional method in greenhouse after suppression, trickle.Grassy weed length is to 2～3 leaf phases, by EXPERIMENTAL DESIGN dosage, carries out stem and leaf spraying process (atomisation pressure 1.95kg/cm on crawler type crops sprayer (Britain EngineerResearchLtd. designs production)2, spouting liquid 500L/hm2, crawler track speeds 1.48km/h).Test sets 3 repetitions.Examination material processes and is placed on handling hall, after medicinal liquid dries in the shade naturally, is put in greenhouse and manages according to a conventional method, observes and record the weeds response situation to medicament, the periodical visual inspection investigation reagent agent preventive effect to weeds after process.
Barnyard grass, Setaria glauca are had high preventive effect by compound of Formula I, and wherein compound 49,37 is at 600ga.i./hm2Under dosage, the preventive effect of barnyard grass being reached more than 70%, compound 49,37 is at 600ga.i./hm2Under dosage, the preventive effect of Setaria glauca is reached more than 75%.
Choosing part of compounds and known compound KC in formula I (in JP54088229 patent No. 1 compound, synthetic example 6 is shown in its preparation) and carried out the parallel comparative test to barnyard grass, Setaria glauca activity, result is in Table 2, table 3.
Table 2: the part of compounds activity to barnyard grass in formula I
Table 3: the part of compounds activity to Setaria glauca in formula I
Note: "/" represents and do not survey
Claims (6)
1. a quaternary ammonium compound, it is characterised in that: as shown in formula I:
In formula:
N is selected from 0-10；
R1Selected from C1-C12Alkyl, C1-C12Haloalkyl or the phenyl replaced by least one substituent group following: halogen, nitro, CN, C1-C6Alkyl or C1-C6Haloalkyl；
R2Selected from C1-C12Alkyl, C1-C12Haloalkyl or the phenyl replaced by least one substituent group following: halogen, nitro, CN, C1-C6Alkyl or C1-C6Haloalkyl；
Or R1And R2Collectively form with the nitrogen connected:
R3Selected from C1-C12Alkyl；
Y-Selected from fluorion, chloride ion, bromide ion, iodide ion, acetate, p-methyl benzenesulfonic acid root or bisulfate ion；
X is selected from NH, O or S；
Q is selected from structure:
2. compound as claimed in claim 1, it is characterised in that in formula I:
In formula:
N is selected from 1,2,3 or 4；
R1Selected from C1-C4Alkyl, C1-C4Haloalkyl or the phenyl replaced by least one substituent group following: halogen, nitro, CN, C1-C6Alkyl or C1-C6Haloalkyl；
R2Selected from C1-C4Alkyl, C1-C4Haloalkyl or the phenyl replaced by least one substituent group following: halogen, nitro, CN, C1-C6Alkyl or C1-C6Haloalkyl；
Or R1And R2Collectively form with the nitrogen connected:
R3Selected from C1-C4Alkyl；
Y-Selected from fluorion, chloride ion, bromide ion or iodide ion；
X is selected from NH or O；
Q is selected from Q1、Q2、Q3、Q4Or Q5。
3. compound as claimed in claim 2, it is characterised in that in formula I:
In formula:
N is selected from 1；
R1Selected from methyl or ethyl；
R2Selected from methyl or ethyl；
R3Selected from methyl；
Y-Selected from iodide ion；
X is selected from NH or O；
Q is selected from Q1、Q3Or Q5。
4. formula (I) compound described in a claim 1 is for preparing the herbicide controlling weeds.
5. a Herbicidal combinations, it is characterised in that: using formula (I) compound described in claim 1 as active component and its agriculturally acceptable carrier；In compositions, the weight percentage of active component is 5-90%.
6. the method controlling weeds, it is characterised in that: on the somatomedin or place of weeds or weeds, use the described Herbicidal combinations of 1 gram of 1000 grams of effective dose of per hectare.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4130413A (en) * | 1976-09-10 | 1978-12-19 | Hoechst Aktiengesellschaft | Heterocyclic phenyl ethers and herbicides containing same |
| DE2745869A1 (en) * | 1977-10-12 | 1979-04-19 | Hoechst Ag | Selective herbicides useful against grassy weeds - contain substd. phenoxy-alkanoic acid or -alkanol derivs. and a methylenedioxy-benzene synergist |
| EP0013144A1 (en) * | 1978-12-22 | 1980-07-09 | Ici Australia Limited | Substituted diphenylamine derivatives, compositions and herbicidal uses thereof, and processes for their preparation |
| US4213774A (en) * | 1978-01-27 | 1980-07-22 | Ciba-Geigy Corporation | Pyridyloxy-phenoxy-α-propionic acid aminoalkyl esters |
| EP0018080A1 (en) * | 1979-03-19 | 1980-10-29 | Ici Australia Limited | Herbicidal compounds, their preparation, compositions and process for the use thereof |
| EP0023785A2 (en) * | 1979-07-17 | 1981-02-11 | Ici Australia Limited | Quinoxalinyloxyphenoxyalkane carboxylic acid derivatives, their preparation and their use as herbicides |
| US4309210A (en) * | 1978-12-01 | 1982-01-05 | Ciba-Geigy Corporation | Preemergence method of selectively controlling weeds in crops of cereals and composition therefor |
| CA1177272A (en) * | 1982-06-18 | 1984-11-06 | Marco Quadranti | Synergistic composition and a process for selectively combating weeds, especially in cereal crops |
| HUT47525A (en) * | 1987-07-02 | 1989-03-28 | Alkaloida Vegyeszeti Gyar | Composition with herbicidal effect and process for producing the optically active or racemic active ingredient |
-
2014
- 2014-12-02 CN CN201410722388.6A patent/CN105712946A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4130413A (en) * | 1976-09-10 | 1978-12-19 | Hoechst Aktiengesellschaft | Heterocyclic phenyl ethers and herbicides containing same |
| DE2745869A1 (en) * | 1977-10-12 | 1979-04-19 | Hoechst Ag | Selective herbicides useful against grassy weeds - contain substd. phenoxy-alkanoic acid or -alkanol derivs. and a methylenedioxy-benzene synergist |
| US4213774A (en) * | 1978-01-27 | 1980-07-22 | Ciba-Geigy Corporation | Pyridyloxy-phenoxy-α-propionic acid aminoalkyl esters |
| US4309210A (en) * | 1978-12-01 | 1982-01-05 | Ciba-Geigy Corporation | Preemergence method of selectively controlling weeds in crops of cereals and composition therefor |
| EP0013144A1 (en) * | 1978-12-22 | 1980-07-09 | Ici Australia Limited | Substituted diphenylamine derivatives, compositions and herbicidal uses thereof, and processes for their preparation |
| EP0018080A1 (en) * | 1979-03-19 | 1980-10-29 | Ici Australia Limited | Herbicidal compounds, their preparation, compositions and process for the use thereof |
| EP0023785A2 (en) * | 1979-07-17 | 1981-02-11 | Ici Australia Limited | Quinoxalinyloxyphenoxyalkane carboxylic acid derivatives, their preparation and their use as herbicides |
| CA1177272A (en) * | 1982-06-18 | 1984-11-06 | Marco Quadranti | Synergistic composition and a process for selectively combating weeds, especially in cereal crops |
| HUT47525A (en) * | 1987-07-02 | 1989-03-28 | Alkaloida Vegyeszeti Gyar | Composition with herbicidal effect and process for producing the optically active or racemic active ingredient |
Non-Patent Citations (1)
| Title |
|---|
| 徐文方: "《新药设计与开发》", 28 February 2001, 科学出版社 * |
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