CN105585521B - A kind of bipiperidine ketone quaternary ammonium salt (alkali) class compound and application thereof - Google Patents
A kind of bipiperidine ketone quaternary ammonium salt (alkali) class compound and application thereof Download PDFInfo
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- CN105585521B CN105585521B CN201410562123.4A CN201410562123A CN105585521B CN 105585521 B CN105585521 B CN 105585521B CN 201410562123 A CN201410562123 A CN 201410562123A CN 105585521 B CN105585521 B CN 105585521B
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Abstract
The invention belongs to disinfectant use in agriculture fields.More particularly to a kind of bipiperidine ketone quaternary ammonium salt (alkali) class compound and application thereof.Structure is as shown in general formula I：
Description
Technical field
The invention belongs to disinfectant use in agriculture fields.More particularly to a kind of bipiperidine ketone quaternary ammonium salt (alkali) class compound and its use
On the way.
Background technology
Bi-quaternary ammonium salt class compound serves not only as surfactant, industrial bactericide, but also can be pharmaceutical
In analgesia, inhibition tumour, reduce blood pressure.
Once drug of the compound containing piperidones available for nervous system as follows was reported in WO9325527.
In the prior art, disclosed compound has bigger difference, and do not have as agricultural bactericidal with the compounds of this invention
The report of agent application.
Invention content
The purpose of the present invention is to provide a kind of bi-quaternary ammonium salt (alkali) classes containing piperidones that can control harmful levels of pathogens
Close object.
Technical scheme is as follows：
The present invention provides a kind of bi-quaternary ammonium salt (alkali) class compound, as shown in general formula I：
In formula：
R1Selected from C1-C6Alkyl, halogenated C1-C6Alkyl, C2-C6Alkenyl, halogenated C2-C6Alkenyl, C2-C6Alkynyl, halogenated C2-C6
Alkynyl, C3-C6Cycloalkyl, C1-C6Alkyl hydroxy, C1-C6Alkylamide or benzyl；
R2、R3、R4、R5It may be the same or different, be respectively selected from hydrogen or C1-C6Alkyl or R2With R3Ring, R are linked to be by carbon phase4
With R5Ring is linked to be by carbon phase；For example, R2With R3、R4With R5It can be connected together and C is collectively formed1-C4Alkylidene；
X is selected from halogen or hydroxyl；
N is selected from 0-20.
More preferably compound is the present invention：In general formula I
R1Selected from C1-C6Alkyl, halogenated C1-C6Alkyl, C1-C6Alkyl hydroxy, C1-C3Alkylamide or benzyl；
R2、R3、R4、R5It may be the same or different, be respectively selected from hydrogen or C1-C3Alkyl or R2With R3、R4With R5It links together
Methylene, ethylidene or propylidene is collectively formed；；
X is selected from halogen or hydroxyl；
N is selected from 0-20；
The further preferred compound of the present invention is：In general formula I
R1Selected from C1-C6Alkyl, halogenated C1-C6Alkyl, C1-C6Alkyl hydroxy, C1-C3Alkylamide or benzyl；
R2With R5It is identical, R3With R4It is identical, it is respectively selected from hydrogen or C1-C3Alkyl or R2With R3、R4With R5It links together altogether
With formation methylene, ethylidene or propylidene；
X is selected from halogen or hydroxyl；
N is selected from 0-20.
Present invention compound still further preferably is：In general formula I
R1Selected from C1-C6Alkyl, C1-C6Alkyl hydroxy or benzyl；
R2、R3、R4、R5All same is respectively selected from hydrogen or C1-C3Alkyl or R2With R3、R4With R5Link together common shape
Into methylene or ethylidene；
X is selected from chlorine, bromine, iodine or hydroxyl；
N be selected from 0-18, specially 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18；
Most preferred compound is：In general formula I
R1Selected from methyl, CH2CH2OH or benzyl；
R2、R3、R4、R5It is selected from hydrogen；
X is selected from chlorine, bromine, iodine or hydroxyl；
N be selected from 0-18, specially 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18.
In the definition of compound of Formula I given above, collect the following substituent group of term general proxy used：
Halogen：Refer to fluorine, chlorine, bromine or iodine.
Alkyl：Linear or branched alkyl group, such as methyl, ethyl, propyl, isopropyl or tertiary butyl.
Cycloalkyl：Substituted or unsubstituted cyclic alkyl, such as cyclopropyl, cyclopenta or cyclohexyl；Substituent group such as methyl,
Halogen etc..
Halogenated alkyl：Linear or branched alkyl group, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen,
For example, chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl etc..
Alkoxy：Linear or branched alkyl group is keyed to through oxygen atom in structure.
Halogenated alkoxy：Straight or branched alkoxyl, the hydrogen atom on these alkoxies can be partly or entirely by halogen
Replaced.For example, chloromethane epoxide, dichloro methoxyl group, trichloromethoxy, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine
Fluorine methoxyl group, trifluoro ethoxy etc..
Alkenyl：Linear chain or branch chain simultaneously can there are double bonds, such as vinyl or pi-allyl on any position.
Alkynyl：Linear chain or branch chain simultaneously can there are three keys, such as acetenyl or propargyl on any position.
Alkyl hydroxy：Alkyl-OH, such as：CH2OH、CH2CH2OH etc..
Alkylamide：Alkyl-CONH2, such as：CH2CONH2、CH2CH2CONH2Deng.
The particular compound listed in table 1 can be used for illustrating the present invention, but do not limit the present invention.
Table 1
The compound of Formula I of the present invention can be prepared in accordance with the following methods：
Raw material II I, IV, V are acquisition purchased in market used by following preparation process, while the raw material of the purchase can be itself
The substance of cyclization, wherein, the definition of each substituent group is referring to above-mentioned record in formula.
Work as R2With R5Or R3With R4When different, compound representated by general formula I can according to route one by raw material II I, IV, V,
VII is made through two-step reaction；Work as R2With R5And R3With R4When identical, the compound representated by general formula I can be according to route two by raw material
V, VII, III are made through two-step reaction.
III, IV, V, VII can be by being commercially available.
Above-mentioned reaction carries out in suitable solvent, the optional tetrahydrofuran freely of suitable solvent, acetonitrile, toluene, diformazan
Benzene, benzene, isopropanol, acetone, butanone, n-hexane, hexamethylene, ether and methyl tertiary butyl ether(MTBE) etc..
Reaction temperature can be in room temperature between suitable solvent boiling point temperature, usually 20-120 DEG C.
Reaction time is 30 minutes to 20 hours, 1-10 hours usual.
Compound of Formula I all shows the germ being harmful in agriculture, civilian and zoo technical field preferable sterilization is lived
Property.Therefore, another technical solution of the invention is related to compound of Formula I anti-pathogen in the other fields such as agricultural and horticulture
Application.Such as purposes of the compound of Formula I in agricultural and horticultural field as fungicide.Especially, compound of Formula I pair
The important kind of following section is active：Cucumber downy mildew, gray mold of cucumber, powdery mildew of cucumber, watermelon anthrax, tomato early epidemic
Disease, tomato late blight, capsicum epidemic disease, downy mildew of garpe, fruit white rot of grape, ring rot of apple, alternaria leaf spot of apple, rice
Banded sclerotial blight, rice blast, wheat rust, speckled leaf blotch, wheat powdery mildew, sclerotinia sclerotiorum, corn rust and corn are small
Pinta etc..
Due to its positive characteristic, above compound is advantageously used for protection agricultural and the important crop of horticulture, family
The environment that poultry and breeding stock and the mankind often go is from the injury of harmful levels of pathogens.
To obtain ideal effect, the dosage of compound changes due to various factors, such as compound used therefor, the work protected in advance
Object, the type of harmful levels of pathogens, gradient of infection, weather conditions, application method, the dosage form used.
The compound dosage of 10 grams -5 kilograms of per hectare can provide sufficient prevention.
Another object of the present invention is further related to by applying compound of Formula I, prevention agricultural and the important crop of horticulture
And/or
The method of pest and disease damage in the environment that domestic animal and breeding stock and/or the mankind often go.Especially, the dosage of compound is every
Change in 10 grams -5 kilograms of hectare.
The use of the composition containing one or more compound of Formula I is typically beneficial to be applied to agricultural.
Therefore, another technical solution of the invention further includes a kind of bactericidal composition, containing as active component
Compound of Formula I and agriculturally acceptable carrier, the weight percent in composition as the compound of Formula I of active component contain
It measures as 0.5-90%.The invention also includes purposes of the composition in agricultural and horticultural field as disinfectant use in agriculture.
The use form of composition can be dry powder, wettable powder, missible oil, microemulsion, paste, granule, solution, hang
Floating agent etc.：The selection of types of compositions depends on specific application.
Composition is prepared in a known way, such as optionally in the presence of surfactant, by using solvent medium
And/or solid diluent or dissolving active material.
Available solid diluent or carrier are for example：Silica, kaolin, bentonite, talcum, diatomite, white clouds
Stone, calcium carbonate, magnesia, chalk, clay, synthetic silicate, Attagel, sepiolite.
Than water, available liquid diluent is such as aromatic organic solvent (mixture of dimethylbenzene or alkylbenzene, chlorine
Benzene etc.), paraffin (petroleum distillate), alcohols (methanol, propyl alcohol, butanol, octanol, glycerine), esters (ethyl acetate, isobutyl acetate
Deng), ketone (cyclohexanone, acetone, acetophenone, isophorone, ethyl pentyl group ketone etc.), amides (n,N-Dimethylformamide, N-
Methyl pyrrolidone etc.).
Available surfactant be alkylsulfonate, alkylaryl sulfonates, polyoxyethylene alkylphenol, sorbierite it is poly-
Sodium, calcium, triethylamine or the triethanolamine salt of ethylene oxide ester, lignosulfonates etc..
Composition can also contain special additive for specific purpose, for example, adhesive for example Arabic gum, polyvinyl alcohol,
Polyvinylpyrrolidone etc..
In above-mentioned composition the concentration of active constituent can according to active constituent, its use purpose, environmental condition and use
Preparation type and change in a wide range.In general, the concentration range of active constituent is 1-90%, preferably 5-50%.
If desired, other active components that can be compatible with compound of Formula I can be added into composition, such as other
Fungicide, plant growth regulator, antibiotic, herbicide, fertilizer.
The preparation method of several dosage forms is exemplified below：
The preparation of suspending agent：Active component content is 5%-35% in common prescription.Using water as medium, by active compound, dispersion
Agent, suspending agent and antifreeze etc. are added in sand mill, are ground, suspending agent is made.
The preparation of aqueous emulsion：Active compound, solvent and emulsifier are added together, make to be dissolved into homogeneous oil phase.By water, antifreeze
Etc. being mixed, become uniform water phase.Under high velocity agitation, water phase is added to oil phase or oil phase is added to water phase, formed
The aqueous emulsion of favorable dispersibility.The aqueous emulsion active component content of the present invention is generally 5%-15%.To prepare emulsifiable concentrate, this hair
Bright compound is dissolvable in water one or several kinds of mixed solvents, adds emulsifier to enhance the dispersion effect of compound in water
Fruit.
The preparation of wettable powder：It is by recipe requirements, active compound, various surfactants and solid diluent etc. is fully mixed
It closes, to get to the wettable powder product of predetermined content (such as 10%-40%) after ultra-fine pulverizer disintegrating.It is suitable to prepare
In the wettable powder of sprinkling, the compound of the present invention can be with finely ground solid powder such as clay, inorganic silicate, carbon
Hydrochlorate and wetting agent, adhesive and/or dispersant composition mixture.
The preparation of water-dispersible granules：Active compound and powdered solid diluents, wetting spreader-sticker and adhesive etc. are mixed
It closes and crushes, after adding water kneading, add in the comminutor equipped with 10 to 100 mesh screens and be granulated, then again through drying, screening
(pressing screen cloth scope).Also active compound, dispersant, disintegrant and wetting agent and solid diluent can be added in sand mill, using water as
Suspending agent is made in medium milling, then carries out spray drying granulation, is typically formulated content as 20%-30% granular products.
Specific embodiment
Specific examples below is used for further illustrating the present invention, but the present invention is limited to absolutely not these examples.
Synthetic example
Embodiment 1：The preparation of compound 2
20g (0.177mol) V-1 is added to 500ml there-necked flasks, adds in 150ml isopropanols, 17.9g is added dropwise
(0.088mol) 1,3- dibromopropanes (III-1) are warming up to reflux, react 10h, steam extra isopropanol, add water, ethyl acetate
Extraction, water layer precipitation obtain the thick objects of 34g.
1H-NMR (300MHz, internal standard TMS, solvent C DCl3)δppm 1.19(2H,m),2.11(8H,m),2.82(4H,t),
3.13(6H,s),3.72(8H,m)。
Embodiment 2：The preparation of compound 4
It is prepared with reference to example 1.Light yellow solid, 229.1 DEG C of fusing point.
1H-NMR (300MHz, internal standard TMS, solvent C DCl3)δ(ppm):1.18(4H,m),1.62(2H,m),2.42(4H,
t),2.51(3H,s),2.72(2H,t),2.63(4H,t),2.89(4H,t),3.32(4H,m),3.43(3H,s),3.54(4H,
t)。
Embodiment 3：The preparation of compound 5
It is prepared with reference to example 1.Thick object.
1H-NMR (300MHz, internal standard TMS, solvent C DCl3)δ(ppm):1.21(4H,m),1.72(4H,m),3.29(8H,
t),3.55(4H,t),3.60(6H,s),3.69(8H,t)。
Embodiment 4：The preparation of compound 9
It is prepared with reference to example 1.Thick object.1HNMR (300MHz, internal standard TMS, solvent C DCl3)δ(ppm):1.21(14H,
m),1.76(2H,m),2.19(4H,t),2.21(3H,s),2.44(2H,t),2.63(4H,t),2.86(4H,t),3.20(2H,
t),3.32(3H,s),3.54(4H,t)。
Example of formulations (each component addition is weight percentage, and reactive compound folding hundred is post-dised)
Embodiment 5：30% compound, 2 wettable powder
Compound 2 and other components are sufficiently mixed, to get to 30% wettable powder after ultra-fine pulverizer disintegrating
Product.
Embodiment 6：40% compound, 4 suspension concentrates
Compound 4 and other components are sufficiently mixed, thus obtained suspension concentrates, and gained suspending agent is diluted with water and can obtain
The dilution of concentration needed for any.
Embodiment 7：60% compound, 5 water-dispersible granules
Compound 560%
Naphthalenesulfonic acid-formaldehyde condensate 12%
N- Nmethyl-N-oleoyls base-sodium taurocholate 8%
Polyvinylpyrrolidone 2%
Carboxymethyl cellulose 2%
Kaolin complements to 100%
By compound 5 and other components co-grinding, after adding water kneading, add in the comminutor of 10-100 mesh screens into
Row is granulated, then again through drying, screening (pressing screen cloth scope).
Biological activity determination embodiment
8 bactericidal activity of example measures
With the compounds of this invention sample a variety of fungal diseases of plant have been carried out with the experiment of live body protecting effect.The side of experiment
Method is as follows：
Using live body potting assay method, i.e., by test compound sample solvent (solvent obtained by above-mentioned synthetic example
Type such as acetone, methanol, DMF etc., and selected, the volume of quantity of solvent and spouting liquid according to its solvability to sample
It 0.05) dissolves than being equal to or less than, is diluted with the water containing 0.1% Tween 80, be configured to required concentration prepare liquid.It is sprayed in crop
Prepare liquid on mist machine, is sprayed on disease host plant to (host plant is the standard Potted orchard cultivated in greenhouse), 24 is small
When after carry out disease inoculation.According to disease feature, it would be desirable to be placed on artificial climate after the disease plant inoculating of temperature control moisturizing culture
It is cultivated in room, after disease completion is infected, moves into hot-house culture；The disease plant of moisturizing culture will not needed to directly in greenhouse
It is inoculated with and cultivates.(being usually week age) carries out compound protection effect assessment after fully morbidity is compareed.
Test result is as follows for part live body protection activity：
When liquor strength is 400mg/L, compound 5,9 etc. is 100% to anthracnose preventive effect；Compound 2,9 etc. is to Huang
Melon downy mildew preventive effect is 70%；2nd, 5,9 etc. 65% is all higher than to corn rust preventive effect.
When liquor strength is 100mg/L, 5 grade of compound is 65% to anthracnose preventive effect.
Claims (4)
1. a kind of bipiperidine ketone quaternary ammonium salt（Alkali）Class compound, as shown in general formula I：
I
In formula：
R1Selected from methyl；
R2、R3、R4、R5It is selected from hydrogen；
X is selected from chlorine, bromine or hydroxyl；
N is selected from 1,2,4 or 8.
2. a kind of purposes of compound of Formula I described in accordance with the claim 1 in agricultural or horticultural field as fungicide.
3. a kind of bactericidal composition, it is characterised in that：Contain the general formula Iization described in accordance with the claim 1 as active component
Object and agriculturally acceptable carrier are closed, the weight percentage of composition formula of Compound I is 0.5-90%.
4. a kind of use of bactericidal composition described in accordance with the claim 3 in agricultural or horticultural field as disinfectant use in agriculture
On the way.
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| CN106554327A (en) * | 2016-10-08 | 2017-04-05 | 陕西科技大学 | It is a kind of double（1 chlorine N hydroxyethyl morpholines, 2 hydroxypropyl）N-octadecane amine quaternary ammonium salt and preparation method thereof |
| CN106957281A (en) * | 2017-03-16 | 2017-07-18 | 陕西科技大学 | It is a kind of double（The hydroxypropyl of 1 chlorine N methyl morpholines 2）N-octadecane amine quaternary ammonium salt and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4167573A (en) * | 1977-05-07 | 1979-09-11 | Basf Aktiengesellschaft | Method of controlling fungi with 3,5-dimethyl-piperidin-4-ones |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK78692D0 (en) * | 1992-06-12 | 1992-06-12 | Lundbeck & Co As H | DIMER PIPERIDINE AND PIPERAZINE DERIVATIVES |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4167573A (en) * | 1977-05-07 | 1979-09-11 | Basf Aktiengesellschaft | Method of controlling fungi with 3,5-dimethyl-piperidin-4-ones |
Non-Patent Citations (3)
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| 两种季铵盐阳离子表面活性剂对番茄灰霉病菌的毒理效应;李祥英等;《植物保护学报》;20110630;第38卷(第3期);265-270 * |
| 对称的奎宁环类和托品类双季铵和多季铵化合物的合成及其神经肌肉阻断作用;陈绳铨等;《药学学报》;19871231;第22卷(第5期);347-353 * |
| 杀菌剂开发的新进展;吴峤等;《农药》;20120131;第51卷(第1期);4-7 * |
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