CN105585521A - Double-piperidone quaternary ammonium salt (alkali) compound and use thereof - Google Patents
Double-piperidone quaternary ammonium salt (alkali) compound and use thereof Download PDFInfo
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Abstract
Belonging to the field of agricultural fungicides, the invention in particular relates to a double-piperidone quaternary ammonium salt (alkali) compound and use thereof. The structure of the compound is shown as general formula I in the specification, and all the substituent groups involved in the formula are defined in the specification. The general formula I compound can be used for controlling diseases caused by oomycetes, basidiomycetes, ascomycetes, imperfect fungi and other germs in a variety of plants, and especially has better activity to downy mildew, powdery mildew, anthracnose, corn rust and other diseases. Therefore, the invention includes the bactericidal use of the general formula I compound in agriculture, gardening and other fields.
Description
Technical field
The invention belongs to disinfectant use in agriculture field. Relate to particularly a kind of two piperidones quaternary ammonium salt (alkali) compounds and uses thereof.
Background technology
Bi-quaternary ammonium salt compounds not only can be used as surfactant, industrial bactericide, but also can be at medicine for analgesia, suppress tumour, reduce blood pressure etc.
In WO9325527, once the following compound containing piperidones of report can be used for neural medicine.
In prior art, disclosed compound and the compounds of this invention all have bigger difference, and do not have the report as disinfectant use in agriculture application.
Summary of the invention
The object of the present invention is to provide a kind of bi-quaternary ammonium salt (alkali) compounds containing piperidones that can control harmful germ.
Technical scheme of the present invention is as follows:
The invention provides a kind of bi-quaternary ammonium salt (alkali) compounds, as shown in general formula I:
In formula:
R1Be selected from C1-C6Alkyl, halo C1-C6Alkyl, C2-C6Thiazolinyl, halo C2-C6Thiazolinyl, C2-C6Alkynyl, halo C2-C6Alkynyl, C3-C6Cycloalkyl, C1-C6Alkyl hydroxy, C1-C6Alkylamide or benzyl;
R2、R3、R4、R5Can be identical or different, be selected from respectively hydrogen or C1-C6Alkyl, or R2With R3Be connected to ring by carbon, R4With R5Be connected to ring by carbon; For example, R2With R3、R4With R5The common C of formation can link together1-C4Alkylidene;
X is selected from halogen or hydroxyl;
N is selected from 0-20.
The present invention more preferably compound is: in general formula I
R1Be selected from C1-C6Alkyl, halo C1-C6Alkyl, C1-C6Alkyl hydroxy, C1-C3Alkylamide or benzyl;
R2、R3、R4、R5Can be identical or different, be selected from respectively hydrogen or C1-C3Alkyl, or R2With R3、R4With R5Common methylene, ethylidene or the propylidene of forming links together; ;
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
R1Be selected from C1-C6Alkyl, halo C1-C6Alkyl, C1-C6Alkyl hydroxy, C1-C3Alkylamide or benzyl;
R2With R5Identical, R3With R4Identical, be selected from respectively hydrogen or C1-C3Alkyl, or R2With R3、R4With R5Common methylene, ethylidene or the propylidene of forming links together;
X is selected from halogen or hydroxyl;
N is selected from 0-20.
The present invention more further preferred compound is: in general formula I
R1Be selected from C1-C6Alkyl, C1-C6Alkyl hydroxy or benzyl;
R2、R3、R4、R5All identical, be selected from respectively hydrogen or C1-C3Alkyl, or R2With R3、R4With R5Common methylene or the ethylidene of forming links together;
X is selected from chlorine, bromine, iodine or hydroxyl;
N is selected from 0-18, is 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
R1Be selected from methyl, CH2CH2OH or benzyl;
R2、R3、R4、R5All be selected from hydrogen;
X is selected from chlorine, bromine, iodine or hydroxyl;
N is selected from 0-18, is specially 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18.
In the definition of the compound of Formula I providing, collect the following substituting group of term general proxy used above:
Halogen: refer to fluorine, chlorine, bromine or iodine.
Alkyl: straight or branched alkyl, for example methyl, ethyl, propyl group, isopropyl or the tert-butyl group.
Cycloalkyl: replace or unsubstituted cyclic alkyl, for example cyclopropyl, cyclopenta or cyclohexyl; Substituting group is as methyl, halogen etc.
Haloalkyl: straight or branched alkyl, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl etc.
Alkoxyl: straight or branched alkyl, is connected in structure through oxygen atom key.
Halogenated alkoxy: straight or branched alkoxyl, the hydrogen atom on these alkoxyls can partly or entirely be replaced by halogen. For example, chlorine methoxyl group, dichloro methoxyl group, trichlorine methoxyl group, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group, trifluoro ethoxy etc.
Thiazolinyl: straight or branched also can have two keys, for example vinyl or pi-allyl on any position.
Alkynyl: straight or branched also can have triple bond, for example acetenyl or propargyl on any position.
Alkyl hydroxy: alkyl-OH, as: CH2OH、CH2CH2OH etc.
Alkylamide: alkyl-CONH2, as: CH2CONH2、CH2CH2CONH2Deng.
The particular compound of listing in table 1 can be used for illustrating the present invention, but does not limit the present invention.
Table 1
Compound of Formula I of the present invention can be prepared in accordance with the following methods:
Raw material II I, IV, V that following preparation process adopts are commercial acquisition, and the raw material of simultaneously described purchase can be the material of self Cheng Huan, and wherein, in formula, each substituent definition is referring to above-mentioned record.
Work as R2With R5Or R3With R4When different, the compound of general formula I representative can be made through two-step reaction by raw material II I, IV, V, VII according to route one; Work as R2With R5And R3With R4When identical, the compound of general formula I representative can be made through two-step reaction by raw material V, VII, III according to route two.
III, IV, V, VII all can obtain by commercially available.
Above-mentioned reaction is carried out in suitable solvent, the optional oxolane freely of suitable solvent, acetonitrile, toluene, dimethylbenzene, benzene, isopropyl alcohol, acetone, butanone, n-hexane, cyclohexane, ether and methyl tertiary butyl ether(MTBE) etc.
Reaction temperature can, in room temperature between suitable solvent boiling point temperature, be generally 20-120 DEG C.
Reaction time is 30 minutes to 20 hours, conventionally 1-10 hour.
Compound of Formula I all demonstrates good bactericidal activity to germ harmful in agriculture, civilian and animal technical field. Therefore, another technical scheme of the present invention relates to compound of Formula I and prevents and treats in agricultural and the other field such as horticulture the application of germ. For example compound of Formula I in agricultural and gardening field as the purposes of bactericide. Especially, compound of Formula I has activity to the important kind of following section: cucumber downy mildew, gray mold of cucumber, powdery mildew of cucumber, watermelon anthrax, early blight of tomato, 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 sheath blight disease, rice blast, wheat rust, speckled leaf blotch, wheat powdery mildew, sclerotinia rot of colza, corn rust and corn southern leaf blight etc.
Due to its positive characteristic, above-claimed cpd can be advantageously used in protection agricultural and important crop, domestic animal and the breeding stock of horticulture, and the environment that often goes of the mankind avoids being harmful to the injury of germ.
For obtaining ideal effect, the consumption of compound changes because of various factors, for example the formulation of the type of the crop of compound used therefor, pre-protection, harmful germ, gradient of infection, weather conditions, application method, employing.
The compound dosage that per hectare is 10 grams-5 kilograms can provide sufficient control.
Another object of the present invention also relates to by using compound of Formula I, the crop that control agricultural and horticulture are important and/or
The method of the disease and pest in the environment that domestic animal and breeding stock and/or the mankind often go. Especially, the consumption of compound changes in 10 grams-5 kilograms of per hectares.
In order to be applied to agricultural, use containing the composition of one or more compound of Formula I normally useful.
Therefore, another technical scheme of the present invention also comprises a kind of bactericidal composition, contains as the compound of Formula I of active component and the upper acceptable carrier of agricultural, and the weight percentage as the compound of Formula I of active component in composition is 0.5-90%. The present invention also comprises said composition purposes as disinfectant use in agriculture in agricultural and gardening field.
The type of service of composition can be dry powder, wettable powder, missible oil, microemulsion, paste, granule, solution, suspending agent etc.: concrete application is depended in the selection of types of compositions.
Composition is prepared in a known way, for example optional under the existence of surfactant, by diluting or lytic activity material with solvent medium and/or solid diluent.
Available solid diluent or carrier are for example: silica, kaolin, bentonite, talcum, diatomite, dolomite, calcium carbonate, magnesia, chalk, clay, synthetic silicate, Attagel, sepiolite.
Beyond dewatering, available liquid diluent is such as aromatics organic solvent (mixture, the chlorobenzene etc. of dimethylbenzene or alkylbenzene), paraffin (petroleum distillate), alcohols (methyl alcohol, propyl alcohol, butanols, octanol, glycerine), ester class (ethyl acetate, isobutyl acetate etc.), ketone (cyclohexanone, acetone, acetophenone, isophorone, ethyl pentyl group ketone etc.), amide-type (DMF, 1-METHYLPYRROLIDONE etc.).
Available surfactant is sodium, calcium, triethylamine or the triethanolamine salt of polyoxyethylene ester, the lignosulfonates etc. of alkylsulfonate, alkylaryl sulfonates, polyoxyethylene alkylphenol, sorbierite.
Composition also can be containing special additive for specific object, and such as adhesive is as Arabic gum, polyvinyl alcohol, polyvinylpyrrolidone etc.
In above-mentioned composition, the concentration of active component can change according to the preparation type of active component, its application target, environmental condition and employing in wide region. Conventionally, the concentration range of active component is 1-90%, preferably 5-50%.
If needed, can to add in composition can with other active components of compound of Formula I compatibility, for example other bactericide, plant growth regulator, antibiotic, herbicide, fertilizer.
The compound method of several formulations is exemplified below:
The preparation of suspending agent: in common prescription, active component content is 5%-35%. Taking water as medium, former medicine, dispersant, suspending agent and antifreeze etc. are added in sand mill, grind, make suspending agent.
The preparation of aqueous emulsion: former medicine, solvent and emulsifying agent are added together, make to be dissolved into even oil phase. Water, antifreeze etc. are mixed, become homogeneous water. Under high-speed stirred, water is joined to oil phase or oil phase is joined to water, form the aqueous emulsion of favorable dispersibility. Aqueous emulsion active component content of the present invention is generally 5%-15%. For preparation emulsifiable concentrate, compound of the present invention is dissolvable in water one or several mixed solvents, then adds emulsifying agent to strengthen the dispersion effect of compound in water.
The preparation of wettable powder: by formula requirement, former medicine, various surfactant and solid diluent etc. are fully mixed, after ultra-fine pulverizer disintegrating, obtain the wettable powder product of predetermined content (for example 10%-40%). For preparation is suitable for spraying the wettable powder of use, compound of the present invention can be with the pressed powder of porphyrize as clay, inorganic silicate, carbonate and wetting agent, adhesive and/or dispersant composition mixture.
The preparation of water-dispersible granules: former medicine and powdery solid diluent, wetting spreader-sticker and adhesive etc. are carried out to co-grinding; add water again after kneading; add and in the comminutor that 10 to 100 eye mesh screens are housed, carry out granulation, and then drying, screening (pressing screen cloth scope). Also former medicine, dispersant, disintegrant and wetting agent and solid diluent can be added in sand mill, taking water as medium milling, make suspending agent, then carry out spray drying granulation, formulation content is 20%-30% granular product conventionally.
Detailed description of the invention
Following specific embodiment 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 joined to 500ml there-necked flask, add 150ml isopropyl alcohol, drip 17.9g (0.088mol) 1,3-dibromopropane (III-1), is warming up to backflow, reaction 10h, steam unnecessary isopropyl alcohol, add water, ethyl acetate extraction, water layer precipitation, obtains the thick thing of 34g.
1H-NMR (300MHz, interior mark TMS, solvent C DCl3)δppm1.19(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
Prepare with reference to example 1. Light yellow solid, 229.1 DEG C of fusing points.
1H-NMR (300MHz, interior mark 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
Prepare with reference to example 1. Thick thing.
1H-NMR (300MHz, interior mark 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
Prepare with reference to example 1. Thick thing.1HNMR (300MHz, interior mark 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, is metered into after reactive compound folding hundred)
Embodiment 5:30% compound 2 wettable powders
Compound 2 and other components are fully mixed, after ultra-fine pulverizer disintegrating, obtain 30% wettable powder product.
Embodiment 6:40% compound 4 suspension concentrates
Compound 4 and other components are fully mixed, the suspension concentrates obtaining thus, and dilute with water gained suspending agent can obtain the dilution of any desired concn.
Embodiment 7:60% compound 5 water-dispersible granules
Compound 560%
Naphthalenesulfonic acid-formaldehyde condensate 12%
N-methyl-N-oleoyl-sodium taurocholate 8%
Polyvinylpyrrolidone 2%
Carboxymethyl cellulose 2%
Kaolin complements to 100%
By compound 5 and other component co-grindings, then after adding water and mediating, add in the comminutor of 10-100 eye mesh screen and carry out granulation, and then drying, screening (pressing screen cloth scope).
Biological activity determination embodiment
Example 8 bactericidal activities are measured
With the compounds of this invention sample, the multiple fungal disease of plant is carried out to live body and protected effect test. The method of test is as follows:
Adopt the potted plant assay method of live body, by above-mentioned synthetic example gained testing compound for sample solvent (kind of solvent is as acetone, methyl alcohol, DMF etc., and the solvability according to it to sample and selecting, the volume ratio of quantity of solvent and spouting liquid is equal to or less than 0.05) dissolve, with the water dilution that contains 0.1% Tween 80, be mixed with desired concn liquid to be measured. On crops sprayer, liquid to be measured is sprayed on disease host plant (host plant is the potted plant seedling of standard of cultivating in greenhouse), after 24 hours, carry out disease inoculation. According to disease feature, will need be placed in phjytotron after the disease plant inoculating cultivated of temperature control moisturizing and cultivate, after disease completes and infects, move into hot-house culture; The disease plant that does not need moisturizing to cultivate is directly also cultivated at warm indoor inoculation. After contrasting abundant morbidity, (be generally week age) and carry out the assessment of compound protection effect.
Part live body prolection test result is as follows:
When liquor strength is 400mg/L, compound 5,9 etc. is 100% to anthracnose preventive effect; Compound 2,9 etc. is 70% to cucumber downy mildew preventive effect; 2,5,9 etc. are all greater than 65% to corn rust preventive effect.
When liquor strength is 100mg/L, compound 5 grades are 65% to anthracnose preventive effect.
Claims (8)
1. two piperidones quaternary ammonium salt (alkali) compounds, as shown in general formula I:
In formula:
R1Be selected from C1-C6Alkyl, halo C1-C6Alkyl, C2-C6Thiazolinyl, halo C2-C6Thiazolinyl, C2-C6Alkynyl,Halo C2-C6Alkynyl, C3-C6Cycloalkyl, C1-C6Alkyl hydroxy, C1-C6Alkylamide or benzyl;
R2、R3、R4、R5Can be identical or different, be selected from respectively hydrogen or C1-C6Alkyl, or R2With R3Be connected by carbonCheng Huan, R4With R5Be connected to ring by carbon;
X is selected from halogen or hydroxyl;
N is selected from 0-20.
2. compound according to claim 1, is characterized in that: in general formula I
R1Be selected from C1-C6Alkyl, halo C1-C6Alkyl, C1-C6Alkyl hydroxy, C1-C3Alkylamide or benzyl;
R2、R3、R4、R5Can be identical or different, be selected from respectively hydrogen or C1-C3Alkyl, or R2With R3Be connected by carbonCheng Huan, R4With R5Be connected to ring by carbon;
X is selected from halogen or hydroxyl;
N is selected from 0-20.
3. compound according to claim 2, is characterized in that: in general formula I
R1Be selected from C1-C6Alkyl, halo C1-C6Alkyl, C1-C6Alkyl hydroxy, C1-C3Alkylamide or benzyl;
R2With R5Identical, R3With R4Identical, be selected from respectively hydrogen or C1-C3Alkyl, or R2With R3Be connected to by carbonRing, R4With R5Be connected to ring by carbon;
X is selected from halogen or hydroxyl;
N is selected from 0-20.
4. compound according to claim 3, is characterized in that: in general formula I
R1Be selected from C1-C6Alkyl, C1-C6Alkyl hydroxy or benzyl;
R2、R3、R4、R5All identical, be selected from respectively hydrogen or C1-C3Alkyl, or R2With R3Be connected to ring by carbon,R4With R5Be connected to ring by carbon;
X is selected from chlorine, bromine, iodine or hydroxyl;
N is selected from 0-18.
5. compound according to claim 4, is characterized in that: in general formula I
R1Be selected from methyl, CH2CH2OH or benzyl;
R2、R3、R4、R5All be selected from hydrogen;
X is selected from chlorine, bromine, iodine or hydroxyl;
N is selected from 0-18.
6. one kind according to compound of Formula I claimed in claim 1 use as bactericide in agricultural or gardening fieldOn the way.
7. a bactericidal composition, is characterized in that: contain as can in the compound of Formula I of active component and agriculturalThe carrier of accepting, the weight percentage of composition formula of I compound is 0.5-90%.
One kind according to bactericidal composition claimed in claim 7 in agricultural or gardening field as disinfectant use in agriculturePurposes.
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| CN201410562123.4A CN105585521B (en) | 2014-10-21 | 2014-10-21 | A kind of bipiperidine ketone quaternary ammonium salt (alkali) class compound and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| US4167573A (en) * | 1977-05-07 | 1979-09-11 | Basf Aktiengesellschaft | Method of controlling fungi with 3,5-dimethyl-piperidin-4-ones |
| WO1993025527A1 (en) * | 1992-06-12 | 1993-12-23 | H. Lundbeck A/S | Dimeric piperidine, tetrahydropyridine and piperazine derivatives |
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2014
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| US4167573A (en) * | 1977-05-07 | 1979-09-11 | Basf Aktiengesellschaft | Method of controlling fungi with 3,5-dimethyl-piperidin-4-ones |
| WO1993025527A1 (en) * | 1992-06-12 | 1993-12-23 | H. Lundbeck A/S | Dimeric piperidine, tetrahydropyridine and piperazine derivatives |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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