CN105585561B - A kind of bi-quaternary ammonium salt (alkali) class compound and application thereof - Google Patents
A kind of bi-quaternary ammonium salt (alkali) class compound and application thereof Download PDFInfo
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Abstract
The invention belongs to disinfectant use in agriculture fields.More particularly to a kind of bi-quaternary ammonium salt (alkali) class compound and application thereof.Compound 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 bi-quaternary ammonium salt (alkali) class compound and application thereof.
Background technology
Bi-quaternary ammonium salt class compound, which was once reported, may be used as surfactant, industrial bactericide, and medicine aspect is used
In analgesia, inhibition tumour, reduce blood pressure.Journal of the American Chemical Society(1954),76,
Once reported that following compound had the function of reducing blood pressure in 5099-5103：
(CAS：30098-65-8)
But compound of Formula I as representative of the present invention and its application as disinfectant use in agriculture have not been reported.
Invention content
The purpose of the present invention is to provide a kind of bi-quaternary ammonium salts that can control harmful levels of pathogens in agricultural and horticultural field
(alkali) class compound.
To achieve the above 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：
What A, B may be the same or different is selected from (CH2)p、(CH2)q-O-(CH2)r、(CH2)q-S-(CH2)r、(CH2)q-NR2-
(CH2)rOr (CH2)q(C=O)-(CH2)r；
R1Selected from CH2、CH2- O or CH2-NR3；
R2、R3What be may be the same or different is selected from hydrogen, C1-C6Alkyl, halogenated C1-C6Alkyl, C2-C6Alkenyl, halogenated C2-C6Alkene
Base, C2-C6Alkynyl, halogenated C2-C6Alkynyl, C3-C6Naphthenic base, C1-C6Alkyl-carbonyl, C1-C6Alkoxy carbonyl or benzyl；
X is selected from halogen or hydroxyl；
M, n may be the same or different, and be respectively selected from 0-20；It is 0 when m and n differences；
P is selected from 2-10；
Q, r may be the same or different, and be respectively selected from 1-10.
More preferably compound is the present invention：In general formula I
What A, B may be the same or different is selected from (CH2)p、(CH2)q-O-(CH2)r、(CH2)q-S-(CH2)r、(CH2)q-NR2-
(CH2)rOr CH2)q(C=O)-(CH2)r；
R1Selected from CH2、CH2- O or CH2-NR3；
R2Selected from hydrogen, C1-C6Alkyl, halogenated C1-C6Alkyl, C2-C6Alkenyl, halogenated C2-C6Alkenyl, C2-C6It is alkynyl, halogenated
C2-C6Alkynyl, C3-C6Naphthenic base, C1-C6Alkyl-carbonyl, C1-C6Alkoxy carbonyl or benzyl；
R3Selected from hydrogen or C1-C6Alkyl；
X is selected from halogen or hydroxyl；
M, n may be the same or different, and be respectively selected from 0-20；It is 0 when m and n differences；
P is selected from 2-10；
Q, r may be the same or different, and be respectively selected from 1-10.
Further preferred compound is：In general formula I
What A, B may be the same or different is selected from (CH2)pOr (CH2)q(C=O)-(CH2)r；
R1Selected from CH2、CH2- O or CH2-NR3；
R3Selected from hydrogen or C1-C6Alkyl；
X is selected from halogen or hydroxyl；
M, n may be the same or different, and be respectively selected from 0-20；
P is selected from 2-6；
Q, r may be the same or different, and be respectively selected from 1-6.
Compound still more preferably is：In general formula I
What A, B may be the same or different is selected from (CH2)pOr (CH2)q(C=O)-(CH2)r；
R1Selected from CH2, m 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；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；
It is 0 when m and n differences；
R3Selected from hydrogen or methyl；
X is selected from chlorine, bromine, iodine or hydroxyl；
P is selected from 4 or 5；
Q, r is selected from 2；
Or
What A, B may be the same or different is selected from (CH2)pOr (CH2)q(C=O)-(CH2)r；
R1Selected from CH2- O or CH2-NR3, m is selected from 2；
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；
R3Selected from hydrogen or methyl；
X is selected from chlorine, bromine, iodine or hydroxyl；
P is selected from 4 or 5；
Q, r is selected from 2.
Most preferred compound is：In general formula I
What A, B may be the same or different is selected from (CH2)pOr (CH2)q(C=O)-(CH2)r；
R1Selected from CH2, m be selected from 1-18, specially 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,
18；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；
R3Selected from hydrogen or methyl；
X is selected from chlorine, bromine or hydroxyl；
P is selected from 4；
Q, r is selected from 2.
Or,
What A, B may be the same or different is selected from (CH2)pOr (CH2)q(C=O)-(CH2)r；
R1Selected from CH2- O or CH2-NR3, m is selected from 2；
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；
R3Selected from hydrogen or methyl；
X is selected from chlorine, bromine or hydroxyl；
P is selected from 4；
Q, r is selected from 2.
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.
Naphthenic base：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 branched chain and can in any position on there are double bonds, such as vinyl or allyl.
Alkynyl：Linear chain or branched chain and can in any position on there are three keys, such as acetenyl or propargyl.
Alkyl-carbonyl：Alkyl-CO, such as：Acetyl group, propiono etc..
Alkoxy carbonyl：Alkyl-O-CO.
In the compound of Formula I of the present inventionWithSpecific preferred substituent group enumerates the Q in table 1,
It is not limited to this.
Table 1
The particular compound listed in table 2 can be used for illustrating the present invention, but not limit the present invention.
Table 2
The compound of Formula I of the present invention can be prepared in accordance with the following methods：
Compound representated by general formula I, which is reacted by intermediate II with intermediate III, to be made：
Intermediate II is reacted with intermediate III in suitable solvent, the optional tetrahydrofuran freely of suitable solvent,
Acetonitrile, toluene, dimethylbenzene, 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.
Intermediate II can be under alkaline condition condensed to yield by secondary amine VI, V and dihalo object IV.
Intermediate III, IV, V, VI can be by being commercially available.
Reaction carried out in suitable solvent, the optional tetrahydrofuran freely of suitable solvent, acetonitrile, toluene, dimethylbenzene,
Benzene, isopropanol, acetone, butanone, ether and methyl tertiary butyl ether(MTBE) etc..
The optional potassium hydroxide freely of suitable alkali, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine,
Sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or sodium tert-butoxide 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 that preferable sterilization is lived to harmful germ in agriculture, civilian and zoo technical field
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 line
Blight, rice blast, wheat rust, speckled leaf blotch, wheat powdery mildew, sclerotinia sclerotiorum, corn rust and corn stigma
Disease etc..
Due to its positive characteristic, above compound is advantageously used for protection agricultural and the important crop of horticulture, family
Injury of the environment that poultry and breeding stock and the mankind often go from harmful levels of pathogens.
To obtain ideal effect, the dosage of compound changes because of 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 of use.
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 for the pest and disease damage in the environment that often goes of domestic animal and breeding stock and/or the mankind.Especially, the dosage of compound is in every public affairs
Change in hectares 10 grams -5 kilograms.
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
Amount is 0.5-90%.Purposes the invention also includes 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 with 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, ethylpentyl 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, carbonic acid
Salt 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, be added 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, is with water
Suspending agent is made in medium milling, then carries out spray drying granulation, and it is 20%-30% granular products to be typically formulated content.
Specific implementation mode
Following specific examples is used for further illustrating the present invention, but the present invention is limited to absolutely not these examples.
Synthetic example example 1：The preparation of compound 173
1000ml there-necked flasks are added in 50g (0.7mol) nafoxidine, 400ml acetonitriles are added, 145g (1.05mol) is added
85g (0.35mol) 1,6- dibromobutanes are slowly added dropwise in potassium carbonate at room temperature, stir 4 hours at this temperature, are filtered after cooling,
Filtrate precipitation, it is cooling that white solid is precipitated, it filters, white solid 35g is obtained after dry, it is not purified to be directly used in next step.
250ml two-mouth bottles are added in 20g (0.089mol) II-1,30ml toluene is added, 18g is added dropwise at room temperature
(0.089mol) 1,3- dibromopropanes (IV-1), are heated to flowing back after being added dropwise, and solution becomes pale yellow muddiness by clarification, is flowing back
It is reacted 24 hours under state.It is down to room temperature, 50ml ethyl acetate is added, is stirred at room temperature 15 minutes, filter, dry white solid
32.6g.300 DEG C of fusing point.1H-NMR (300MHz, internal standard TMS, solvent C DCl3)δppm 1.55(4H,m),1.87(4H,m),
2.52(2H,m),2.27(8H,m),3.61(8H,m),3.74(8H,m)。
Example 2：The preparation of compound 175
250ml two-mouth bottles are added in 20g (0.089mol) II-1,30ml toluene is added, 20.5g is added dropwise at room temperature
(0.089mol) 1, pentamethylene bromide (IV-2), is heated to flowing back after being added dropwise, and solution becomes pale yellow muddiness by clarification.It is flowing back
It is reacted for 24 hours under state.It is cooled to room temperature and 50ml ethyl acetate is added, form dope, water is added to extract, retain water phase and depressurize steaming
It evaporates, obtains 36g yellow oils.1H-NMR (300MHz, internal standard TMS, solvent C DCl3)δppm 1.49(6H,m),1.82(8H,m),
2.23(8H,m),3.32(8H,m),3.59(8H,m)。
Example 3：The preparation of compound 179
The preparation of method same 175.Yellow oil.1H-NMR (300MHz, internal standard TMS, solvent C DCl3)δppm1.42
(14H,m),1.77(8H,m),2.19(8H,m),3.28(8H,m),3.59(8H,m)。
Example 4：The preparation of compound 180
The preparation of method same 175.Light yellow oil.1H-NMR (300MHz, internal standard TMS, solvent C DCl3)δppm1.22
(4H,m),1.39(14H,m),1.77(6H,m),2.20(6H,m),3.29(6H,m),3.55(6H,m),3.68(6H,m)。
Example of formulations (each component addition is weight percentage, and reactive compound folding hundred is post-dised)
Embodiment 5：30% compound, 173 wettable powder
Compound 173 and other components are sufficiently mixed, to get to 30% wettable powder after ultra-fine pulverizer disintegrating
Agent product.
Embodiment 6：40% compound, 175 suspension concentrates
Compound 175 and other components are sufficiently mixed, thus obtained suspension concentrates, and gained suspending agent, which is diluted with water, to be obtained
To the dilution of any required concentration.
Embodiment 7：60% compound, 179 water-dispersible granules
By compound 179 and other components co-grinding, after adding water kneading, it is added in the comminutor of 10-100 mesh screens
It is granulated, then again through drying, screening (pressing screen cloth scope).
Biological activity determination embodiment
8 bactericidal activity of embodiment measures
Live body protecting effect or in vitro antibacterial work have been carried out to a variety of fungal diseases of plant with the compounds of this invention sample
Property experiment.The method of experiment is as follows：
Live body protection activity measures：Using live body potting assay method, i.e., by test compounds obtained by above-mentioned synthetic example
Object sample with solvent (type of solvent such as acetone, methanol, DMF etc., and being selected according to its solvability to sample, it is molten
0.05) volume ratio of dosage and spouting liquid, which is equal to or less than, to be dissolved, diluted with the water containing 0.1% Tween 80, is configured to required
Concentration prepare liquid.On crops sprayer, prepare liquid is sprayed on disease host plant to (host plant is to be cultivated in greenhouse
Standard Potted orchard), after 24 hours carry out disease inoculation.According to disease feature, it would be desirable to the disease plant of temperature control moisturizing culture
It is placed in phjytotron and cultivates after inoculation, after disease completion is infected, move into hot-house culture；The disease of moisturizing culture will not needed
Evil plant directly in warm indoor inoculation and is cultivated.(being usually week age) carries out compound diseases prevention effect after the onset of waiting for control fully
Fruit is assessed.
Antifungal Activity in Vitro measures：Using high-throughput screening method, i.e., by untested compound obtained by above-mentioned synthetic example
The suitable solvent of sample (type of solvent such as acetone, methanol, DMF etc., and selected according to its solvability to sample
Select) dissolving, it is configured to required concentration prepare liquid.Under ultra-clean working environment, prepare liquid is added to the micropore of 96 well culture plates
In, then pathogen breeding liquid suspension is added thereto, treated, and culture plate is placed in constant incubator cultivates.24 hours
After investigated, range estimation pathogen brood body sprouts or growing state when investigation, and according to the sprouting of control treatment or growth feelings
Condition evaluates compound bacteriostatic activity.
Test result is as follows for part live body protection activity：
When liquor strength is 400mg/L, compound 179,180 etc. is all higher than 60% to cucumber downy mildew；173、175
It is all higher than 80% Deng to corn rust preventive effect；Compounds 180 etc. are more than 98% to anthracnose preventive effect；Compound 179,180 etc. pair
Gray mold of cucumber preventive effect is all higher than 50%.
Test result is as follows for part Antifungal Activity in Vitro：
When liquor strength is 25mg/L, compound 179,180 etc. is all higher than 80% to rice blast preventive effect.
Claims (4)
1. a kind of bi-quaternary ammonium salt class compound, as shown in general formula I：
I
In formula：
A, B identical can be selected from (CH2)p；
R1Selected from CH2, m is selected from 3-18, and n is selected from 2-18；
X is selected from chlorine or bromine；
P is selected from 4.
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 compound of Formula I described in claim 1 as active component
The weight percentage of agriculturally acceptable carrier, 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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| 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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| US3542538A (en) * | 1967-01-04 | 1970-11-24 | Basf Ag | Method of retarding plant growth with heterocyclic quaternary ammonium salts |
| CN1413984A (en) * | 2002-06-26 | 2003-04-30 | 西南石油学院 | Diquaternary-base diphenyl surface reactive agent and its preparation process |
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|---|---|---|---|---|
| US3542538A (en) * | 1967-01-04 | 1970-11-24 | Basf Ag | Method of retarding plant growth with heterocyclic quaternary ammonium salts |
| CN1413984A (en) * | 2002-06-26 | 2003-04-30 | 西南石油学院 | Diquaternary-base diphenyl surface reactive agent and its preparation process |
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