CN102827025A - 2-methoxy-N-(4-fluorophenyl) benzamide as well as preparation method and application of 2-methoxy-N-(4-fluorophenyl) benzamide - Google Patents
2-methoxy-N-(4-fluorophenyl) benzamide as well as preparation method and application of 2-methoxy-N-(4-fluorophenyl) benzamide Download PDFInfo
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Abstract
The invention relates to 2-methoxy-N-(4-fluorophenyl) benzamide and a preparation method and application of 2-methoxy-N-(4-fluorophenyl) benzamide, belonging to the field of pesticides. The invention aims to solve the technical problem that a compound which can kill or inhibit pathogenic bacteria of crops is provided. The structural formula of the compound is shown in a formula (I) in the specification.
Description
Technical field
The present invention relates to 2-methoxyl group-N-(4-fluorophenyl) BM, belong to pesticide field.
Background technology
Agricultural chemicals is meant in agriculture prodn, for ensureing, promote the growth of plant and farm crop, the desinsection of being used, sterilization, the vegeto-animal one type of medicine general designation of kill harmful.Refer in particular to and on agricultural, be used for medicaments such as insect pests and coordinate plant growth, weeding.Agricultural chemicals and agricultural, livestock industry close relation, closely bound up with life.Therefore people early know and utilize agricultural chemicals that the disease and pest of farm crop is prevented and treated.B.C. more than 1000 years, in ancient Greek, existing using
Sulfur fumigationThe record of insect and diseases prevention, China also in B.C. 5-7 century, brings into use
Thick grass, clam charcoal ash, male bring up etc. kill insect.The agricultural chemicals that initial people use is mainly derived from natural plant; Utilize some position of plant or extract its effective constituent and process agricultural chemicals or utilize mineral to be raw material, the mineral compound agricultural chemicals that comes out through simple processing and manufacturing with desinsection or germicidal action.This type agricultural chemicals source is natural; Therefore have nuisanceless, can with characteristics such as environmentally compatible, mechanism of action uniqueness and development cost are cheap; Yet abstraction process is loaded down with trivial details from plant, and the material composition that extracts is complicated, so functioning efficiency is low; Usage quantity is big, and the effective object of desinsection, diseases prevention or weeding is single.Since the forties in 20th century, along with the continuous development of chemistry subject, the organic chemistry synthetic pesticide is by feat of wide in variety, and drug effect is high, the effective object variation, and advantage such as easy to use has substituted initial agricultural chemical of natural plant and inorganic pesticide.Yet along with a large amount of uses of chemical pesticide, produced a series of serious problems, like pesticide residue, harmful organism develops immunity to drugs, environmental pollution, destroys ecotope etc.Therefore the novel agrochemical of seeking efficient, low toxicity, low residue has become current sixty-four dollar question.
Natural product is meant that various endogenic chemical ingredients general designations are made natural product in the intravital moity of animal, plant, insect, sea life and mikrobe or its meta-bolites and the humans and animals body, wherein mainly comprises naturally occurring chemical ingredientss such as protein, polypeptide, amino acid, nucleic acid, various enzyme, monose, oligosaccharides, polysaccharide, gp, resin, colloid thing, xylogen, VITAMINs, fat, grease, wax, vegeto-alkali, volatile oil, flavones, glucosides class, terpene, the plain class of phenylpropyl alcohol, organic acid, phenols, quinones, lactone, steroidal compounds, tannins, antibiotics.80% derives from plant in the natural product of being found at present; And therefore these major parts biologically active is all sought the novel agrochemical of efficient, low toxicity, low residue can explore among the natural product from plant, and the screening biological activity is strong from plant source natural product; The compound that typical structure is arranged; According to this as the important source of agricultural chemicals elder generation guide structure, and its structure derived and optimizes, be seek efficiently now, the effective way of the novel agrochemical of low toxicity.
In agricultural, corps diseases is the significant problem in the agriculture prodn, also is the major reason that causes financial loss; The crop production reduction that annual due to illness evil causes reaches more than 10%, and in Plant diseases, fungal disease accounts for 80%; But the most of sterilant that now use all are the chemical sterilant; Cause environmental pollution easily, biology develops immunity to drugs, shortcomings such as pesticide residue.At present, the sterilant of commercially available efficient, low toxicity, safety less, therefore, sterilant how to research and develop efficient, low toxicity, safety becomes the technical barrier that this area presses for solution.
Summary of the invention
First technical problem to be solved by this invention provides a kind of compound that can kill or suppress pathogen of crop.
The structural formula of The compounds of this invention is shown in formula I:
Second technical problem to be solved by this invention provides a kind of method for preparing above-claimed cpd.
The method that the present invention prepares compound shown in the formula I is: 4-fluoroaniline and the reaction of 2-methoxy benzoyl chloride are obtained 2-methoxyl group-N-(4-fluorophenyl) BM.Reaction formula is following:
Wherein, the reaction of 4-fluoroaniline and 2-methoxy benzoyl chloride is more abundant, the reaction times is faster in order to make, and 4-fluoroaniline and 2-methoxy benzoyl chloride are preferred uses dissolution with solvents respectively earlier, reacts then; Wherein, described solvent is at least a in methylene dichloride, trichloromethane, ETHYLE ACETATE, ethanol, the acetone.
Further, more thorough in order to make reaction, thus the yield of raising product, the pH value of preferably also controlling solution when 4-fluoroaniline in the aforesaid method and the reaction of 2-methoxy benzoyl chloride is 8～13.Wherein, Can be through adding the pH value of acyl chlorides and amine reaction catalyzer regulator solution commonly used; Such as, can add pyridine, triethylamine, concentration is sodium hydroxide-ethanol solution of 50～150g/L, the pH value of a kind of regulator solution in the saturated solution of sodium bicarbonate.
Wherein, the temperature in aforesaid method when reaction crosses that low then speed of response is slow excessively, and efficient is lower; Possibly cause synthetics coking or by product too much if temperature of reaction is too high, also can reduce the yield of title product.Take all factors into consideration above-mentioned factor, preferred temperature is controlled at 20～40 ℃ during the aforesaid method reaction, and the reaction times is 3～4h.
Further, aforesaid method is also used the hydrochloric acid wash-out of 5-20%v/v after reaction is accomplished, leave standstill to solid in 2～6 ℃ then and separate out fully, filters at last, washs, and obtain 2-methoxyl group-N-(4-fluorophenyl) BM highly finished product with the absolute ethyl alcohol recrystallization.
The 3rd technical problem to be solved by this invention provides a kind of crop bactericide, and its activeconstituents is the compound shown in the formula I.
The 4th technical problem to be solved by this invention provides the compound shown in the formula I and suppressing or killing the purposes in the plant pathogenic fungi.Further, described plant pathogenic fungi is preferably the pathogenic bacteria of rice sheath blight disease, sclerotinia rot of colza, graw mold of tomato, wheat scab or corn southern leaf blight.Described plant pathogenic fungi most preferably is the pathogenic bacteria of graw mold of tomato or corn southern leaf blight.
Whitfield's ointment is the crude substance that a kind of vegitabilia extensively exists; It not only has important pharmacological effect; And plant growth and development process and disease resistance of plant aspect there is regulating and controlling effect widely; Contriver of the present invention is that the guide derives and optimizes the structure that obtains adjacent acetoxyl group Benzoyl chloride 99min. with this structure; Further obtain The compounds of this invention thus, and investigate its bacteriostatic action to plant pathogenic fungi, experimental result shows; Its to common farm crop as: plant pathogenic fungis such as paddy rice, rape, tomato, wheat and corn have certain inhibition or killing action, and are particularly higher to the inhibiting rate of the pathogenic bacteria of graw mold of tomato and corn southern leaf blight.The The compounds of this invention preparation method is simple, and cost is lower, has the characteristics of efficient, low toxicity, safety, has vast market prospect.
Embodiment
The structural formula of The compounds of this invention is shown in formula I:
The method that the present invention prepares compound shown in the formula I is: 4-fluoroaniline and the reaction of 2-methoxy benzoyl chloride are obtained 2-methoxyl group-N-(4-fluorophenyl) BM.Reaction formula is following:
Wherein, the reaction of 4-fluoroaniline and 2-methoxy benzoyl chloride is more abundant, the reaction times is faster in order to make, and 4-fluoroaniline and 2-methoxy benzoyl chloride are preferred uses dissolution with solvents respectively earlier, reacts then; Wherein, described solvent is at least a in methylene dichloride, trichloromethane, ETHYLE ACETATE, ethanol, the acetone.
Further, more thorough in order to make reaction, thus the yield of raising product, the pH value of preferably also controlling solution when 4-fluoroaniline in the aforesaid method and the reaction of 2-methoxy benzoyl chloride is 8～13.Wherein, Can be through adding the pH value of acyl chlorides and amine reaction catalyzer regulator solution commonly used; Such as, can add pyridine, triethylamine, concentration is sodium hydroxide-ethanol solution of 50～150g/L, the pH value of a kind of regulator solution in the saturated solution of sodium bicarbonate.
Wherein, the temperature in aforesaid method when reaction crosses that low then speed of response is slow excessively, and efficient is lower; Possibly cause synthetics coking or by product too much if temperature of reaction is too high, also can reduce the yield of title product.Take all factors into consideration above-mentioned factor, preferred temperature is controlled at 20～40 ℃ during the aforesaid method reaction, and the reaction times is 3～4h.
Further, aforesaid method is also used the hydrochloric acid wash-out of 5-20%v/v after reaction is accomplished, leave standstill to solid in 2～6 ℃ then and separate out fully, filters at last, washs, and obtain 2-methoxyl group-N-(4-fluorophenyl) BM highly finished product with the absolute ethyl alcohol recrystallization.
The present invention also provides a kind of crop bactericide, and its activeconstituents is the compound shown in the formula I.
The present invention also provides the compound shown in the formula I suppressing or killing the purposes in the plant pathogenic fungi.Further, described plant pathogenic fungi is preferably the pathogenic bacteria of rice sheath blight disease, sclerotinia rot of colza, graw mold of tomato, wheat scab or corn southern leaf blight.Described plant pathogenic fungi most preferably is the pathogenic bacteria of graw mold of tomato or corn southern leaf blight.
Do further description below in conjunction with the embodiment specific embodiments of the invention, therefore do not limit the present invention among the described scope of embodiments.
The preparation of embodiment 1 2-methoxyl group-N-(4-fluorophenyl) BM
With 4-fluoroaniline material (30mmol), 2-methoxy benzoyl chloride (03mmol) all is dissolved in respectively in the methylene dichloride of 10mL, and the 4-fluorobenzene amine substance that dissolving is good is put in the there-necked flask; Add pyridine (30mmol) again, put into 30 ℃ of thermostat water baths, will dissolve good 2-methoxy benzoyl chloride splashing in the there-necked flask slowly again; Adopt magnetic stirring apparatus constantly to stir 3-4 hour; Take out with 2 times to 10% hydrochloric acid wash-out of reaction solution volume 2-3 time, be placed in the 2-6 ℃ of refrigerator and place, up to there being solid to separate out; Filter, washing, with the absolute ethyl alcohol recrystallization till obtaining pure substance.
The structure of prepared 2-methoxyl group-N-(4-fluorophenyl) BM material is identified as follows:
Through IR,
1H NMR carries out structural confirmation, and the result of analysis is following:
2-methoxyl group-N-(4-fluorophenyl) BM is faint yellow needle-like crystal, and productive rate is: 70%, and m.p.97-98 ℃; IR (KBr) ν max (cm-1): 3329,3284,3075,3027,2983,2842,1647,1601,1579,1464,1317,1287,1210,1181,1094,1022,831,759,638,591; 1H NMR (400MHz, CDCl3) δ (ppm), 4.05 (s, 3H), 7.02-7.07 (m, 3H), 7.13 (t, J=8.0Hz, 1H), 7.48-7.52 (m, 1H), 7.62-7.65 (m, 2H), 8.27-8.29 (m, 1H), 9.78 (s, 1H)
In the ir spectra: 3329,3284cm
-1Absorption peak occurs and show have secondary amine to exist, 3075,2983cm
-1With 1647,1601,1579cm
-1' and 1464cm
-1Absorption peak occurring representes to have phenyl ring to have 2842cm
-1Absorption peak occurring representes to have methoxyl group to have 1647cm
-1Absorption peak occurring representes to have carboxamido-group to have 1317cm
-1Absorption peak occurs and represent to have methyl to exist, 1287,1210,1022cm
-1Absorption peak occurring representes to have fragrant ehter bond to exist.831cm
-1Absorption peak occurs and represent to have 1,4-disubstituted benzenes ring, 759cm
-1Absorption peak occurs and represent to have 1,2-disubstituted benzenes ring, 638,591cm
-1Absorption peak occurring representes to have the two keys of carbon oxygen in the carboxamido-group to exist.
1In the H NMR spectrum, δ 4.05 is three H on the methoxyl group on 13, and δ 7.02-7.07 is the H on 3, and the H on it and 4,5 intercouples and is that multiplet, coupling constant are 8.4Hz.δ 7.11-7.15 is the H on 5, and the H on it and 4,6 intercouples and is multiplet.δ 7.13 is the H on 8, and it and 7 intercouple with H on the secondary amine and are that triplet, coupling constant are 8.0Hz.δ 7.48-7.52 is the H on 4, and the H on it and 3,5 intercouples and is multiplet.δ 7.62-7.65 is 7 and goes up H, it with 8 with secondary amine on H intercouple to being multiplet, δ 8.27-8.29 is the H on 6, the H on it and 4,5 intercouples and is multiplet.δ 9.78 is the H on the secondary amine.
The structural formula that comprehensive infrared and MASS SPECTRAL DATA ANALYSIS have been identified the compound that try has confirmed that the synthetic material just is 2-methoxyl group-N-(4-fluorophenyl) BM shown in formula II.
The research of Test Example 2-methoxyl group-N-(4-fluorophenyl) BM material bacteriostatic activity
Method: test compound and derosal are dissolved in respectively in the methyl-sulphoxide (DMSO); Add 0.1% tween tap water again; Adopt doubling dilution; Process a series of 2-methoxyl group-N-(4-fluorophenyl) BM and each 1.0mL of carbendazim solution, and add Streptomycin sulphate 1.0mg (making Streptomycin sulphate is 50mg/L in the ultimate density of substratum) respectively.Corresponding solution not contain compound is made blank, is mixed with the uniform pastille flat board of thickness subsequent use (substratum sterilize earlier adding medicine again), every processing triplicate.Use the punch tool of sterilizing to beat to get and choose Ф 5mm well-grown; Pollution-free; The bacterium cake of the uniform rhizoctonia bacterium colony of growing way; Under aseptic condition, insert pastille substratum center (bacterium cake of each plating), measure colony diameter (time is that colony diameter is the incubation time about 50mm) behind the constant temperature culture 1-3d respectively at 28 ℃.Press Abbott
[16]Formula is proofreaied and correct bacteriostasis rate, again according to probability value analytical method, adopts SPSS computed in software EC
50Value and fiducial interval thereof are also obtained relation conefficient and regression equation.The bacteriostasis rate formula is following relatively:
Result: draw 2-methoxyl group-N-(4-fluorophenyl) BM through above method and when concentration is 100mg/L, the inhibiting rate of Rhizoctonia solani Kuhn, Sclerotinia sclerotiorum, botrytis cinerea, fusarium graminearum and southern corn leaf blight is respectively: 57.08%, 62.04%, 85.35%, 47.12%, 87.57%, wherein to the inhibition best results of graw mold of tomato and southern corn leaf blight.This material is seen table 1,2 respectively to the bacteriostatic activity of these two kinds of bacterium.The compounds of this invention 2-methoxyl group-N-(4-fluorophenyl) BM is active to the inhibition of southern corn leaf blight, its EC
50Value 11.58mg/L exists significant correlationship between concentration and drug effect, its equation of linear regression is 0.9577 for the Y=1.1664X+3.7594 relation conefficient, (χ 2=0.419, df=3, P > through card side; 0.05) the consequently reliable inhibition activity of check to botrytis cinerea, its EC
50Value 11.10mg/L exists significant correlationship between concentration and drug effect, its equation of linear regression is 0.9547 for the Y=1.0585X+3.89348 relation conefficient.Through card side (χ
2=0.657, df=3, P>0.05) check consequently reliable.
Table 1 The compounds of this invention is active to the inhibition of southern corn leaf blight
Table 2 The compounds of this invention is active to the inhibition of botrytis cinerea
Claims (10)
1. the compound of structural formula shown in formula I:
2. the method for the compound shown in the preparation formula I is characterized in that: 4-fluoroaniline and the reaction of 2-methoxy benzoyl chloride are obtained 2-methoxyl group-N-(4-fluorophenyl) BM.
3. the method for the compound shown in the preparation formula I according to claim 2 is characterized in that: 4-fluoroaniline and 2-methoxy benzoyl chloride are used dissolution with solvents respectively earlier, react then; Wherein, described solvent is at least a in methylene dichloride, trichloromethane, ETHYLE ACETATE, ethanol, the acetone.
4. according to the method for the compound shown in claim 2 or the 3 described preparation formula I, it is characterized in that: the pH value of also controlling solution when 4-fluoroaniline and the reaction of 2-methoxy benzoyl chloride is 8～13.
5. the method for the compound shown in the preparation formula I according to claim 4 is characterized in that: be sodium hydroxide-ethanol solution of 50～150g/L through adding pyridine, triethylamine, concentration, the pH value of at least a regulator solution in the saturated solution of sodium bicarbonate.
6. according to the method for the compound shown in each described preparation formula I of claim 2～5, it is characterized in that: the temperature during reaction is controlled at 20～40 ℃, and the reaction times is 3～4h.
7. according to the method for the compound shown in each described preparation formula I of claim 2～6; It is characterized in that: the hydrochloric acid wash-out of also using 5-20%v/v after reaction is accomplished; Leave standstill to solid in 2～6 ℃ then and separate out fully; Filter at last, wash, and obtain 2-methoxyl group-N-(4-fluorophenyl) BM highly finished product with the absolute ethyl alcohol recrystallization.
8. crop bactericide, it is characterized in that: its activeconstituents is the compound shown in the formula I.
9. the compound shown in the formula I is suppressing or is killing the purposes in the plant pathogenic fungi.
10. purposes according to claim 9 is characterized in that: described plant pathogenic fungi is the pathogenic bacteria of rice sheath blight disease, sclerotinia rot of colza, graw mold of tomato, wheat scab or corn southern leaf blight; Described plant pathogenic fungi is preferably the pathogenic bacteria of graw mold of tomato or corn southern leaf blight.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372529A (en) * | 2019-08-08 | 2019-10-25 | 黄河水利职业技术学院 | N- [(3,4,5- trifluoro) phenyl] acrylamide and preparation method thereof |
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| JPS5318732A (en) * | 1976-07-31 | 1978-02-21 | Hokko Chem Ind Co Ltd | Fungicides for horticultural use |
| JPH05318732A (en) * | 1992-05-25 | 1993-12-03 | Ricoh Co Ltd | Ink jet recording head |
| US20050032832A1 (en) * | 2003-08-08 | 2005-02-10 | China Medical University | Substituted 2-phenyl-4-quinolone-3-carboxylic acid compounds and their use as antitumor agents |
| WO2012054718A2 (en) * | 2010-10-22 | 2012-04-26 | The General Hospital Corporation | Treating long qt syndrome |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5318732B2 (en) * | 2009-11-25 | 2013-10-16 | 株式会社コロナ | Hot water heater |
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Patent Citations (4)
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| JPS5318732A (en) * | 1976-07-31 | 1978-02-21 | Hokko Chem Ind Co Ltd | Fungicides for horticultural use |
| JPH05318732A (en) * | 1992-05-25 | 1993-12-03 | Ricoh Co Ltd | Ink jet recording head |
| US20050032832A1 (en) * | 2003-08-08 | 2005-02-10 | China Medical University | Substituted 2-phenyl-4-quinolone-3-carboxylic acid compounds and their use as antitumor agents |
| WO2012054718A2 (en) * | 2010-10-22 | 2012-04-26 | The General Hospital Corporation | Treating long qt syndrome |
Non-Patent Citations (2)
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| HIROKO SUEZAWA等: "Studies on the Conformation of Antimicrobial Salicylanilide Derivatives by Spectroscopy", 《BULL.CHEM.SOC.JPN》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372529A (en) * | 2019-08-08 | 2019-10-25 | 黄河水利职业技术学院 | N- [(3,4,5- trifluoro) phenyl] acrylamide and preparation method thereof |
| CN110372529B (en) * | 2019-08-08 | 2022-05-24 | 黄河水利职业技术学院 | N- [ (3,4, 5-trifluoro) phenyl ] acrylamide and preparation method thereof |
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