CN102827024B - 2-methoxyl-N-(4-methylphenyl) benzamide, as well as preparation method and application thereof - Google Patents
2-methoxyl-N-(4-methylphenyl) benzamide, as well as preparation method and application thereof Download PDFInfo
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- CN102827024B CN102827024B CN201210355684.8A CN201210355684A CN102827024B CN 102827024 B CN102827024 B CN 102827024B CN 201210355684 A CN201210355684 A CN 201210355684A CN 102827024 B CN102827024 B CN 102827024B
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Abstract
The invention relates to 2-methoxyl-N-(4-methylphenyl) benzamide, as well as a preparation method and application thereof, belonging to the field of pesticides. The invention solves the technical problem of providing a compound capable of killing or inhibiting pathogenic bacteria of crops. The structural formula of the compound is shown as formula (I) in the specification.
Description
Technical field
The present invention relates to 2-methoxyl group-N-(4-aminomethyl phenyl) benzamide and its production and use, belong to pesticide field.
Background technology
Agricultural chemicals refers in agriculture production, and for ensureing, promoting the growth of plant and farm crop, the desinsection used, sterilization, the vegeto-animal class medicine of kill harmful are referred to as.Refer in particular to agriculturally for insect pests and the medicament such as coordinate plant growth, weeding.Agricultural chemicals and agricultural, livestock industry close relation, closely bound up with life.Therefore people early know and utilize the disease and pest of agricultural chemicals to farm crop to prevent and treat.B.C. more than 1000 years, in ancient Greek, existing use
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 to 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 make the agricultural chemicals with desinsection or germicidal action or utilize mineral for raw material, through simple processing and manufacturing mineral compound agricultural chemicals out.This kind of agricultural chemicals source is natural, therefore have nuisanceless, can the features such as unique and development cost are cheap with environmentally compatible, the mechanism of action, but abstraction process is loaded down with trivial details from plant, the material composition extracted is complicated, therefore functioning efficiency is low, usage quantity is large, and the effective object of desinsection, diseases prevention or weeding is single.Since the forties in 20th century, along with the development of chemistry subject, organic chemical synthesis agricultural chemicals is by feat of wide in variety, and drug effect is high, effective object variation, and the advantage such as easy to use instead of initial agricultural chemical of natural plant and inorganic pesticide.But along with a large amount of uses of chemical pesticide, create a series of serious problem, as pesticide residue, harmful organism develop immunity to drugs, environmental pollution, destroy ecotope etc.Therefore find efficient, low toxicity, low residue novel agrochemical and become current sixty-four dollar question.
Natural product refers to animal, plant, insect, in moiety in marine organisms and microbe or its meta-bolites and humans and animals body, various endogenic chemical composition is referred to as natural product, wherein mainly comprise protein, polypeptide, amino acid, nucleic acid, various enzyme, monose, oligosaccharides, polysaccharide, glycoprotein, resin, colloid substances, xylogen, VITAMIN, fat, grease, wax, alkaloid, volatile oil, flavones, glucosides class, terpene, Phenylpropanoid Glycosides class, organic acid, phenols, quinones, lactone, steroidal compounds, tannins, the naturally occurring chemical composition such as antibiotics.In the natural product found at present, 80% derives from plant, and these major parts all have biological activity, therefore find efficient, low toxicity, low residue novel agrochemical to explore among the natural product plant, biological activity is screened strong from plant source natural product, there is the compound of typical structure, according to this as the important sources of agricultural chemicals guide structure, and carrying out deriving and optimizing to its structure, is that current searching is efficient, the effective way of the novel agrochemical of low toxicity.
In agricultural, corps diseases is the significant problem in agriculture production, also be the major reason causing financial loss, the crop production reduction caused because of disease every year reaches more than 10%, and in Plant diseases, fungal disease accounts for 80%, but the most of sterilant used now are all chemical sterilant, easily cause environmental pollution, the shortcomings such as biology develops immunity to drugs, pesticide residue.At present, the sterilant of commercially available efficient, low toxicity, safety less, therefore, how researching and developing efficient, low toxicity, safety sterilant becomes this area technical barrier in the urgent need to address.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of compound can killing or suppress pathogen of crop.
The structural formula of the compounds of this invention is as shown in formula I:
Second technical problem to be solved by this invention is to provide a kind of method preparing above-claimed cpd.
The method that the present invention prepares compound shown in formula I is: 4-monomethylaniline and 2-methoxy benzoyl chloride are obtained by reacting 2-methoxyl group-N-(4-aminomethyl phenyl) benzamide.Reaction formula is as follows:
Wherein, in order to make, 4-monomethylaniline and 2-methoxy benzoyl chloride react more abundant, the reaction times is faster, and 4-monomethylaniline and 2-methoxy benzoyl chloride preferably first use dissolution with solvents respectively, then react; Wherein, described solvent is at least one in methylene dichloride, trichloromethane, ethyl acetate, ethanol, acetone.
Further, in order to make reaction more thorough, thus improve the yield of product, the pH value preferably also controlling solution when the 4-monomethylaniline in aforesaid method and 2-methoxy benzoyl chloride react is 8 ~ 13.Wherein, the pH value of conventional catalyzer regulator solution can be reacted by adding acyl chlorides and amine, such as, pyridine can be added, the pH value of a kind of regulator solution in sodium hydroxide-ethanol solution that triethylamine, concentration are 50 ~ 150g/L, saturated solution of sodium bicarbonate.
Wherein, the too low then speed of response of temperature during aforesaid method reaction is excessively slow, and efficiency is lower; If temperature of reaction is too high, synthetics coking or by product may be caused too much, also can reduce the yield of target product.Consider above-mentioned factor, during aforesaid method reaction, preferable temperature controls at 20 ~ 40 DEG C, and the reaction times is 3 ~ 4h.
Further, aforesaid method also uses the hydrochloric acid wash-out of 5-20%v/v after completion of the reaction, then leave standstill in 2 ~ 6 DEG C and separate out completely to solid, finally filter, wash, and obtain 2-methoxyl group-N-(4-aminomethyl phenyl) benzamide highly finished product with dehydrated alcohol recrystallization.
3rd technical problem to be solved by this invention is to provide a kind of crop bactericide, and its activeconstituents is the compound shown in formula I.
4th technical problem to be solved by this invention is to provide the compound shown in formula I in the purposes suppressed or kill in 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.
Whitfield's ointment is the crude substance that a kind of vegitabilia extensively exists, it not only has important pharmacological effect, and have regulating and controlling effect widely to plant growth and development process and disease resistance of plant aspect, the present inventor with this structure for guide carries out deriving and optimize the structure obtaining adjacent acetoxyl group Benzoyl chloride, obtain the compounds of this invention further thus, and investigate its bacteriostatic action to plant pathogenic fungi, experimental result shows, its to common farm crop as paddy rice, rape, tomato, the plant pathogenic fungis such as wheat and maize have certain suppression or killing action, the particularly pathogenic bacteria of graw mold of tomato, concentration be the compounds of this invention of 100mg/l to its inhibiting rate up to 88.25%.The compounds of this invention preparation method is simple, and cost is lower, has efficient, low toxicity, safety feature, has wide market outlook.
Embodiment
The structural formula of the compounds of this invention is as shown in formula I:
The method that the present invention prepares compound shown in formula I is: 4-monomethylaniline and 2-methoxy benzoyl chloride are obtained by reacting 2-methoxyl group-N-(4-aminomethyl phenyl) benzamide.Reaction formula is as follows:
Wherein, in order to make, 4-monomethylaniline and 2-methoxy benzoyl chloride react more abundant, the reaction times is faster, and 4-monomethylaniline and 2-methoxy benzoyl chloride preferably first use dissolution with solvents respectively, then react; Wherein, described solvent is at least one in methylene dichloride, trichloromethane, ethyl acetate, ethanol, acetone.
Further, in order to make reaction more thorough, thus improve the yield of product, the pH value preferably also controlling solution when the 4-monomethylaniline in aforesaid method and 2-methoxy benzoyl chloride react is 8 ~ 13.Wherein, the pH value of conventional catalyzer regulator solution can be reacted by adding acyl chlorides and amine, such as, pyridine can be added, the pH value of a kind of regulator solution in sodium hydroxide-ethanol solution that triethylamine, concentration are 50 ~ 150g/L, saturated solution of sodium bicarbonate.
Wherein, the too low then speed of response of temperature during aforesaid method reaction is excessively slow, and efficiency is lower; If temperature of reaction is too high, synthetics coking or by product may be caused too much, also can reduce the yield of target product.Consider above-mentioned factor, during aforesaid method reaction, preferable temperature controls at 20 ~ 40 DEG C, and the reaction times is 3 ~ 4h.
Further, aforesaid method also uses the hydrochloric acid wash-out of 5-20%v/v after completion of the reaction, then leave standstill in 2 ~ 6 DEG C and separate out completely to solid, finally filter, wash, and obtain 2-methoxyl group-N-(4-aminomethyl phenyl) benzamide highly finished product with dehydrated alcohol recrystallization.
Present invention also offers a kind of crop bactericide, its activeconstituents is the compound shown in formula I.
Present invention also offers the compound shown in formula I in the purposes suppressed or kill in 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.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
The preparation of embodiment 12-methoxyl group-N-(4-aminomethyl phenyl) benzamide
By 4-monomethylaniline material (0.03mmol), 2-methoxy benzoyl chloride (0.03mmol) is all dissolved in the methylene dichloride of 10mL respectively, the 4-methylbenzene amine substance dissolved is put in there-necked flask, add pyridine (0.03mmol) again, put into 30 DEG C of thermostat water baths, again the 2-methoxy benzoyl chloride dissolved is instilled in there-necked flask slowly, magnetic stirring apparatus is adopted constantly to stir 3-4 hour, take out with 2 times to reaction solution volume 10% hydrochloric acid wash-out 2-3 time, place in 2-6 DEG C of refrigerator, until there is solid to separate out, filter, washing, with dehydrated alcohol recrystallization until obtain pure substance.
The Structural Identification of prepared 2-methoxyl group-N-(4-aminomethyl phenyl) benzamide material is as follows:
By IR,
1h NMR carries out structural confirmation, and the result of analysis is as follows:
2-methoxyl group-N-(4-aminomethyl phenyl) benzamide is white crystal, and productive rate is: 83%, m.p.66-67 DEG C; IR (KBr) ν max (cm-1): 3444,3345,3070,3015,2993,2846,1667,1513,1483,1451,1403,1346,1256,1233,1128,017,822,757,709,674; 1H NMR (400MHz, CDCl3) δ (ppm): 2.33 (s, 3H), 4.03 (s, 3H), 7.01 (d, J=8.0Hz, 1H), 7.10 (t, J=6.8Hz, 1H), 7.14-7.17 (m, 3H), 7.45-7.50 (m, 1H), 7.56 (d, J=8.8Hz, 1H), 8.27-8.30 (m, 1H), 9.74 (s, 1H).
In infrared spectra: 3444,3345cm
-1occur that absorption peak shows have secondary amine to exist, 3015,2993cm
-1and 1513cm
-1, and 1483,1451cm
-1occur that absorption peak indicates that phenyl ring exists, 2846cm
-1occur that absorption peak indicates that methoxyl group exists, 1667cm
-1occur that absorption peak indicates that amide group exists, 1403,13436cm
-1occur absorption peak indicate that methyl exists, 1256,1128,1017cm
-1occur that absorption peak indicates that fragrant ehter bond exists.822cm
-1occur that absorption peak indicates Isosorbide-5-Nitrae-disubstituted benzenes ring, 757cm
-1occur that absorption peak indicates 1,2-disubstituted benzenes ring, 709,674cm
-1occur that absorption peak indicates that the C=O bond in amide group exists.
1in H NMR spectrum, δ 2.33 is that on the methyl on 14, three H, δ 4.03 are that on methoxyl group on 13, three H, δ 7.01 are the H on 3, and the H on it and 4 intercouples to split and is divided into doublet, and coupling constant is 8.0Hz.δ 7.10 is the H on 5, and the H on it and 4 intercouples to split and is divided into doublet, and coupling constant is 6.8Hz.δ 7.14-7.17 is the H on 8, and the H in it and 7 and secondary amine intercouples as multiplet.δ 7.45-7.50 is the H on 4, and the H on it and 3,5 intercouples as multiplet.δ 7.56 is 11 upper H, and it splits with the H phase mutual coupling on 7 and is divided into doublet, and coupling constant is 8.8Hz.。δ 8.27-8.30 is the H on 6, and the H in it and 5 and secondary amine intercouples as multiplet.δ 9.74 is the H in secondary amine.
Comprehensively infrared and MASS SPECTRAL DATA ANALYSIS identifies the structural formula of test compound as shown in formula II, and the material determining synthesis is just 2-methoxyl group-N-(4-aminomethyl phenyl) benzamide.
Test example 2-methoxyl group-N-(4-aminomethyl phenyl) benzamide material bacteriostatic activity is studied
Method: test compound and derosal are dissolved in respectively in methyl-sulphoxide (DMSO), add 0.1% tween tap water again, adopt doubling dilution, make a series of 2-methoxyl group-N-(4-aminomethyl phenyl) benzamide and each 1.0mL of carbendazim solution, and add Streptomycin sulphate 1.0mg (making Streptomycin sulphate be 50mg/L in the ultimate density of substratum) respectively.Make blank with the corresponding solution not containing compound, be mixed with thickness uniform pastille flat board (the first sterilizing of substratum adding medicine again) for subsequent use, often process in triplicate.Beat to get with the punch tool of sterilizing and choose Ф 5mm well-grown, pollution-free, the bacterium cake of the uniform rhizoctonia bacterium colony of growing way, aseptically access pastille substratum center (each plating bacterium cake), after 28 DEG C respectively constant temperature culture 1-3d, measure the colony diameter incubation time of about 50mm (time, to be colony diameter be).By Abbott
[16]formula corrects bacteriostasis rate, then according to probability value analytical method, adopts SPSS computed in software EC
50value and fiducial interval thereof also obtain relation conefficient and regression equation.Relative bacteriostasis rate formula is as follows:
Result: show that the compounds of this invention 2-methoxyl group-N-(4-aminomethyl phenyl) benzamide is respectively the inhibiting rate of Rhizoctonia solani Kuhn, Sclerotinia sclerotiorum, botrytis cinerea, fusarium graminearum and southern corn leaf blight when concentration is 100mg/L by above method: 44.88%, 74.16%, 88.25%, 58.17%, 69.39%, the inhibition wherein for botrytis cinerea is best.This material to the bacteriostatic activity of this bacterium respectively in table 1.2-methoxyl group-N-(4-aminomethyl phenyl) benzamide to the inhibit activities of botrytis cinerea, its EC
50value 19.49mg/L, there is significant correlationship between concentration and drug effect, its equation of linear regression is Y=1.5396X+3.0142 relation conefficient is 0.9517, through card side (χ
2=3.313, df=3, P>0.05) inspection is consequently reliable.
Table 1 the compounds of this invention is to the inhibit activities of botrytis cinerea
Claims (1)
1. the compound shown in formula I is in the purposes suppressed or kill in botrytis cinerea
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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 |
| US7429593B2 (en) * | 2001-09-14 | 2008-09-30 | Shionogi & Co., Ltd. | Utilities of amide compounds |
| US9447027B2 (en) * | 2010-10-22 | 2016-09-20 | The General Hospital Corporation | Treating long QT syndrome |
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| Studies on the Conformation of Antimicrobial Salicylanilide Derivatives by Spectroscopy;Hiroko Suezawa等;《Bull.Chem.Soc.Jpn》;20001231;第73卷;第2335-2339页 * |
| Synthesis and Antifungal Activity of 2-Chloro-N-phenylbenzamide;Xiaorong Tang等;《Asian Journal of Chemistry》;20120731;第24卷(第7期);第860-2862页 * |
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