CN101584338B - N-nitryl-N-phenyl-N'-pyridylurea derivatives with sterilizing activity and preparing method thereof - Google Patents
N-nitryl-N-phenyl-N'-pyridylurea derivatives with sterilizing activity and preparing method thereof Download PDFInfo
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- CN101584338B CN101584338B CN200910088198A CN200910088198A CN101584338B CN 101584338 B CN101584338 B CN 101584338B CN 200910088198 A CN200910088198 A CN 200910088198A CN 200910088198 A CN200910088198 A CN 200910088198A CN 101584338 B CN101584338 B CN 101584338B
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Abstract
The invention belongs to the pesticides synthesizing technical field, especially relates to N-nitryl-N-phenyl-N'-pyridylurea derivatives with sterilizing activity and preparing method and application thereof. The invention discloses N-nitryl-N-phenyl-N'-pyridylurea derivatives with sterilizing activity and preparing method represented by the general formula (I)m, the chemical structural formulas are represented, wherein, R is hydrogen, 3-methyl. The compound of the invention has good inhibition activity for rice sheath blight disease bacterium, green cucumber gray mold bacterium and wheat gibberellic disease bacterium, can be used as sterilizing agent, and has remarkable sterilizing effect.
Description
Technical field
The invention belongs to the chemical pesticide synthesis technical field, be specifically related to sterilant and the preparation method and the application of a kind of N-nitro-N-phenyl-N '-pyridyl urea derivatives.
Background technology
The eighties in 20th century, the O ' Neal and the Barrington Cross report N-nitrotrimethylolmethane chloroaniline of the U.S. had effect in the strong sprout of dwarfing (EP0034281) to wheat, barley, cotton, Soybean and Other Crops.The Barrington Cross of the U.S. in 1978 and Dawe reported once that the N-nitroanilin compounds had fungicidal activity (US4130645).Process is to these compounds years of researches; Domestic scholars has filtered out a kind of new plant growth regulator that crops such as paddy rice, cotton, wheat and rape is had short production-increasing function---the plain (Xie Jiugao etc. of economic benefits and social benefits; Chinese invention patent number: ZL 94119117.6); It has stronger physiological regulatory action to single, double cotyledon crop, has tangible effect of increasing production.Through assessment in many ways, its plant growth regulating activity is better than PP-333 (PP333) and helps strong element (claiming mepiquat chloride again), proves that it is a new plant-growth regulator.(Zhang Qiaoling, Li Liangchao, Li Shuiqing such as the pesticide research chamber Zhang Qiaoling of college of science of Hua Zhong Agriculture University; Xie Jiugao, the research of N-nitrophenyl urea derivatives structure activity relationship, Hua Zhong Agriculture University's journal; 2001; 20:501-505), N-nitrotrimethylolmethane chloroaniline and the phenylurea reactive group with weeding activity are organically combined, synthesized a series of N-nitrophenyl urea derivativess with phosgenation; Li Xuegang (Li Xuegang; Synthetic and the preliminary biological activity determination of N-nitrophenyl urea derivatives, [master thesis], Wuhan: Hua Zhong Agriculture University Library; 2003, middle National IP Network) adopt solid phosgene to synthesize N-nitrophenyl urea and carried out determination of activity with chloride method.Above institute synthetic compound all is a N-nitrophenyl ureas structure; Certain weeding or fungicidal activity are arranged; Institute of the present invention synthetic compound have be different from the aforementioned structure characteristics contain N-nitro heterocyclic urea class formation, and fungicidal activity obviously is superior to N-nitrophenyl carbamide compounds.
Summary of the invention
The objective of the invention is to N-nitro-N-phenyl-N '-pyridyl urea derivatives with fungicidal activity of synthetic a kind of new texture, one type of N-nitro-N-phenyl-N '-pyridyl urea derivatives and compound method thereof with fungicidal activity is provided.
General structure of the present invention is shown in (I):
In the formula, R representes: hydrogen or 3-methyl.
Compound with said structure general formula (I) of the present invention is to Rhizoctonia solani Kuhn, botrytis cinerea pers, and bacterial classifications such as fusarium graminearum have significant inhibitory effect, can be used as the effective ingredient of sterilant.
Particularly, the synthetic route of compound of the present invention is following:
In the above-mentioned reaction formula: compound (II) is 1: 0.4 with the solid phosgene mol ratio; Make solvent with toluene or ethylene dichloride; Triethylamine is made catalyzer, under ice bath, react midbody (IV), with midbody (IV) and EL-970 50 ℃ of reactions 4-5 hour; Obtain N-nitro-N-phenyl-N '-pyridyl urea derivatives I, yield is 66%.
More detailed technical scheme is seen " embodiment ".
Description of drawings
Fig. 1: proton nmr spectra (1H NMR) spectrogram that is the compound I-1 for preparing of the present invention;
Fig. 2: mass spectrum (Mass) spectrogram that is the compound I-1 for preparing of the present invention;
Fig. 3: ir spectra (IR) spectrogram that is the compound I-1 for preparing of the present invention.
Embodiment
The preparation of embodiment 1 (preparing embodiment basically) compound I-1
The compound I-1 of present embodiment preparation has the structure that is shown below:
Compound method: in the 250ml there-necked flask, add 0.004mol solid phosgene and 20mL toluene; Cryosel is bathed temperature control and is dripped 0.01mol N-nitro-2,4, the solution that 6-trichloroaniline and 50mL toluene and 5mL triethylamine are formed down for 0～5 ℃; 2h dropwises; Room temperature reaction 1h behind 50 ℃ of reaction 4h, blows with nitrogen and to catch up with unnecessary phosgene.Drip the solution that 0.01mol 2-EL-970 and 30mL toluene and 3mL triethylamine are formed, 2h dropwises, and continues insulation reaction 5h, and decompress filter, solid product are successively through 10%NaCO
3Wash, massive laundering is dried behind 10 * 3mL washing with acetone, acetone recrystallization, and drying gets white needle-like crystals, and yield is 66%, m.p.172～174 ℃ (the Tianjin analytical instrument RY-2 of factory type fusing point appearance (TM is not proofreaied and correct) mensuration).
It is the AVATAR 330 type IRs (KBr pressed disc method) that U.S. Nicolet company produces that ir spectra (IR) is measured used instrument; The used instrument of mass spectroscopy is Varian CP-3800Saturn 2200GC-Mass gas-matter coupling mass spectrograph, proton nmr spectra (
1H NMR) measuring used instrument is the German Bruker AV-400MHz of company type NMR (with DMSO is solvent, and TMS is interior mark).Test data is following:
IR (KBr), v (cm
-1): 3228,3064 (N-H), 3100-3000 (Ar-H), 1695 (C=O), 1581,1532,1483 (phenyl ring and pyridine ring skeletal vibrations), 1565,1413 (N-NO
2), 1307 (aromatic secondary amine C-N), 1229 (fragrant tertiary amine C-N), 854 (phenyl ring four replaces);
MS(m/z)：360(M
++1，3％)，359(4％)，282(35％)，281(95％)，79(45％)；
1H?NMR(400MHz，DMSO)δ：6.96-7.09(q，1H，Py-H)，7.30(d，1H，Py-H)，7.76(t，1H，Py-H)，7.79(s，2H，Ar-H)，8.22(t，1H，Py-H)，9.80(s，1H，NH)。
The preparation of embodiment 2 compound I-2
The compound I-2 of present embodiment preparation has the structure that is shown below:
The preparation method is with reference to embodiment 1 (detecting instrument is the same).The pure article of gained are white needle-like crystals, yield 66%, m.p.208～210 ℃.
The structure appraising datum is following:
IR (KBr), v (cm
-1): 3367,3224 (N-H), 3081,3048 (Ar-H), 2917 (Py-CH
3), 1691 (C=O), 1626,1556,1511 (phenyl ring and pyridine ring skeletal vibrations), 1475,1389 (N-NO2), 1303 (aromatic secondary amine C-N), 1262 (fragrant tertiary amine C-N), 899 (phenyl ring four replaces);
MS(m/z)：374(M
++1，1％)，281(78％)，91(55％)，61(20％)，45(100％)；
1H?NMR(400MHz，DMSO)δ：2.29(s，3H，CH
3)，6.82(t，1H，Py-H)，7.15(s，1H，Py-H)，7.76(s，2H，Ar-H)，8.10(d，1H，Py-H)，9.73(s，1H，NH)。
Embodiment 3 (application implementation example)
The bacteriostatic activity test (reference: Fang Zhong reaches., plant the disease research method, the third edition, Beijing: Chinese agriculture press, 1998).
Supplying the examination bacterial classification is Rhizoctonia solani Kuhn (Pellicularia sasakii); Botrytis cinerea pers (Botrytis cinerea) and fusarium graminearum (Gibberellazeae), above-mentioned three kinds of germs are provided by plant technical college Pesticide Science teaching and research room of Hua Zhong Agriculture University.
The preparation of test medicine:
Compound compound I-1, the solubility property of compound I-2 in different solvents and the toxicity of solvent itself according to the present invention's preparation; The selected solvent of present embodiment is a DMSO 99.8MIN.; Emulsifying agent is Tween-80 (Chemical Reagent Co., Ltd., Sinopharm Group's product), is made into 1% missible oil.Supply the reagent agent concentration to see table 1, establishing clear water and solvent simultaneously is two contrasts.
Table 1 test design table
Testing method:
Adopt watch-glass isolated activity assay method.
Concrete preparation process: in 1500mL boiling water, add the potato flakes that 300 grams cut, boil after 5-10 minute and use filtered through gauze, gained filtrating adds 30g glucose; 25g agar treats after the agar dissolving that again with filtered through gauze once, filtrating is poured in the Erlenmeyer flask of 7 250mL; Seal; 121 ℃ of high pressure steam sterilization 30min obtain the yam inoculation medium, and are subsequent use.
With above-mentioned yam inoculation medium fusing; In Bechtop; Get above-mentioned yam inoculation medium 9mL, add 1mL synthetic compound I-1 of the present invention or compound I-2 in the yam inoculation medium of sterilization petridish, thorough mixing is even; Process and mix medicine substratum plane, each concentration of treatment triplicate.
Use punch tool to beat and get the bacterium piece, the substratum fritter that will carry bacterium with tweezers is placed on the media surface that contains synthetic compound of the present invention, perform label after, in 25 ℃ of following constant temperature culture 48～72 hours.
After supplying the examination bacterium to cultivate about 48～72 hours, check test result when the bacterium colony of control treatment grows to nearly petridish edge.Measuring each colony diameter with the ruler right-angled intersection, is colony diameter with its mean number.Calculate and suppress growth rate:
Active is reference with the bacteriostasis rate, rank standard: A level:>=90%, and the B level: 70～89%, the C level: 50～69%, D level :≤49%.
The compound I-1 of the present invention's preparation and the mensuration result of compound I-2 see table 2.
Table 2 compound I of the present invention-1 and compound I-2 couple Rhizoctonia solani Kuhn activity experiment result
Can know by table 2; Compound I-1, I-2 all suppress the growth of Rhizoctonia solani Kuhn in whole concentration range; Restraining effect increases along with the increase of concentration, and concentration and the bacterium inhibiting rate of compound I-1, I-2 all be proportionate, and wherein the biocidal property of compound I-1 pair Rhizoctonia solani Kuhn is best.
Table 3 compound concentration (X) and the correlation analysis of medicament to Rhizoctonia solani Kuhn inhibiting rate (Y)
Can be known that by table 3 each compound concentration and medicament are relatively good to the inhibiting rate dependency of Rhizoctonia solani Kuhn, be compound I-1＞I-2 to the inhibition activity of Rhizoctonia solani Kuhn.
Table 4 compound of the present invention is to botrytis cinerea pers activity experiment result
Can know by table 4; Compound I-1, compound I-2 all suppress the growth of botrytis cinerea pers in whole concentration range; Restraining effect increases along with the increase of concentration; And the concentration of compound I-1, I-2 and bacterium inhibiting rate all are proportionate, and wherein the biocidal property of compound I-1 pair botrytis cinerea pers is best.
Each compound concentration of table 5 (X) and the correlation analysis of medicament to botrytis cinerea pers inhibiting rate (Y)
Can know that from table 5 each compound concentration and medicament are relatively good to the inhibiting rate dependency of botrytis cinerea pers, be compound I-1＞I-2 to the inhibition activity of botrytis cinerea pers.
Table 6 compound of the present invention is to fusarium graminearum activity experiment result
Can know that from table 6 synthetic compound I-1 of the present invention, compound I-2 all suppress the growth of fusarium graminearum in whole concentration range, and the concentration and the bacterium inhibiting rate of compound I-1, compound I-2 are proportionate all.
Table 7 compound concentration (X) and the correlation analysis of medicament to fusarium graminearum inhibiting rate (Y)
Can know that from table 7 the inhibition activity of synthetic compound I-1 of the present invention, compound I-2 pair fusarium graminearum is I-2＞I-1.
Claims (2)
1. the compound with fungicidal activity is characterized in that this compound has suc as formula shown in I-1, the I-2
Structure.
2. the described application of compound of claim 1 is characterized in that the effective ingredient as Rhizoctonia solani Kuhn and botrytis cinerea pers sterilant.
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Non-Patent Citations (4)
| Title |
|---|
| 许洪涛等.N-硝基-N N′-二苯基脲衍生物的合成及抑菌活性.《应用化学》.2009 |
| 许洪涛等.N-硝基-N N"-二苯基脲的合成、除草活性及QSAR研究.《农药》.2008 |
| 许洪涛等.N-硝基-N, N′-二苯基脲衍生物的合成及抑菌活性.《应用化学》.2009,第26卷(第5期),507-510. * |
| 许洪涛等.N-硝基-N,N"-二苯基脲的合成、除草活性及QSAR研究.《农药》.2008,第47卷(第8期),563-565. * |
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