CN113214125B - Azide selenizing method of metal-free catalytic olefin - Google Patents

Azide selenizing method of metal-free catalytic olefin Download PDF

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CN113214125B
CN113214125B CN202110511216.4A CN202110511216A CN113214125B CN 113214125 B CN113214125 B CN 113214125B CN 202110511216 A CN202110511216 A CN 202110511216A CN 113214125 B CN113214125 B CN 113214125B
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azide
cyanophenyl
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CN113214125A (en
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孙凯
王薪
张震
李立梅
刘颖杰
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Yantai University
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
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    • C07C391/00—Compounds containing selenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00—Compounds containing selenium
    • C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
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Abstract

A metal-free catalytic alkene azide selenization method relates to the field of chemical preparation, in particular to a catalytic alkene azide selenization method. The invention aims to solve the technical problems of high production cost, increased probability of side reaction and environmental pollution caused by metal catalysis. The method comprises the following steps: methacrylamide, a pre-activated azidotrimethylsilane solution and 2mL of dimethyl sulfoxide were added to a reaction tube at room temperature, and stirred for 12 hours, after completion of the reaction, the mixture was treated with H2Quenching with O and CH2Cl2Extracting for 3 times, vacuum concentrating the organic solvent, purifying the residue by flash column chromatography, and eluting with mixture of petroleum ether and ethyl acetate. The invention solves the technical problems of high production cost, increased probability of side reaction and environmental pollution caused by metal catalysis, and the obtained compound has the activity of inhibiting phytopathogen and can be applied to the control of the phytopathogen.

Description

Azide selenizing method of metal-free catalytic olefin
Technical Field
The invention relates to the field of chemical preparation, in particular to an azide selenization method for catalyzing olefin.
Background
Green sustainable chemistry has been proposed to solve global chemical pollution and resource exhaustion problems by creating cleaner chemical production flows. In this case, no metal is involved and the organic reaction under room temperature is an ideal strategy for green chemistry, but the reaction efficiency under mild conditions is a problem of high concern to chemists. The search for a synthetic method with high selectivity and high efficiency of chemical reaction to construct a series of valuable chemical structure frameworks is a great challenge.
The organic azide has wide application in the fields of fine chemical industry and pharmaceutical industryApplication is carried out. The azide group is not only a good functional group for organic synthesis and transformation, but also a functional group in the medicine. carbon-N3Bonds are important synthetic methods that provide a means for the introduction of nitrogen atoms into a variety of organic molecules. Therefore, how to introduce azide ions into organic molecules has been a hot point of research for organic chemists. Thus, there is a continuing need in synthetic organic chemistry to develop sustainable and practical methods to form carbon-N3A key. Nitrogen-containing heterocycles, on the other hand, are key backbone structures for many drug molecules.
The organic selenium compounds are important intermediates in synthetic chemistry, and exist in a considerable number of bioactive drug molecules as a core structural framework. The organic selenium compound has wide application in the fields of organic synthesis, medicines, organic materials and the like. Therefore, the development of a novel, efficient and practical synthesis method of organic selenium compounds has attracted great attention from chemists.
Disclosure of Invention
The invention aims to solve the technical problems of high production cost, increased probability of side reaction and environmental pollution caused by metal catalysis, and provides a metal-free olefin nitridizing and selenizing method.
The nitrine selenizing method of the metal-free catalytic olefin comprises the following steps:
to a reaction tube were added 66mg of N- (2-cyanophenyl) methacrylamide, 102mg of dibenzyldiselenide, diethyl iodobenzene PhI (OAc)2145mg and 127. mu.L of azidotrimethylsilane TMSN3(93% of specification) and then in 2mL of dimethyl sulfoxide (DMSO) at room temperature for 12 hours with stirring until complete consumption of starting material is monitored by TLC analysis, after completion of the reaction the mixture is taken up in H2Quenching with O and CH2Cl2Extraction was performed 3 times, then the organic solvent was concentrated in vacuo and the residue was purified by flash column chromatography with Rf ═ 0.38 using a mixture of petroleum ether and ethyl acetate as eluent to give 3-azido-2- (benzylseleno) -N- (2-cyanophenyl) -2-methylpropanamide in yield: 55%, 65.7 mg.
The nitrine selenizing method of the metal-free catalytic olefin comprises the following steps:
56mg of N- (2-cyanophenyl) methacrylamide, 93.6mg of bis (3-chlorophenyl) diselenide, 145mg of diethyliodobenzene and trimethylsilyl azide TMSN were added to a reaction tube at room temperature3127 μ L (specification 93%) was then reacted in 2mL of dimethyl sulfoxide, the reaction tube was stirred at room temperature for 12 hours until complete consumption of starting material was monitored by TLC analysis, and after completion of the reaction the mixture was washed with H2Quenching with O and CH2Cl2Extraction was followed by concentration of the organic solvent in vacuo and the residue was purified by flash column chromatography with a mixture of petroleum ether and ethyl acetate as eluent, Rf ═ 0.47, to give 3-azido-2- ((3-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide.
The nitrine selenizing method of the metal-free catalytic olefin comprises the following steps:
56mg of N- (2-cyanophenyl) methacrylamide, 114mg of bis (4-chlorophenyl) diselenide, 145mg of iodobenzene diethyl ester and trimethylsilyl azide TMSN were added to a reaction tube at room temperature3127 μ L (specification 93%) was then reacted in 2mL of dimethyl sulfoxide, the reaction tube was stirred at room temperature for 12 hours until complete consumption of starting material was monitored by TLC analysis, and after completion of the reaction the mixture was washed with H2Quenching with O and CH2Cl2Extraction was followed by concentration of the organic solvent in vacuo and the residue was purified by flash column chromatography with a mixture of petroleum ether and ethyl acetate as eluent, Rf ═ 0.45, to give 3-azido-2- ((4-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide.
The nitrine selenizing method of the metal-free catalytic olefin comprises the following steps:
56mg of N- (2-cyanophenyl) methacrylamide, 102mg of bis (4-methylphenyl) diselenide, 145mg of diethyliodobenzene and trimethylsilyl azide (TMSN) were added to a reaction tube at room temperature3127 μ L (specification 93%), then in 2mL of dimethyl sulfoxide, then the reaction tube is stirred at room temperature for 12 hours until complete consumption of starting material is monitored by TLC analysis, after completion of the reaction the mixture is washed with H2Quenching with O and CH2Cl2Extraction followed by concentration of the organic solvent in vacuo and purification of the residue by flash column chromatography with a mixture of petroleum ether and ethyl acetate as eluent, Rf ═ 0.45, gave 3-azido-N- (2-cyanophenyl) -2-methyl-2- (p-tolylselenyl) propionamide.
The azide selenizing method of the metal-free catalytic olefin comprises the following steps:
56mg of N- (2-cyanophenyl) methacrylamide, 112mg of bis (4-methoxyphenyl) diselenide, 145mg of diethyliodobenzene and trimethylsilyl azide (TMSN) were added to a reaction tube at room temperature3127 μ L (specification 93%), then in 2mL dimethyl sulfoxide, then the reaction tube was stirred at room temperature for 12 hours until complete consumption of starting material was monitored by TLC analysis, after completion of the reaction, the mixture was treated with H2Quenching with O and CH2Cl2Extraction was followed by concentration of the organic solvent in vacuo and the residue was purified by flash column chromatography with a mixture of petroleum ether and ethyl acetate as eluent, Rf ═ 0.34, to give 3-azido-N- (2-cyanophenyl) -2- ((4-methoxyphenyl) seleno) -2-methylpropanamide.
The nitrine selenizing method of the metal-free catalytic olefin comprises the following steps:
at room temperature, 66mg of N- (2-cyanophenyl) methacrylamide, 141mg of bis (4-bromophenyl) diselenide, 145mg of iodobenzene diethyl ester and trimethylsilyl azide3127 μ L (specification 93%), then in 2mL dimethyl sulfoxide, then the reaction tube was stirred at room temperature for 12 hours until complete consumption of starting material was monitored by TLC analysis, after completion of the reaction, the mixture was treated with H2Quenching with O and CH2Cl2Extraction was then performed by vacuum concentration of the organic solvent and the residue was purified by flash column chromatography with a mixture of petroleum ether and ethyl acetate as eluent, Rf ═ 0.45, to give 3-azido-2- ((4-bromophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide.
The reaction mechanism of the invention is as follows: the azido group was initially formed by ligand exchange and PhI (OAc)2And TMSN3Weak I-N bonds between the interactions.The azide group then attacks the activated alkenyl moiety of substrate 1 to give the group intermediate a. Subsequent direct coupling between intermediate a and diselenide gives the corresponding product 2.
Figure BDA0003060459610000031
The invention solves the technical problems of high production cost, increased probability of side reaction and environmental pollution caused by adopting metal catalysis. The chemical process of the invention conforms to two principles of green chemistry: environment protection and energy saving. The obtained compound has the activity of inhibiting plant pathogenic bacteria, and can be applied to the prevention and treatment of the plant pathogenic bacteria.
Drawings
FIG. 1 is a drawing of compound 2h of embodiment two1H NMR spectrum;
FIG. 2 is a drawing of compound 2h of embodiment two13C NMR spectrum;
FIG. 3 is an HR-ESI-MS spectrum of compound 2h of the second embodiment;
FIG. 4 is a drawing of Compound 2f according to one embodiment1H NMR spectrum;
FIG. 5 is a drawing of Compound 2f according to one embodiment13C NMR spectrum;
FIG. 6 is an HR-ESI-MS spectrum of compound 2f according to one embodiment;
FIG. 7 shows the preparation of Compound 2i in accordance with the third embodiment1H NMR spectrum;
FIG. 8 is a drawing of Compound 2i in accordance with a third embodiment13C NMR spectrum;
FIG. 9 is an HR-ESI-MS spectrum of Compound 2i, according to a third embodiment;
FIG. 10 shows Compound 2k of the fourth embodiment1H NMR spectrum;
FIG. 11 is a drawing of Compound 2k in accordance with the fourth embodiment13C NMR spectrum;
FIG. 12 is an HR-ESI-MS spectrum of compound 2k, according to a fourth embodiment;
FIG. 13 is a drawing of Compound 2l in accordance with the fifth embodiment1H NMR spectrum；
FIG. 14 is a drawing of Compound 2l of the fifth embodiment13C NMR spectrum;
FIG. 15 is an HR-ESI-MS spectrum of compound 2l, according to fifth embodiment;
FIG. 16 is a drawing of Compound 2n in accordance with the sixth embodiment1H NMR spectrum;
FIG. 17 is a drawing of Compound 2n in accordance with a sixth embodiment13C NMR spectrum;
FIG. 18 is an HR-ESI-MS spectrum of Compound 2n, example six.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first specific implementation way is as follows: the azide selenization method of the metal-free catalytic olefin in the embodiment is as follows:
to a reaction tube were added N- (2-cyanophenyl) methacrylamide (1f) (0.3mmol,66mg), dibenzyldiselenide (0.3mmol, 102mg), diethyliodobenzene PhI (OAc) at room temperature2(0.45mmol, 145mg) and azidotrimethylsilane TMSN3(93%, 3.0equiv,0.9mmol, 127. mu.L) was performed in DMSO (2 mL). The reaction tube was then stirred at room temperature for 12 hours until complete consumption of starting material was monitored by TLC analysis. After the reaction is completed, the mixture is washed with H2Quenching with O (15mL) and CH2Cl2(3X 5 mL). The organic solvent was then concentrated in vacuo. The residue was purified by flash column chromatography using petroleum ether and ethyl acetate as eluent, Rf ═ 0.38, to give 3-azido-2- (benzylseleno) -N- (2-cyanophenyl) -2-methylpropanamide (2f) in the following yield: 55%, 65.7 mg.
The equation for the reaction is:
Figure BDA0003060459610000041
of compound 2f1H NMR、13The structure of the compound is known by C NMR and HR-ESI-MS spectra. Specifically, the method comprises the following steps: the compound 2f is yellow liquidBody, Rf (Petroleum Ether: Ethyl acetate): 0.38.1H NMR(600MHz,CDCl3):δ8.86(s,1H),8.31(d,J＝8.1Hz,1H),7.60-7.57(m,2H),7.31-7.28(m,2H),7.21-7.17(m,3H),7.10(t,J＝7.4Hz,1H),4.03(q,J＝11.7Hz,2H),3.93(d,J＝12.6Hz,1H),3.76(d,J＝12.6Hz,1H),1.76(s,3H).13C NMR(150MHz,CDCl3):δ170.87,140.33,137.06,134.07,132.23,129.11,128.70,127.14,124.35,120.95,116.23,102.37,58.68,49.24,28.57,22.96.HRMS(ESI)calcd for C18H17N5OSe[M+Na]+:422.0491,found:422.0490。
the second embodiment is as follows: the azide selenizing method of the metal-free catalytic olefin in the embodiment comprises the following steps:
to a reaction tube were added N- (2-cyanophenyl) methacrylamide (1h) (0.3mmol,56mg), bis (3-chlorophenyl) diselenide (0.3mmol, 93.6mg), iodobenzene diethyl ester PhI (OAc) at room temperature2(0.45mmol, 145mg) and azidotrimethylsilane TMSN3The reaction (93%, 3.0equiv,0.9mmol, 127. mu.L) was carried out in DMSO (2 mL). The reaction tube was then stirred at room temperature for 12 hours until complete consumption of starting material was monitored by TLC analysis. After the reaction is completed, the mixture is treated with H2O (15mL) quench and CH2Cl2(3X 5 mL). The organic solvent was then concentrated in vacuo. The residue was purified by flash column chromatography using petroleum ether and ethyl acetate as eluent, Rf ═ 0.47, to give 3-azido-2- ((3-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide (2h) in: 71%, 89 mg.
The equation for the reaction is:
Figure BDA0003060459610000051
of Compound 2h1H NMR、13The structure of the compound is known by C NMR and HR-ESI-MS spectra. Specifically, the method comprises the following steps: compound 2h is a yellow liquid, Rf (petroleum ether: ethyl acetate): 0.47.1H NMR(600MHz,CDCl3):δ8.71(s,1H),8.30(d,J＝8.3Hz,1H),7.61-7.59(m,3H),7.51-7.49(m,1H),7.38-7.36(m,1H),7.27-7.23(m,1H),7.22-7.19(m,1H),3.93(d,J＝12.6Hz,1H),3.72(d,J＝12.6Hz,1H),1.71(s,3H).13CNMR(150MHz,CDCl3):δ170.21,140.15,137.19,135.58,134.77,134.27,132.30,130.43,130.22,126.61,124.52,121.05,116.26,102.37,58.07,51.73,22.44.HRMS(ESI)calcd for C17H14ClN5OSe[M+Na]+:441.9944,found:441.9944。
the third concrete implementation mode: the azide selenization method of the metal-free catalytic olefin in the embodiment is as follows:
to a reaction tube were added N- (2-cyanophenyl) methacrylamide (1i) (0.3mmol,56mg), bis (4-chlorophenyl) diselenide (0.3mmol, 114mg), diethyliodobenzene PhI (OAc) at room temperature2(0.45mmol, 145mg) and azidotrimethylsilane TMSN3The reaction (93%, 3.0equiv,0.9mmol, 127. mu.L) was carried out in DMSO (2 mL). The reaction tube was then stirred at room temperature for 12 hours until complete consumption of starting material was monitored by TLC analysis. After the reaction is completed, the mixture is washed with H2Quenching with O (15mL) and CH2Cl2(3X 5mL) was extracted. The organic solvent was then concentrated in vacuo. The residue was purified by flash column chromatography using petroleum ether and ethyl acetate as eluent, Rf ═ 0.45, to give 3-azido-2- ((4-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide (2i) in: 52%, 65.3 mg.
The reaction equation is as follows:
Figure BDA0003060459610000061
of Compound 2i1H NMR、13The structure of the compound is known by C NMR and HR-ESI-MS spectra. Specifically, the method comprises the following steps: compound 2i is a yellow liquid, Rf (Petroleum ether: ethyl acetate): 0.45.1H NMR(600MHz,CDCl3):δ8.74(s,1H),8.30(d,J＝8.4Hz,1H),7.62-7.58(m,2H),7.54-7.52(m,2H),7.29-7.26(m,2H),7.22-7.19(m,1H),3.91(d,J＝12.6Hz,1H),3.70(d,J＝12.6Hz,1H),1.69(s,3H).13C NMR(150MHz,CDCl3):δ170.34,140.23,138.84,136.73,134.26,132.32,129.70,124.48,123.47,120.94,116.26,102.29,58.04,51.52,22.45.HRMS(ESI)calcd for C17H14ClN5OSe[M+Na]+:441.9944,found:441.9942。
the fourth concrete implementation mode: the azide selenization method of the metal-free catalytic olefin in the embodiment is as follows:
to a reaction tube were added N- (2-cyanophenyl) methacrylamide (1k) (0.3mmol,56mg), bis (4-methylphenyl) diselenide (0.3mmol, 102mg), diethyliodobenzene PhI (OAc) at room temperature2(0.45mmol, 145mg) and azidotrimethylsilane TMSN3The reaction (93%, 3.0equiv,0.9mmol, 127. mu.L) was carried out in DMSO (2 mL). The reaction tube was then stirred at room temperature for 12 hours until complete consumption of starting material was monitored by TLC analysis. After the reaction is completed, the mixture is washed with H2O (15mL) quench and CH2Cl2(3X 5 mL). The organic solvent was then concentrated in vacuo. The residue was purified by flash column chromatography using petroleum ether and ethyl acetate as eluent, Rf ═ 0.45, to give 3-azido-N- (2-cyanophenyl) -2-methyl-2- (p-tolylselenyl) propionamide (2k) in the following yield: 25%, 30 mg.
The reaction equation is as follows:
Figure BDA0003060459610000062
of Compound 2k1H NMR、13The structure of the compound is known from C NMR and HR-ESI-MS spectra. Specifically, the method comprises the following steps: compound 2k is a colorless liquid, Rf (petroleum ether: ethyl acetate): 0.45.1H NMR(600MHz,CDCl3):δ8.70(s,1H),8.33(d,J＝8.4Hz,1H),7.61-7.58(m,2H),7.48(d,J＝8.0Hz,2H),7.20-7.18(m,1H),7.11(d,J＝7.8Hz,2H),3.91(d,J＝12.6Hz,1H),3.66(d,J＝12.6Hz,1H),2.34(s,3H),1.69(s,3H).13CNMR(150MHz,CDCl3):δ170.76,140.39,140.37,137.57,134.19,132.25,130.28,124.28,121.76,120.91,116.25,102.19,58.06,51.09,22.43,21.32,18.46.HRMS(ESI)calcd for C18H17N5OSe[M+Na]+:422.0491,found:422.0489.
the fifth concrete implementation mode: the azide selenization method of the metal-free catalytic olefin in the embodiment is as follows:
to a reaction tube were added N- (2-cyanophenyl) methacrylamide (1l) (0.3mmol,56mg), bis (4-methoxyphenyl) diselenide (0.3mmol, 112mg), diethyliodobenzene PhI (OAc) at room temperature2(0.45mmol, 145mg) and azidotrimethylsilane TMSN3The reaction (93%, 3.0equiv,0.9mmol, 127. mu.L) was carried out in DMSO (2 mL). The reaction tube was then stirred at room temperature for 12 hours until complete consumption of starting material was monitored by TLC analysis. After the reaction is completed, the mixture is washed with H2Quenching with O (15mL) and CH2Cl2(3X 5mL) was extracted. The organic solvent was then concentrated in vacuo. The residue was purified by flash column chromatography using petroleum ether and ethyl acetate as eluent, Rf ═ 0.34, to give 3-azido-N- (2-cyanophenyl) -2- ((4-methoxyphenyl) seleno) -2-methylpropanamide (2l) in yield: 29%, 36 mg.
The reaction equation is as follows:
Figure BDA0003060459610000071
of Compound 2l1H NMR、13The structure of the compound is known by C NMR and HR-ESI-MS spectra. Specifically, the method comprises the following steps: compound 2l is a yellow liquid, Rf (petroleum ether: ethyl acetate): 0.34.1H NMR(600MHz,CDCl3):δ8.66(s,1H),8.33(d,J＝8.4Hz,1H),7.61-7.57(m,2H),7.53-7.50(m,2H),7.19(t,J＝7.6Hz,1H),6.82(d,J＝8.7Hz,2H),3.90(d,J＝12.6Hz,1H),3.79(s,3H),3.67-3.63(m,1H),1.67(s,3H).13C NMR(150MHz,CDCl3):δ170.77,161.17,140.40,139.26,134.20,132.26,124.27,120.91,116.27,115.77,115.09,102.16,58.03,55.32,51.05,22.30.HRMS(ESI)calcd for C18H17N5O2Se[M+Na]+:438.0440,found:438.0436.
the sixth specific implementation mode: the azide selenization method of the metal-free catalytic olefin in the embodiment is as follows:
adding N- (2-cyanophenyl) methylpropane into a reaction tube at room temperatureEnamide (1n) (0.3mmol,66mg), bis (4-bromophenyl) diselenide (0.3mmol, 141mg), diethyliodobenzene PhI (OAc)2(0.45mmol, 145mg) and azidotrimethylsilane TMSN3The reaction (93%, 3.0equiv,0.9mmol, 127. mu.L) was carried out in DMSO (2 mL). The reaction tube was then stirred at room temperature for 12 hours until complete consumption of starting material was monitored by TLC analysis. After the reaction is completed, the mixture is treated with H2Quenching with O (15mL) and CH2Cl2(3X 5 mL). The organic solvent was then concentrated in vacuo. The residue was purified by flash column chromatography using petroleum ether and ethyl acetate as eluent, Rf ═ 0.45, to give 3-azido-2- ((4-bromophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide (2N) in yield: 52%, 72 mg.
The reaction equation is as follows:
Figure BDA0003060459610000081
of compound 2n1H NMR、13The structure of the compound is known by C NMR and HR-ESI-MS spectra. Specifically, the method comprises the following steps: compound 2n is a yellow liquid, Rf (petroleum ether: ethyl acetate): 0.45.1H NMR(600MHz,CDCl3):δ8.75(s,1H),8.29(d,J＝8.4Hz,1H),7.62-7.58(m,2H),7.47-7.42(m,4H),7.22-7.19(m,1H),3.91(d,J＝12.6Hz,1H),3.70(d,J＝12.6Hz,1H),1.69(s,3H).13C NMR(150MHz,CDCl3):δ170.33,140.23,139.04,134.26,132.65,132.33,125.08,124.49,124.11,120.94,116.26,102.30,58.05,51.51,22.47.HRMS(ESI)calcd for C17H14BrN5OSe[M+Na]+:485.9439,found:485.9438.
experiment one:
the compounds prepared in the first to sixth embodiments are subjected to activity experiments for inhibiting phytopathogen:
4 pathogenic bacteria were selected, including blueberry canker (Botryosphaeria dothidea), spruce rhizoctonia (Fusarium verticillioides), poplar canker (Dothiorella gregaria), and poplar canker (Cytospora chrysosperma).
Four diseasesCulturing original bacteria in PDA plate constant temperature biochemical incubator at 28 deg.C for 5d, allowing a large amount of spores to grow on the surface of the bacterial colony, washing the spores with sterile water to obtain spore suspension, and observing spore concentration under the lens at 1x107one/mL. The confrontation experiment adopts a cup-dish method, 100mL of PDA is uniformly mixed with 5mL of spore suspension, the mixture is poured into a rectangular glass culture dish, and an Oxford cup is placed. 6 compounds were diluted to 10mg/mL with dichloromethane, 200uL was added to the Oxford cup, and dichloromethane was used as a control. Culturing at 28 deg.C for 3 days, and measuring the diameter of the bacteria-inhibiting agent in mm (see Table 1).
Table 1.6 compounds inhibit phytopathogen activity (n ═ 3)
Figure BDA0003060459610000091
As can be seen from Table 1, the compounds prepared by the method of the present invention have activity of inhibiting plant pathogenic bacteria, and can be applied to the control of plant pathogenic bacteria.

Claims (6)

1. The azide selenizing method of the metal-free catalytic olefin is characterized in that the azide selenizing method of the metal-free catalytic olefin is as follows:
to a reaction tube were added 66mg of N- (2-cyanophenyl) methacrylamide, 102mg of dibenzyldiselenide, 145mg of diethyliodobenzene and 127. mu.L of azidotrimethylsilane at room temperature, followed by reaction in 2mL of dimethyl sulfoxide at room temperature with stirring for 12 hours until complete consumption of the starting material was monitored by TLC analysis, and after completion of the reaction, the mixture was treated with H2Quenching with O and CH2Cl2Extraction was performed 3 times, then the organic solvent was concentrated in vacuo, and the residue was purified by flash column chromatography with Rf ═ 0.38 using a mixture of petroleum ether and ethyl acetate as eluent to obtain 3-azido-2- (benzylseleno) -N- (2-cyanophenyl) -2-methylpropanamide.
2. The azide selenizing method of the metal-free catalytic olefin is characterized in that the azide selenizing method of the metal-free catalytic olefin is as follows:
at room temperature, to the reaction tubeTo this mixture were added 56mg of N- (2-cyanophenyl) methacrylamide, 93.6mg of bis (3-chlorophenyl) diselenide, 145mg of diethyliodobenzene and 127. mu.L of trimethylsilyl azide, followed by reaction in 2mL of dimethyl sulfoxide, and the reaction tube was stirred at room temperature for 12 hours until complete consumption of the starting material was monitored by TLC analysis, after completion of the reaction, the mixture was treated with H2Quenching with O and CH2Cl2Extraction was followed by concentration of the organic solvent in vacuo and the residue was purified by flash column chromatography with a mixture of petroleum ether and ethyl acetate as eluent, Rf ═ 0.47, to give 3-azido-2- ((3-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide.
3. The azide selenizing method of the metal-free catalytic olefin is characterized by comprising the following steps:
56mg of N- (2-cyanophenyl) methacrylamide, 114mg of bis (4-chlorophenyl) diselenide, 145mg of diethyliodobenzene and 127. mu.L of trimethylsilyl azide were added to a reaction tube at room temperature, followed by reaction in 2mL of dimethyl sulfoxide, and the reaction tube was stirred at room temperature for 12 hours until complete consumption of the starting material was monitored by TLC analysis, after completion of the reaction, the mixture was treated with H2Quenching with O and CH2Cl2Extraction was followed by concentration of the organic solvent in vacuo and the residue was purified by flash column chromatography with a mixture of petroleum ether and ethyl acetate as eluent, Rf ═ 0.45, to give 3-azido-2- ((4-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide.
4. The azide selenizing method of the metal-free catalytic olefin is characterized by comprising the following steps:
56mg of N- (2-cyanophenyl) methacrylamide, 102mg of bis (4-methylphenyl) diselenide, 145mg of diethyliodobenzene and 127. mu.L of trimethylsilyl azide were added to a reaction tube at room temperature, followed by reaction in 2mL of dimethyl sulfoxide, and the reaction tube was stirred at room temperature for 12 hours until complete consumption of the starting material was monitored by TLC analysis, and thenAfter completion of the reaction, the mixture is washed with H2Quenching with O and CH2Cl2Extraction was then carried out, the organic solvent was concentrated in vacuo, and the residue was purified by flash column chromatography with a mixture of petroleum ether and ethyl acetate as an eluent, Rf ═ 0.45, to give 3-azido-N- (2-cyanophenyl) -2-methyl-2- (p-tolylselenyl) propionamide.
5. The azide selenizing method of the metal-free catalytic olefin is characterized in that the azide selenizing method of the metal-free catalytic olefin is as follows:
56mg of N- (2-cyanophenyl) methacrylamide, 112mg of bis (4-methoxyphenyl) diselenide, 145mg of diethyliodobenzene and 127. mu.L of trimethylsilyl azide were added to a reaction tube at room temperature, followed by reaction in 2mL of dimethyl sulfoxide, and the reaction tube was stirred at room temperature for 12 hours until complete consumption of the raw materials was monitored by TLC analysis, after completion of the reaction, the mixture was treated with H2Quenching with O and CH2Cl2Extraction followed by concentration of the organic solvent in vacuo and purification of the residue by flash column chromatography with a mixture of petroleum ether and ethyl acetate as eluent, Rf ═ 0.34, gave 3-azido-N- (2-cyanophenyl) -2- ((4-methoxyphenyl) seleno) -2-methylpropanamide.
6. The azide selenizing method of the metal-free catalytic olefin is characterized by comprising the following steps:
to a reaction tube were added 66mg of N- (2-cyanophenyl) methacrylamide, 141mg of bis (4-bromophenyl) diselenide, 145mg of diethyliodobenzene and 127. mu.L of azidotrimethylsilane at room temperature, followed by reaction in 2mL of dimethyl sulfoxide, followed by stirring the reaction tube at room temperature for 12 hours until complete consumption of the raw materials was monitored by TLC analysis, and after completion of the reaction, the mixture was treated with H2Quenching with O and CH2Cl2Extraction, followed by vacuum concentration of the organic solvent and purification of the residue by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent, Rf 0.45, gave 3-azido-2- ((4-bromophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide.
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