CN113214125A - Azide selenizing method of metal-free catalytic olefin - Google Patents
Azide selenizing method of metal-free catalytic olefin Download PDFInfo
- Publication number
- CN113214125A CN113214125A CN202110511216.4A CN202110511216A CN113214125A CN 113214125 A CN113214125 A CN 113214125A CN 202110511216 A CN202110511216 A CN 202110511216A CN 113214125 A CN113214125 A CN 113214125A
- Authority
- CN
- China
- Prior art keywords
- reaction
- mixture
- room temperature
- cyanophenyl
- reaction tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- 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
- A01P3/00—Fungicides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mycology (AREA)
- Microbiology (AREA)
- Agronomy & Crop Science (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
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 industry. 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. mu.L (specification 93%) was reacted in 2mL of dimethyl sulfoxide, the reaction tube was stirred at room temperature for 12 hours,until complete consumption of starting material as monitored by TLC analysis, after completion of the reaction, the mixture was taken up in 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 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.
The nitrine 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 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 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 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 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 originally 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.
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, according to example two;
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 is a drawing of Compound 2k in accordance with 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, according to the sixth embodiment.
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 embodiment 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 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 ═ 0.38, 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:
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: compound 2f is a yellow liquid, 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 selenization method of the metal-free catalytic olefin in the embodiment is as follows:
to a reaction tube were added N- (2-cyanophenyl) methacrylamide (1h) (0.3mmol,56mg), bis (3-chlorophenyl) diselenide (0.3mmol, 93.6mg), 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 finishedMixing the mixture 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 ═ 0.47, to give 3-azido-2- ((3-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide (2h) in: 71%, 89 mg.
The equation for the reaction is:
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 stoneOily ether and ethyl acetate as eluent, Rf 0.45, gave 3-azido-2- ((4-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide (2i) in yield: 52%, 65.3 mg.
The reaction equation is as follows:
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 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-N- (2-cyanophenyl) -2-methyl-2- (p-tolylselenyl) propionamide (2k) in the following yield: 25%, 30 mg.
The reaction equation is as follows:
of Compound 2k1H NMR、13The structure of the compound is known by 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:
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:
to a reaction tube were added N- (2-cyanophenyl) methacrylamide (1N) (0.3mmol,66mg), bis (4-bromophenyl) diselenide (0.3mmol, 141mg), 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-bromophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide (2N) in yield: 52%, 72 mg.
The reaction equation is as follows:
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 liquidRf (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 pathogen (Botryosphaeria dothidea), spruce verticillium (Fusarium verticillioides), poplar canker pathogen (Dothiorella gregaria), and poplar canker pathogen (Cytospora chrysosperma).
Culturing the four pathogenic bacteria in a 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 colony, washing the spores with sterile water to obtain spore suspension, and observing the spore concentration under the microscope to obtain 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)
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 by comprising the following steps:
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 by comprising the following steps:
56mg of N- (2-cyanophenyl) methacrylamide, 93.6mg of bis (3-chlorophenyl) diselenide, 145mg of diethyliodobenzene and 127. mu.L of azidotrimethylsilane 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 materials 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 azidotrimethylsilane 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 the reaction tube reachedUntil complete consumption of starting material as monitored by TLC analysis, after completion of the reaction, the mixture was taken up 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, after completion of the reaction, the mixture was treated 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 by comprising the following steps:
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 CH2Cl2Extracting, vacuum concentrating the organic solvent, and purifying the residue by flash column chromatography using a mixture of petroleum ether and ethyl acetateTo give an eluent, Rf ═ 0.34, and 3-azido-N- (2-cyanophenyl) -2- ((4-methoxyphenyl) seleno) -2-methylpropanamide was obtained.
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 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.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210722201.7A CN115152784B (en) | 2021-05-11 | 2021-05-11 | 3-azido-2- ((3-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide |
CN202210703975.5A CN114946875B (en) | 2021-05-11 | 2021-05-11 | Application of 3-azido-2- (benzyl seleno) -N- (2-cyanophenyl) -2-methylpropanamide in bacteriostasis |
CN202110511216.4A CN113214125B (en) | 2021-05-11 | 2021-05-11 | Azide selenizing method of metal-free catalytic olefin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110511216.4A CN113214125B (en) | 2021-05-11 | 2021-05-11 | Azide selenizing method of metal-free catalytic olefin |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210703975.5A Division CN114946875B (en) | 2021-05-11 | 2021-05-11 | Application of 3-azido-2- (benzyl seleno) -N- (2-cyanophenyl) -2-methylpropanamide in bacteriostasis |
CN202210722201.7A Division CN115152784B (en) | 2021-05-11 | 2021-05-11 | 3-azido-2- ((3-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113214125A true CN113214125A (en) | 2021-08-06 |
CN113214125B CN113214125B (en) | 2022-07-19 |
Family
ID=77094689
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110511216.4A Active CN113214125B (en) | 2021-05-11 | 2021-05-11 | Azide selenizing method of metal-free catalytic olefin |
CN202210703975.5A Active CN114946875B (en) | 2021-05-11 | 2021-05-11 | Application of 3-azido-2- (benzyl seleno) -N- (2-cyanophenyl) -2-methylpropanamide in bacteriostasis |
CN202210722201.7A Active CN115152784B (en) | 2021-05-11 | 2021-05-11 | 3-azido-2- ((3-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210703975.5A Active CN114946875B (en) | 2021-05-11 | 2021-05-11 | Application of 3-azido-2- (benzyl seleno) -N- (2-cyanophenyl) -2-methylpropanamide in bacteriostasis |
CN202210722201.7A Active CN115152784B (en) | 2021-05-11 | 2021-05-11 | 3-azido-2- ((3-chlorophenyl) seleno) -N- (2-cyanophenyl) -2-methylpropanamide |
Country Status (1)
Country | Link |
---|---|
CN (3) | CN113214125B (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040062706A1 (en) * | 2002-08-02 | 2004-04-01 | Gifu University | Selenating reagent |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3513070A1 (en) * | 1985-04-12 | 1986-10-30 | A. Nattermann & Cie GmbH, 5000 Köln | Diselenobis-benzamides of primary amines, processes for their preparation and pharmaceutical preparations containing them |
CN106883189A (en) * | 2017-04-18 | 2017-06-23 | 广西师范大学 | The method for synthesizing the triazole compound containing selenium with diselenide, acetylenic acid and nitrine |
-
2021
- 2021-05-11 CN CN202110511216.4A patent/CN113214125B/en active Active
- 2021-05-11 CN CN202210703975.5A patent/CN114946875B/en active Active
- 2021-05-11 CN CN202210722201.7A patent/CN115152784B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040062706A1 (en) * | 2002-08-02 | 2004-04-01 | Gifu University | Selenating reagent |
Non-Patent Citations (1)
Title |
---|
XIN WANG ET AL.: "Metal-Free Organoselenium-Enabled Radical Relay Azidation-Carbocyclization", 《ADV. SYNTH. CATAL.》 * |
Also Published As
Publication number | Publication date |
---|---|
CN114946875A (en) | 2022-08-30 |
CN115152784A (en) | 2022-10-11 |
CN115152784B (en) | 2023-07-21 |
CN114946875B (en) | 2023-07-18 |
CN113214125B (en) | 2022-07-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112979461B (en) | Full continuous flow preparation method of 3-chloro-4-oxoacetic acid amyl ester | |
Zhang et al. | A mild and fast continuous-flow trifluoromethylation of coumarins with the CF 3 radical derived from CF 3 SO 2 Na and TBHP | |
US11505734B2 (en) | Nonionic Gemini surfactant of (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether and its synthesis method | |
CN113264845B (en) | Method for continuously preparing chloramphenicol by using micro-reaction system | |
CN106966973A (en) | N phenyl N(The quinolyl of 2 methyl 8)The preparation method of benzamide | |
CN113214125B (en) | Azide selenizing method of metal-free catalytic olefin | |
CN113735751B (en) | Method for preparing aryl isothiourea | |
Qian et al. | Interaction of naphthyl heterocycles with DNA: effects of thiono and thio groups | |
CN106045938A (en) | Synthesis method of dehydroabietic-acid-based B ring-fused-thiazole-thiocarbamide compounds | |
CN113264877A (en) | Method for preparing azide-substituted quinoline-2, 4-diketone through metal-free catalytic free radical series carbon cyclization reaction | |
CN108276299B (en) | Synthesis method of dapoxetine related substances | |
Munirathinam et al. | Regioselectivity control of the ring opening of epoxides with sodium azide in a microreactor | |
CN109651367B (en) | Method for preparing 1, 4-dihydroquinoline and pyrrolo [1,2-a ] quinoline compounds | |
CN114539088B (en) | Preparation method of oseltamivir | |
CN110922409A (en) | Method for preparing BTK inhibitor zebritinib | |
CN112679521B (en) | Method for synthesizing mild azaspiro tricyclic framework molecule | |
CN110317170B (en) | Green synthesis method of 3-phenanthridinyl propyl formate compound | |
CN113024411B (en) | Preparation method of tralkoxydim | |
Xu et al. | A new approach to the synthesis of tazobactam using an organosilver compound | |
CN111978208A (en) | Preparation method of 4-ethyl-5-methyl-2- ((2-nitrophenyl) amino) isophthalonitrile | |
CN113603655B (en) | Preparation method of 4-hydroxy-2-methyl-3- (benzenesulfonyl) thiazolidine-2-carboxylic acid methyl ester compound | |
CN114940657B (en) | Amidine compound synthesized from N, N, N ', N' -tetramethyl ethylenediamine | |
CN110304982A (en) | A kind of pyrenyl six substituted benzenes class compound and its synthetic method and application with aggregation-induced emission enhancement | |
CN112142664B (en) | Synthesis method of polysubstituted naphtho-nitrogen heterocyclic compound | |
CN113264818B (en) | Method for carbon-carbon cross-coupling reaction of quinone compound and alcohol under catalysis of silver |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |