CN111285809B - Green synthesis method of imidazoline under visible light catalysis - Google Patents
Green synthesis method of imidazoline under visible light catalysis Download PDFInfo
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Abstract
The invention discloses a green synthesis method of imidazoline under visible light catalysis, and belongs to the technical field of organic synthesis. The method comprises the following steps: 1) Adding N-phenylglycine, a photocatalyst, an oxidant, a solvent, an arylamine compound, an aldehyde compound or an imine compound into a dried Schlenk tube; 2) Carrying out three times of air pumping and air changing operations on a reaction bottle filled with materials so as to ensure that the reaction tube is sealed after no water and no oxygen exist, placing the reaction bottle under the irradiation of Blue LEDs, stirring for reaction, and ending the reaction after TLC detects that the aldehyde compounds disappear; 4) The reaction solution in the Schlenk tube was transferred to a eggplant-shaped bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography to obtain the product imidazoline. Compared with the prior art, the method has the characteristics of simple synthetic route, cheap and easily available raw materials, simple and convenient operation, environment friendliness, mild reaction conditions, wide substrate application range and the like.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a green synthesis method of imidazoline under visible light catalysis.
Background
Imidazoline, chemical formula:
is a very important N-containing heterocyclic compound. The 1,3 positions of the ring respectively contain an N atom, and the existence of two N atoms leads the imidazoline to have certain alkalinity. In addition, the lone pair electron on the N atom can coordinate with the metal ion to obtain the coordination compound with changeable structure. Imidazolines are widely used in the chemical, biological, pharmaceutical fields, for example: (-) -Dysietaine PP, chaetominine, kifunensine, etc. In addition, in the field of pesticides, imidazoline compounds also play an important role, for example, iprodione is used as a high-efficiency spectrum contact-killing type bactericide, and can inhibit germination and generation of fungal spores and hypha growth; hydantocidinCan block purine biosynthesis in plant tissues to inhibit plant cell growth. Therefore, the synthesis of the imidazoline compound is widely interesting to chemists, and the development of a method for preparing the imidazoline, which has the advantages of simple synthetic route, environment friendliness, low cost and easy availability of raw materials, is one of the research hotspots in recent years.
The related literature on the imidazoline synthesis method in the prior art is: organic Letters; vol.11; nb.11; (2009); p.2365-2368; angewandteChemie International Edition; vol.48; nb.7; (2009); p.1190-1193; the Journal of Organic Chmistry; vol.74; nb.21; (2009); p.8392-8395 relates to a process for preparing an o-diamine compound by reacting an olefin with an aziridine; chemical Communication; vol.48; nb.52; (2012); p.6601-6603; journal of Organic Chemistry; vol.75; nb.21; (2010); p.7468-7471; angewandteChemie International Edition; vol.54; nb.34; (2015); p.9926-9930; organic Letters; vol.20; nb.1; (2018); p.92-95; tetrahedron: asymmetry; vol.13; nb.9; (2002); p.933-938; journal of Organic Chemistry; vol.67; nb.9; (2002); p.3109-3114; tetrahedron Letters; vol.48; nb.46; (2007); p.8116-8119; bioorganic & Medicinal Chemistry; vol.16; nb.5; (2008); p.2226-2234; bioorganic & Medicinal Chemistry Letters; vol.22; nb.17; (2012); p.5493-5497.
The method has the defects of difficult raw material acquisition, relatively more synthesis steps and lower efficiency; in addition, the aspects of catalyst dosage, reaction selectivity control, substrate expansion and the like also need to be studied deeply, so that the development of the imidazoline synthesis method with high green and high efficiency, mild conditions, environment friendliness, simple and easily obtained raw materials and high selectivity has very important significance.
Disclosure of Invention
In view of the problems existing in the prior art, the invention aims to provide a green synthesis method of imidazoline, which has the advantages of simple synthesis steps, high reaction speed, mild conditions, small environmental pollution and high atom economy.
The invention is realized by the following technical scheme:
the green synthesis method of the imidazoline under the catalysis of the visible light is characterized in that the synthesis chemical equation of the imidazoline is as follows:
the specific synthesis method comprises the following steps:
1) The following materials were added to the Schlenk tube dried in the reaction flask: n-phenylglycine, a photocatalyst, an oxidizing agent, a solvent, an arylamine compound, an aldehyde compound or an imine compound;
2) Carrying out three times of air pumping and air exchanging operations on the reaction bottle filled with the materials in the step 1) so as to ensure that the Schlenk tube is sealed after being anhydrous and anaerobic;
3) Placing the reaction bottle in the step 2) under the irradiation of Blue LED, stirring for reaction, and ending the reaction after TLC detects that the aldehyde compound disappears to obtain a reaction solution;
4) The reaction solution in the Schlenk tube was transferred to a eggplant-shaped bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography to obtain the product imidazoline compound.
The green synthesis method of the imidazoline under the catalysis of visible light is characterized in that the photocatalyst in the step 1) is Ir (ppy) 3 、[Ir(ppy) 2 dtbbpy]PF 6 、{Ir[dF(CF 3 )ppy] 2 bpy}PF 6 、{Ir[dF(CF 3 )ppy] 2 dtbpy}PF 6 、Ru(bpy) 3 (PF 6 ) 2 Any of 4-CzIPN. Preferably { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 。
The green synthesis method of the imidazoline under the catalysis of the visible light is characterized in that the oxidant in the step 1) is Co (dmgH) 2 )Cl 2 、Co(dmgH 2 ) 2 DMAP·Cl、Co(dmg 3 F 2 ) 2 (CH 3 CN) 2 、Co(dmgH 2 ) 2 PyCl、O 2 Any one of them. Co (dmgH) is preferred 2 ) 2 PyCl。
The green synthesis method of the imidazoline under the catalysis of the visible light is characterized in that the solvent in the step 1) is any one of diethyl ether, acetonitrile, dichloromethane or 1, 2-dichloroethane, and the concentration of the solvent is 0.1M. 1, 2-dichloroethane is preferred.
The green synthesis method of the imidazoline under the catalysis of visible light is characterized in that the aldehyde compound in the step 1) is any one of benzaldehyde, p-methylbenzaldehyde, o-fluorobenzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, 2-naphthaldehyde, p-phenylbenzaldehyde, 2-thiophenecarboxaldehyde and salicylaldehyde.
The green synthesis method of the imidazoline under the catalysis of visible light is characterized in that the arylamine compound in the step 1) is any one of aniline, p-methylaniline, p-tertiary butylaniline, p-fluoroaniline and p-cyanoaniline; the imine compound is N- (4-methoxyphenyl) -1-phenyl azomethine and N- (benzo [ d ] thiazole-2-yl) -1-phenyl azomethine, and the chemical structural formula is shown as follows:
the green synthesis method of the imidazoline under the catalysis of the visible light is characterized by comprising the following steps of: aryl amine compound: n-phenylglycine: and (3) a photocatalyst: the ratio of the amounts of the substances of the oxidizing agent is 1:1:3:0.01:0.15.
The green synthesis method of the imidazoline under the catalysis of the visible light is characterized by comprising the following steps of: n-phenylglycine: and (3) a photocatalyst: the ratio of the amounts of the substances of the oxidizing agent was 1:3:0.01:0.15.
The green synthesis method of the imidazoline under the catalysis of the visible light is characterized in that two Blue LEDs are arranged in the step 3), a reaction bottle is irradiated simultaneously, the distance between a Schlenk tube and a Blue LED lamp is 3cm, and the lamp source of the Blue LED is characterized by 10w and lambda max ＝255nm。
The green synthesis method of the imidazoline under the catalysis of visible light is characterized in that the stirring time in the step 3) is 2 hours, and the stirring temperature is room temperature; the developing reagent ratio used for detecting the reaction progress degree by TLC plate is PE: EA=20:1.
The invention has the beneficial effects that:
the imidazoline is synthesized by a free radical mechanism under the catalysis of visible light, is different from the complexity of other chemical synthesis methods, and has the characteristics of cheap and easily available raw materials, simple synthesis steps, simple route, simple and convenient operation, mild reaction conditions and the like.
Compared with a plurality of synthesis methods, the method for synthesizing the imidazoline has the advantages of low cost, no need of expensive catalysts and reactants, convenient and easily obtained raw materials and light sources and good yield.
The substrate of the method has wide application range, and the corresponding imidazoline can be prepared by the method no matter the benzaldehyde derivative with electron withdrawing groups or electron donating groups. Aromatic amines with different substituents can also better participate in the reaction to prepare corresponding diamine compounds. Notably, besides cobalt compounds, oxygen can also be used as an oxidant to promote the generation of imidazoline products, and the reaction conditions are green and mild.
Drawings
Fig. 1: the nuclear magnetism hydrogen spectrogram of the 3- (4-methoxyphenyl) -1, 4-diphenyl imidazolidine synthesized by the invention;
fig. 2: the nuclear magnetic carbon spectrogram of the 3- (4-methoxyphenyl) -1, 4-diphenyl imidazolidine synthesized by the invention;
fig. 3: the nuclear magnetism hydrogen spectrogram of the 3- (4-methoxyphenyl) -1-phenyl-4- (amyl) imidazolidine synthesized by the invention;
fig. 4: the nuclear magnetic carbon spectrogram of the 3- (4-methoxyphenyl) -1-phenyl-4- (amyl) imidazolidine synthesized by the invention;
fig. 5: the nuclear magnetism hydrogen spectrogram of the 4- (2-fluorophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine synthesized by the invention;
fig. 6: the nuclear magnetic carbon spectrogram of the 4- (2-fluorophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine synthesized by the method;
fig. 7: the nuclear magnetism hydrogen spectrogram of the 4- (4-fluorophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine synthesized by the method is shown in the specification;
fig. 8: the nuclear magnetic carbon spectrogram of the 4- (4-fluorophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine obtained by the synthesis of the invention;
fig. 9: the nuclear magnetism hydrogen spectrogram of the 4- (4-chlorophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine synthesized by the invention;
fig. 10: the nuclear magnetic carbon spectrogram of the 4- (4-chlorophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine synthesized by the invention;
fig. 11: the nuclear magnetism hydrogen spectrogram of the 4- (4-bromophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine synthesized by the invention;
fig. 12: the nuclear magnetic carbon spectrogram of the 4- (4-bromophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine synthesized by the method;
fig. 13: the nuclear magnetism hydrogen spectrogram of the 3- (4-methoxyphenyl) -4- (naphthalene-2-yl) -1-phenylimidazolidine synthesized by the invention;
fig. 14: the nuclear magnetic carbon spectrogram of the 3- (4-methoxyphenyl) -4- (naphthalene-2-yl) -1-phenylimidazolidine synthesized by the method;
fig. 15: nuclear magnetic hydrogen spectrogram of the 4- ([ 1,1' -biphenyl ] -4-yl) -3- (4-methoxyphenyl) -1-phenylimidazolidine synthesized by the method;
fig. 16: nuclear magnetic carbon spectrogram of the 4- ([ 1,1' -biphenyl ] -4-yl) -3- (4-methoxyphenyl) -1-phenylimidazolidine synthesized by the method;
fig. 17: the nuclear magnetism hydrogen spectrogram of the 3- (4-methoxyphenyl) -1-phenyl-4- (thiophene-2-yl) imidazolidine synthesized by the invention;
fig. 18: the nuclear magnetic carbon spectrogram of the 3- (4-methoxyphenyl) -1-phenyl-4- (thiophene-2-yl) imidazolidine synthesized by the invention;
fig. 19: the nuclear magnetism hydrogen spectrogram of the 2- (3- (4-methoxyphenyl) -1-phenylimidazoline-4-yl) phenol obtained by the synthesis of the invention;
FIG. 20 is a nuclear magnetic resonance spectrum of 2- (3- (4-methoxyphenyl) -1-phenylimidazolin-4-yl) phenol synthesized according to the present invention;
fig. 21: the nuclear magnetism hydrogen spectrogram of the 1,3, 4-triphenyl imidazolidine synthesized by the method;
fig. 22: the nuclear magnetic carbon spectrogram of the 1,3, 4-triphenylimidazolidine synthesized by the invention;
fig. 23: the nuclear magnetism hydrogen spectrogram of the 1, 4-diphenyl-3- (p-tolyl) imidazolidine synthesized by the method;
fig. 24: the nuclear magnetic carbon spectrogram of the 1, 4-diphenyl-3- (p-tolyl) imidazolidine synthesized by the method;
fig. 25: the nuclear magnetism hydrogen spectrogram of the 3- (4- (tertiary butyl) phenyl) -1, 4-diphenyl imidazolidine synthesized by the invention;
fig. 26: the nuclear magnetic carbon spectrogram of the 3- (4- (tertiary butyl) phenyl) -1, 4-diphenyl imidazolidine synthesized by the invention;
fig. 27: the nuclear magnetism hydrogen spectrogram of the 3- (4-fluorophenyl) -1, 4-diphenyl imidazolidine synthesized by the invention;
fig. 28: the nuclear magnetic carbon spectrogram of the 3- (4-fluorophenyl) -1, 4-diphenyl imidazolidine synthesized by the invention;
fig. 29: the nuclear magnetism hydrogen spectrogram of the 4- (3, 5-diphenyl imidazoline-1-yl) benzonitrile synthesized by the invention;
fig. 30: the nuclear magnetic carbon spectrogram of the 4- (3, 5-diphenyl imidazoline-1-yl) benzonitrile synthesized by the invention;
fig. 31: the nuclear magnetism hydrogen spectrogram of the 2- (3, 5-diphenyl imidazoline-1-yl) benzo [ d ] thiazole synthesized by the invention;
fig. 32: the nuclear magnetic carbon spectrogram of the 2- (3, 5-diphenyl imidazoline-1-yl) benzo [ d ] thiazole synthesized by the invention.
Detailed Description
The invention is further described below with reference to the drawings and the specific embodiments, but the scope of protection of the invention is not limited to the described scope.
The imidazoline product structures referred to in the examples are of the formula:
example 1
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 21.2mg of benzaldehyde, benzaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 1-2, and the synthesized product was 3- (4-methoxyphenyl) -1, 4-diphenylimidazolidine 4a by qualitative and quantitative analysis. The isolation yield was 74%.
In example 1, the photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 Transition from ground state to excited state, oxidation of N-phenylglycine to Ir [II] The oxidized N-phenylglycine rapidly decarboxylates to form the N-radical intermediate A. Imine intermediate B formed by easy dehydration of benzaldehyde and p-methoxyaniline is obtained by Ir [II] Reducing to form a free radical intermediate C, which can undergo a free radical coupling reaction with the free radical intermediate A to obtain a diamine intermediate D. In addition, co [III] Is Ir by [II] Reduction of Co produced [II] The free radical intermediate A is further oxidized to obtain Co [I] And an imine ion intermediate E. And E is hydrolyzed to generate formaldehyde E under the action of water molecules, and then reacts with a diamine intermediate D to obtain the target product imidazoline 4a. Co (Co) [I] Removing one molecule of hydrogen after reacting with hydrogen ions, and completing the catalytic cycle to Co [III] . The N-phenylglycine is easily oxidized by the excited photocatalyst, so that the reaction speed of the reaction is high, the 2h reaction is basically finished, and the specific reaction mechanism is as follows:
benzaldehyde in this example 1: p-methoxyaniline: n-phenylglycine: photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 :Co(dmgH 2 ) 2 The amount of PyCl was 1:1:3:0.01:0.15, and the specified reaction amount was used. The amount of N-phenylglycine is reduced, the reaction is incomplete, and the yield is reduced; if the amount of N-phenylglycine is further increased, the reaction yield hardly changes. Without adding photocatalyst, the reaction cannot proceed. As the photocatalyst increases, the reaction proceeds more completely. When the amount of the photocatalyst is 1mol%, the reaction proceeds to completion. The oxidant Co (dmgH) added during the reaction 2 ) 2 The reaction proceeds best when the equivalent of PyCl is 15 mol%. When the reaction is not irradiated with the Blue LED lamp, the reaction does not proceed because the photocatalyst cannot obtain energy transition from the ground state to the excited state.
Example 2
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 24.1mg of p-methylbenzaldehyde, p-methylbenzaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 3-4, and the product synthesized by qualitative and quantitative analysis was 3- (4-methoxyphenyl) -1-phenyl-4- (pentyl) imidazolidine 4b, isolated in 55% yield.
Example 3
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 24.9mg of o-fluorobenzaldehyde, o-fluorobenzaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 5 to 6, and the synthesized product was 4- (2-fluorophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine 4c by qualitative and quantitative analysis, and the isolation yield was 42%.
Example 4
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 24.9mg of p-fluorobenzaldehyde, p-fluorobenzaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 7 to 8, and the product synthesized by qualitative and quantitative analysis was 4- (4-fluorophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine 4d, isolated in 58% yield.
Example 5
Into a dried 10mL Schlenk tube, 90.4mg of N-phenylglycine, followed by,24.7mg of p-methoxyaniline, 2.6mg of photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 28.1mg of p-chlorobenzaldehyde, p-chlorobenzaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 9 to 10, and the synthesized product was 4- (4-chlorophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine 4e by qualitative and quantitative analysis, and the isolation yield was 55%.
Example 6
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 37.0mg of p-bromobenzaldehyde, p-bromobenzaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 11 to 12, and the synthesized product was 4- (4-bromophenyl) -3- (4-methoxyphenyl) -1-phenylimidazolidine 4f by qualitative and quantitative analysis, with a separation yield of 53%.
Example 7
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 31.7mg of 2-naphthaldehyde, 2-naphthaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 13 to 14, and the product synthesized by qualitative and quantitative analysis was 4g of 3- (4-methoxyphenyl) -4- (naphthalen-2-yl) -1-phenylimidazolidine, with an isolation yield of 40%.
Example 8
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 36.5mg of p-phenylbenzaldehyde, p-phenylbenzaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 15-16, and the synthesized product was 4- ([ 1,1' -biphenyl) by qualitative and quantitative analysis]-4-yl) -3- (4-methoxyphenyl) -1-phenylimidazolidine 4h in 43% isolated yield.
Example 9
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl2ml of 1, 2-dichloroethane, 22.5mg of thiophene-2-aldehyde, thiophene-2-aldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 17 to 18, and the synthesized product was 3- (4-methoxyphenyl) -1-phenyl-4- (thiophen-2-yl) imidazolidine 4i by qualitative and quantitative analysis, isolated in 57% yield.
Example 10
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 24.4mg of salicylaldehyde, salicylaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 19 to 20, and the synthesized product was 2- (3- (4-methoxyphenyl) -1-phenylimidazolin-4-yl) phenol 4j by qualitative and quantitative analysis, and the isolation yield was 65%.
Example 11
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 18.7mg of aniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 21.2mg of benzaldehyde, benzaldehyde: aniline: n-phenylglycine: and (3) a photocatalyst: oxidationThe mass of the agent is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 21 to 22, and the synthesized product was 1,3, 4-triphenylimidazolidine 4k by qualitative and quantitative analysis, isolated in a yield of 76%.
Example 12
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 21.5mg of p-methylaniline, 2.6mg of photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 21.2mg of benzaldehyde, benzaldehyde: para-methylaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 23 to 24, and the synthesized product was 1, 4-diphenyl-3- (p-tolyl) imidazolidine 4l by qualitative and quantitative analysis, and the isolation yield was 75%.
Example 13
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 29.9mg of p-tert-butylaniline, 2.6mg of photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 21.2mg of benzaldehyde, benzaldehyde: para-tertiary butyl aniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air changing operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is placed in 455nm is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp), and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 25 to 26, and the synthesized product was 3- (4- (tert-butyl) phenyl) -1, 4-diphenylimidazolidine 4m by qualitative and quantitative analysis, isolated in a yield of 87%.
Example 14
Into a dried 10mL Schlenk tube were successively added 90.4mg N-phenylglycine, 22.3mg p-fluoroaniline, 2.6mg of photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 21.2mg of benzaldehyde, benzaldehyde: para-fluoroaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 27 to 28, and the product synthesized by qualitative and quantitative analysis was 3- (4-fluorophenyl) -1, 4-diphenylimidazolidine 4n, isolated in 40% yield.
Example 15
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 23.7mg of p-aminobenzonitrile, 2.6mg of photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, 21.2mg of benzaldehyde, benzaldehyde: para-aminobenzonitrile: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to a eggplant-type bottleAn appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 29-30, and the synthesized product was 4- (3, 5-diphenylimidazolin-1-yl) benzonitrile 4o by qualitative and quantitative analysis, isolated in 42% yield.
Example 16
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 42.3mg of N- (4-methoxyphenyl) -1-phenylazomethine, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, N- (4-methoxyphenyl) -1-phenylazomethine: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 1-2, and the synthesized product was 3- (4-methoxyphenyl) -1, 4-diphenylimidazolidine 4a by qualitative and quantitative analysis. The isolation yield was 76%.
Example 17
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 47.7mg of N- (benzo [ d ])]Thiazole-2-yl) -1-phenyl-azomethine, 2.6mg photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of 1, 2-dichloroethane, N- (benzo [ d)]Thiazol-2-yl) -1-phenyl azomethine: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1) purification, as shown in FIGS. 31-32, the synthesized product was 2- (3, 5-diphenylimidazolin-1-yl) benzo [ d ] by qualitative and quantitative analysis]Thiazole 4p. The isolation yield was 31%.
Example 18
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 2ml of 1, 2-dichloroethane, 21.2mg of benzaldehyde: p-methoxyaniline: n-phenylglycine: the mass of the photocatalyst is 1:1:3:0.01. The reaction bottle is subjected to three times of oxygen pumping and air exchanging operations, so that the reaction tube is sealed after being filled with oxygen, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 1-2, and the synthesized product was 3- (4-methoxyphenyl) -1, 4-diphenylimidazolidine 4a by qualitative and quantitative analysis. The isolation yield was 67%.
Example 19
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL diethyl ether, 21.2mg benzaldehyde, benzaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 1-2, and the synthesized product was 3- (4-methoxyphenyl) -1, 4-diphenylimidazolidine 4a by qualitative and quantitative analysis. The isolation yield was 65%.
Example 20
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL acetonitrile, 21.2mg benzaldehyde, benzaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 1-2, and the synthesized product was 3- (4-methoxyphenyl) -1, 4-diphenylimidazolidine 4a by qualitative and quantitative analysis. The isolation yield was 44%.
Example 21
Into a dried 10mL Schlenk tube were successively added 90.4mg of N-phenylglycine, 24.7mg of p-methoxyaniline, and 2.6mg of a photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 12.1mg of oxidant Co (dmgH) 2 ) 2 PyCl, 2mL of dichloromethane, 21.2mg of benzaldehyde, benzaldehyde: p-methoxyaniline: n-phenylglycine: and (3) a photocatalyst: the content of the oxidant is 1:1:3:0.01:0.15. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 2 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After the TLC detection reaction was completed, the reaction solution was transferred to an eggplant-type bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography (PE/ea=100:1), as shown in fig. 1-2, and the synthesized product was 3- (4-methoxyphenyl) -1, 4-diphenylimidazolidine 4a by qualitative and quantitative analysis. The isolation yield was 68%.
Example 22
Into a dry 100ml round bottom flask was added 2.30g N-phenylglycine, 0.616g p-Methoxyaniline, 0.0076g photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 0.036g of oxidant Co (dmgH) 2 ) 2 PyCl, 50ml of 1, 2-dichloroethane, 0.53g of benzaldehyde, benzaldehyde: n-phenylglycine: the mass of the photocatalyst is 1:3:0.01. The reaction bottle is subjected to three times of air pumping and air exchanging operations to ensure that the reaction tube is sealed after no water and no oxygen exist, and the reaction is stirred for 3 hours under the irradiation of Blue light (Blue LED lamp) with the wavelength of 455nm, and the distance between the Blue LED lamp and the Schlenk tube is 3cm. After completion of the TLC detection reaction, 150mL of water was added and quenched, and extracted 2 times with 50mL of ethyl acetate, the organic phase was collected, and dried over anhydrous Na 2 SO 4 Drying, adding an appropriate amount of silica gel, concentrating under reduced pressure, and purifying the obtained residue by column chromatography (PE/ea=20:1) to give product N 1 - (4-methoxyphenyl) -N 2 1-diphenylethane-1, 2-diamine. The isolation yield was 79%.
Claims (7)
1. The green synthesis method of the imidazoline under the catalysis of visible light is characterized in that the synthesis chemical equation of the imidazoline is as follows:
the specific synthesis method comprises the following steps:
1) The following materials were added to the Schlenk tube dried in the reaction flask:N-phenylglycine, photocatalyst, oxidant, solvent, arylamine compound, aldehyde compound or imine compound; the photocatalyst is { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 The method comprises the steps of carrying out a first treatment on the surface of the The oxidant is Co (dmgH) 2 ) 2 PyCl; the solvent is any one of diethyl ether, acetonitrile, dichloromethane or 1, 2-dichloroethane; the aldehyde compound is any one of benzaldehyde, p-methylbenzaldehyde, o-fluorobenzaldehyde, p-chlorobenzaldehyde, p-bromobenzaldehyde, 2-naphthaldehyde, p-phenylbenzaldehyde, 2-thiophenecarboxaldehyde and salicylaldehyde; the arylamine compound is any one of aniline, p-methylaniline, p-tertiary butylaniline, p-fluoroaniline and p-cyanoaniline; imine compoundIs thatN- (4-methoxyphenyl) -1-phenylazomethine,N- (benzo [ d ]]Thiazol-2-yl) -1-phenyl azomethine having the chemical structural formula shown below:
2) Carrying out three times of air pumping and air exchanging operations on the reaction bottle filled with the materials in the step 1) so as to ensure that the Schlenk tube is sealed after being anhydrous and anaerobic;
3) Placing the reaction bottle in the step 2) under the irradiation of Blue LED, stirring for reaction, and ending the reaction after TLC detects that the aldehyde compound disappears to obtain a reaction solution;
4) The reaction solution in the Schlenk tube was transferred to a eggplant-shaped bottle, an appropriate amount of silica gel was added to concentrate under reduced pressure, and the resulting residue was purified by column chromatography to obtain the product imidazoline compound.
2. A green synthesis of imidazoline under visible light catalysis according to claim 1, wherein the concentration of solvent in step 1) is 0.1M.
3. The green synthesis method of imidazoline under visible light catalysis of claim 1, wherein in step 1), the aldehyde compound is: aryl amine compound: n-phenylglycine: and (3) a photocatalyst: the ratio of the amounts of the substances of the oxidizing agent is 1:1:3:0.01:0.15.
4. The green synthesis method of imidazoline under visible light catalysis of claim 1, wherein the imine compound of step 1) is:N-phenylglycine: and (3) a photocatalyst: the ratio of the amounts of the substances of the oxidizing agent was 1:3:0.01:0.15.
5. The method for green synthesis of imidazoline under visible light catalysis as claimed in claim 1, wherein in the step 3), two Blue LEDs are provided, the reaction bottle is irradiated simultaneously, the distance between the Schlenk tube and the Blue LED lamp is 3cm, and the lamp source of the Blue LED is characterized by 10w, lambda max = 255nm。
6. The green synthesis method of imidazoline under visible light catalysis of claim 1, wherein in step 3), stirring time is 2h, and stirring temperature is room temperature; the developing reagent ratio used for detecting the reaction progress degree by TLC plate is PE: EA=20:1.
7. A green synthesis method of imidazoline under visible light catalysis is characterized in that: 90.4mg were added sequentially to a dry 10mL Schlenk tubeN-phenylglycine, 24.7mg p-methoxyaniline, 2.6mg photocatalyst { Ir [ dF (CF) 3 )ppy] 2 bpy}PF 6 2ml of 1, 2-dichloroethane, 21.2mg of benzaldehyde: p-methoxyaniline:N-phenylglycine: the mass of the photocatalyst is 1:1:3:0.01; and (3) carrying out three times of oxygen pumping and air exchanging operations on the reaction bottle to ensure that the reaction tube is filled with oxygen and then sealed, stirring the reaction under the irradiation of a Blue LED lamp with the wavelength of 455nm for 2 hours, after the TLC detection is finished, transferring the reaction liquid into an eggplant type bottle, adding a proper amount of silica gel, concentrating under reduced pressure, and carrying out column chromatography on the obtained residue to obtain the imidazoline compound.
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| CN110550992A (en) * | 2019-09-20 | 2019-12-10 | 杭州师范大学 | green synthesis method of amino alcohol compound under catalysis of visible light |
| CN111285776A (en) * | 2020-02-28 | 2020-06-16 | 杭州师范大学 | Green synthesis method of visible light catalytic 1, 2-diamine compound |
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| CN110550992A (en) * | 2019-09-20 | 2019-12-10 | 杭州师范大学 | green synthesis method of amino alcohol compound under catalysis of visible light |
| CN111285776A (en) * | 2020-02-28 | 2020-06-16 | 杭州师范大学 | Green synthesis method of visible light catalytic 1, 2-diamine compound |
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