CN113582896A - Method for realizing S-H bond insertion reaction of sulfhydryl compound by using photocatalytic microchannel reactor - Google Patents
Method for realizing S-H bond insertion reaction of sulfhydryl compound by using photocatalytic microchannel reactor Download PDFInfo
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Abstract
The invention discloses a method for realizing S-H bond insertion reaction of a sulfhydryl compound by using a photocatalytic microchannel reactor, which comprises the following steps: (1) dissolving a compound containing a mercapto functional group (-SH) and a diazoate compound in a solvent to prepare a homogeneous solution; (2) pumping the homogeneous solution prepared in the step (1) into a micro-reactor in a micro-channel reaction device provided with a light source for reaction; (3) and collecting the effluent of the microreactor to complete the insertion of the S-H bond. The reaction involved in the invention is a brand-new method for realizing mercaptan insertion reaction, a homogeneous system of catalysts and other additives is not needed in the method, and the method has good applicability to ortho-position, meta-position and para-position substituted diazoalkane.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for realizing S-H bond insertion reaction of a sulfhydryl compound by using a photocatalytic microchannel reactor.
Background
Thiol compounds are widely concerned by people because they are important industrial raw materials and important pharmaceutical intermediates, and research and development of modification methods thereof have become important research points of chemists. Due to the needs of social development, people have stronger environmental protection consciousness, and research and development of a synthetic route with low pollution and few byproducts is urgent need of social development.
In recent years, visible light catalysis has attracted more and more attention, and compared with other catalysis methods, visible light catalysis can be carried out under a milder condition, and meanwhile, visible light is used as sustainable energy and better meets the requirement of environmental protection. Furthermore, reactions based on visible light catalysis generally show high selectivity, and side reactions are rarely observed.
At present, the method of using photocatalytic technology to realize the insertion reaction of sulfhydryl compounds, especially combining photocatalysis with micro-flow field technology, is only reported, and Thierry Ollevier reports the insertion reaction of diazoalkane and sulfhydryl compounds in 2017 (J.org.chem.2017,82, 3000-3010). Although this reaction is effective in effecting the insertion reaction of the mercapto compound, a transition metal catalyst is added to the reaction system and a long reaction time is required. The Rudi Fasan project group reported that insertion of thiophenol and diazoalkanes was achieved using biocatalysts in 2015. This process requires the use of strong oxidizers. The conventional insertion reaction of the sulfhydryl compound often has the defects of multiple synthesis steps, serious energy waste, environmental unfriendliness and the like, and the defects limit the application of the traditional insertion reaction in industrialization, so that the development of a catalyst-free and additive-free insertion reaction method of the sulfhydryl compound, which is environmentally friendly, is very meaningful.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides a method for realizing the S-H bond insertion reaction of a sulfhydryl compound by using a photocatalytic microchannel reactor.
The technical scheme is as follows: in order to solve the technical problem, the invention discloses a method for realizing S-H bond insertion reaction of a sulfhydryl compound by using a photocatalytic microchannel reactor, which comprises the following steps:
(1) dissolving a compound containing a mercapto functional group (-SH) and a diazoate compound in a solvent to prepare a homogeneous solution;
(2) pumping the homogeneous solution prepared in the step (1) into a microchannel reactor in a microchannel reaction device provided with a light source for reaction;
(3) collecting the effluent of the microreactor to complete the insertion of the S-H bond;
preferably, the sulfhydryl compound S-H bond insertion reaction is to react a compound II containing a sulfhydryl functional group (-SH) with a diazo ester compound III to generate a compound shown in formula I, wherein the reaction flow is as follows:
wherein:
R1selected from alkyl, alkane derivative groups, cycloalkyl, aryl or aryl derivative groups;
R2selected from the group consisting of H, halogen, alkyl, alkoxy, aryl or aryl derivative groups;
R3selected from alkyl, aryl or aryl derivative groups.
Further preferably:
R1selected from C1-C5 alkyl, R4-O-CO-(CH2)n-, 3-6 membered cycloalkyl,Phenyl or benzyl, wherein R4Selected from C1-C5 alkyl, n ═ 1-5;
R2selected from H, halogen, C1-C5 alkyl, C1-C5 alkoxy, the substituent can be at ortho-position, meta-position or para-position;
R3selected from C1-C5 alkyl, phenyl or benzyl;
the phenyl or benzyl comprises substituted or unsubstituted phenyl or benzyl, wherein the substituted phenyl is phenyl substituted by halogen, C1-C5 alkyl, C1-C5 alkoxy, nitro or cyano, the substituted benzyl is benzyl substituted by halogen, C1-C5 alkyl, C1-C5 alkoxy, nitro or cyano, and the substituents can be in ortho, meta or para positions.
Further preferably:
R1is selected from R4-O-CO-(CH2)n-, phenyl or benzyl, where R4Selected from methyl or ethyl, n ═ 1 or 2;
R2selected from H or methoxy, the substituent can be at ortho-position, meta-position or para-position;
R3selected from methyl or ethyl;
the phenyl or benzyl group comprises a substituted or unsubstituted phenyl or benzyl group, wherein the substituted phenyl group is a phenyl group substituted by halogen, methyl or methoxy, the substituted benzyl group is a benzyl group substituted by halogen, methyl or methoxy, and the substituents can be in ortho, meta or para positions.
Preferably, in the step (1), the solvent is any one or more of dichloromethane, N-methylpyrrolidone, acetonitrile, 1, 2-dichloroethane, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and dimethyl sulfoxide; more preferably dichloromethane.
Preferably, in the step (1), the molar concentration of the compound containing a mercapto functional group (-SH) is 0.04 to 0.4mmol/L, more preferably 0.2 mmol/L.
Preferably, in the step (1), the molar ratio of the compound half containing a mercapto functional group (-SH) to the diazoalkane compound is 1: 1-5, and more preferably 1: 2; the concentration of the diazo acid ester compound is 0.08-2.0 mmol/mL; more preferably 0.4 mmol/L.
Preferably, in the step (2), the microchannel reactor device provided with the light source comprises a feed pump, a microchannel reactor, a light source and a receiver; wherein, the injector is connected with the micro-channel reactor and the receiver in series in turn through the pipeline, and the micro-channel reactor is placed under the irradiation of the light source, as shown in figure 1 and figure 2.
Preferably, the microchannel reactor is of a pore channel structure, the number of pore channels is increased or reduced according to needs, the pore channel material is perfluoroalkoxy alkane (PFA), the inner diameter of the dimension of the microchannel reactor is 0.5-1.0 mm, the length of the microchannel reactor is 5-20 m, and the volume of the microchannel reactor is 1-15.7 mL; the inner diameter is preferably 0.5mm, the volume is preferably 1mL, and the flow rate is 0.1-5.0 mL/min.
Preferably, in the step (2), the reaction temperature is controlled to be 0-30 ℃, and the reaction residence time is 30 s-2 h; among them, the reaction residence time is preferably 5 to 60min, more preferably 5 to 30min, further preferably 5 to 10min, and most preferably 10 min.
Preferably, in the step (2), the light source is a lamp strip or a bulb, the intensity is 5W-60W, and the wavelength is 435-577 nm; the light source is preferably a blue LED light source, and the wavelength is preferably 450-470 nm, more preferably 455 nm.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the invention is a brand-new method for realizing the insertion reaction of the sulfhydryl-containing compound, and the insertion reaction of the S-H bond can be realized only by dissolving the sulfhydryl-containing compound and the diazoalkane compound in a solvent under the irradiation of light.
(2) The invention can realize the insertion reaction of the S-H bond without using a catalyst, and overcomes the problems of high production cost, high energy consumption, environmental pollution and the like in the prior art.
(3) The method does not need to add any additive, reduces the steps of post-treatment and is beneficial to the application to industrial scale-up production.
(4) The system designed by the invention has no solid insoluble substances and no micro-channel blockage problem, is simple to operate and high in safety, overcomes the defects of the traditional method, shortens the reaction time, improves the reaction conversion rate and the yield, and is high in reaction continuity and favorable for continuous and uninterrupted amplification production.
(5) The light source used by the invention is visible light, is sustainable energy and is a green synthesis method.
(6) The invention can realize the insertion reaction of S-H bond of thiophenol compound besides the insertion reaction of common thiol.
(7) The product conversion rate is 84-97%, and the yield is as high as 80-95%.
Drawings
FIG. 1 is a schematic diagram of the reaction scheme of the present invention.
FIG. 2 shows a photocatalytic microchannel reactor device.
FIG. 3 is a hydrogen spectrum of ethyl 2- (4-methoxyphenyl) -2- (p-toluenesulfonyl) acetate.
FIG. 4 is a carbon spectrum diagram of ethyl 2- (4-methoxyphenyl) -2- (p-toluenesulfonyl) acetate.
FIG. 5 is a hydrogen spectrum of methyl 3- ((2-ethoxy-1- (4-methoxyphenyl) -2-oxoethyl) thio) propionate.
FIG. 6 is a carbon spectrum of methyl 3- ((2-ethoxy-1- (4-methoxyphenyl) -2-oxoethyl) thio) propionate.
FIG. 7 is a hydrogen spectrum of ethyl 2- ((2-methoxy-2-oxyethyl) thio) -2- (4-methoxyphenyl) acetate.
FIG. 8 is a carbon spectrum of ethyl 2- ((2-methoxy-2-oxyethyl) thio) -2- (4-methoxyphenyl) acetate.
FIG. 9 is a hydrogen spectrum of ethyl 2- ((4-methoxybenzyl) thio) -2- (4-methoxyphenyl) acetate.
FIG. 10 is a carbon spectrum diagram of ethyl 2- ((4-methoxybenzyl) thio) -2- (4-methoxyphenyl) acetate.
FIG. 11 is a hydrogen spectrum of ethyl 2- ((4-chlorobenzyl) thio) -2- (4-methoxyphenyl) acetate.
FIG. 12 is a carbon spectrum of ethyl 2- ((4-chlorobenzyl) thio) -2- (4-methoxyphenyl) acetate.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
The following examples employed microchannel reactor devices provided with light sources, as shown in fig. 1 and 2, including a feed pump (bagging Leifu Fluid Technology co.ltd, (TYD01-01-CE type)), a microchannel reactor, a light source, and a receiver; wherein, the injector is connected with the micro-channel reactor and the receiver in series in turn through pipelines, and the micro-channel reactor is placed under the irradiation of the light source. The microchannel reactor is of a pore channel structure, the number of pore channels is increased or reduced according to needs, the pore channel material is perfluoroalkoxy alkane (PFA), and the length of the microchannel reactor is 5-20 m.
Example 1
0.062g (0.5mmol,1.0equiv) of p-methylthiophenol and 0.220g (1.0mmol,2.0equiv) of ethyl 2-diazo-2- (4-methoxyphenyl) acetate were weighed, dissolved in 2.5mL of 1, 2-dichloroethane, and loaded into a syringe after complete dissolution. Pumping the reaction solution into a reactor with a coil inner diameter of 0.5mm, a volume of 1mL and a micro-reactor flow rate of 0.1mL/min, irradiating by a blue LED light source (50W, 455nm), reacting at 25 ℃ and staying for 10 min. After the completion of the reaction, TLC detection was performed, and column chromatography (petroleum ether: ethyl acetate: 20: 1) gave 126.4mg of the final product in 80% yield. As shown in fig. 3 and 4, the characterization data are as follows:1H NMR(400MHz,Chloroform-d)δ7.36(d,J＝8.8Hz,2H),7.28(d,J＝8.2Hz,2H),7.07(d,J＝7.9Hz,2H),6.84(d,J＝8.8Hz,2H),4.80(s,1H),4.17–4.04(m,2H),3.80(s,3H),2.31(s,3H),1.16(t,J＝7.1Hz,3H).13C NMR(100MHz,Chloroform-d)δ170.7,159.5,138.2,133.3,130.2,129.7(4),129.6(9),127.8,114.0,61.6,56.1,55.3,21.2,14.0.HRMS(ESI)m/z:calcd for C18H20O3SNa[M+Na]+:339.1025,found:339.1027.
example 2
0.062g (0.5mmol,1.0equiv) of p-methylthiophenol and 0.22g (1.0mmol,2.0equiv) of ethyl 2-diazo-2- (4-methoxyphenyl) acetate were weighed, dissolved in 2.5mL of tetrahydrofuran, and loaded into a syringe after complete dissolution. Pumping the reaction solution into a reactor with a coil inner diameter of 0.5mm, a volume of 1mL and a micro-reactor flow rate of 0.1mL/min, irradiating by a blue LED light source (50W, 455nm), reacting at 25 ℃ and staying for 10 min. After completion of the reaction, TLC detection was performed, and column chromatography (petroleum ether: ethyl acetate: 20: 1) gave 131.1mg of the final product in 83% yield.
Example 3
0.062g (0.5mmol,1.0equiv) of p-methylthiophenol and 0.220g (1.0mmol,2.0equiv) of ethyl 2-diazo-2- (4-methoxyphenyl) acetate were weighed, dissolved in 2.5mL of dichloromethane, and loaded into a syringe after completely dissolved. Pumping the reaction solution into a reactor with a coil inner diameter of 0.5mm, a volume of 1mL and a micro-reactor flow rate of 0.1mL/min, irradiating by a blue LED light source (50W, 455nm), reacting at 25 ℃ and staying for 10 min. After the completion of the reaction, TLC detection was performed, and column chromatography (petroleum ether: ethyl acetate: 20: 1) gave 135.9mg of the final product in 86% yield.
Example 4
0.062g (0.5mmol,1.0equiv) of p-methylthiophenol and 0.220g (1.0mmol,2.0equiv) of ethyl 2-diazo-2- (4-methoxyphenyl) acetate were weighed, dissolved in 2.5mL of dichloromethane, and loaded into a syringe after completely dissolved. The reaction solution is pumped into a reactor with the inner diameter of a coil pipe of 0.5mm, the volume is 1mL, the flow rate of the microreactor is 0.3mL/min, a blue LED light source (50W, 455nm) is used for irradiation, the reaction is carried out at 25 ℃, and the retention time is 3.3 min. After the completion of the reaction, TLC detection was performed, and column chromatography (petroleum ether: ethyl acetate: 20: 1) gave 126.3mg of the final product in 80% yield.
Example 5
0.062g (0.5mmol,1.0equiv) of p-methylthiophenol and 0.220g (1.0mmol,2.0equiv) of ethyl 2-diazo-2- (4-methoxyphenyl) acetate were weighed, dissolved in 2.5mL of dichloromethane, and loaded into a syringe after completely dissolved. The reaction solution is pumped into a reactor with the inner diameter of a coil pipe of 0.5mm, the volume is 1mL, the flow rate of the microreactor is 0.15mL/min, a blue LED light source (50W, 455nm) is used for irradiation, the reaction is carried out at the temperature of 25 ℃, and the retention time is 6.5 min. After completion of the reaction, TLC detection was performed, and column chromatography (petroleum ether: ethyl acetate: 20: 1) gave 132.7mg of the final product in 84% yield.
Example 6
0.062g (0.5mmol,1.0equiv) of p-methylthiophenol and 0.220g (1.0mmol,2.0equiv) of ethyl 2-diazo-2- (4-methoxyphenyl) acetate were weighed, dissolved in 2.5mL of dichloromethane, and loaded into a syringe after completely dissolved. Pumping the reaction solution into a reactor with a coil inner diameter of 0.5mm, a volume of 1mL and a micro-reactor flow rate of 0.05mL/min, irradiating by a blue LED light source (50W, 455nm), reacting at 25 ℃ and staying for 20 min. After the completion of the reaction, TLC detection was performed, and column chromatography (petroleum ether: ethyl acetate: 20: 1) gave 135.9mg of the final product in 86% yield.
Example 7
0.0600g (0.5mmol,1.0equiv) of methyl 3-mercaptopropionate and 0.220g (1.0mmol,2.0equiv) of ethyl 2-diazo-2- (4-methoxyphenyl) acetate were weighed, dissolved in 2.5mL of dichloromethane, and loaded into a syringe after complete dissolution. Pumping the reaction solution into a reactor with a coil inner diameter of 0.5mm, a volume of 1mL and a micro-reactor flow rate of 0.1mL/min, irradiating by a blue LED light source (50W, 455nm), reacting at 25 ℃ and staying for 10 min. After completion of the reaction, TLC detection was performed, and column chromatography (petroleum ether: ethyl acetate: 10: 1) was performed to obtain 140.4mg of the product in 90% yield. As shown in fig. 5 and 6, the characterization data are as follows:1H NMR(400MHz,Chloroform-d)δ7.39(d,J＝8.6Hz,2H),6.87(d,J＝8.6Hz,2H),4.58(s,1H),4.28–4.09(m,2H),3.80(s,3H),3.68(s,3H),2.86–2.69(m,2H),2.64–2.48(d,J＝7.3Hz,2H),1.25(t,J＝7.1Hz,3H).13C NMR(100MHz,Chloroform-d)δ172.1,170.8,159.5,129.7,127.8,114.1,61.7,55.3,51.8,51.7,34.2,26.6,14.1.HRMS(ESI)m/z:calcd for C15H20O5SNa[M+Na]+:335.0924,found:335.0911.
example 8
Methyl thioglycolate 0.053g (0.5mmol,1.0equiv), ethyl 2-diazo-2- (4-methoxyphenyl) acetate 0.220g (1.0mmol,2.0equiv) were weighed, dissolved with 2.5mL of dichloromethane, and loaded into a syringe after complete dissolution. Pumping the reaction solution into a reactor with a coil inner diameter of 0.5mm, a volume of 1mL and a micro-reactor flow rate of 0.1mL/min, irradiating by a blue LED light source (50W, 455nm), reacting at 25 ℃ and staying for 10 min. After completion of the reaction, TLC detection was performed, and column chromatography (petroleum ether: ethyl acetate: 10: 1) was performed to obtain 135.6mg of the product in 91% yield. As shown in fig. 7 and 8, the characterization data are as follows:1H NMR(400MHz,Chloroform-d)δ7.38(d,J＝8.7Hz,2H),6.87(d,J＝8.7Hz,2H),4.80(s,1H),4.26–4.10(m,2H),3.80(s,3H),3.71(s,3H),3.27(d,J＝15.1Hz,1H),3.09(d,J＝15.1Hz,1H),1.25(t,J＝7.1Hz,3H).13C NMR(100MHz,Chloroform-d)δ170.3(8),170.3(5),159.6,129.9,127.2,114.2,61.8,55.3,52.4,51.8,32.7,14.1.HRMS(ESI)m/z:calcd for C14H18O5SNa[M+Na]+:321.0767,found:321.0744.
example 9
0.077g (0.5mmol,1.0equiv) of 4-methoxybenzylthiol and 0.220g (1.0mmol,2.0equiv) of ethyl 2-diazo-2- (4-methoxyphenyl) acetate were weighed, dissolved in 2.5mL of dichloromethane, and after complete dissolution, loaded into a syringe. Pumping the reaction solution into a reactor with a coil inner diameter of 0.5mm, a volume of 1mL and a micro-reactor flow rate of 0.1mL/min, irradiating by a blue LED light source (50W, 455nm), reacting at 25 ℃ and staying for 10 min. After completion of the reaction, TLC detection was performed, and column chromatography (petroleum ether: ethyl acetate: 10: 1) was performed to obtain 164.3mg of the product in 95% yield. As shown in FIGS. 9 and 10, the characterization dataThe following were used:1H NMR(400MHz,Chloroform-d)δ7.33(d,J＝8.7Hz,2H),7.18(d,J＝8.6Hz,2H),6.84(t,J＝8.0Hz,4H),4.36(s,1H),4.19–4.08(m,2H),3.77(d,J＝1.9Hz,6H),3.73–3.68(m,1H),3.60–3.54(m,1H),1.22(t,J＝7.1Hz,3H).13C NMR(100MHz,Chloroform-d)δ170.9,159.4,158.8,130.2,129.8,129.2,127.9,114.0,113.9,61.6,55.3,50.9,35.6,14.1.HRMS(ESI)m/z:calcd for C19H22O4SNa[M+Na]+:369.1131,found:369.1114.
example 10
0.0629g (0.5mmol,1.0equiv) of 4-chlorobenzenethiol and 0.220g (1.0mmol,2.0equiv) of ethyl 2-diazo-2- (4-methoxyphenyl) acetate were weighed, dissolved in 2.5mL of dichloromethane, and loaded into a syringe after completely dissolved. Pumping the reaction solution into a reactor with a coil inner diameter of 0.5mm, a volume of 1mL and a micro-reactor flow rate of 0.1mL/min, irradiating by a blue LED light source (50W, 455nm), reacting at 25 ℃ and staying for 10 min. After completion of the reaction, TLC detection was performed, and column chromatography (petroleum ether: ethyl acetate: 30: 1) gave 162.7mg of the product in 93% yield. As shown in fig. 11 and 12, the characterization data are as follows:1H NMR(400MHz,Chloroform-d)δ7.32(d,J＝8.7Hz,2H),7.27(d,J＝8.5Hz,2H),7.19(d,J＝8.4Hz,2H),6.85(d,J＝8.7Hz,2H),4.34(s,1H),4.19–4.09(m,2H),3.79(s,3H),3.74–3.68(m,1H),3.59–3.53(m,1H),1.23(t,J＝7.1 Hz,3H).13C NMR(100 MHz,Chloroform-d)δ170.7,159.5,135.9,132.98,130.4,129.8,128.7,127.6,61.7,55.3,51.0,35.5,14.1.HRMS(ESI)m/z:calcd for C18H19ClO3SNa[M+Na]+:373.0636,found:373.0613.
[a]reaction conditions are as follows: the mercapto compound (0.5mmol,1.0equiv) and diazoalkane (1.0 mm) were weighed out separatelyol,2.0equiv), dissolved in 2.5mL of solvent, and loaded in a syringe after complete dissolution. Pumping the reaction liquid into a reactor with the inner diameter of a coil pipe of 0.5mm, the volume of the reactor is 1mL, the flow rate of the microreactor is 0.1-2.0 mL/min, irradiating the reactor by using a blue LED light source (10-50W, 455nm), and reacting at 25 ℃ for 30 s-20 min. And (4) carrying out TLC detection after the reaction is finished, and carrying out column chromatography to obtain a product.
[b]Reaction conditions are as follows: mercapto compound (0.5mmol,1.0equiv) was weighed, added to a dry Schlenk reaction tube, and argon was replaced three times; diazoalkane (1.0mmol,2.0equiv), dissolved in 2.5mL of solvent, was injected into the Schlenk reaction tube with a syringe. Irradiating by using a blue LED light source (10-50W, 455nm), and reacting at 15-25 ℃ for 12 h. And (4) carrying out TLC detection after the reaction is finished, and carrying out column chromatography to obtain a product.
The present invention provides a thought and a method for implementing the S-H bond insertion reaction of a thiol compound by using a photocatalytic microchannel reactor, and the method and the way for implementing the technical scheme are many, and the above description is only a preferred embodiment of the present invention, it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. A method for realizing S-H bond insertion reaction of a sulfhydryl compound by using a photocatalytic microchannel reactor is characterized by comprising the following steps:
(1) dissolving a compound containing a mercapto functional group (-SH) and a diazoate compound in a solvent to prepare a homogeneous solution;
(2) pumping the homogeneous solution prepared in the step (1) into a microchannel reactor in a microchannel reaction device provided with a light source for reaction;
(3) and collecting the effluent of the microreactor to complete the insertion of the S-H bond.
2. The method for implementing the S-H bond insertion reaction of the mercapto compound by using the photocatalytic microchannel reactor as claimed in claim 1, wherein the S-H bond insertion reaction of the mercapto compound is to react a compound II containing a mercapto functional group (-SH) with a diazo ester compound III to generate the compound represented by formula I, and the reaction flow is as follows:
wherein:
R1selected from alkyl, alkane derivative groups, cycloalkyl, aryl or aryl derivative groups;
R2selected from the group consisting of H, halogen, alkyl, alkoxy, aryl or aryl derivative groups;
R3selected from alkyl, aryl or aryl derivative groups.
3. The method for implementing S-H bond insertion reaction of sulfhydryl compound by using photocatalytic microchannel reactor as claimed in claim 2, wherein:
R1selected from C1-C5 alkyl, R4-O-CO-(CH2)n-, 3-6 membered cycloalkyl, phenyl or benzyl, where R4Selected from C1-C5 alkyl, n ═ 1-5;
R2selected from H, halogen, C1-C5 alkyl, C1-C5 alkoxy;
R3selected from C1-C5 alkyl, phenyl or benzyl;
the phenyl or benzyl comprises substituted or unsubstituted phenyl or benzyl, wherein the substituted phenyl is phenyl substituted by halogen, C1-C5 alkyl, C1-C5 alkoxy, nitro or cyano, and the substituted benzyl is benzyl substituted by halogen, C1-C5 alkyl, C1-C5 alkoxy, nitro or cyano.
4. The method for implementing S-H bond insertion reaction of sulfhydryl compound by using photocatalytic microchannel reactor as claimed in claim 2, wherein:
R1is selected from R4-O-CO-(CH2)n-, phenyl or benzyl, where R4Selected from methyl or ethyl, n ═ 1 or 2;
R2selected from H or methoxy;
R3selected from methyl or ethyl;
the phenyl or benzyl group comprises a substituted or unsubstituted phenyl or benzyl group, wherein the substituted phenyl group is a phenyl group substituted by halogen, methyl or methoxy, and the substituted benzyl group is a benzyl group substituted by halogen, methyl or methoxy.
5. The method for performing S-H bond insertion reaction of a thiol compound by using a photocatalytic microchannel reactor as claimed in claim 1, wherein in step (1), the solvent is any one or more of dichloromethane, N-methylpyrrolidone, acetonitrile, 1, 2-dichloroethane, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and dimethylsulfoxide.
6. The method for implementing S-H bond insertion reaction of mercapto compound by using photocatalytic microchannel reactor as claimed in claim 1, wherein in step (1), the molar concentration of the compound containing mercapto functional group (-SH) is 0.04-0.4 mmol/L; the molar ratio of the compound containing a mercapto functional group (-SH) to the diazoate compound is 1: 1-5.
7. The method for S-H bond insertion reaction of a thiol compound using a photocatalytic microchannel reactor as claimed in claim 1, wherein in step (2), the microchannel reactor device with the light source comprises a feed pump, a microchannel reactor, a light source and a receiver; wherein, the injector is connected with the micro-channel reactor and the receiver in series in turn through pipelines, and the micro-channel reactor is placed under the irradiation of the light source.
8. The method of claim 1, wherein the microchannel reactor has a pore structure, the pore material is perfluoroalkoxy alkane, and the microchannel reactor has a dimension of 0.5-1.0 mm in inner diameter and a length of 5-20 m.
9. The method for realizing S-H bond insertion reaction of a mercapto compound by using the photocatalytic microchannel reactor as claimed in claim 1, wherein in the step (2), the reaction temperature is controlled to be 0-30 ℃, and the reaction residence time is 30S-2H; the flow rate of the micro-reactor is 0.1-5.0 mL/min.
10. The method for performing S-H bond insertion reaction of a thiol compound by using a photocatalytic microchannel reactor as claimed in claim 1, wherein in step (2), the intensity of the light source is 5W-60W, and the wavelength is 435-577 nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114213299A (en) * | 2021-12-31 | 2022-03-22 | 南京工业大学 | Method for preparing S-alkynyl functionalized compound by using microchannel reaction device |
| CN114315793A (en) * | 2021-12-31 | 2022-04-12 | 南京工业大学 | Method for preparing S-diazoalkane compound by using microchannel reaction device |
| CN114716367A (en) * | 2022-04-20 | 2022-07-08 | 南京工业大学 | Method for preparing 4-mercaptopyridine compound by virtue of micro-flow field reactor technology |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213299A (en) * | 2021-12-31 | 2022-03-22 | 南京工业大学 | Method for preparing S-alkynyl functionalized compound by using microchannel reaction device |
| CN114315793A (en) * | 2021-12-31 | 2022-04-12 | 南京工业大学 | Method for preparing S-diazoalkane compound by using microchannel reaction device |
| CN114716367A (en) * | 2022-04-20 | 2022-07-08 | 南京工业大学 | Method for preparing 4-mercaptopyridine compound by virtue of micro-flow field reactor technology |
| CN114716367B (en) * | 2022-04-20 | 2024-04-12 | 南京工业大学 | Method for preparing 4-mercaptopyridine compound by micro-flow field reactor technology |
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