CN110714208B - Method for preparing 6- (sulfonyl methyl) phenanthridine compound through electrocatalysis - Google Patents
Method for preparing 6- (sulfonyl methyl) phenanthridine compound through electrocatalysis Download PDFInfo
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Abstract
The invention discloses a method for preparing 6- (sulfonyl methyl) phenanthridine compounds through electrocatalysis, and belongs to the technical field of chemical synthesis. The 6- (sulfonyl methyl) phenanthridine derivative is prepared by electrocatalysis, so that the defects of high equipment requirement, high cost and the like caused by a reaction route for preparing sulfonyl substituted phenanthridine compounds in the prior art, the need of an oxidant and a metal catalyst are overcome. The organic electrochemical catalysis directly or indirectly realizes the oxidation-reduction reaction by means of electron gain and loss on the surface of the electrode, so that the use of toxic and harmful oxidation-reduction reagents can be avoided.
Description
Technical Field
The invention relates to a method for preparing 6- (sulfonyl methyl) phenanthridine compounds through electrocatalysis, and belongs to the technical field of chemical synthesis.
Background
The phenanthridine derivatives are important organic compounds, and have great practical significance from natural bioactive products to artificially synthesized medicinal preparations and functional materials. In addition, sulfonyl is an important and common functional group in the field of organic synthesis, and is present in many natural products and drug molecules having biological activity, and how to efficiently introduce sulfonyl into organic molecules, particularly organic molecules having biological activity, is a problem of great interest in recent years by converting sulfonyl into various functional groups such as thio, sulfoxide, and the like through chemical reaction.
Early cyclization by Bischler-Napieralski (Bischler-Napieralski reaction) has been widely used to prepare phenanthridine derivatives. The method has the disadvantages of harsh reaction conditions, poor functional group tolerance and high requirements on reaction equipment. In contrast, free radical sulfonylation has become an efficient and mild method to prepare the corresponding compounds. In recent years, there have been reports of relevant literature on methods for preparing 6- (sulfonylmethyl) phenanthridines using radical sulfonylation: the first method is that under the condition of nitrogen atmosphere, dichloromethane is used as solvent, terpyridine ruthenium chloride hexahydrate is used as catalyst, LED blue light is irradiated, sulfonyl chloride derivative and 2- (1-vinyl azide) -1,1' -biphenyl are reacted at room temperature, and the yield is 26-93% (Visible-light-induced sulfonation/cyclization of vinyl azides: one-pot conjugation of 6- (sulfonyl methyl) phenyl anthraquinones [ J ]. Organic Chemistry Frontiers 2018,2: 232-236.); second, under argon atmosphere, acetonitrile is used as solvent, terpyridine ruthenium chloride hexahydrate is used as catalyst, LED blue Light irradiation is carried out, so that Sulfonyl hydrazide derivative and 2- (1-azidovinyl) -1,1' -biphenyl react, and the yield is 20-84% (Visible-Light-medial sulfonic sulfonation/Cyclization of Vinyl Azides with sulfo Hydrazines for the Synthesis of 6- (sulfo methyl) phenyl amides under Mill Condition [ J ] Synlett 2019,8: 955-. In both methods, noble metal terpyridyl ruthenium chloride hexahydrate is used as a photosensitizer, tert-butyl perbenzoate is used as an initiator, a pure organic solvent is used for reaction, and in addition, special light is required for irradiation, so that the requirements on reaction equipment are high.
The method comprises the following steps:
the second method comprises the following steps:
the technology needs expensive metal ruthenium, metal residues are easy to exist in products, the cost is high, the terpyridine ruthenium chloride hexahydrate photosensitizer is expensive, the market selling price is 20.4 ten thousand yuan/Kg, a specific light source is needed, and the scale-up preparation is difficult. The reaction system completely uses organic solvent, and is easy to cause pollution to the environment.
The sulfonyl free radical is led to attack the alkene azide by an electrochemical method and is cyclized to prepare the 6- (sulfonyl methyl) phenanthridine compound, the light irradiation is not needed, water and acetonitrile are used as mixed solvents, the use of organic solvents is reduced, and a similar reaction method is not reported at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the method for preparing the 6- (sulfonyl methyl) phenanthridine compound by using olefin azide and sulfonyl hydrazide as raw materials and acetonitrile and water as solvents and utilizing electrocatalytic equipment, which does not need to add any initiator, uses a mixed solvent of acetonitrile and water, reduces the use of organic solvents, reduces the pollution to the environment, does not have metal residues in products, and reduces the cost.
The first purpose of the invention is to provide a method for preparing 6- (sulfonyl methyl) phenanthridine compounds through electrocatalysis, wherein the preparation method is represented by the following general formula:
in the formula R1Is halogen, alkoxy, alkyl aryl, aliphatic radical; r2Is alkyl, phenyl substituted with a substituent which is alkyl or halogen.
In one embodiment, the preparing step comprises:
(1) in a nitrogen atmosphere, mixing an olefin azide compound (1), a sulfonyl hydrazine compound (2) and potassium carbonate in a molar ratio of 1: 1-1.5: 1-1.5, adding the mixture into a reaction bottle, and adding electrolyte [ n-Bu4N]BF4Then adding a mixed solution of acetonitrile and water, wherein the volume ratio of the acetonitrile to the water is (15-20) to 1;
(2) and (2) stirring the mixture obtained in the step (1) to dissolve the mixture, inserting two electrodes, electrifying the graphite electrode for the positive electrode and the platinum electrode for the negative electrode for 10-16 mA for 3-5h, adding water to the mixture after the reaction is finished, stirring, extracting, drying and purifying to obtain the 6- (sulfonyl methyl) phenanthridine compound (3).
In one embodiment, R in the general formula of the preparation method1F, Cl, OMe, Me; r24-methyl benzene, 4-chlorobenzene and ethyl.
In one embodiment, the electrochemical device in the preparing step (2) is: ika ElectroSyn 2.0.
In one embodiment, the 6- (sulfonylmethyl) phenanthridine compound (3) has the structural formula:
In one embodiment, the alkene azide compound (1) in the preparation method specifically refers to one of 2- (1-azidovinyl) -1,1' -biphenyl, 2- (1-azidovinyl) -4' -chloro-1, 1' -biphenyl, 2- (1-azidovinyl) -4' -methoxy-1, 1' -biphenyl, 2- (1-azidovinyl) -4' -fluoro-1, 1' -biphenyl, 2- (1-azidovinyl) -5-chloro-1, 1' -biphenyl, and 2- (1-azidovinyl) -4-methyl-1, 1' -biphenyl.
In one embodiment, the sulfonyl hydrazide compound (2) in the preparation method specifically refers to one of 4-methylsulfonyl phenylhydrazine, 4-chlorosulfonyl phenylhydrazine and ethyl sulfonyl phenylhydrazine.
In one embodiment, the synthesis process comprises [ n-Bu ]4N]BF4The concentration of (2) is 0.1 mol/L.
In one embodiment, the synthesis method comprises mixing acetonitrile and water in a volume ratio of 18: 1.
In one embodiment, the concentration of the alkene azide in the solvent in the synthetic method is 2 mol/L.
In one embodiment, the electrochemical reaction conditions in the synthesis process are: the current was 12mA, the reaction time was 3 hours, and the reaction temperature was 30 ℃.
In one embodiment, the extractant used for extraction in the synthesis process is dichloromethane.
In one embodiment, the method of purification by the synthetic method is column chromatography.
The invention has the beneficial effects that:
(1) the method takes olefin azide and sulfonyl hydrazide as raw materials, acetonitrile and water as solvents, and utilizes electrocatalytic equipment to prepare the phenanthridine derivative, wherein the yield is not lower than 70%;
(2) compared with the reaction reported in the literature, the reaction has the advantages of cost saving, mild condition, high yield and simple operation steps, and the organic electrochemical catalysis directly or indirectly realizes the redox reaction by means of electron loss on the surface of the electrode, so that the use of toxic and harmful redox reagents can be avoided, and the method can be applied to the fields of scientific research, medical treatment, industry and the like.
Drawings
FIG. 16 is a method for synthesizing a (sulfonylmethyl) phenanthridine compound.
FIG. 2 is a NMR spectrum of 6- (tosylmethyl) phenanthridine in example 1.
Detailed Description
All reagents were commercially available and used without further treatment.
The method for calculating the yield comprises the following steps: yield is the amount of the target product (actually) produced/theoretical amount of the target product × 100%
The nuclear magnetic test method comprises the following steps: weighing a certain mass of the final product, placing the final product in a nuclear magnetic tube, dissolving the final product by using a deuterated reagent DMSO, and performing 1H NMR test by using an Aduance III nuclear magnetic resonance spectrometer at 25 ℃, wherein the resonance frequency of 1H is 400 MHz.
Example 16 preparation of (tosylmethyl) phenanthridine:
tetrabutylammonium tetrafluoroborate (26.3mg,0.08mmol), anhydrous potassium carbonate (41.4mg,0.3mmol), 4-methylbenzenesulfonyl hydrazide (55.9mg,0.3mmol), distyryl azide (44.2mg,0.2mmol) were added to a 5mL reaction flask under nitrogen, 4mL of a mixed solvent of acetonitrile and water (acetonitrile to water volume ratio 18:1) was used to dissolve the above substances, a carbon electrode was used as a working electrode, a platinum sheet electrode was used as a counter electrode, and the reaction mixture was reacted at a constant current of 12 milliamps for 3 hours. After the reaction was completed, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, and the extracted and dried reaction solution was separated by column chromatography to obtain 59.68mg of a white solid, i.e., 59.68mg of 6- (tosylmethyl) phenanthridine, with a calculated yield of 86%. The resulting product has the following structural formula:
FIG. 2 is a chart of a NMR spectrum of 6- (tosylmethyl) phenanthridine, and it can be seen from the chart of the NMR spectrum of 6- (tosylmethyl) phenanthridine that chemical shifts of respective hydrogens coincide with those of the target 6- (tosylmethyl) phenanthridine, indicating that the final product is obtained.
1H NMR(400MHz,DMSO)8.62(d,J＝7.6Hz,1H),8.53(t,J＝8.5Hz,1H),8.33(d,J＝7.5Hz,1H),7.87-7.82(m,2H),7.73-7.62(m,3H),7.56(d,J＝6.9Hz,3H),7.17(d,J＝6.9Hz,2H),5.14(s,2H),2.37(s,3H).13C NMR(100MHz,DMSO)160.22,151.12,144.98,144.84,136.76,133.19,131.60,130.02,128.67,128.08,126.89,126.01,124.82,124.45,122.43,118.77,117.97,109.94,61.78,21.49。
Comparative example 1 No tetrabutylammonium tetrafluoroborate was added
Based on example 1, no tetrabutylammonium tetrafluoroborate was added, and the same reaction conditions as in example 1 were used, and it was found that no reaction occurred, and 6- (tosylmethyl) phenanthridine could not be produced.
Comparative example 2 use of lithium perchlorate instead of tetrabutylammonium tetrafluoroborate
Based on example 1, tetrabutylammonium tetrafluoroborate was used as lithium perchlorate, and other reaction conditions were the same as in example 1, and 38.87mg of a white solid was obtained by column chromatography, and the calculated yield was 56%.
Example 2: effect of different acetonitrile to Water volume ratios on the preparation of 6- (tosylmethyl) phenanthridine
On the basis of example 1, further investigating the effect of different acetonitrile-water volume ratios on the preparation of 6- (tosylmethyl) phenanthridine, 6- (tosylmethyl) phenanthridine was prepared by mixing acetonitrile and water in the volume ratios of 1:1, 10:1, 15:1, 18:1, and 20:1, and under the same reaction conditions as in example 1, respectively, and the results are shown in table 1. As is clear from Table 1, when the volume ratio of acetonitrile to water was 1:1, the product mass was only 13.88mg and the yield was only 20%, and when the volume ratio of acetonitrile to water was gradually increased, the product mass and yield were also gradually increased, and when the volume ratio of acetonitrile to water was 18:1, the product mass was 59.68mg and the yield was 86%. When the volume ratio of the acetonitrile to the water is increased, the mass and the yield of the product are reduced, and when the volume ratio of the acetonitrile to the water is 20:1, the mass of the product is 55.52mg, and the yield is 80%.
TABLE 1
| Volume ratio of acetonitrile to water | Quality of the product | Yield of |
| 1:1 | 13.88mg | 20％ |
| 10:1 | 27.07mg | 39％ |
| 15:1 | 55.52mg | 80％ |
| 18:1 | 59.68mg | 86％ |
| 20:1 | 55.52mg | 80％ |
Example 3: effect of different electrocatalytic currents on preparation of 6- (tosylmethyl) phenanthridine
On the basis of example 1, the influence of different electrocatalytic currents on the preparation of 6-azidomethylphenanthridine was further explored. 6-Azidomethylphenanthridine was prepared separately with the same reaction conditions as in example 1, with the energization currents set at 6mA, 8mA, 10mA, 12mA, 16mA, 20mA, and the results are shown in Table 2. As can be seen from Table 2, when the electrocatalytic current was 6mA, the product mass was 5.55mg and the yield was only 8%, and when the electrocatalytic current was gradually increased, the product mass and yield were also gradually increased, and when the electrocatalytic current was increased to 12mA, the product mass was 59.68mg and the yield was 86%. When the electrocatalytic current was further increased, the mass and yield of the product began to decrease again, and when the electrocatalytic current was increased to 20mA, the mass of the product was 47.90mg and the yield was 69%.
TABLE 2
EXAMPLE 43 preparation of chloro-6- (tosylmethyl) phenanthridine
Tetrabutylammonium tetrafluoroborate (26.3mg,0.08mmol), anhydrous potassium carbonate (41.4mg,0.3mmol), 4-methylbenzenesulfonylhydrazide (55.9mg,0.3mmol), 2- (1-azidovinyl) -4 '-chloro-1, 1' -biphenyl (51.1mg, 0.2mmol) were added to a 5mL reaction flask under nitrogen, the above substances were dissolved in 4mL of a mixed solvent of acetonitrile and water (acetonitrile/water volume ratio 18:1), a carbon electrode was used as a working electrode, a platinum sheet electrode was used as a counter electrode, and the reaction mixture was reacted at a constant current of 12 milliamps for 3 hours. After the reaction was completed, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, and the extracted and dried reaction solution was separated by column chromatography to obtain 57.9mg of a white solid, i.e., 57.9mg of 3-chloro-6- (tosylmethyl) phenanthridine, in a calculated yield of 76%. The resulting product has the following structural formula:
1H NMR(400MHz,CDCl3)8.55(d,J＝8.0Hz,1H),8.44(d,J＝8.6Hz,1H),8.35(d,J＝8.0Hz,1H),7.87(t,J＝7.3Hz,1H),7.76(dd,J＝19.0,11.5Hz,2H),7.64–7.49(m,3H),7.20(d,J＝7.4Hz,2H),5.12(s,2H),2.40(s,3H).13C NMR(100MHz,CDCl3)151.22,144.86,143.89,135.49,134.33,132.75,131.33,129.51,129.04,128.63,128.15,127.96,127.23,125.54,123.37,122.47,122.20,62.66,21.58。
EXAMPLE 53 preparation of methoxy-6- (tosylmethyl) phenanthridine
Tetrabutylammonium tetrafluoroborate (26.3mg,0.08mmol), anhydrous potassium carbonate (41.4mg,0.3mmol), 4-methylbenzenesulfonylhydrazide (55.9mg,0.3mmol), 2- (1-azidovinyl) -4 '-methoxy-1, 1' -biphenyl (50.2mg, 0.2mmol) were added to a 5mL reaction flask under nitrogen, the above substances were dissolved in 4mL of a mixed solvent of acetonitrile and water (acetonitrile/water volume ratio 18:1), a carbon electrode was used as a working electrode, a platinum sheet electrode was used as a counter electrode, and the reaction mixture was reacted at a constant current of 12 milliamps for 3 hours. After the reaction was completed, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, and the extracted and dried reaction solution was separated by column chromatography to obtain 64.8mg of a white solid, i.e., 64.8mg of 3-methoxy-6- (tosylmethyl) phenanthridine, with a calculated yield of 86%. The resulting product has the following structural formula:
1H NMR(400MHz,DMSO)8.71(d,J＝7.6Hz,1H),8.65(d,J＝8.5Hz,1H),8.38(d,J＝7.5Hz,1H),7.88(s,1H),7.64(d,J＝6.9Hz,3H),7.35(d,J＝6.9Hz,3H),7.26(s,1H),5.38(s,2H),3.90(s,3H),2.37(s,3H).13C NMR(101MHz,DMSO)160.22,151.12,144.98,144.84,136.76,133.19,131.60,130.02,128.67,128.08,126.89,126.01,124.82,124.45,122.43,118.77,117.97,109.94,61.78,55.91,21.49。
EXAMPLE 68 preparation of chloro-6- (tosylmethyl) phenanthridine
Tetrabutylammonium tetrafluoroborate (26.3mg,0.08mmol), anhydrous potassium carbonate (41.4mg,0.3mmol), 4-methylbenzenesulfonylhydrazide (55.9mg,0.3mmol), 2- (1-azidovinyl) -4-chloro-1, 1' -biphenyl (51.1mg, 0.2mmol) were added to a 5mL reaction flask under nitrogen, the above substances were dissolved in 4mL of a mixed solvent of acetonitrile and water (acetonitrile/water volume ratio 18:1), a carbon electrode was used as a working electrode, a platinum sheet electrode was used as a counter electrode, and the reaction mixture was reacted at a constant current of 12 milliamps for 3 hours. After the reaction was completed, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, and the extracted and dried reaction solution was separated by column chromatography to obtain 63.7mg of a white solid, i.e., 63.7mg of 8-chloro-6- (tosylmethyl) phenanthridine, with a calculated yield of 83%. The resulting product has the following structural formula:
1H NMR(400MHz,CDCl3)8.52(d,J＝8.4Hz,1H),8.47-8.46(m,1H),8.15(d,J＝1.2Hz,1H),7.91(d,J＝7.2Hz,1H),7.77-7.76(m,1H),7.71-7.67(m,2H),7.58(d,J＝8.0Hz,2H),7.20(d,J＝8.0Hz,2H),5.10(s,2H),2.39(s,3H)；13C NMR(100MHz,CDCl3)148.7,145.0,135.4,133.7,131.61,131.56,129.9,129.6,129.2,128.7,128.2,126.3,126.2,124.0,123.4,121.9,62.4,21.6。
example 79 preparation of methyl-6- (tosylmethyl) phenanthridine
Tetrabutylammonium tetrafluoroborate (26.3mg,0.08mmol), anhydrous potassium carbonate (41.4mg,0.3mmol), 4-methylbenzenesulfonyl hydrazide (55.9mg,0.3mmol), distyryl azide (47.1mg, 0.2mmol) were added to a 5mL reaction flask under nitrogen, 4mL of a mixed solvent of acetonitrile and water (acetonitrile to water volume ratio 18:1) was used to dissolve the above substances, a carbon electrode was used as a working electrode, a platinum sheet electrode was used as a counter electrode, and the reaction mixture was reacted at a constant current of 12 milliamps for 3 hours. After the reaction was completed, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, and the extracted and dried reaction solution was separated by column chromatography to obtain 57.0mg of a white solid, i.e., 57.0mg of 9-methyl-6- (tosylmethyl) phenanthridine, in a calculated yield of 79%. The resulting product has the following structural formula:
1H NMR(400MHz,CDCl3)8.54-8.51(m,1H),8.41(s,1H),8.24(d,J＝8.4Hz,1H),7.80-7.78(m,1H),7.66-7.62(m,2H),7.57-7.52(m,3H),7.17(d,J＝8.4Hz,2H),5.11(s,2H),2.64(s,3H),2.37(s,3H)；13C NMR(100MHz,CDCl3)149.6,144.6,143.5,141.5,135.5,133.3,129.8,129.4,128.7,128.5,127.3,126.9,123.9,123.8,121.94,121.89,62.7,22.3,21.5。
EXAMPLE 83 preparation of fluoro-6- (tosylmethyl) phenanthridine
Tetrabutylammonium tetrafluoroborate (26.3mg,0.08mmol), anhydrous potassium carbonate (41.4mg,0.3mmol), 4-methylbenzenesulfonylhydrazide (55.9mg,0.3mmol), 47.8mg (0.2mmol) of 2- (1-azidovinyl) -4 '-fluoro-1, 1' -biphenyl were added to a 5mL reaction flask under nitrogen, the above substances were dissolved in 4mL of a mixed solvent of acetonitrile and water (the volume ratio of acetonitrile to water was 18:1), a carbon electrode was used as a working electrode, a platinum sheet electrode was used as a counter electrode, and the reaction mixture was reacted under a constant current of 12 milliamps for 3 hours. After the reaction was completed, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, and the extracted and dried reaction solution was separated by column chromatography to obtain 60.6mg of a white solid, i.e., 60.6mg of 3-fluoro-6- (tosylmethyl) phenanthridine, with a calculated yield of 83%. The resulting product has the following structural formula:
1H NMR(400MHz,CDCl3)8.53(d,J＝8.4Hz,1H),8.49(dd,J＝6.0Hz,J＝9.0Hz,1H),8.34(d,J＝8.4Hz,1H),7.87-7.84(m,1H),7.72-7.70(m,1H),7.56(d,J＝8.4Hz,2H),7.46(dd,J＝3.0Hz,J＝9.0Hz,1H),7.42-7.38(m,1H),7.19(d,J＝8.4Hz,2H),5.12(s,2H),2.39(s,3H)；13CNMR(100MHz,CDCl3)162.5(d,J＝247.5Hz),151.2,144.8,144.4(d,J＝12.0Hz),135.5,132.9,131.3,129.5,128.6,127.5,127.2,125.2,124.0(d,J＝9.0Hz),122.1,120.7(d,J＝1.5Hz),116.7(d,J＝24.0Hz),114.2(d,J＝19.5Hz),62.6,21.6。
example preparation of 96- ((ethylsulfonyl) methyl) phenanthridine
To a 5ml reaction flask, tetrabutylammonium tetrafluoroborate (26.3mg,0.08mmol), anhydrous potassium carbonate (41.4mg,0.3mmol), ethanesulfonylhydrazide (37.2mg,0.3mmol), distyryl azide (44.2mg,0.2mmol), acetonitrile: the above-mentioned substance was dissolved in 4mL of a mixed solvent of acetonitrile and water (acetonitrile/water volume ratio: 18:1), and the reaction mixture was reacted for 3 hours under a constant current of 12mA using a carbon electrode as a working electrode and a platinum sheet electrode as a counter electrode. After the reaction was completed, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, and the extracted and dried reaction solution was separated by column chromatography to obtain 54.7mg of a white solid, i.e., 54.7mg of 6- ((ethylsulfonyl) methyl) phenanthridine, with a calculated yield of 96%. The resulting product has the following structural formula:
1H NMR(400MHz,CDCl3)8.66(d,J＝7.8Hz,1H),8.59(d,J＝7.8Hz,1H),8.39(d,J＝8.4Hz,1H),8.12(d,J＝8.4Hz,1H),7.89(t,J＝7.2Hz,1H),7.78-7.75(m,2H),7.72(t,J＝7.8Hz,1H),5.02(s,2H),3.21(q,J＝7.2Hz,2H),1.48(t,J＝7.2Hz,3H)；13C NMR(100MHz,CDCl3)150.4,143.3,133.3,131.2,129.9,128.9,127.9,127.8,127.1,125.6,124.3,122.4,122.1,58.2,46.6,6.5。
EXAMPLE 106 preparation of- ((((4-chlorophenyl) sulfonyl) methyl) phenanthridine
Tetrabutylammonium tetrafluoroborate (26.3mg,0.08mmol), anhydrous potassium carbonate (41.4mg,0.3mmol), 4-chlorobenzenesulfonyl hydrazide (61.5mg,0.3mmol), distyryl azide (44.2mg,0.2mmol) were added to a 5mL reaction flask under nitrogen, 4mL of a mixed solvent of acetonitrile and water (acetonitrile/water volume ratio 18:1) was used to dissolve the above substances, a carbon electrode was used as a working electrode, a platinum sheet electrode was used as a counter electrode, and the reaction mixture was reacted at a constant current of 12 milliamps for 3 hours. After the reaction, the aqueous phase was extracted with dichloromethane, the organic phase was dried with anhydrous sodium sulfate, and the extracted and dried reaction solution was separated by column chromatography to obtain 62.4mg of a white solid, i.e., 62.4mg of 6- ((((4-chlorophenyl) sulfonyl) methyl) phenanthridine, in a calculated yield of 85%, the obtained product had the following structural formula:
1H NMR(400MHz,CDCl3)8.67(d,J＝8.4Hz,1H),8.58-8.56(m,1H),8.36(d,J＝8.4Hz,1H),7.92-7.89(m,1H),7.80-7.76(m,2H),7.70-7.69(m,2H),7.59-7.57(m,2H),7.37-7.35(m,2H),5.17(s,2H)；13C NMR(100MHz,CDCl3)149.4,143.2,140.5,136.7,133.2,131.1,130.3,129.8,129.1,128.9,127.9,127.8,126.9,125.5,124.0,122.4,122.0,62.4。
although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A method for preparing 6- (sulfonyl methyl) phenanthridine compounds is characterized in that the general formula of the synthetic method is as follows:
in the formula R1Is halogen, alkoxy, alkyl aryl, aliphatic radical, hydrogen; r2Is alkyl, phenyl substituted with a substituent which is alkyl or halogen; rt means room temperature; C-Pt refers to the electrode, carbon electrode for anode, and platinum electrode for cathode.
2. The method of claim 1, wherein the steps of the method of making comprise:
(1) in a nitrogen atmosphere, mixing an olefin azide compound (1), a sulfonyl hydrazine compound (2) and potassium carbonate in a molar ratio of 1: 1-1.5: 1-1.5, adding the mixture into a reaction bottle, and adding electrolyte [ n-Bu4N]BF4Then adding a mixed solution of acetonitrile and water, wherein the volume ratio of the acetonitrile to the water is (15-20) to 1;
(2) and (2) stirring the mixture in the step (1) to dissolve the mixture, inserting two electrodes, electrifying the graphite electrode for the anode and the platinum electrode for the cathode for 10-16 mA for 3-5h, adding water to the mixture after the reaction is finished, stirring, extracting, drying and purifying to obtain the 6- (sulfonyl methyl) phenanthridine compound (3).
3. The process according to claim 1 or 2, characterized in that the alkene azide compound (1) is: one of 2- (1-azidovinyl) -1,1' -biphenyl, 2- (1-azidovinyl) -4' -chloro-1, 1' -biphenyl, 2- (1-azidovinyl) -4' -methoxy-1, 1' -biphenyl, 2- (1-azidovinyl) -4' -fluoro-1, 1' -biphenyl, 2- (1-azidovinyl) -5-chloro-1, 1' -biphenyl, 2- (1-azidovinyl) -4-methyl-1, 1' -biphenyl; the sulfonyl hydrazide compound (2) is as follows: 4-methylsulfonylphenylhydrazine, 4-chlorosulfonylphenylhydrazine and ethylsulfonylphenylhydrazine.
4. The method according to claim 1 or 2, wherein the 6- (sulfonylmethyl) phenanthridine compound (3) has a compound structural formula:
5. The process according to claim 1 or 2, characterized in that in the synthesis process acetonitrile and water are mixed in a volume ratio of 18: 1.
6. According to claim 2The method is characterized in that the concentration of the olefin azide compound (1) in the synthesis method is 2mol/L, [ n-Bu ]4N]BF4The concentration of (2) is 0.1 mol/L.
7. The method according to claim 2, characterized in that the electrochemical reaction conditions in the synthesis process are: the energization current was 12mA, energization was carried out for 3 hours, and the reaction temperature was 30 ℃.
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