CN109651209B - Method for preparing (E) -1-phenyl-4-sulfonyl butyl-1-alkene compound by activating carbon-carbon sigma-bond - Google Patents
Method for preparing (E) -1-phenyl-4-sulfonyl butyl-1-alkene compound by activating carbon-carbon sigma-bond Download PDFInfo
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Abstract
The invention disclosesA composition ofE) The synthesis process of (E) -1-phenyl-4-sulfonyl butane-1-ene compound with methylene cyclopropane compound and organic sulfonate compound as material and in oxidant K2S2O8And a certain amount of water to prepare a compound having various substituentsE) -1-phenyl-4-sulfonylbut-1-enes. The method does not need to use transition metal and/or alkali, is economic and environment-friendly, and has the advantages of easily available raw material sources, simple process route, mild reaction conditions, low process cost, wide substrate application range and high yield of target products.
Description
Technical Field
The application belongs to the technical field of organic synthesis, and particularly relates to a method for preparing (E) -1-phenyl-4-sulfonyl butan-1-ene compounds by activating carbon-carbon sigma-bonds.
Background
Carbon-carbon sigma-bonds are a common class of chemical bonds with high stability. Recently, activation of carbon-carbon sigma bonds has become a useful strategy for simple construction of complex molecular frameworks, and many excellent carbon-carbon sigma-bond activation transformations have been developed to construct new carbon-carbon or carbon-hybrid bonds. Recently, various effective carbon-carbon sigma-bond activation strategies have been developed, including halogenation, oxidative cleavage, and cleavage of functional substrates bearing ester, carboxyl, carbonyl, hydroxyl, cyano, or oxime groups. Most of these reactions require the use of transition metals such as Ir, Pd, Ru, Rh, and Cu (see, for example, SYNLETT 2003, number 13, pp 2080-2082). However, it would be highly desirable if these transformations could be achieved without the transition metals, which would provide a simpler and more environmentally friendly option.
The organic sulfonic acid sodium salt is widely used in organic synthesis and pharmaceutical synthesis as a highly active salt which is easily available. Thus, a series of interesting transformations were developed by using organic sulfonic acid sodium salts as sulfonyl or hydrocarbyl sources. Recently, many chemists have proposed a number of sulfonylation methods for cross-coupling reactions and bifunctional reactions by using organic sulfonic acid sodium salts as the sulfonyl source. In 2011, Maloney and colleagues reported a cross-coupling reaction between chloropyridine and sodium sulfonate for the construction of sulfonylated bipyrimidines (see, e.g., k. -m. Maloney, j. Kuethe, k. linn, org. lett. 2011, 13, 102). For coupling to C-H, various C-H bonds, including C (sp) -H bonds (see, e.g., j. Yang, y. -y. Liu, r. -j. Song, z. -H. Peng, j. -H. Li, adv. synth.cat. 2016, 358, 2286), C (sp 2) -H bonds (see, e.g., f. Wang, x. -z. Yu, z. -s. Qi, x. -w.li, chem. eur. j. 2016, 22, 511.) and C (sp 3) -H bonds (see, e.g., w. -H. Rao, b. -b. Zhan, k. Chen, p. -x. Ling, z. -z. Zhang, b. -f. Shi, org. lett. 2015, 17, 3552) can be successfully cross-coupled. The Kuhakarn group proposed a cross-coupling sulfonylation reaction of aryl acetylenes (C (sp) -H bonds) with sodium sulfonate. Li and coworkers developed Rh catalyzed cross-coupling reactions between the C (sp 2) -H bonds of aromatic hydrocarbons and sodium sulfonate. The group of Shi described a palladium-catalyzed cross-coupling sulfonylation of C (sp 3) -H bonds with sodium sulfonate. Interestingly, the sodium salt of the organosulfonic acid can also be used for sulfonylation and bifunctional of the unsaturated bonds, including carbon-carbon double bonds and carbon-carbon triple bonds. In 2016, his group introduced 1, 2-difunctionalization of alkynes with sodium sulfonate and water without transition metals and additives. The Li research group reported 1, 2-bifunctional synthesis of alpha-sulfonylethaneoximes of alkenes with tert-butyl nitrite and sodium sulfonate. However, the reaction of saturated carbon-carbon sigma-bonds with sodium salts of organic sulfonic acids has not been disclosed in the prior art.
Ternary carbocyclic compounds, in particular Methylenecyclopropane Compounds (MCPs), which are highly reactive and of readily available structure, are often used as important starting materials in organic synthesis. In this context, we have developed a novel synthesis strategy for the selective synthesis of (E) -1-phenyl-4-sulfonylbut-1-ene compounds by carbon-carbon sigma-bond bifunctional in methylenecyclopropane, reaction with an organic sulfonic acid sodium salt compound and water without the need to use transition metals and bases.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for selectively synthesizing (A) by taking methylene cyclopropane compounds as starting materials and activating double functionalization through carbon-carbon sigma-bonds under the condition of not needing transition metals and alkaliE) A novel process for producing (E) -1-phenyl-4-sulfonylbut-1-enes.
The invention provides aE) -1-phenyl-4-sulfonylbut-1-enes, characterized in that it comprises the following steps:
in a Schlenk tube sealing reactor, methylene cyclopropane compounds shown in formula I and organic radical sulfonate compounds shown in formula II are used as reaction raw materials, a certain amount of water, an oxidant and an organic solvent are added, the mixture is heated and stirred for reaction, and after the reaction is monitored by TLC or GC-MS to be finished, the (C) shown in formula III is obtained through post-treatmentE) -1-phenyl-4-sulfonylbut-1-enes.
Wherein, in formula I, formula II and/or formula III, R1Represents one or more substituents on the attached phenyl ring selected from hydrogen, C1-C20Alkyl of (C)1-C20Alkoxy group of (C)1-C20Alkylthio of, C6-C20Aryl of (C)3-C20Heteroaryl of (A), C3-C20Cycloalkyl of, C6~C20aryl-C1~C20Alkyl radical, C6~C20aryl-C1~C20Alkoxy, nitro, halogen, -OH, -SH, -CN, -COOR4、-COR5、-OCOR6、-NR7R8(ii) a Wherein R is4、R5、R6、R7、R8Each independently selected from hydrogen and C1-C20Alkyl of (C)6-C20Aryl of (C)3-C20Any one or more of cycloalkyl groups of (a).
R2Selected from hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C20Aryl of (C)6~C20aryl-C1~C20An alkyl group; wherein the substituted or unsubstituted substituent is selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl group, halogen-NO2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a), -NMe2。
R3Selected from substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C3-C20The heteroaryl group of (a); wherein the substituted or unsubstituted substituent is selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a), -NMe2。
It will be understood by those skilled in the art that the number of substituents in the expression "substituted or unsubstituted" as referred to in any of the above description of the invention may be one or more, for example two, three, four, five; when two or more substituents are present, the substituents can then be selected independently of one another from the substituent definitions given above. The heteroaryl group has a definition well known in the art and the heteroatom may be selected from heteroatom species such as O, S, N, etc., such that the heteroaryl group may be selected from, for example, furyl, pyridyl, thienyl, quinolyl, etc.
Preferably, R in formula I, formula II and/or formula III1Represents one or more substituents on the attached phenyl ring selected from hydrogen, C1-C6Alkyl of (C)1-C6Alkoxy group of (C)6-C14Aryl of (C)6~C14aryl-C1~C6Alkyl radical, C6~C14aryl-C1~C6Alkoxy, nitro, halogen, -OH, -SH, -CN, -COOR4、-COR5、-OCOR6、-NR7R8(ii) a Wherein R is4、R5、R6、R7、R8Each independently selected from hydrogen and C1-C6Alkyl of (C)6-C14Any one of the aryl groups of (1).
R2Selected from hydrogen, substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C6-C14Aryl of (C)6~C14aryl-C1~C6An alkyl group; wherein the substituted or unsubstituted substituent is selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C14Aryl of (C)3-C6Cycloalkyl of (a), -NMe2。
R3Selected from substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C6-C14Aryl, substituted or unsubstituted C3-C14The heteroaryl group of (a); wherein the substituted or unsubstituted substituent is selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a), -NMe2。
Most preferably, the compound of formula I is selected from compounds represented by the following structures I-1 to I-17:
the compound of formula II is selected from: sodium trifluoromethanesulfonate, sodium benzenesulfonate, sodium p-methoxybenzenesulfonate, sodium p-methylbenzenesulfonate, sodium p-fluorobenzenesulfonate, sodium p-chlorobenzenesulfonate, sodium p-bromobenzenesulfonate, sodium p-trifluoromethylbenzenesulfonate, sodium p-cyanobenzenesulfonate, sodium p-nitrobenzenesulfonate, sodium m-methylbenzenesulfonate, sodium 2,4, 6-trimethylbenzenesulfonate, sodium 2-naphthalenesulfonate, sodium benzylsulfonate, sodium 2-thiophenesulfonate, sodium methanesulfonate.
The method according to the present invention, wherein the oxidant is K2S2O8。
According to the aforementioned method of the present invention, the reaction is carried out under an inert atmosphere or an air atmosphere, preferably under an inert atmosphere (argon). By inert atmosphere is understood an atmosphere inert to the reaction and not mechanically considered an inert gas. For those skilled in the art, the inert atmosphere commonly used for organic reactions may be selected from an argon atmosphere or a nitrogen atmosphere. An argon atmosphere is preferred.
According to the method of the present invention, the organic solvent is selected from any one of toluene, tetrahydrofuran, 1, 4-dioxane, and acetonitrile. Preferably, the organic solvent is toluene. The amount of organic solvent used may be determined by those skilled in the art depending on the actual reaction.
According to the aforementioned method of the present invention, the reaction temperature of the heating and stirring reaction is 40 to 120 ℃, preferably 60 to 100 ℃, and most preferably 80 ℃. The reaction time is 12-72 hours, preferably 24-48 hours.
According to the aforementioned method of the invention, wherein the compound of formula I, the compound of formula II, the oxidizing agent (K)2S2O8) The molar ratio of water is 1 (1-3) to (2-8), preferably, the compound of formula I, the compound of formula II and the oxidant (K)2S2O8) The molar ratio of water is 1:2:2: 4.
The aforementioned reaction according to the present invention, wherein the post-treatment operation is as follows: and (3) concentrating the mixed solution after the reaction is finished under reduced pressure to obtain a residue, and separating the residue by using column chromatography to obtain the target product shown in the formula III, wherein the eluent separated by using the column chromatography is the mixed solution of normal hexane and ethyl acetate.
The invention has the following beneficial effects:
(1) the invention provides a method for preparing (III) shown in formula by taking methylene cyclopropane compound shown in formula I and organic sulfonate compound shown in formula II as reaction raw materialsE) A synthetic route of the 1-phenyl-4-sulfonyl butyl-1-alkene compound, and the synthetic method is not reported in the prior art;
(2) the method does not need to use transition metal and/or alkali, is economic and environment-friendly, and has the advantages of easily available raw material sources, simple process route, mild reaction conditions, low process cost, wide substrate application range and high yield of target products.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Examples 1-17 optimization of reaction conditions
The compound shown in the formula I-1 and the sodium trifluoromethanesulfonate shown in the formula II-1 are used as reaction raw materials, the influence of different reaction conditions on the optimization result of the synthesis process is discussed, and representative examples 1-17 are selected. The results are shown in table one.
A typical experimental procedure for example 1 is as follows:
to a schlenk closed tube reactor was added a compound represented by formula I-1 (0.2mmol), sodium trifluoromethanesulfonate represented by formula II-1 (2 equiv., 0.4mmol), and an oxidizing agent (K)2S2O82 eq, 0.4mmol), H2O (4 equivalent, 0.6mmol) and toluene (2 mL), then stirring and reacting for 48 hours under the condition of argon protection and 80 ℃, monitoring the completion of the reaction by TLC or GC-MS, removing the solvent by reduced pressure distillation, and separating the residue by column chromatography (the eluent is n-hexane/ethyl acetate) to obtain the target product of the formula III-1 with the yield of 82%;1H NMR (400 MHz, CDCl3) : 7.44-7.32 (m, 6H), 7.20 (t,J= 7.6 Hz, 1H), 6.96-6.87 (m, 3H), 6.20-6.12 (m, 1H), 5.10 (s, 2H), 4.48-4.42(m, 1H), 4.25-4.19 (m, 1H), 2.70-2.65 (m, 2H);13C NMR (100 MHz, CDCl3) :155.6, 137.0, 128.6, 128.6, 128.6, 127.9, 127.3, 126.8, 126.2, 124.1, 122.9(d,J= 336.9 Hz), 121.0, 112.4, 70.3, 68.1, 33.8;19F NMR (282 MHz, CDCl3) :-78.3 (s, 1F);
table one:
the specific operations and parameters of examples 2-17 were the same as in example 1, except that the variables listed in Table one above were different from those of example 1.
As can be seen from the above examples 1-17, the optimum reaction conditions are those of example 1. The inventors further prepared various target compounds of formula III (examples 18-34) by extending the reaction substrate under the reaction conditions of example 1.
| Formula I | Formula II | Formula III | |
| 18 |
 |
CF3SO2Na | The yield is 88%;1H NMR (500 MHz, CDCl3): 6.96 (s, 1H), 6.83-6.75 (m, 3H), 6.17-6.10 (m, 1H), 4.49- 4.45 (m, 1H), 4.26-4.23 (m, 1H), 3.80 (s, 3H), 3.79 (s, 3H), 2.72-2.66 (m, 2H). |
| 19 |
 |
CF3SO2Na | the yield is 82%;1H NMR (500 MHz, CDCl3): 7.23 (t, J = 8.0 Hz, 1H), 6.95 (d, J = 7.6 Hz, 1H), 6.89 (s, 1H), 6.80 (t, J = 8.0 Hz, 1H), 6.49 (t, J = 16.0 Hz, 1H), 6.17-6.10 (m, 1H), 4.50-4.44 (m, 1H), 4.27-4.21 (m, 1H), 3.82 (s, 3H), 2.70-2.64 (m, 2H). |
| 20 |
 |
CF3SO2Na | the yield is 78%;1H NMR (500 MHz, CDCl3): 7.41-7.39 (m, 1H), 7.17-7.15 (m,3H),6.73 (d, J = 16.0 Hz, 1H), 6.04-5.97 (m, 1H), 4.51- 4.46 (m, 1H), 4.28-4.23 (m, 1H), 2.72-2.67 (m, 2H), 2.33 (s, 3H). |
| 21 |
 |
CF3SO2Na | the yield is 90%;1H NMR (500 MHz, CDCl3): 7.61-7.55(m,4H),7.46-7.41(m, 4H),7.36-7.32 (m, 1H), 6.55 (d, J = 16.0 Hz, 1H),6.22-6.14(m, 1H),4.52-4.46(m, 1H), 4.28-4.22 (m, 1H), 2.72-2.67 (m, 2H). |
| 22 |
 |
CF3SO2Na | the yield is 85%;1H NMR (500 MHz, CDCl3): 7.28-7.26(m,4H),6.49-6.45(m, 1H),6.16-6.08 (m, 1H), 4.51- 4.45 (m, 1H), 4.27-4.22 (m, 1H), 2.70-2.64 (m, 2H). |
| 23 |
 |
CF3SO2Na | the yield is 76%;1H NMR (500 MHz, CDCl3): 7.11 (d,J=8.4Hz,1H),7.03(d,J= 8.4 Hz, 1H), 6.89(t,J=8.4Hz, 1H),6.41(d,J= 15.6 Hz, 1H), 6.04-5.96 (m, 1H), 4.48-4.44 (m, 1H),4.24-4.22(m,1H),3.89(s, 3H), 2.68-2.63 (m, 2H). |
| 24 |
 |
CF3SO2Na | the yield is 65%;1H NMR (500 MHz, CDCl3): 7.36-7.30(m,4H),7.25-7.22(m, 1H),6.52 (d, J = 15.6 Hz, 1H), 6.18-6.10 (m, 1H),4.50-4.44(m, 1H),4.27-4.21(m, 1H), 2.70-2.65 (m, 2H). |
| 25 |
 |
CF3SO2Na | the yield is 90%;1H NMR (500 MHz, CDCl3): 7.41-7.33(m,3H),7.28-7.21(m, 5H),7.16 (d, J = 6.4 Hz, 2H), 6.05 (t, J = 7.6 Hz,1H),4.44- 4.38(m,1H),4.20-4.15 (m, 1H), 2.61-2.56 (m, 2H). |
| 26 |
 |
CF3SO2Na | the yield is 84%;1H NMR (500 MHz, CDCl3): 7.12 (d,J=8.0Hz,2H),7.05-6.96 (m,6H), 5.97 (t, J = 7.2 Hz, 1H), 4.42-4.37 (m, 1H),4.19- 4.14(m,1H),2.61-2.56(m, 2H), 2.39 (s, 3H), 2.32 (s, 3H). |
| 27 |
 |
CF3SO2Na | the yield is 90%;1H NMR (500 MHz, CDCl3): 7.16-7.14(m,2H),7.09-7.07(m, 2H),6.93-6.90 (m, 2H), 6.83- 6.79 (m, 2H), 5.89 (t,J=7.6Hz, 1H),4.42-4.37(m,1H), 4.19-4.14 (m, 1H), 3.83 (s, 3H), 3.78 (s, 3H),2.61-2.56(m,2H). |
| 28 |
 |
CF3SO2Na | the yield is 81%;1H NMR (500 MHz, CDCl3): 7.39-7.36(m,2H),7.28(s,1H), 7.26-7.24 (m, 1H), 7.14-7.08 (m, 4H), 6.03 (d, J=7.6Hz,1H), 4.46-4.40(m,1H),4.20-4.15 (m, 1H), 2.59-2.54 (m, 2H). |
| 29 |
 |
benzenesulfinic acid sodium salt | The yield is 80%;1H NMR (500 MHz, CDCl3): 7.70-7.68(m,2H),7.54-7.48(m, 3H),7.14-7.11 (m, 2H), 7.03- 7.00 (m, 2H), 6.89-6.86(m,2H), 6.81-6.78(m,2H),5.84 (t, J = 7.6 Hz, 1H), 4.12-4.06 (m, 1H), 3.89(s,3H),3.83(s,3H),3.71-3.65 (m, 1H), 2.47-2.42 (m, 2H). |
| 30 |
 |
p-methoxybenzylidene Sodium sulfonate | The yield is 87%;1H NMR (500 MHz, CDCl3): 7.81 (d,J=8.8Hz,2H),7.07(d,J= 8.8 Hz, 2H), 7.00(d,J=8.4Hz, 2H),6.95(d,J= 9.2 Hz, 2H), 6.87 (d, J = 8.8 Hz, 2H), 6.78 (d,J= 8.8Hz,2H),5.76(t,J=7.2 Hz, 1H), 4.06(t,J=6.8Hz,2H),3.86(s,3H), 3.83 (s, 3H), 3.79 (s, 3H), 2.46-2.41 (m, 2H). |
| 31 |
 |
p-fluorobenzene sulfinic acid Sodium salt | The yield is 90%;1H NMR (500 MHz, CDCl3): 7.84-7.80 (m, 2H), 7.17 (t, J = 8.8 Hz, 2H), 7.07 (d, J = 8.8 Hz, 2H), 6.95 (d, J = 8.4 Hz, 2H), 6.83 (d, J = 8.8 Hz, 2H), 6.78 (d, J = 8.8 Hz, 2H), 5.81 (t, J = 7.2 Hz, 1H), 3.84 (s, 3H), 3.78 (s, 3H), 3.17-3.13 (m, 2H), 2.52-2.47 (m, 2H). |
| 32 |
 |
p-nitrophenylsulfino Sodium salt | The yield is 75%;1H NMR (500 MHz, CDCl3): 8.32 (d, J = 8.4 Hz, 2H), 7.86 (d, J = 8.4 Hz, 2H), 7.11 (d, J = 8.4 Hz, 2H), 7.01 (d, J = 8.4 Hz, 2H), 6.88 (d, J = 8.4 Hz, 2H), 6.80 (d, J = 8.4 Hz, 2H), 5.79 (t, J = 7.6 Hz, 1H), 4.17- 4.11 (m, 1H), 3.83 (s, 3H), 3.8-3.72 (m, 4H), 2.50-2.44 (m, 2H). |
| 33 |
 |
2,4, 6-trimethyl Benzenesulfinic acid sodium salt | The yield is 80%;1H NMR (500 MHz, CDCl3): 7.07 (d, J = 8.8 Hz, 2H), 7.00 (d, J = 8.8 Hz, 2H), 6.93 (s, 2H), 6.86 (d, J = 8.4 Hz, 2H), 7.78 (d, J = 8.8 Hz, 2H), 5.78 (t, J = 7.6 Hz, 1H), 4.00 (t, J = 6.8 Hz, 2H), 3.83 (s, 3H), 3.78 (s, 3H), 2.60 (s, 6H), 2.48-2.43 (m, 2H), 2.30 (s, 3H). |
| 34 |
 |
2-Naphthalenesulfinic acid sodium salt | The yield is 85%;1H NMR (500 MHz, CDCl3): 8.48 (s, 1H), 7.97-7.91 (m, 3H), 7.83 (d, J = 8.8 Hz, 1H), 7.69-7.63 (m, 2H), 7.01-6.94 (m, 4H), 6.84-6.81 (m, 2H), 6.75-6.71 (m, 2H), 5.73 (t, J = 7.6 Hz, 1H), 4.13 (t, J = 6.4 Hz, 2H), 3.81 (s, 3H), 3.78 (s, 3H), 2.48-2.43 (m, 2H). |
the embodiments described above are only preferred embodiments of the invention and are not exhaustive of the possible implementations of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.
Claims (13)
1. Preparation of carbon-carbon sigma bond by activationE) -1-phenyl-4-sulfonylbut-1-enes, characterized in that it comprises the following steps:
in a Schlenk tube sealing reactor, methylene cyclopropane compounds shown in formula I and organic sodium sulfinate compounds shown in formula II are used as reaction raw materials, a certain amount of water, an oxidant and an organic solvent are added, the mixture is heated and stirred for reaction, and after the reaction is monitored by TLC or GC-MS, the product (A) shown in formula III is obtained by post-treatmentE) -1-phenyl-4-sulfonylbut-1-enes;
wherein, in formula I, formula II and/or formula III, R1Represents one or more substituents on the attached phenyl ring selected from hydrogen, C1-C20Alkyl of (C)1-C20Alkoxy group of (C)1-C20Alkylthio of, C6-C20Aryl of (C)3-C20Heteroaryl of (A), C3-C20Cycloalkyl of, C6~C20aryl-C1~C20Alkyl radical, C6~C20aryl-C1~C20Alkoxy, nitro, halogen, -OH, -SH, -CN, -COOR4、-COR5、-OCOR6、-NR7R8(ii) a Wherein R is4、R5、R6、R7、R8Each independentlySelected from hydrogen, C1-C20Alkyl of (C)6-C20Aryl of (C)3-C20Any one or more of cycloalkyl groups of (a);
R2selected from hydrogen, substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C20Aryl of (C)6~C20aryl-C1~C20An alkyl group; wherein the substituted or unsubstituted substituent is selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a), -NMe2；
R3Selected from substituted or unsubstituted C1-C20Alkyl, substituted or unsubstituted C6-C20Aryl, substituted or unsubstituted C3-C20The heteroaryl group of (a); wherein the substituted or unsubstituted substituent is selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a), -NMe2；
Wherein the oxidant is K2S2O8。
2. The method of claim 1, wherein R is selected from the group consisting of formula I, formula II, and formula III1Represents one or more substituents on the attached phenyl ring selected from hydrogen, C1-C6Alkyl of (C)1-C6Alkoxy group of (C)6-C14Aryl of (C)6~C14aryl-C1~C6Alkyl radical, C6~C14aryl-C1~C6Alkoxy, nitro, halogen, -OH, -SH, -CN, -COOR4、-COR5、-OCOR6、-NR7R8(ii) a It is composed ofIn, R4、R5、R6、R7、R8Each independently selected from hydrogen and C1-C6Alkyl of (C)6-C14Any one of the aryl groups of (a);
R2selected from hydrogen, substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C6-C14Aryl of (C)6~C14aryl-C1~C6An alkyl group; wherein the substituted or unsubstituted substituent is selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C14Aryl of (C)3-C6Cycloalkyl of (a), -NMe2；
R3Selected from substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C6-C14Aryl, substituted or unsubstituted C3-C14The heteroaryl group of (a); wherein the substituted or unsubstituted substituent is selected from C1-C6Alkyl of (C)1-C6Alkoxy group of (C)1-C6Acyl, halogen, -NO of2、-CN、-OH、C6-C20Aryl of (C)3-C6Cycloalkyl of (a), -NMe2。
3. The method of any one of claims 1-2, wherein the compound of formula I is selected from the group consisting of compounds represented by the following structures I-1 to I-22:
4. the method of any one of claims 1-2, wherein the compound of formula II is selected from the group consisting of sodium trifluoromethanesulfonie, sodium benzene sulfinate, sodium p-methoxybenzene sulfinate, sodium p-methylbenzene sulfinate, sodium p-fluorobenzene sulfinate, sodium p-chlorobenzene sulfinate, sodium p-bromobenzene sulfinate, sodium p-trifluoromethylbenzene sulfinate, sodium p-cyanobenzene sulfinate, sodium p-nitrobenzene sulfinate, sodium m-methylbenzene sulfinate, sodium 2,4, 6-trimethylbenzene sulfinate, sodium 2-naphthalene sulfinate, sodium benzyl sulfinate, sodium 2-thiophenedisulfite, and sodium methanesulfinate.
5. The method of any one of claims 1-2, wherein the reaction is performed under an inert atmosphere or an air atmosphere.
6. The method of synthesis according to claim 5, wherein the reaction is carried out under an argon atmosphere.
7. The synthesis method according to any one of claims 1 to 2, wherein the organic solvent is selected from any one of toluene, tetrahydrofuran, 1, 4-dioxane and acetonitrile.
8. The method of claim 7, wherein the organic solvent is toluene.
9. The synthesis method according to any one of claims 1 to 2, wherein the reaction temperature of the heating and stirring reaction is 40 to 120 ℃; the reaction time of the reaction is 12 to 72 hours.
10. The synthesis method of claim 9, wherein the reaction temperature of the heating stirring reaction is 80 ℃; the reaction time is 24-48 hours.
11. The method of any one of claims 1-2, wherein the compound of formula I, the compound of formula II, the oxidant K2S2O8The molar ratio of water is 1 (1-3) to (2-8).
12. According to claim11, the synthesis method is characterized in that the compound of the formula I, the compound of the formula II and an oxidant K2S2O8The molar ratio of water is 1:2:2: 4.
13. The synthesis method according to any one of claims 1 to 2, characterized in that the post-treatment operation is as follows: and (3) concentrating the mixed solution after the reaction is finished under reduced pressure to obtain a residue, and separating the residue by using column chromatography to obtain the target product shown in the formula III, wherein the eluent separated by using the column chromatography is the mixed solution of normal hexane and ethyl acetate.
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