CN111848467A - Preparation method of asymmetric organic persulfate compound - Google Patents

Preparation method of asymmetric organic persulfate compound Download PDF

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CN111848467A
CN111848467A CN202010648947.9A CN202010648947A CN111848467A CN 111848467 A CN111848467 A CN 111848467A CN 202010648947 A CN202010648947 A CN 202010648947A CN 111848467 A CN111848467 A CN 111848467A
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ethyl acetate
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潘远江
王敦盖
高展
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Zhejiang University ZJU
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Abstract

The invention discloses a preparation method of an asymmetric organic persulfate compound, which comprises the following steps: under the catalysis of alkali, the compound of formula (II), the compound of formula (III) and sodium thiosulfate are reacted in a solvent by a one-pot method to obtain the asymmetric organic persulfate compound shown in formula (I). The preparation method disclosed by the invention is mild in reaction conditions, simple to operate and high in yield; and can realize the over-sulfuration modification of molecules of natural products such as quinolinone, coumarin, glucose and the like.

Description

Preparation method of asymmetric organic persulfate compound
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of an asymmetric organic persulfate compound.
Background
The asymmetric organic persulfuric compound is a compound containing a persulfur bond (S-S), is named due to different groups at two ends of the persulfur bond, and is a sulfur-containing organic substance with great application prospect.
In the field of natural products, polythiodiketopiperazines and derivatives thereof (ETPs) are prominent representatives of asymmetric organic persulfur compounds, more than 126 ETPs have been found and their good anti-inflammatory and antibacterial effects have been confirmed.
In clinical medicine, asymmetric organic peroxy compounds have been used as drugs. Such as propanethiamine, furanthiamine for the treatment of vitamin B1 deficiency; romidepsin for treating malignant tumor.
In addition, in a living body, the persulfate bond plays an essential role in the formation and stabilization of proteins. Meanwhile, the asymmetric organic persulfate compound is also an important carrier for researching drug delivery and slow release. As such, chemists have increased the research effort in recent years for the preparation of asymmetric organic peroxy compounds.
At present, the method for preparing the asymmetric organic persulfate compound comprises the following steps:
(1) different types of thiophenol derivatives directly form S-S bonds through nucleophilic substitution reaction in which bimolecules participate. The method needs to pre-modify the thiophenol, and has complex steps and complex system.
(2) Different thiophenols are used for preparing the asymmetric organic persulfur compound through cross coupling reaction. The method uses thiophenol, which can generate offensive odor which is difficult to avoid, and the self-coupling of the thiophenol is difficult to avoid.
(3) Publication No. CN106278965A discloses a cross-coupling reaction involving an over-sulfurizing reagent. The method prepares the asymmetric organic persulfate compound by preparing a substrate with an S-S bond in advance and then constructing the S-C bond under the action of a heavy metal catalyst. In this strategy, the preparation of the over-sulfurizing reagent is extremely cumbersome.
In addition, the Chinese patent application with publication No. CN104387303A discloses a sulfur redox mechanism using sodium sulfinate, halohydrocarbon and Na2S2O3The method for preparing the aryl-aryl, aryl-alkyl and alkyl-alkyl asymmetric persulfuric compounds by reacting raw materials without the action of transition metal is complex in system, high in material ratio of raw materials of sodium thiosulfate, halogenated hydrocarbon and sodium sulfinate, incapable of realizing one-pot reaction and complex in operation, and the reaction solvent is a mixed solution of an organic solvent and water, and incapable of realizing the oversulfurization modification of glycosyl.
The above methods suffer from a number of disadvantages: including strong toxicity or corrosivity of reagents used in the reaction, difficult acquisition of raw materials, strict requirements on reaction process, high production cost, environmental pollution and the like. Therefore, there is a need to develop new methods for preparing asymmetric organic persulfate compounds.
Disclosure of Invention
The invention provides a preparation method of an asymmetric organic persulfate compound, which is characterized in that thioacetate, sodium thiosulfate and halohydrocarbon are used as raw materials, the asymmetric organic persulfate compound is prepared by a one-pot method, the operation is simple, the reaction solvent is water, and the over-vulcanization modification of natural products such as sugar is realized.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of an asymmetric organic persulfate compound comprises the steps of carrying out one-pot reaction on a compound of a formula (II), a compound of a formula (III) and sodium thiosulfate in a solvent under the catalysis of alkali to obtain the asymmetric organic persulfate compound shown in the formula (I);
Figure BDA0002573597300000021
wherein the content of the first and second substances,
n is 1, 2, 3, 4 or 5;
m is 1, 2, 3, 4 or 5;
L1is-CH2-or a single bond, when L1is-CH2When the pressure in the air is higher than the preset pressure,
Figure BDA0002573597300000022
different;
ring A is C6～12A meta-aryl group, a 5-to 12-membered heteroaryl group or a 5-to 10-membered heterocycloalkyl group;
x is F, Cl, Br or I;
R1are respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -C1～5Alkyl, -C (═ O) -O-C1～5Alkyl or-O-C (═ O) -C1～5Alkyl radical, said C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -C1～5Alkyl, -C (═ O) -O-C1～5Alkyl or-O-C (═ O) -C1～5Alkyl is optionally substituted by 1, 2 or 3RaSubstitution;
or, two R1Taken together and bound to the phenyl group to which it is attached to form a naphthyl, anthryl or phenanthryl group;
R2are respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -C1～5Alkyl, -C (═ O) -O-C1～5Alkyl or-O-C (═ O) -C1～5Alkyl radical, said C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -C 1～5Alkyl, -C (═ O) -O-C1～5Alkyl or-O-C (═ O) -C1～5Alkyl is optionally substituted by 1, 2 or 3RbSubstitution;
said RaAre respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、CH3Or CF3；
Said RbAre respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、CH3Or CF3。
The compound of formula (II) is hydrolyzed in an aqueous alkali solution to the sulfide anion S-and at the same time, the compound of formula (III) is reacted with sodium thiosulfate to produce a Bunte salt intermediate, and the sulfide anion S-attacks the Bunte salt intermediate, thereby obtaining the compound of formula (I).
Figure BDA0002573597300000031
The ring A is
Figure BDA0002573597300000032
The structural unit
Figure BDA0002573597300000033
Figure BDA0002573597300000034
Said R1Are respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、C1～4Alkyl radical, C1～4Alkoxy, -C (═ O) -C1～3Alkyl, -C (═ O) -O-C1～3Alkyl or-O-C (═ O) -C1～3Alkyl radical, said C1～4Alkyl radical, C1～4Alkoxy, -C (═ O) -C1～3Alkyl, -C (═ O) -O-C1～3Alkyl or-O-C (═ O) -C1～3Alkyl is optionally substituted by 1, 2 or 3RaAnd (4) substitution.
Said R1Are respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、CH3、CF3、-C(CH)3、-O-CH3、
Figure BDA0002573597300000035
Said R2Are respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、C1～4Alkyl radical, C1～4Alkoxy, -C (═ O) -C1～3Alkyl, -C (═ O) -O-C1～3Alkyl or-O-C (═ O) -C1～3Alkyl radical, said C1～4Alkyl radical, C1～4Alkoxy, -C (═ O) -C1～3Alkyl, -C (═ O) -O-C1～3Alkyl or-O-C (═ O) -C 1～3Alkyl is optionally substituted by 1, 2 or 3RbAnd (4) substitution.
R2Are respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、CH3、CF3、-C(CH)3、-O-CH3、
Figure BDA0002573597300000041
The solvent is water.
The alkali is organic alkali or inorganic alkali.
The inorganic base is cesium carbonate, potassium carbonate, sodium carbonate, potassium dihydrogen phosphate or potassium hydroxide. The inorganic base is preferably cesium carbonate.
The organic base is triethylamine, diisopropylethylenediamine and 1, 8-diazabicycloundecen-7-ene (DBU).
The dosage of the alkali is 15 to 30 percent of the mass of the compound of the formula (II).
The molar ratio of the compound of the formula (II) to the compound of the formula (III) to the sodium thiosulfate is 1: 1-2: 2-4, preferably 1: 1.3-1.7: 2.8-3.2, and more preferably 1: 1.5: 3.
The reaction temperature of the one-pot reaction is 60-120 ℃, and the reaction time is 10-30 hours.
The post-treatment of the one-pot reaction comprises the following steps: cooling after the reaction is finished, extracting by using an organic solvent, and separating by using column chromatography to obtain the product of the asymmetric organic persulfate compound shown in the formula (I).
The eluent for column chromatographic separation is a mixed solution of ethyl acetate and petroleum ether, and the volume ratio of the mixed solution of ethyl acetate and petroleum ether is 1: 50-1: 3.
The invention has the following beneficial effects:
(1) the method takes the sodium thiosulfate and the thioacetate as sulfur sources, thereby avoiding the stink brought by the thiophenol.
(2) The preparation method provided by the invention has the advantages that the raw materials are cheap and easy to obtain, the feeding ratio of the raw materials of the sodium thiosulfate to the compound of the formula (III) to the compound of the formula (II) is low, and the feeding cost is effectively reduced.
(3) According to the preparation method provided by the invention, the reaction solvent is water, and the over-vulcanization modification of natural products such as sugar can be realized.
(4) The preparation method provided by the invention uses a small amount of alkali as the catalyst, avoids the use of heavy metal catalyst, and has a simple system.
(5) The preparation method provided by the invention adopts a synthesis means of one-pot reaction, all raw materials are added simultaneously, and the operation is simple.
Definition and description.
As used herein, the following terms and phrases are intended to have the following meanings, unless otherwise indicated. A particular term or phrase, unless specifically defined, should not be considered as indefinite or unclear, but rather construed according to ordinary meaning. When a trade name appears herein, it is intended to refer to its corresponding commodity or its active ingredient.
Unless otherwise indicated, the term "substituted" means that any one or more hydrogen atoms on a particular atom is replaced with a substituent, and may include variations of deuterium and hydrogen, so long as the valency of the particular atom is normal and the substituted compound is stable. When the substituent is oxygen (i.e., ═ O), it means that two hydrogen atoms are substituted. Oxygen substitution does not occur on aromatic groups.
The term "optionally substituted" means that it may or may not be substituted, unless otherwise specified.
When any variable (e.g., R) occurs more than one time in the composition or structure of a compound, its definition in each case is independent. Thus, for example, if a group is substituted with 0-2R, the group may optionally be substituted with up to two R, and there are separate options for R in each case. Furthermore, combinations of substituents and/or variants thereof are permissible only if such combinations result in stable compounds.
When the number of one linking group is 0,such as- (CRR)0-, represents that the linking group is a single bond.
When a variable is selected from a single bond, it means that the two groups to which it is attached are directly connected, for example where L represents a single bond in A-L-Z, it means that the structure is actually A-Z.
Unless otherwise specified, the term "C1-5Alkyl "is used to denote a straight or branched chain saturated carbon group containing 1 to 5 carbon atoms. Said C is1-5The alkyl group comprising C1-5、C1-4、C1-3、C1-2、C2-5、C2-4、C2-3、C3-5、C3-4、C4-5、C1、C2、C3、C4、C5Alkyl groups, and the like. It may be monovalent (e.g., methyl), divalent (e.g., methylene), or multivalent (e.g., methine). C1-5Examples of alkyl groups include, but are not limited to, methyl (Me), ethyl (Et), propyl (including n-propyl and isopropyl), butyl (including n-butyl, isobutyl, s-butyl and t-butyl), pentyl (including n-pentyl, isopentyl and neopentyl).
Unless otherwise specified, the term "C1-4Alkyl "is used to denote a straight or branched chain saturated carbon group containing 1 to 4 carbon atoms. Said C is1-4The alkyl group comprising C1-4、C1-3、C1-2、C2-4、C2-3、C3-4、C1、C2、C3、C4Alkyl groups, and the like. It may be monovalent (e.g., methyl), divalent (e.g., methylene), or multivalent (e.g., methine). C1-4Examples of alkyl groups include, but are not limited to, methyl (Me), ethyl (Et), propyl (including n-propyl and isopropyl), butyl (including n-butyl, isobutyl, s-butyl and t-butyl).
Unless otherwise specified, the term "G1-3Alkyl "is used to denote a straight or branched chain saturated carbon group containing 1 to 3 carbon atoms. Said C is1-3The alkyl group comprising C1-3、C1-2、C2-3、C1、C2、C3Alkyl groups, and the like. It may be monovalent (e.g., methyl), divalent (e.g., methylene), or multivalent (e.g., methine). C1-3Examples of alkyl groups include, but are not limited to, methyl (Me), ethyl (Et), propyl (including n-propyl and isopropyl).
The terms "alkoxy", "alkylamino" and "alkylthio" (or thioalkoxy) are used in the conventional sense to refer to those alkyl groups attached to the rest of the molecule through an oxygen atom, an amino group or a sulfur atom, respectively. Unless otherwise specified, the term "alkoxy" represents an alkyl group as defined above having the specified number of carbon atoms attached through an oxygen bridge, and unless otherwise specified, the term "C 1-5Alkoxy "includes C1-5、C1-4、C1-3、C1-2、C2-5、C2-4、C2-3、C3-5、C3-4、C4-5、C1、C2、C3、C4、C5Alkoxy, and the like. C1-5Examples of alkoxy groups include, but are not limited to, methoxy (Me), ethoxy (Et), propoxy (including n-propoxy and isopropoxy), butoxy (including n-butoxy, isobutoxy, s-butoxy and t-butoxy), pentyloxy (including n-pentyloxy, isopentyloxy and neopentyloxy).
Unless otherwise specified, the term "aryl" means a polyunsaturated aromatic hydrocarbon substituent which may be mono-, di-or poly-substituted, and may be mono-, di-or polyvalent, and which may be monocyclic or polycyclic (e.g., 1 to 3 rings; wherein at least one ring is aromatic), fused together or covalently linked.
The term "5-12 membered heteroaryl" refers to an aryl (or ring) containing one to four heteroatoms selected from B, N, O and S, wherein the nitrogen and sulfur atoms are optionally oxidized and the nitrogen atoms are optionally quaternized. The heteroaryl group may be attached to the rest of the molecule through a heteroatom. The term "5-12 membered heteroaryl" includes 5-12 membered heteroaryl, 5-11 membered heteroaryl, 5-10 membered heteroaryl, 5-9 membered heteroaryl, 5-8 membered heteroaryl, 5-7 membered heteroaryl, 5-6 membered heteroaryl, 6-12 membered heteroaryl, 6-11 membered heteroaryl, 6-10 membered heteroaryl, 6-9 membered heteroaryl, 6-8 membered heteroaryl, 6-7 membered heteroaryl, 7-12 membered heteroaryl, 7-11 membered heteroaryl, 7-10 membered heteroaryl, 7-9 membered heteroaryl, 7-8 membered heteroaryl, 8-12 membered heteroaryl, 8-11 membered heteroaryl, 8-10 membered heteroaryl, 8-9 membered heteroaryl, 9-12 membered heteroaryl, 9-11 membered heteroaryl, 9-10 membered heteroaryl, 10-12 membered heteroaryl, 10-11 membered heteroaryl, 11-12 membered heteroaryl.
The term "5-10 membered heterocycloalkyl" refers to a cycloalkyl group containing one to four heteroatoms selected from B, N, O and S, wherein the nitrogen and sulfur atoms are optionally oxidized and the nitrogen atoms are optionally quaternized. The heterocycloalkyl radical may be attached to the rest of the molecule through a heteroatom, and any carbon atom of said cycloalkyl radical is saturated and may be mono-or polysubstituted. The term "5-to 10-membered heterocycloalkyl" includes 5-to 10-membered heterocycloalkyl, 5-to 9-membered heterocycloalkyl, 5-to 8-membered heterocycloalkyl, 5-to 7-membered heterocycloalkyl, 5-to 6-membered heterocycloalkyl, 6-to 10-membered heterocycloalkyl, 6-to 9-membered heterocycloalkyl, 6-to 8-membered heterocycloalkyl, 6-to 7-membered heterocycloalkyl, 7-to 10-membered heterocycloalkyl, 7-to 9-membered heterocycloalkyl, 7-to 8-membered heterocycloalkyl, 8-to 10-membered heterocycloalkyl, 8-to 9-membered heterocycloalkyl, 9-to 10-membered heterocycloalkyl.
Compounds are named according to the conventional naming principles in the art or using software, and commercially available compounds are referred to by the supplier's catalog name.
Detailed Description
For further understanding of the present invention, the following examples are given to illustrate the preparation of an asymmetric organic persulfate compound, but the present invention is not limited to these examples, and those skilled in the art can make insubstantial modifications and adaptations of the invention under the core teaching of the present invention.
The intermediate compound of formula (II) can be prepared commercially or by reference to reference examples 1 to 3.
Reference example 1 Synthesis of intermediate Compound of formula (II-1)
Figure BDA0002573597300000071
Wherein R is2M, ring A is as defined herein.
To 10mL of two-necked SchThe lenk tube was charged with 4mL of toluene. In N2A compound of formula (IV-1) (0.5mmol), CuI (10 mol%, 0.05mmol), 1, 10-phenanthroline (20 mol%, 0.1mmol) were added under an atmosphere, and finally potassium thioacetate (1.5 equiv., 0.75mmol) was added, and the reaction mixture was reacted at 100 ℃ for 24 hours. Cooled at room temperature, poured into ether (20mL) and water (20mL), the organic phase separated and the aqueous phase extracted with 2 equal parts of ether (20mL), the organic phases combined and washed with anhydrous Na2SO4Drying and filtering, and separating the crude product by column chromatography to obtain the compound of formula (II-1).
Reference example 2 Synthesis of intermediate Compound of formula (II-2)
Figure BDA0002573597300000072
Wherein R is2M, ring A is as defined herein; and X is Cl or Br.
Dissolving the compound of formula (IV-2) (1 eq) in DMF, adding potassium thioacetate (1.5 eq) and stirring at 70 deg.C, monitoring the reaction by TLC until RX disappears, adding brine and ethyl acetate, separating the organic layer, extracting the aqueous phase with ethyl acetate, washing the combined organic layers with brine, and washing over Na2SO4Drying and evaporation in vacuo afforded the crude compound of formula (II-2), which was used in the next step without purification.
Reference example 3 Synthesis of intermediate Compound of formula (II-3)
Figure BDA0002573597300000081
Dissolving the compound of formula (IV-3) (1 eq) in DMF, adding potassium thioacetate (1.5 eq) and stirring at room temperature, adding brine and ethyl acetate, separating the organic layer, extracting the aqueous phase with ethyl acetate, washing the combined organic layers with brine, and washing with Na2SO4Drying and vacuum evaporation to obtain the crude compound of formula (II-3). The crude product was used in the next step without purification.
Example 1
Figure BDA0002573597300000082
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 80 percent.
1H NMR(400MHz，CDCl3)7.39-7.35(m，2H)，7.30-7.22(m，5H)，6.83-6.80(m，2H)，3.93(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)159.5，136.7，131.9，129.4，128.5，127.9，127.3，114.5，55.3，43.2。
Example 2
Figure BDA0002573597300000083
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of benzyl bromide, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 73 percent.
1H NMR(400MHz，CDCl3)7.39-7.35(m，2H)，7.30-7.22(m，5H)，6.83-6.80(m，2H)，3.93(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)159.5，136.7，131.9，129.4，128.5，127.9，127.3，114.5，55.3，43.2。
Example 3
Figure BDA0002573597300000091
To a dry 25mL Schlenk reaction tube, 0.5mmol of 4-methoxy group was addedPhenylthioacetate, 1.0mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of cesium carbonate, 3mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 76%.
1H NMR(400MHz，CDCl3)7.39-7.35(m，2H)，7.30-7.22(m，5H)，6.83-6.80(m，2H)，3.93(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)159.5，136.7，131.9，129.4，128.5，127.9，127.3，114.5，55.3，43.2。
Example 4
Figure BDA0002573597300000092
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.0mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of potassium carbonate, 3mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 70 percent.
1H NMR(400MHz，CDCl3)7.39-7.35(m，2H)，7.30-7.22(m，5H)，6.83-6.80(m，2H)，3.93(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)159.5，136.7，131.9，129.4，128.5，127.9，127.3，114.5，55.3，43.2。
Example 5
Figure BDA0002573597300000093
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.0mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of sodium carbonate and 3mL of water. Stirred at 70 ℃ for 24 hours. Cooling to room temperature after the reaction is finished, and reacting with ethyl acetateThe ester is extracted and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 63 percent.
1H NMR(400MHz，CDCl3)7.39-7.35(m，2H)，7.30-7.22(m，5H)，6.83-6.80(m，2H)，3.93(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)159.5，136.7，131.9，129.4，128.5，127.9，127.3，114.5，55.3，43.2。
Example 6
Figure BDA0002573597300000101
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.0mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of potassium hydroxide and 3mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain the product with the yield of 39 percent.
1H NMR(400MHz，CDCl3)7.39-7.35(m，2H)，7.30-7.22(m，5H)，6.83-6.80(m，2H)，3.93(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)159.5，136.7，131.9，129.4，128.5，127.9，127.3，114.5，55.3，43.2。
Example 7
Figure BDA0002573597300000102
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.0mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of triethylamine and 3mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 53 percent.
1H NMR(400MHz，CDCl3)7.39-7.35(m，2H)，7.30-7.22(m，5H)，6.83-6.80(m，2H)，3.93(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)159.5，136.7，131.9，129.4，128.5，127.9，127.3，114.5，55.3，43.2。
Example 8
Figure BDA0002573597300000103
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.0mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of diisopropylethylenediamine and 3mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 60 percent.
1H NMR(400MHz，CDCl3)7.39-7.35(m，2H)，7.30-7.22(m，5H)，6.83-6.80(m，2H)，3.93(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)159.5，136.7，131.9，129.4，128.5，127.9，127.3，114.5，55.3，43.2。
Example 9
Figure BDA0002573597300000111
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.0mmol of Na2S2O30.5mmo1 of benzyl chloride, 0.075mmol of cesium carbonate, 3mL of water. Stirred at 100 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 80 percent.
1H NMR(400MHz，CDCl3)7.39-7.35(m，2H)，7.30-7.22(m，5H)，6.83-6.80(m，2H)，3.93(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)159.5，136.7，131.9，129.4，128.5，127.9，127.3，114.5，55.3，43.2。
Example 10
Figure BDA0002573597300000112
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.0mmol of Na2S2O30.5mmol of benzyl chloride, 0.075mmol of cesium carbonate, 3mL of water. Stirred at 50 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 71 percent.
1H NMR(400MHz，CDCl3)7.39-7.35(m，2H)，7.30-7.22(m，5H)，6.83-6.80(m，2H)，3.93(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)159.5，136.7，131.9，129.4，128.5，127.9，127.3，114.5，55.3，43.2。
Example 11
Figure BDA0002573597300000113
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 2-methylbenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 84 percent.
1H NMR(400MHz，CDCl3)7.40-7.36(m，2H)，7.19-7.09(m，4H)，6.84-6.81(m，2H)，3.97(s，2H)，3.79(s，3H)，2.31(s，3H)；13C NMR(100MHz，CDCl3)159.5，136.9，134.3，131.7，130.6，130.5，128.1，127.8，125.9，114.5，55.4，41.4，19.1。
Example 12
Figure BDA0002573597300000121
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 3-methylbenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 83 percent.
1H NMR(400MHz，CDCl3)7.43-7.39(m，2H)，7.22-7.18(m，1H)，7.09-7.06(m，3H)，6.87-6.83(m，2H)，3.93(s，2H)，3.82(s，3H)，2.32(s，3H)；13C NMR(100MHz，CDCl3)159.5，138.1，136.5，131.9，130.1，128.3，128.1，128.0，126.4，114.5，55.4，43.4，21.3。
Example 13
Figure BDA0002573597300000122
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 4-methylbenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain the product with the yield of 78 percent.
1H NMR(400MHz，CDCl3)7.42-7.39(m，2H)，7.19-7.10(m，4H)，6.87-6.83(m，2H)，3.93(s，2H)，3.82(s，3H)，2.34(s，3H)；13C NMR(100MHz，CDCl3)159.5，137.2，133.6，131.9，129.3，129.2，128.1，114.5，55.4，43.0，21.1。
Example 14
Figure BDA0002573597300000123
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 4-tert-butylbenzyl chloride, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 69 percent.
1H NMR(400MHz，CDCl3)7.35-7.29(m，4H)，7.24-7.20(m，2H)，6.83-6.78(m，2H)，3.93(s，2H)，3.79(s，3H)，1.30(s，9H)；13C NMR(100MHz，CDCl3)159.4，150.4，133.7，131.8，129.1，128.1，125.4，114.5，55.3，43.1，34.5，31.3。
Example 15
Figure BDA0002573597300000131
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 2-chlorobenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 76%.
1H NMR(400MHz，CDCl3)7.39-7.36(m，2H)，7.34-7.32(m，1H)，7.30-7.27(m，1H)，7.18-7.14(m，2H)，6.83-6.78(m，2H)，4.04(s，2H)，3.79(s，3H)；13C NMR(100MHz，CDCl3)159.4，134.5，134.2，131.6，131.4，129.6，128.9，127.8，126.6，114.5，55.4，40.8。
Example 16
Figure BDA0002573597300000132
To a dry 25mL Schlenk reaction tube, 0.5mmol of 4-formazan was addedOxyphenylthioacetate, 1.5mmol of Na2S2O30.75mmol of 3-chlorobenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 74 percent.
1H NMR(400MHz，CDCl3)7.38-7.35(m，2H)，7.26-7.24(m，1H)，7.21-7.20(m，2H)，7.15-7.13(m，1H)，6.84-6.79(m，2H)，3.89(s，2H)，3.81(s，3H)；13C NMR(100MHz，CDCl3)159.6，138.8，134.2，132.1，129.6，129.5，127.6，127.5，127.5，114.6，55.4，42.6。
Example 17
Figure BDA0002573597300000133
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 4-chlorobenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 85 percent.
1H NMR(400MHz，CDCl3)7.33(d，J＝8.2Hz，2H)，7.24-7.16(m，4H)，6.80(d，J＝8.3Hz，2H)，3.87(s，1H)，3.79(s，2H)；13C NMR(100MHz，CDCl3)159.6，135.4，133.2，132.0，130.7，128.5，127.6，114.5，55.4，42.4。
Example 18
Figure BDA0002573597300000141
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 2, 6-dichlorobenzyl chloride0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 74 percent.
1H NMR(400MHz，CDCl3)7.45-7.41(m，2H)，7.25-7.23(m，2H)，7.10-7.06(m，1H)，6.83-6.78(m，2H)，4.31(s，2H)，3.79(s，3H)；13C NMR(100MHz，CDCl3)159.4，135.9，134.4，133.1，131.2，128.9，128.2，114.4，55.4，38.6。
Example 19
Figure BDA0002573597300000142
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 4-bromobenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 82 percent.
1H NMR(400MHz，CDCl3)7.40-7.33(m，4H)，7.13-7.11(m，2H)，6.83-6.80(m，2H)，3.87(s，2H)，3.81(s，3H)；13C NMR(100MHz，CDCl3)159.6，135.9，132.0，131.5，131.1，127.6，121.3，114.5，55.4，42.4。
Example 20
Figure BDA0002573597300000143
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 4-fluorobenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. Cooling to room temperature after the reaction, extracting with ethyl acetate, and passing through silica gel column (mixture of ethyl acetate and petroleum ether) Product ratio of 1: 50-1: 3) to give the product in 74% yield.
1H NMR(400MHz，CDCl3)7.35(d，J＝8.7Hz，2H)，7.24-7.19(m，2H)，6.95(t，J＝8.6Hz，2H)，6.81(d，J＝8.7Hz，2H)，3.89(s，1H)，3.79(s，3H)；13C NMR(100MHz，CDCl3)162.1(d，J＝246.1Hz)，159.6，132.6(d，J＝3.2Hz)，131.9，131.0(d，J＝8.1Hz)，127.78，115.3(d，J＝21.5Hz)，114.6，55.4，42.3。
Example 21
Figure BDA0002573597300000151
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 4-trifluoromethylbenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 77 percent.
1H NMR(400MHz，CDCl3)7.51(d，J＝8.0Hz，2H)，7.36(d，J＝8.0Hz，2H)，7.31-7.28(m，2H)，6.80-6.76(m，2H)，3.96(s，2H)，3.79(s，3H)；13C NMR(100MHz，CDCl3)159.6，141.0，134.5，132.1，129.7，127.4，125.3(q，J＝3.7Hz)，124.1(q，J＝270Hz)，114.5，55.3，42.5。
Example 22
Figure BDA0002573597300000152
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 3-cyanobenzyl chloride, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. Cooling to room temperature after the reaction, extracting with ethyl acetate, and passing through silica gel column (of ethyl acetate and petroleum ether)Volume ratio of 1: 50 to 1: 3) to give the product in 66% yield.
1H NMR(400MHz，CDCl3)7.51-7.47(m，3H)，7.36-7.31(m，3H)，6.83-6.79(m，2H)，3.91(s，2H)，3.81(s，3H)；13C NMR(100MHz，CDCl3)159.7，138.5，133.7，132.8，132.0，130.9，129.2，127.1，118.5，114.6，112.4，55.4，42.1。
Example 23
Figure BDA0002573597300000153
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 4-cyanobenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 70 percent.
1H NMR(400MHz，CDCl3)7.55-7.52(m，2H)，7.36-7.30(m，4H)，6.82-6.79(m，2H)，3.93(s，2H)，3.80(s，3H)；13C NMR(100MHz，CDCl3)159.7，142.5，132.1，130.1，127.1，118.7，114.6，111.1，5.4，42.5。
Example 24
Figure BDA0002573597300000161
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 4-nitrobenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 71 percent.
1H NMR(400MHz，CDCl3)8.11-8.08(m，2H)，7.41-7.39(m，2H)，7.33-7.31(m，2H)，6.80-6.77(m，2H)，3.97(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)159.8，147.1，144.6，132.1，130.2，127.0，123.5，114.6，55.4，42.1。
Example 25
Figure BDA0002573597300000162
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 4-carbomethoxybenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain the product with the yield of 90 percent.
1H NMR(400MHz，CDCl3)7.95-7.93(m，2H)，7.37-7.31(m，4H)，6.82-6.78(m，2H)，3.95(s，2H)，3.91(s，3H)，3.79(s，3H)；13C NMR(100MHz，CDCl3)166.7，159.6，142.1，132.1，129.7，129.3，129.1，127.5，114.6，55.3，52.1，42.7。
Example 26
Figure BDA0002573597300000163
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of 1-naphthylbenzyl chloride, 0.075mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain the product with the yield of 78 percent.
1H NMR(400MHz，CDCl3)8.01-7.99(m，1H)，7.87-7.75(m，2H)，7.52-7.47(m，2H)，7.41-7.34(m，4H)，6.86-6.78(m，2H)，4.43(s，2H)，3.81(s，3H)；13C NMR(100MHz，CDCl3)159.4，133.9，132.0，131.7，131.3，128.7，128.6，128.2，127.8，126.2，125.8，125.1，123.8，114.5，55.4，41.3。
Example 27
Figure BDA0002573597300000171
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 2-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 80 percent.
1H NMR(400MHz，CDCl3)7.63-7.59(m，1H)，7.33-7.19(m，6H)，6.98-6.93(m，1H)，6.87-6.84(m，1H)，3.97(s，2H)，3.89(s，3H)；13C NMR(100MHz，CDCl3)156.7，136.7，129.3，128.5，128.2，128.0，127.5，124.9，121.2，110.7，55.9，43.4。
Example 28
Figure BDA0002573597300000172
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 3-methoxyphenyl thioacetate and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 80 percent.
1H NMR(400MHz，CDCl3)7.29-7.17(m，6H)，7.03-7.01(m，2H)，6.75-6.72(m，1H)，3.94(s，2H)，3.78(s，3H)；13C NMR(100MHz，CDCl3)160.0，138.3，136.5，129.7，129.3，128.5，127.5，119.6，112.8，112.3，55.3，43.4。
Example 29
Figure BDA0002573597300000181
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 3-cyanophenylthioacetate and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 66 percent.
1H NMR(400MHz，CDCl3)7.54-7.50(m，2H)，7.40-7.37(m，1H)，7.32-7.29(m，1H)，7.27-7.22(m，5H)，3.94(s，2H)；13C NMR(100MHz，CDCl3)139.4，136.1，131.0，129.8，129.7，129.3，129.2，128.6，127.8，118.2，113.0，43.6。
Example 30
Figure BDA0002573597300000182
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-cyanophenylthioacetate and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 82 percent.
1H NMR(400MHz，CDCl3)7.49-7.41(m，4H)，7.25-7.22(m，5H)，3.95(s，2H)；13CNMR(100MHz，CDCl3)144.1，136.0，132.1，129.3，128.6，127.8，126.2，118.6，109.4，43.5。
Example 31
Figure BDA0002573597300000183
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 2-ethoxyformylphenyl thioacetate, 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 89 percent.
1H NMR(400MHz，CDCl3)8.10(t，J＝1.8Hz，1H)，7.86-7.83(m，1H)，7.59-7.56(m，1H)，7.34-7.20(m，6H)，4.39(q，J＝7.1Hz，2H)，3.95(s，2H)，1.41(t，J＝7.1Hz，3H)；13C NMR(100MHz，CDCl3)165.9，137.8，136.2，131.4，131.1，129.3，128.8，128.5，128.2，127.7，127.6，61.2，43.4，14.3。
Example 32
Figure BDA0002573597300000191
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-ethoxyformylphenyl thioacetate, 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 76%.
1H NMR(400MHz，CDCl3)7.94-7.90(m，2H)，7.46-7.44(m，2H)，7.27-7.23(m，5H)，4.36(q，J＝7.1Hz，2H)，3.94(s，2H)，1.39(t，J＝7.1Hz，3H)；13C NMR(100MHz，CDCl3)166.1，143.2，136.2，129.9，129.3，128.6，128.4，127.7，125.7，61.0，43.4，14.3。
Example 33
Figure BDA0002573597300000192
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-acetylphenylthioacetate and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 81 percent.
1H NMR(400MHz，CDCl3)7.85-7.82(m，2H)，7.48-7.45(m，2H)，7.27-7.21(m，5H)，3.95(s，2H)，2.57(s，3H)；13C NMR(100MHz，CDCl3)197.1，143.7，136.1，135.0，129.3，128.7，128.6，127.7，125.8，43.4，26.5。
Example 34
Figure BDA0002573597300000193
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methylphenylthioacetate and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.075mmol of cesium carbonate, 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 67 percent.
1H NMR(400MHz，CDCl3)7.40-7.37(m，2H)，7.33-7.28(m，5H)，7.15-7.12(m，2H)，3.97(s，2H)，2.37(s，3H)；13C NMR(100MHz，CDCl3)137.1，136.6，133.6，129.7，129.4，128.6，128.5，127.4，43.3，21.0。
Example 35
Figure BDA0002573597300000201
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 2, 5-methoxyphenyl thioacetate and 1.5mmol of Na2S2O3、0.75mmol benzyl chloride, 0.075mmol cesium carbonate, 5mL water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 53 percent.
1H NMR(400MHz，CDCl3)7.36-7.21(m，6H)，6.59(d，J＝8.4Hz，2H)，4.11(s，2H)，3.90(s，6H)；13C NMR(100MHz，CDCl3)161.1，137.8，131.2，129.1，128.3，127.1，113.3，104.1，56.2，44.0。
Example 36
Figure BDA0002573597300000202
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxybenzylthioacetate and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.15mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 59 percent.
1H NMR(400MHz，CDCl3)7.36-7.24(m，5H)，7.18-7.14(m，2H)，6.87-6.84(m，2H)，3.80(s，3H)，3.64(s，2H)，3.56(s，2H)；13C NMR(100MHz，CDCl3)159.0，137.5，130.5，129.4，129.2，128.5，127.4，113.9，55.3，43.3，42.7。
Example 37
Figure BDA0002573597300000203
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-cyanobenzylthioacetate, 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.15mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. Cooling to room temperature after the reaction is finished, extracting with ethyl acetate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1: 1)50-1: 3) to give the product in 76% yield.
1H NMR(400MHz，CDCl3)7.58-7.56(m，2H)，7.37-7.30(m，3H)，7.29-7.23(m，4H)，3.69(s，2H)，3.48(s，2H)；13C NMR(100MHz，CDCl3)142.9，137.1，132.1，130.0，129.3，128.6，127.6，118.7，111.0，43.3，42.3。
Example 38
Figure BDA0002573597300000211
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-nitrobenzyl thioacetate, 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.15mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 80 percent.
1H NMR(400MHz，CDCl3)8.17-8.14(m，2H)，7.38-7.27(m，7H)，3.73(s，2H)，3.51(s，2H)；13C NMR(100MHz，CDCl3)147.1，145.0，137.2，130.1，129.3，128.6，127.6，123.6，43.4，41.9。
Example 39
Figure BDA0002573597300000212
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyformylbenzylthioacetate, 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.15mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 49 percent.
1H NMR(400MHz，CDCl3)8.00-7.97(m，2H)，7.35-7.22(m，7H)，3.91(s，3H)，3.62(s，2H)，3.57(s，2H)；13C NMR(100MHz，CDCl3)166.8，142.7，137.2，129.7，129.4，129.1，128.5，127.5，52.1，43.3，42.7。
Example 40
Figure BDA0002573597300000221
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methylbenzylthioacetate and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.15mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 35 percent.
1H NMR(400MHz，CDCl3)7.37-7.26(m，5H)，7.15-7.14(m，4H)，3.65(s，2H)，3.59(s，2H)，2.36(s，3H)；13C NMR(100MHz，CDCl3)137.4，137.1，134.2，129.4，129.3，129.1，128.4，127.4，43.2，43.0，21.2。
EXAMPLE 41
Figure BDA0002573597300000222
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-chlorobenzylthioacetate and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.15mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 35 percent.
1H NMR(400MHz，CDCl3)7.35-7.24(m，7H)，7.13-7.10(m，2H)，3.65(s，2H)，3.49(s，2H)；13C NMR(100MHz，CDCl3)137.3，135.8，133.2，130.7，129.4，128.6，128.5，127.5，43.3，42.3。
Example 42
Figure BDA0002573597300000223
To a dry 25mL Schlenk reaction tube were added 0.5mmol of S- ((tetrahydrofuran-2-yl) methyl) ethanethiolate, 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.15mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain a product with the yield of 50 percent.
1H NMR(400MHz，CDCl3)7.33-7.32(m，4H)，7.30-7.26(m，1H)，4.03-3.96(m，1H)，3.93(s，2H)，3.88-3.82(m，1H)，3.76-3.71(m，1H)，2.64(dd，J＝13.3，6.5Hz，1H)，2.49(dd，J＝13.3，6.0Hz，1H)，1.98(dt，J＝12.2，6.5Hz，1H)，1.90-1.83(m，2H)，1.58-1.50(m，1H)；13C NMR(100MHz，CDCl3)137.3，129.3，128.5，127.4，77.5，68.1，44.1，43.7，30.7，25.7。
Example 43
Figure BDA0002573597300000231
To a dry 25mL Schlenk reaction tube were added 0.5mmol of the compound of formula (II-3) and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.15mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain the product with the yield of 61%.
1H NMR(400MHz，CDCl3)7.33-7.28(m，5H)，5.32(t，J＝9.4Hz，1H)，5.23(t，J＝9.3Hz，1H)，5.13(t，J＝9.6Hz，1H)，4.49(d，J＝9.6Hz，1H)，4.27(dd，J＝12.4，4.8Hz，1H)，4.18(dd，J＝12.4，2.4Hz，1H)，4.02(s，2H)，3.74-3.70(m，1H)，2.08(s，3H)，2.04(s，3H)，2.03(s，3H)，2.02(s，3H)；13C NMR(100MHz，CDCl3)170.5，170.2，169.3，169.1，136.6，129.4，128.5，127.5，87.7，76.0，73.8，69.1，68.0，62.0，44.4，20.7，20.6，20.6，20.5。
Example 44
Figure BDA0002573597300000232
To a dry 25mL Schlenk reaction tube were added 0.5mmol of the compound of formula (II-3) and 1.5mmol of Na2S2O30.75mmol of 4-cyanobenzyl chloride, 0.15mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain the product with the yield of 61%.
1H NMR(400MHz，CDCl3)7.61(d，J＝8.3Hz，2H)，7.40(d，J＝8.2Hz，2H)，5.36(t，J＝9.4Hz，1H)，5.26(t，J＝9.3Hz，1H)，5.13(t，J＝9.7Hz，1H)，4.55(d，J＝9.6Hz，2H)，4.32-4.19(m，2H)，4.05-3.93(m，2H)，3.78-3.74(m，1H)，2.08(s，3H)，2.04(s，3H)，2.01(s，6H)；13C NMR(100MHz，CDCl3)170.3，170.1，169.4，169.1，142.3，132.2，130.2，118.7，111.3，87.3，76.2，73.6，68.8，67.9，62.0，43.2，20.7，20.6，20.6，20.5。
Example 45
Figure BDA0002573597300000241
To a dry 25mL Schlenk reaction tube were added 0.5mmol of the compound of formula (II-4) and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.15mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain the product with the yield of 62 percent.
1H NMR(400MHz，CDCl3)7.41(d，J＝8.8Hz，1H)，7.36-7.27(m，5H)，6.85-6.79(m，2H)，5.92(s，1H)，3.85(s，3H)，3.81(s，2H)，3.39(s，2H)；13C NMR(100MHz，CDCl3)162.7，160.6，155.7，149.9，136.9，129.4，128.7，127.7，125.6，113.0，112.3，111.2，101.1，55.7，43.4，38.7。
Example 46
Figure BDA0002573597300000242
To a dry 25mL Schlenk reaction tube were added 0.5mmol of the compound of formula (II-5) and 1.5mmol of Na2S2O30.75mmol of benzyl chloride, 0.15mmol of cesium carbonate and 5mL of water. Stirred at 70 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, extracted by ethyl acetate and directly passes through a silica gel column (the volume ratio of the ethyl acetate to the petroleum ether is 1: 50-1: 3) to obtain the product with the yield of 61%.
1H NMR(400MHz，DMSO-d6)11.75(s，1H)，7.79-7.77(m，1H)，7.52-7.48(m，1H)，7.33-7.27(m，4H)，7.23-7.17(m，3H)，6.39(s，1H)，3.96(s，2H)，3.82(s，2H)；13C NMR(100MHz，DMSO-d6)161.6，146.2，139.7，137.5，130.9，129.9，128.9，127.9，125.6，123.1，122.1，117.9，116.2，41.9，37.9。

Claims (10)

1. A method for preparing an asymmetric organic persulfate compound, comprising the steps of: under the catalysis of alkali, carrying out one-pot reaction on a compound of a formula (II), a compound of a formula (III) and sodium thiosulfate in a solvent to obtain an asymmetric organic persulfate compound shown in a formula (I);
Figure FDA0002573597290000011
wherein the content of the first and second substances,
n is 1, 2, 3, 4 or 5;
m is 1, 2, 3, 4 or 5;
L1is-CH2-or a single bond, when L 1is-CH2When the pressure in the air is higher than the preset pressure,
Figure FDA0002573597290000012
different;
ring A is C6～12A meta-aryl group, a 5-to 12-membered heteroaryl group or a 5-to 10-membered heterocycloalkyl group;
x is F, Cl, Br or I;
R1are respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -C1～5Alkyl, -C (═ O) -O-C1～5Alkyl or-O-C (═ O) -C1～5Alkyl radical, said C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -C1～5Alkyl, -C (═ O) -O-C1～5Alkyl or-O-C (═ O) -C1～5Alkyl is optionally substituted by 1, 2 or 3RaSubstitution;
or, two R1And the phenyl group to which it is attached form a naphthyl, anthryl or phenanthryl group;
R2are respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -C1～5Alkyl, -C (═ O) -O-C1～5Alkyl or-O-C (═ O) -C1～5Alkyl radical, said C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -C1～5Alkyl, -C (═ O) -O-C1～5Alkyl or-O-C (═ O) -C1～5Alkyl is optionally substituted by 1, 2 or 3RbSubstitution;
Raare respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、CH3Or CF3；
RbAre respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、CH3Or CF3。
2. The process for preparing an asymmetric organic persulfate compound as claimed in claim 1, wherein ring A is
Figure FDA0002573597290000013
3. The process for preparing an asymmetric organic persulfate compound as claimed in claim 2, wherein the structural unit is
Figure FDA0002573597290000021
Is composed of
Figure FDA0002573597290000022
Figure FDA0002573597290000023
4. The method for preparing an asymmetric organic persulfate compound as claimed in claim 1, wherein R is1Are respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、CH3、CF3、-C(CH)3、-O-CH3、
Figure FDA0002573597290000024
5. The method for preparing an asymmetric organic persulfate compound as claimed in claim 1, wherein R is2Are respectively H, F, Cl, Br, I, OH and NH independently2、CN、NO2、CH3、CF3、-C(CH)3、-O-CH3、
Figure FDA0002573597290000025
6. The method for producing an asymmetric organic persulfate compound according to any one of claims 1 to 5, wherein the solvent is water.
7. The method for preparing an asymmetric organic persulfate compound according to any one of claims 1 to 5, wherein the reaction temperature of the one-pot reaction is 60 to 120 ℃ and the reaction time is 10 to 30 hours.
8. The method for preparing an asymmetric organic persulfate compound according to any one of claims 1 to 5, wherein the base is cesium carbonate, potassium carbonate, sodium carbonate, potassium dihydrogen phosphate, potassium hydroxide, triethylamine, diisopropylethylenediamine or 1, 8-diazabicycloundecen-7-ene.
9. The process for preparing an asymmetric organic persulfate compound as claimed in any one of claims 1 to 5, wherein the amount of the base used is 15 to 30% by mass of the compound of formula (II).
10. The method for preparing an asymmetric organic persulfate compound as claimed in any one of claims 1 to 5, wherein the molar ratio of the compound of formula (II), the compound of formula (III) and the sodium thiosulfate is 1: 1 to 2: 2 to 4.
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