CN112724054B - Preparation method of alkali-promoted asymmetric organic persulfate compound - Google Patents

Preparation method of alkali-promoted asymmetric organic persulfate compound Download PDF

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CN112724054B
CN112724054B CN202011518309.1A CN202011518309A CN112724054B CN 112724054 B CN112724054 B CN 112724054B CN 202011518309 A CN202011518309 A CN 202011518309A CN 112724054 B CN112724054 B CN 112724054B
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潘远江
王敦盖
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Zhejiang University ZJU
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    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/20—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms
    • C07D211/24—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by singly bound oxygen or sulphur atoms by sulfur atoms to which a second hetero atom is attached
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    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
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    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
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Abstract

The invention discloses a preparation method of an asymmetric organic persulfate compound, which comprises the following steps: under the promotion of alkali, the compound of formula (I), the compound of formula (II) and thiourea are subjected to one-pot reaction to obtain the asymmetric organic persulfate compound shown in formula (III). The preparation method disclosed by the invention is mild in reaction conditions, simple to operate and high in yield. Can be used for preparing organic per-sulfur compounds, and for preparing acetaminophen, estrol and other medicinal molecules, zingerone and amino acidAnd the like, and the natural product molecules are subjected to over-sulfuration modification.

Description

Preparation method of alkali-promoted asymmetric organic persulfate compound
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of an asymmetric organic persulfate compound.
Background
The asymmetric organic persulfate compound is a sulfur-containing organic substance with extremely high medical value, and currently commercially available sulfur-containing medicines such as propanethiothiamine, furanthiamine and romidepsin all have sulfur bridges. In the chemistry of natural products, over 120 polysulfidediopiprazines and their derivatives have been discovered, and their good anti-inflammatory and antibacterial effects have also attracted attention from medicinal chemists. Meanwhile, in the aspect of research on targeted drugs, the compound with the disulfide bond is a good carrier for drug transportation and release. As such, chemists have increased the development of asymmetric organic persulfur compounds in recent years.
At present, the method for preparing the asymmetric organic persulfate compound comprises the following steps:
(1) different types of sulfur-containing substrates are subjected to nucleophilic substitution reaction, cross coupling reaction and exchange reaction which participate in bimolecular reaction to directly form S-S bonds. The method needs to design and pre-prepare the sulfur-containing substrate, and has complex steps and complex system.
(2) Asymmetric organic persulfur compounds are prepared directly from disulfide or tetrasulfide substrates and sulfur-free compounds by free radical or metal-catalyzed reactions.
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 agent is very cumbersome.
In addition, the Chinese patent application with publication No. CN104387303A discloses a sulfur redox mechanism using sodium sulfinate, halohydrocarbon and Na2S2O3·5H2O is used as a reaction raw material, and the asymmetric persulfate compound is obtained through two-step reaction. The method has complex system, high material ratio of the raw materials of sodium thiosulfate, halogenated hydrocarbon and sodium sulfinate, and can not realize the one-pot reaction.
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 thiosulfonate, thiourea and an electrophilic reagent are used as raw materials, the asymmetric organic persulfate compound is prepared by a one-pot method under the action of alkali, the operation is simple, the organic persulfate compound is constructed, and the over-vulcanization modification of various drug molecules and natural products is realized.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing an asymmetric organic persulfate compound, comprising the steps of: under the promotion of alkali, carrying out one-pot reaction on the compound of the formula (I), the compound of the formula (II) and thiourea to obtain an asymmetric organic persulfate compound shown in the formula (III);
Figure BDA0002848711840000011
wherein the content of the first and second substances,
R1is alkyl, heteroalkyl, alkenyl, aryl, arylmethylene, heteroaryl, heteroarylmethylene, heterocycloalkyl or heterocycloalkylmethylene, and R is1Optionally substituted by 1, 2 or 3RaSubstitution;
Rais F, Cl, Br, I, OH, NH2、NO2CN, phenyl, C1-10Alkyl, -C (═ O) -O-C1～5Alkyl, said phenyl, C1-10Alkyl is optionally substituted by 1, 2 or 3 halogens or-C (═ O) -O-C1～5Alkyl substitution;
R2is alkyl, alkenylene, heteroalkyl, heterocycloalkyl, heterocycloalkylmethylene, aryl, arylmethylene, heteroaryl or heteroarylmethylene, and R is2Optionally substituted by 1, 2 or 3RbSubstitution;
Rbis F, Cl, Br, I, OH, NH2、NO2、CN、C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -O-C1～5Alkyl, -NHBoc, -NH-C (═ O) -Ph, -Boc, aryl, Ph, and alkyl,Heteroaryl, heterocycloalkyl or-S (═ O)2-C1～5Alkyl, said RbOptionally substituted by 1, 2 or 3RdSubstitution;
Rdis F, Cl, Br, I, OH, NH2、NO2CN, phenyl, C1-10Alkoxy, -NHAc, -CHO or- (C)1-6Alkylene) -C (═ O) - (C)1-6Alkyl) or-C (═ O) -O-C1～5An alkyl group;
x is F, Cl, Br, I, OTs or OTf;
ring A is aryl, heteroaryl or heterocycloalkyl, said ring A optionally substituted with 1, 2 or 3RcSubstitution;
Rcis C1-10An alkyl group.
The reaction mechanism of the preparation method of the asymmetric organic persulfate compound is shown as follows:
reacting the compound shown in the formula (I) with thiourea to generate organic isothiourea salt, and attacking a bivalent sulfur atom of the thiosulfonate shown in the formula (II) under an alkaline condition to obtain the compound shown in the formula (III).
Figure BDA0002848711840000021
Said R1Is C1-10Alkyl radical, C1-10Alkenyl radical, C1-10Heteroalkyl group, C6～14Aryl radical, C6～14Arylmethylene, 5-15 membered heteroaryl, 5-15 membered heteroarylmethylene, 4-15 membered heterocycloalkyl methylene, R1Optionally substituted by 1, 2 or 3RaAnd (4) substitution.
Said R1Is allyl, butyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, phenyl, benzyl, or a salt thereof,
Figure BDA0002848711840000022
Said R1Optionally substituted by 1, 2 or 3RaAnd (4) substitution.
Said R2Is C1-10Alkyl, aryl, heteroaryl, and heteroaryl,C1-13Heteroalkyl group, 4-15 heterocycloalkyl methylene group, C6～14Aryl radical, C6～14Arylmethylene, 5-15 membered heteroaryl, 5-15 membered heteroarylmethylene, R2Optionally substituted by 1, 2 or 3RbAnd (4) substitution.
Said R2Is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
Figure BDA0002848711840000023
Figure BDA0002848711840000024
Phenyl, benzyl, or a salt thereof,
Figure BDA0002848711840000025
Said R2Optionally substituted by 1, 2 or 3RbAnd (4) substitution.
The ring A is C6～12A meta aryl, 5-12 membered heteroaryl or 4-10 membered heterocycloalkyl, said ring A optionally substituted with 1, 2 or 3RcAnd (4) substitution.
Said ring A is phenyl optionally substituted with 1, 2 or 3RcAnd (4) substitution.
Said RaIs F, Cl, Br, I, OH, NH2、NO2CN, phenyl, CF3、C1-4Alkyl, -C (═ O) -O-C1～5Alkyl, aryl, heteroaryl, and heteroaryl,
Figure BDA0002848711840000031
Said RbIs F, Cl, Br, I, OH, NH2、NO2、CN、C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -O-C1～5Alkyl, -NHBoc, -NH-C (═ O) -Ph, -Boc, phenyl, Ph,
Figure BDA0002848711840000032
Figure BDA0002848711840000033
or-S (═ O)2-C1～5Alkyl, said RbOptionally substituted by 1, 2 or 3RdAnd (4) substitution.
Said RcIs CH3。
The reaction solvent of the one-pot reaction is toluene, dimethyl sulfoxide, dimethylformamide, acetonitrile, ethanol, 1, 4-dioxane or water, and toluene and 1, 4-dioxane are preferred.
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 potassium carbonate or cesium carbonate.
The organic base is triethylamine or diisopropyl ethylenediamine.
The reaction temperature of the one-pot reaction is 60-120 ℃, and the reaction time is 10-30 hours.
The molar ratio of the base to the compound of formula (II) is 1:1 to 2.
The molar ratio of the compound of the formula (I) to the compound of the formula (II) to thiourea is 1: 1.5-2.5: 1.5 to 2.5.
The post-treatment of the one-pot reaction comprises the following steps: after the reaction is finished, cooling, filtering to remove insoluble substances, concentrating the organic solvent, and separating by column chromatography to obtain the product of the asymmetric organic persulfate compound shown in the formula (III).
The eluent for column chromatography 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: 100-1: 1.
The invention has the following beneficial effects:
(1) the method takes thiourea and thiosulfonate as sulfur sources, thereby avoiding the stink brought by 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 thiourea, the compound shown in the formula (I) and the compound shown in the formula (II) is low, and the feeding cost is effectively reduced.
(3) The preparation method provided by the invention uses alkali as an additive, avoids the use of a heavy metal catalyst, and has a simple system.
(4) 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, e.g. - (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.
The term "alkyl" refers to a group of formula CnH2n+1A hydrocarbon group of (1). The alkyl group may be linear or branched. For example, the term "C1-10Alkyl "means containing 1 to 10 carbonsAn atomic alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-methylpentyl, etc.), a heptyl group, an octyl group, a nonyl group, and a decyl group.
The term "alkenyl" refers to a straight or branched chain unsaturated aliphatic hydrocarbon group having at least one double bond, consisting of carbon atoms and hydrogen atoms. Non-limiting examples of alkenyl groups include, but are not limited to, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, isobutenyl, 1, 3-butadienyl, and the like.
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 described above having the specified number of carbon atoms attached through an oxygen bridge.
The term "cycloalkyl" refers to an all-carbon ring that is fully saturated and may exist as a single ring, a bridged ring, or a spiro ring. Unless otherwise indicated, the carbocycle is typically a 3 to 10 membered ring. Non-limiting examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl (bicyclo [2.2.1] heptyl), bicyclo [2.2.2] octyl, adamantyl, and the like.
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 terms "cycloalkyl", "heterocycloalkyl", or its derivatives (such as aryl, heteroaryl, cycloalkyl, heterocycloalkyl, cycloalkenyl, heterocycloalkenyl, cycloalkynyl, heterocycloalkynyl, and the like) by themselves or in combination with other terms mean cyclized "alkyl", "heterocarbyl", respectively. Further, in the case of a heterohydrocarbyl or heterocycloalkyi (e.g., heteroalkyl, heterocycloalkyl), a heteroatom may occupy a position where the heterohydrocarbyl or heterocycloalkyi is attached to the remainder of the molecule. Examples of cycloalkyl groups include, but are not limited to, cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl, cycloheptyl, and the like. Non-limiting examples of heterocyclyl groups include 1- (1, 2, 5, 6-tetrahydropyridinyl), 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-morpholinyl, 3-morpholinyl, tetrahydrofuran-2-yl, tetrahydrofuran indol-3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, 1-piperazinyl, and 2-piperazinyl.
Unless otherwise specified, "cyclic" means substituted or unsubstituted cycloalkyl, heterocycloalkyl, cycloalkenyl, heterocycloalkenyl, cycloalkynyl, heterocycloalkynyl, aryl, or heteroaryl. The term "ring" includes monocyclic, bicyclic, spiro, fused, or bridged rings. The number of atoms in the ring is generally defined as the number of ring members, for example, "5 to 7 membered ring" means 5 to 7 atoms arranged around the ring. Unless otherwise specified, the ring optionally contains 1-3 heteroatoms.
Unless otherwise specified, the term "hetero" denotes a heteroatom or a heteroatom group (i.e., a heteroatom-containing radical) including atoms other than carbon (C) and hydrogen (H) and radicals containing such heteroatoms, including, for example, oxygen (O), nitrogen (N), sulfur (S), silicon (Si), germanium (Ge), aluminum (Al), boron (B), -O-, -S-, ═ O, ═ S, -C (═ O) O-, -C (═ O) -, -C (═ S) -, -S (═ O)2-, and optionally substituted-C (═ O) n (h) -, -C (═ NH) -, -S (═ O)2N (h) -or-S (═ O) n (h) -.
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 starting compound of formula (II) can be prepared commercially or by reference to reference examples 1-2.
Reference example 1 Synthesis of starting Compound of formula (II)
Figure BDA0002848711840000051
Wherein R is2Ring a is as defined herein; y is Cl or Br.
To a 10mL two-necked Schlenk tube was added 4mL of acetonitrile. The compound of formula (IV-1) (0.5mmol) and the compound of formula (V) (1.5 equiv., 0.75mmol) were added and the reaction mixture was allowed to react at 100 ℃ for 3h, then turned to room temperature and stirred overnight. Filtering, concentrating the filtrate to obtain a crude product, and separating the crude product by column chromatography to obtain the compound shown in the formula (II).
Reference example 2 Synthesis of starting Compound of formula (II)
Figure BDA0002848711840000052
Wherein R is2Ring a is as defined herein.
Dissolving the compound of formula (IV-2) (1 eq) in acetonitrile, adding the compound of formula (V) (1.5 eq), NBS (2.0 eq) and stirring at room temperature, monitoring the reaction by TLC until the starting material disappeared, adding brine and ethyl acetate, separating the organic layer, extracting the aqueous phase with ethyl acetate, washing the combined organic layers with brine, Na over Na2SO4Drying and vacuum evaporation to obtain a crude compound of formula (II-2), and separating the crude product by column chromatography to obtain the compound of formula (II).
Example 1
Figure BDA0002848711840000053
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, 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 92%.
1H NMR(400MHz,CDCl3)δ7.36–7.27(m,5H),7.18–7.15(m,2H),6.87–6.85(m,2H),3.81(s,3H),3.65(s,2H),3.57(s,2H)；13C NMR(100MHz,CDCl3)δ159.0,137.4,130.5,129.4,129.2,128.4,127.4,113.8,55.2,43.3,42.7。
Example 2
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of dimethyl sulfoxide. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 43%.
Example 3
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of dimethylformamide. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 56%.
Example 4
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of 1, 4-dioxane. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, filtering, concentrating the filtrate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 90%.
Example 5
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of acetonitrile. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 18%.
Example 6
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of ethanol. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 22%.
Example 7
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 60 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 68%.
Example 8
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 40 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 65%.
Example 9
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 100 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 87%.
Example 10
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of cesium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 69%.
Example 11
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of sodium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, 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 37%.
Example 12
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium phosphate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 75%.
Example 13
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium hydroxide, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 43%.
Example 14
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of triethylamine, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, filtering, concentrating the filtrate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 35%.
Example 15
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of diisopropylethylenediamine, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, filtering, concentrating the filtrate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 20%.
Example 16
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.25mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 43%.
Example 17
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 1.0mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, filtering, concentrating the filtrate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 80%.
Example 18
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 0.75mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 83 percent.
Example 19
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 0.75mmol of thiourea, 0.75mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 83 percent.
Example 20
Figure BDA0002848711840000081
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 3-methoxyphenyl thiosulfonate II-2, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, filtering, concentrating the filtrate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 90%.
1H NMR(400MHz,CDCl3)δ7.33–7.20(m,6H),6.83–6.79(m,2H),6.77(s,1H),3.80(s,3H),3.62(s,2H),3.55(s,2H)；13C NMR(100MHz,CDCl3)δ159.6,138.8,137.3,129.4,129.4,128.4,127.4,121.7,114.8,113.0,55.2,43.3,43.2。
Example 21
Figure BDA0002848711840000082
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 2-methoxyphenyl thiosulfonate II-3, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 38%.
1H NMR(400MHz,CDCl3)δ7.34–7.23(m,6H),7.19(dd,J＝7.6,1.6Hz,1H),6.93(td,J＝7.4,1.2Hz,1H),6.88(dd,J＝8.4,1.2Hz,1H),3.87(s,3H),3.75(s,2H),3.63(s,2H)；13C NMR(100MHz,CDCl3)δ157.3,137.4,131.0,129.3,128.9,128.4,127.3,125.7,120.2,110.6,55.5,43.4,38.2。
Example 22
Figure BDA0002848711840000083
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-trifluoromethoxyphenyl thiosulfonate II-4, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 73%.
1H NMR(400MHz,CDCl3)δ7.36–7.28(m,3H),7.26–7.24(m,2H),7.22–7.19(m,2H),7.16–7.14(m,2H),3.65(s,2H),3.51(s,2H)；13C NMR(100MHz,CDCl3)δ148.5,137.2,136.1,130.7,129.4,128.5,127.5,120.9,120.4(d,J＝256.0Hz),43.3,42.2。
Example 23
Figure BDA0002848711840000091
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-5, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 75%.
1H NMR(400MHz,CDCl3)δ7.98–7.95(m,2H),7.33–7.20(m,7H),3.89(s,3H),3.60(s,2H),3.55(s,2H)；13C NMR(100MHz,CDCl3)δ166.8,142.7,137.2,129.7,129.4,129.4,129.1,128.5,127.5,52.1,43.3,42.7。
Example 24
Figure BDA0002848711840000092
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-6, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 68%.
1H NMR(400MHz,CDCl3)δ7.59–7.57(m,2H),7.37–7.30(m,3H),7.28–7.24(m,4H),3.69(s,2H),3.48(s,2H)；13C NMR(100MHz,CDCl3)δ142.9,137.1,132.1,130.0,129.3,128.6,127.6,118.7,111.1,43.3,42.3。
Example 25
Figure BDA0002848711840000093
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-7, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 74%.
1H NMR(400MHz,CDCl3)δ7.56–7.53(m,1H),7.43–7.27(m,8H),3.70(s,2H),3.46(s,2H)；13C NMR(100MHz,CDCl3)δ138.9,137.2,133.7,132.8,130.9,129.4,129.2,128.6,127.6,118.6,112.4,43.3,41.8。
Example 26
Figure BDA0002848711840000101
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-8, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 46%.
1H NMR(400MHz,CDCl3)δ7.87(d,J＝8.4Hz,2H),7.37–7.26(m,7H),3.73(s,2H),3.51(s,2H),3.03(s,3H)；13C NMR(100MHz,CDCl3)δ143.8,139.3,137.1,130.2,129.4,128.6,127.6,127.5,44.5,43.3,42.1。
Example 27
Figure BDA0002848711840000102
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-9, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 65%.
1H NMR(400MHz,CDCl3)δ7.77–7.75(m,1H),7.64(td,J＝7.6,1.4Hz,1H),7.54–7.49(m,3H),7.44(td,J＝7.6,1.2Hz,1H),7.37–7.34(m,4H),7.31–7.27(m,3H),3.70(s,2H),3.62(s,2H)；13C NMR(100MHz,CDCl3)δ145.0,138.0,137.3,137.2,133.7,132.8,129.9,129.7,129.4,128.8,128.5,127.6,127.5,118.6,111.2,43.3,42.8。
Example 28
Figure BDA0002848711840000103
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-10, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 74%.
1H NMR(400MHz,CDCl3)δ7.81(dd,J＝7.6,1.2Hz,1H),7.51(td,J＝7.6,1.2Hz,1H),7.39(td,J＝7.6,1.2Hz,1H),7.36–7.30(m,3H),7.28–7.24(m,7H),3.67(s,2H),3.63(s,2H),3.59(s,3H)；13C NMR(100MHz,CDCl3)δ169.0,142.0,140.5,137.3,136.3,131.3,130.7,130.7,129.8,129.4,129.1,128.5,128.4,127.4,127.2,51.9,43.3,43.0。
Example 29
Figure BDA0002848711840000111
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-11, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 61%.
1H NMR(400MHz,CDCl3)δ7.40–7.37(m,2H),7.32–7.24(m,5H),6.85–6.82(m,2H),3.95(s,2H),3.81(s,3H)；13C NMR(100MHz,CDCl3)δ159.5,136.8,131.9,129.4,128.5,127.9,127.4,114.6,55.4,43.3。
Example 30
Figure BDA0002848711840000112
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-12, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 56%.
1H NMR(400MHz,CDCl3)δ8.17(t,J＝2.0Hz,1H),7.96–7.93(m,1H),7.62–7.59(m,1H),7.36(t,J＝8.0Hz,1H),7.27–7.24(m,2H),7.23–7.13(m,3H),3.97(s,2H)；13C NMR(100MHz,CDCl3)δ148.4,140.1,136.0,132.3,129.4,129.3,128.5,127.7,121.2,121.1,43.6。
Example 31
Figure BDA0002848711840000113
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-13, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 46%.
1H NMR(400MHz,CDCl3)δ8.97(s,1H),8.56(dd,J＝8.4,1.2Hz,1H),7.93–7.91(m,2H),7.57–7.41(m,6H),7.25(s,4H),7.10–7.06(m,1H),3.97(s,2H)；13C NMR(100MHz,CDCl3)δ165.1,139.1,135.8,134.7,134.5,132.0,130.8,129.4,128.9,128.6,127.7,127.1,124.3,124.1,121.1,42.6。
Example 32
Figure BDA0002848711840000114
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-14, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 34%.
1H NMR(400MHz,CDCl3)δ7.40(dd,J＝5.3,1.2Hz,1H),7.33–7.28(m,5H),7.13(dd,J＝3.6,1.2Hz,1H),6.96(dd,J＝5.3,3.6Hz,1H),4.05(s,2H)；13C NMR(100MHz,CDCl3)δ136.5,134.0,130.7,129.5,128.5,127.6,127.5,43.4。
Example 33
Figure BDA0002848711840000121
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-15, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 86%.
1H NMR(400MHz,CDCl3)δ8.05(d,J＝8.0Hz,2H),7.57(t,J＝8.0Hz,1H),7.45(t,J＝8.0Hz,2H),7.34–7.28(m,5H),4.45(t,J＝6.5Hz,2H),3.93(s,2H),2.72(t,J＝6.5Hz,2H)；13C NMR(100MHz,CDCl3)δ166.3,137.1,133.1,129.9,129.6,129.3,128.6,128.4,127.5,62.7,43.7,36.8。
Example 34
Figure BDA0002848711840000122
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-16, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 84%.
1H NMR(400MHz,CDCl3)δ8.12(d,J＝8.6Hz,2H),7.35–7.29(m,5H),7.21(d,J＝8.6Hz,2H),3.90(s,2H),2.91(t,J＝8.0Hz,2H),2.51(t,J＝8.0Hz,2H)；13C NMR(100MHz,CDCl3)δ147.6,146.5,137.6,129.4,129.3,128.6,127.5,123.6,43.5,38.3,34.9。
Example 35
Figure BDA0002848711840000123
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-17, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 81%.
1H NMR(400MHz,CDCl3)δ7.84(dd,J＝5.6,3.2Hz,2H),7.71(dd,J＝5.6,3.2Hz,2H),7.32–7.25(m,5H),3.87(s,2H),3.64(t,J＝6.9Hz,2H),2.40(t,J＝7.1Hz,2H),1.82–1.38(m,4H)；13C NMR(100MHz,CDCl3)δ168.3,137.4,133.9,132.0,129.3,128.4,127.4,123.2,43.6,37.7,37.4,37.3,26.2。
Example 36
Figure BDA0002848711840000131
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-18, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 86%.
1H NMR(400MHz,CDCl3)δ7.38–7.29(m,5H),6.93(d,J＝1.8Hz,1H),6.83(dd,J＝8.0,1.7Hz,1H),6.69(d,J＝8.0Hz,1H),4.55(t,J＝8.7Hz,2H),3.91(s,2H),3.18(t,J＝8.7Hz,2H),2.77(dd,J＝9.2,6.4Hz,2H),2.58(dd,J＝9.1,6.5Hz,2H)；13C NMR(100MHz,CDCl3)δ158.6,137.6,132.0,129.3,128.5,128.0,127.4,127.1,125.1,109.0,71.2,43.7,40.0,34.8,29.7。
Example 37
Figure BDA0002848711840000132
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-19, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 68%.
1H NMR(400MHz,CDCl3)δ7.33–7.27(m,5H),4.07–4.01(m,2H),3.88(s,2H),2.64(td,J＝13.2,2.8Hz,2H),2.25(d,J＝6.7Hz,2H),1.68–1.55(m,3H),1.44(s,9H),1.05–0.95(m,2H)；13C NMR(100MHz,CDCl3)δ154.7,137.5,129.3,128.5,127.4,79.3,45.1,43.6,43.5,35.5,31.2,28.4。
Example 38
Figure BDA0002848711840000133
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-20, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, filtering, concentrating the filtrate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 40%.
1H NMR(400MHz,CDCl3)δ7.34–7.27(m,5H),3.91(s,2H),3.72(t,J＝5.7Hz,2H),2.52(t,J＝5.7Hz,2H),1.84(s,1H)；13C NMR(100MHz,CDCl3)δ137.1,129.3,128.6,127.6,60.1,43.4,40.8。
Example 39
Figure BDA0002848711840000134
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-21, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 78%.
1H NMR(400MHz,CDCl3)δ7.33–7.26(m,5H),4.12(q,J＝7.1Hz,2H),3.88(s,2H),2.37(t,J＝7.5Hz,2H),2.28(t,J＝7.5Hz,2H),1.63–1.51(m,4H),1.30–1.24(m,7H)；13C NMR(100MHz,CDCl3)δ173.7,137.6,129.3,128.4,127.3,60.2,43.7,38.4,34.2,28.7,28.6,28.0,24.8,14.2。
Example 40
Figure BDA0002848711840000141
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-12, 1.0mmol of thiourea, 1.0mmol of cinnamyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 58%.
1H NMR(400MHz,CDCl3)δ8.38(t,J＝2.0Hz,1H),7.93(ddd,J＝8.2,2.2,0.9Hz,1H),7.76(ddd,J＝7.9,1.8,0.9Hz,1H),7.37(t,J＝8.0Hz,1H),7.24–7.17(m,5H),6.45(d,J＝15.7Hz,1H),6.09(dt,J＝15.5,7.7Hz,1H),3.59(dd,J＝7.7,1.0Hz,2H)；13C NMR(100MHz,CDCl3)δ148.5,140.7,136.0,134.6,132.5,129.5,128.4,127.9,126.2,123.1,121.4,121.1,42.1。
EXAMPLE 41
Figure BDA0002848711840000142
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-17, 1.0mmol of thiourea, 1.0mmol of cinnamyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 68%.
1H NMR(400MHz,CDCl3)δ7.84(dd,J＝5.4,3.1Hz,2H),7.70(dd,J＝5.5,3.0Hz,2H),7.38–7.35(m,2H),7.30(t,J＝8.0Hz,2H),7.24–7.19(m,1H),6.51(d,J＝15.6Hz,1H),6.23–6.16(m,1H),3.66(t,J＝6.6Hz,2H),3.48(dd,J＝7.6,1.1Hz,2H),2.70(t,J＝6.7Hz,2H),1.84–1.59(m,4H)；13C NMR(100MHz,CDCl3)δ168.3,136.6,133.9,133.5,132.0,128.6,127.6,126.4,124.5,123.2,42.0,38.5,37.3,27.3,26.4。
Example 42
Figure BDA0002848711840000143
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-22, 1.0mmol of thiourea, 1.0mmol of bromide I-25, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 64%.
1H NMR(400MHz,DMSO-d6)δ11.75(s,1H),7.78(d,J＝8.0Hz,1H),7.50(t,J＝7.6Hz,1H),7.32(d,J＝8.2Hz,1H),7.19(t,J＝7.6Hz,1H),7.11(t,J＝5.2Hz,4H),6.40(s,1H),3.98(s,2H),3.77(s,2H),2.27(s,3H)；13C NMR(100MHz,DMSO-d6)δ161.6,146.2,139.7,137.1,134.3,130.9,129.8,129.5,125.6,123.1,122.1,118.0,116.2,41.6,37.9,21.2。
Example 43
Figure BDA0002848711840000151
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-23, 1.0mmol of thiourea, 1.0mmol of bromide I-25, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 44%.
1H NMR(400MHz,DMSO-d6)δ11.76(s,1H),7.78(d,J＝7.8Hz,1H),7.50(d,J＝8.4Hz,3H),7.32(d,J＝8.0Hz,1H),7.17(dd,J＝12.6,8.2Hz,3H),6.42(s,1H),4.02(s,2H),3.81(s,2H)；13C NMR(100MHz,DMSO-d6)δ161.1,145.6,139.1,136.6,131.5,131.2,130.4,125.1,122.6,121.6,120.5,117.4,115.7,37.2。
Example 44
Figure BDA0002848711840000152
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-24, 1.0mmol of thiourea, 1.0mmol of bromide I-25, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 56%.
1H NMR(400MHz,DMSO-d6)δ12.76(s,1H),8.78(d,J＝7.6Hz,1H),8.51(t,J＝8.2Hz,1H),8.34(dd,J＝17.5,8.0Hz,3H),8.21(dd,J＝7.7,5.8Hz,3H),7.41(s,1H),5.02(s,2H),4.83(s,2H)；13C NMR(100MHz,DMSO-d6)δ161.1,145.6,139.1,136.2,132.0,131.1,130.4,128.3,125.1,122.6,121.6,117.4,115.7,37.2。
Example 45
Figure BDA0002848711840000153
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-2, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 78%.
1H NMR(400MHz,CDCl3)δ7.19–7.15(m,6H),6.88–6.86(m,2H),3.81(s,3H),3.62(s,2H),3.60(s,2H),2.35(s,3H)；13C NMR(100MHz,CDCl3)δ159.0,137.1,134.3,130.5,129.3,129.3,129.1,113.8,55.2,43.0,42.7,21.2。
Example 46
Figure BDA0002848711840000161
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-3, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, filtering, concentrating the filtrate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 80%.
1H NMR(400MHz,CDCl3)δ7.37–7.35(m,2H),7.22–7.20(m,2H),7.18–7.14(m,2H),6.87–6.85(m,2H),3.80(s,3H),3.63(s,2H),3.58(s,2H),1.32(s,9H)；13C NMR(100MHz,CDCl3)δ159.0,150.5,134.3,130.5,129.3,129.1,125.4,113.8,55.3,43.0,34.5,31.3。
Example 47
Figure BDA0002848711840000162
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-4, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 77%.
1H NMR(400MHz,CDCl3)δ7.25–7.21(m,1H),7.18–7.16(m,2H),7.11–7.06(m,3H),6.88–6.85(m,2H),3.81(s,3H),3.62(s,2H),3.59(s,2H),2.37(s,3H)；13C NMR(100MHz,CDCl3)δ159.0,138.1,137.3,130.5,130.1,129.3,128.3,128.1,126.4,113.9,55.2,43.4,42.7,21.4。
Example 48
Figure BDA0002848711840000163
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-5, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, 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 92%.
1H NMR(400MHz,CDCl3)δ7.22–7.20(m,2H),7.10–7.00(m,3H),6.87–6.85(m,2H),3.84(s,2H),3.80(s,3H),3.73(s,2H),2.39(s,6H)；13C NMR(100MHz,CDCl3)δ159.0,137.5,133.2,130.4,129.4,128.2,127.4,114.0,55.2,43.0,38.5,20.0。
Example 49
Figure BDA0002848711840000171
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-6, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 85%.
H NMR(400MHz,CDCl3)δ7.22–7.15(m,4H),7.04–6.99(m,2H),6.88–6.85(m,2H),3.81(s,3H),3.61(s,2H),3.57(s,2H)；13C NMR(101MHz,CDCl3)δ162.2(d,J＝246.0Hz),159.0,133.2(d,J＝3.2Hz),130.9(d,J＝8.0Hz),130.5,129.2,115.3(d,J＝21.5Hz),113.9,55.3,42.8,42.3。
Example 50
Figure BDA0002848711840000172
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-7, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 77%.
1H NMR(400MHz,CDCl3)δ7.31–7.27(m,2H),7.19–7.15(m,4H),6.88–6.86(m,2H),3.81(s,3H),3.62(s,2H),3.55(s,2H)；13C NMR(100MHz,CDCl3)δ159.1,136.0,133.2,130.7,130.5,129.2,128.6,113.9,55.3,42.7,42.4。
Example 51
Figure BDA0002848711840000173
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-8, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, filtering, concentrating the filtrate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 70%.
1H NMR(400MHz,CDCl3)δ7.46–7.42(m,2H),7.19–7.15(m,2H),7.11–7.08(m,2H),6.88–6.85(m,2H),3.81(s,3H),3.62(s,2H),3.53(s,2H)；13C NMR(100MHz,CDCl3)δ159.1,136.5,131.5,131.0,130.5,129.2,121.3,113.9,55.3,42.8,42.4。
Example 52
Figure BDA0002848711840000174
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-9, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 87%.
1H NMR(400MHz,CDCl3)δ7.57(d,J＝8.0Hz,1H),7.29–7.27(m,2H),7.18–7.13(m,3H),6.87–6.83(m,2H),3.81(s,2H),3.80(s,3H),3.59(s,2H)；13C NMR(100MHz,CDCl3)δ159.0,136.8,133.0,131.6,130.5,129.1,129.1,127.2,124.6,113.9,55.3,43.5,42.9。
Example 53
Figure BDA0002848711840000181
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-10, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 83 percent.
1H NMR(400MHz,CDCl3)δ7.23–7.21(m,2H),6.90–6.88(m,2H),6.82–6.75(m,2H),3.82(s,3H),3.72(s,2H),3.38(s,2H)；13C NMR(100MHz,CDCl3)δ159.2,150.9(ddd,J＝49,10,4Hz),139.0(dt,J＝25,15Hz),133.9–133.7(m),113.3–113.1(m),130.5,129.1,114.0,55.3,42.8,41.8。
Example 54
Figure BDA0002848711840000182
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-11, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 58%.
1H NMR(400MHz,CDCl3)δ7.58(d,J＝8.0Hz,2H),7.33(d,J＝8.0Hz,2H),7.19–7.16(m,2H),6.89–6.86(m,2H),3.81(s,3H),3.64(s,2H),3.59(s,2H)；13C NMR(100MHz,CDCl3)δ159.1,141.6,130.5,129.6,129.4,129.1,125.32(q,J＝3.7Hz),124.1(q,J＝270Hz),113.9,55.3,42.8,42.4。
Example 55
Figure BDA0002848711840000183
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-12, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 77%.
1H NMR(400MHz,CDCl3)δ7.55–7.53(m,1H),7.46–7.42(m,3H),7.19–7.15(m,2H),6.90–6.86(m,2H),3.81(s,3H),3.61(s,2H),3.59(s,2H)；13C NMR(100MHz,CDCl3)δ159.1,138.5,132.6,130.8,130.5,129.1,128.9,126.2(q,J＝3.8Hz),124.1(q,J＝3.8Hz),124.0(q,J＝270.0Hz),113.9,55.2,42.7,42.4。
Example 56
Figure BDA0002848711840000191
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-13, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 84%.
1H NMR(400MHz,CDCl3)δ7.61–7.58(m,2H),7.30–7.28(m,2H),7.19–7.16(m,2H),6.89–6.85(m,2H),3.81(s,3H),3.65(s,2H),3.53(s,2H)；13C NMR(100MHz,CDCl3)δ159.1,143.1,132.1,130.4,130.0,129.0,118.7,114.0,111.1,55.3,42.8,42.4。
Example 57
Figure BDA0002848711840000192
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-14, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 82%.
1H NMR(400MHz,CDCl3)δ7.56–7.54(m,1H),7.44–7.39(m,3H),7.21–7.17(m,2H),6.91–6.87(m,2H),3.82(s,3H),3.65(s,2H),3.50(s,2H)；13C NMR(100MHz,CDCl3)δ159.2,139.1,133.7,132.9,130.9,130.5,129.2,129.0,118.6,114.0,112.4,55.3,42.8,41.8。
Example 58
Figure BDA0002848711840000193
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-15, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 74%.
1H NMR(400MHz,CDCl3)δ8.00–7.98(m,2H),7.31–7.29(m,2H),7.17–7.13(m,2H),6.87–6.84(m,2H),3.91(s,3H),3.80(s,3H),3.62(s,2H),3.58(s,2H)；13C NMR(100MHz,CDCl3)δ166.8,159.1,142.8,130.5,129.7,129.4,129.1,129.1,113.9,55.3,52.1,42.8,42.7。
Example 59
Figure BDA0002848711840000201
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-16, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 74%.
H NMR(400MHz,CDCl3)δ8.18–8.15(m,2H),7.34–7.31(m,2H),7.20–7.18(m,2H),6.88–6.86(m,2H),3.81(s,3H),3.67(s,2H),3.56(s,2H)；13C NMR(100MHz,CDCl3)δ159.2,147.1,145.2,130.5,130.1,129.0,123.6,114.0,55.3,42.8,42.0。
Example 60
Figure BDA0002848711840000202
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-17, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 85%.
1H NMR(400MHz,CDCl3)δ8.04–8.02(m,1H),7.59–7.55(m,1H),7.46–7.42(m,1H),7.33–7.31(m,1H),7.18–7.14(m,2H),6.87–6.83(m,2H),3.98(s,2H),3.80(s,3H),3.62(s,2H)；13C NMR(100MHz,CDCl3)δ159.1,148.1,133.5,133.0,132.8,130.4,128.8,128.4,125.4,114.0,55.2,43.0,40.4。
Example 61
Figure BDA0002848711840000203
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-18, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 76%.
1H NMR(400MHz,CDCl3)δ7.63–7.61(m,2H),7.56–7.38(m,6H),7.27–7.25(m,1H),7.14–7.12(m,2H),6.83–6.81(m,2H),3.78(s,3H),3.70(s,2H),3.58(s,2H)；13C NMR(100MHz,CDCl3)δ159.0,141.4,140.8,138.0,130.5,129.2,128.9,128.8,128.3,128.2,127.4,127.1,126.2,113.9,55.2,43.3,42.7。
Example 62
Figure BDA0002848711840000211
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-19, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, and directly passes through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 79%.
1H NMR(400MHz,CDCl3)δ7.82(dd,J＝7.6,1.4Hz,1H),7.53(td,J＝7.6,1.6Hz,1H),7.43–7.35(m,2H),7.31–7.29(m,4H),7.21–7.17(m,2H),6.88–6.84(m,2H),3.80(s,3H),3.68(s,2H),3.63(s,2H),3.60(s,3H)；13C NMR(100MHz,CDCl3)δ169.0,159.0,142.0,140.5,136.4,131.3,130.7,130.7,130.5,129.8,129.3,129.1,128.4,127.2,113.9,55.2,51.9,43.1,42.7。
Example 63
Figure BDA0002848711840000212
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-20, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 69%.
1H NMR(400MHz,CDCl3)δ7.84–7.81(m,3H),7.66–7.66(m,1H),7.49(tt,J＝7.0,5.4Hz,2H),7.42(dd,J＝8.4,1.8Hz,1H),7.10–7.07(m,2H),6.85–6.81(m,2H),3.81(s,2H),3.80(s,3H),3.53(s,2H)；13C NMR(100MHz,CDCl3)δ159.0,134.7,133.2,132.6,130.5,129.2,128.3,128.2,127.7,127.3,126.2,126.0,113.8,55.2,43.6,42.8。
Example 64
Figure BDA0002848711840000213
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-21, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 56%.
1H NMR(400MHz,CDCl3)δ8.97(dd,J＝4.2,1.6Hz,1H),8.15(dd,J＝8.2,1.6Hz,1H),7.77(dd,J＝8.0,1.6Hz,1H),7.62(dd,J＝7.2,1.6Hz,1H),7.53–7.49(m,1H),7.43(dd,J＝8.2,4.2Hz,1H),7.11–7.07(m,2H),6.83–6.79(m,2H),4.41(s,2H),3.78(s,3H),3.57(s,2H)；13C NMR(100MHz,CDCl3)δ158.9,149.6,136.4,135.9,130.4,130.2,129.7,129.3,128.5,127.7,126.0,121.1,113.8,55.2,42.8,39.1。
Example 65
Figure BDA0002848711840000221
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-22, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 74%.
1H NMR(400MHz,CDCl3)δ7.38–7.35(m,2H),6.87–6.83(m,2H),5.85–5.72(m,1H),5.14–5.05(m,2H),3.86(s,1H),3.80(s,3H),3.62(s,1H),3.06–3.01(m,2H)；13C NMR(100MHz,CDCl3)δ159.0 158.5,134.2 133.3,130.4 130.0,130.2 29.3,118.4 117.2,113.9 113.8,55.2,43.0 41.9,34.2 34.0。
Example 66
Figure BDA0002848711840000222
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-23, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 66%.
1H NMR(400MHz,CDCl3)δ7.38–7.35(m,2H),7.33–7.29(m,2H),7.25–7.21(m,1H),7.19–7.16(m,2H),6.85–6.81(m,2H),6.38(d,J＝16.0Hz,1H),6.16–6.08(m,1H),3.84(s,2H),3.78(s,3H),3.24(dd,J＝7.6,1.2Hz,2H)；13C NMR(100MHz,CDCl3)δ159.0,136.6,133.6,130.4,129.2,128.6,127.7,126.4,124.5,113.9,55.2,43.4,41.8。
Example 67
Figure BDA0002848711840000223
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-24, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, filtering, concentrating the filtrate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 32%.
1H NMR(400MHz,CDCl3)δ7.43(d,J＝12Hz,1H),7.21–7.17(m,2H),6.87–6.80(m,4H),5.97(s,1H),3.86(s,3H),3.80(s,3H),3.77(s,2H),3.44(s,2H)；13C NMR(100MHz,CDCl3)δ162.7,160.7,159.2,155.8,150.1,130.5,128.7,125.7,114.1,113.0,112.3,111.3,101.1,55.8,55.3,42.9,38.9。
Example 68
Figure BDA0002848711840000231
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of bromide I-25, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the reaction product is cooled to room temperature, filtered, concentrated, and directly passed 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 62%.
1H NMR(400MHz,CDCl3)δ12.70(s,1H),7.65(d,J＝8.0Hz,1H),7.56–7.48(m,2H),7.27–7.23(m,1H),7.16–7.12(m,2H),6.83–6.80(m,2H),6.56(s,1H),3.77(s,3H),3.69(s,4H)；13C NMR(100MHz,CDCl3)δ163.8,159.1,147.2,138.8,130.7,130.5,128.8,124.5,122.6,121.6,118.4,116.9,114.0,55.2,42.8,39.7。
Example 68
Figure BDA0002848711840000232
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of iodo I-26, 0.5mmol of potassium carbonate, and 3mL of water. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, extracting, concentrating the extract, and directly passing 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 52%.
1H NMR(400MHz,CDCl3)δ7.25(d,J＝8.7Hz,2H),6.87–6.84(m,2H),3.86(s,2H),3.80(s,3H),2.44(t,J＝8.0Hz,2H),1.59–1.52(m,2H),1.38–1.29(m,2H),0.88(t,J＝7.4Hz,3H)；13C NMR(100MHz,CDCl3)δ159.0,130.4,129.5,113.9,55.3,43.1,38.4,31.1,21.6,13.6。
Example 69
Figure BDA0002848711840000233
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of the alkyl compound II-27, 0.5mmol of potassium carbonate, and 3mL of water. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, extracting, concentrating the extract, and directly passing 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 40%.
1H NMR(400MHz,CDCl3)δ7.25(d,J＝8.7Hz,2H),6.87–6.84(m,2H),3.86(s,2H),3.80(s,3H),2.44(t,J＝8.0Hz,2H),1.59–1.52(m,2H),1.38–1.29(m,2H),0.88(t,J＝7.4Hz,3H)；13C NMR(100MHz,CDCl3)δ159.0,130.4,129.5,113.9,55.3,43.1,38.4,31.1,21.6,13.6。
Example 70
Figure BDA0002848711840000234
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of the alkyl compound I-27, 0.5mmol of potassium carbonate, and 3mL of water. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, extracting, concentrating the extract, and directly passing 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 50%.
1H NMR(400MHz,CDCl3)δ7.27–7.23(m,2H),6.87–6.83(m,2H),3.86(s,2H),3.80(s,3H),2.43(t,J＝8.0Hz,2H),1.59–1.53(m,2H),1.31–1.22(m,10H),0.89(t,J＝6.8Hz,3H)；13C NMR(100MHz,CDCl3)δ159.0,130.4,129.5,113.9,55.2,43.1,38.7,31.8,29.2,29.1,29.1,28.5,22.6,14.1。
Example 71
Figure BDA0002848711840000241
To a dry 25mL Schlenk reaction tube were added 0.5mmol of 4-methoxyphenyl thiosulfonate, 1.0mmol of thiourea, 1.0mmol of the alkyl compound I-28, 0.5mmol of potassium carbonate, and 3mL of water. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, extracting, concentrating the extract, and directly passing 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 35%.
1H NMR(400MHz,CDCl3)δ7.25(d,J＝8.7Hz,2H),6.85(d,J＝8.6Hz,2H),3.93(dd,J＝11.1,3.8Hz,2H),3.85(s,2H),3.80(s,3H),3.34(td,J＝11.8,1.8Hz,2H),2.32(d,J＝6.8Hz,2H),1.74–1.70(m,1H),1.65(d,J＝13.1Hz,2H),1.21(qd,J＝12.9,12.3,4.3Hz,2H)；13C NMR(100MHz,CDCl3)δ159.0,130.4,129.4,113.9,67.7,55.3,45.4,43.0,34.5,32.2。
Example 72
Figure BDA0002848711840000242
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-25, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 42%.
1H NMR(400MHz,CDCl3)δ7.38(d,J＝8.8Hz,2H),7.31–7.28(m,5H),6.81(d,J＝8.8Hz,2H),4.04(t,J＝6.6Hz,2H),3.90(s,2H),2.73(t,J＝6.6Hz,2H),2.14(s,3H)；13C NMR(100MHz,CDCl3)δ168.3,155.1,137.2,131.3,129.3,128.6,127.5,121.8,114.9,66.4,43.7,37.2,24.3。
Example 73
Figure BDA0002848711840000243
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-26, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 58%.
1H NMR(400MHz,DMSO-d6)δ7.36–7.25(m,5H),7.15(d,J＝8.0Hz,1H),6.68(dd,J＝8.6,2.8Hz,1H),6.62(d,J＝2.7Hz,1H),4.06(t,J＝6.3Hz,2H),3.97(s,2H),2.86(t,J＝6.3Hz,2H),2.82–2.78(m,2H),2.45–2.38(m,1H),2.33–2.26(m,1H),2.17–2.11(m,1H),2.03(dd,J＝18.7,9.0Hz,1H),1.96–1.88(m,2H),1.75(dd,J＝8.9,2.6Hz,1H),1.59–1.42(m,3H),1.37–1.29(m,3H),0.80(s,3H)；13C NMR(100MHz,DMSO-d6)δ220.0,156.4,138.0,137.8,132.5,129.8,128.9,127.8,126.7,114.7,112.6,65.9,50.0,47.8,43.9,42.6,38.3,37.3,35.8,31.8,29.6,26.5,26.0,21.6,14.0。
Example 74
Figure BDA0002848711840000251
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-27, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 66%.
1H NMR(400MHz,CDCl3)δ7.32–7.26(m,5H),6.77(d,J＝8.1Hz,1H),6.72–6.68(m,2H),4.13(t,J＝7.0Hz,2H),3.92(s,2H),3.83(s,3H),2.82(t,J＝7.0Hz,4H),2.76–2.72(m,2H),2.14(s,3H)；13C NMR(100MHz,CDCl3)δ208.0,149.4,146.0,137.1,134.5,129.3,128.5,127.5,120.1,114.0,112.3,67.5,55.9,45.3,43.6,36.9,30.1,29.3。
Example 75
Figure BDA0002848711840000252
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-28, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 66%.
1H NMR(400MHz,CDCl3)δ9.85(s,1H),7.44–7.40(m,2H),7.34–7.25(m,5H),6.91(d,J＝8.0Hz,1H),4.20(t,J＝7.0Hz,2H),3.92(s,2H),3.90(s,3H),2.83(t,J＝7.0Hz,2H)；13C NMR(100MHz,CDCl3)δ190.8,153.2,149.7,137.1,130.3,129.3,128.6,127.6,126.5,111.7,109.4,67.2,56.0,43.6,36.3。
Example 76
Figure BDA0002848711840000253
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-29, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 74%.
1H NMR(400MHz,CDCl3)δ7.68(d,J＝9.1Hz,1H),7.33–7.27(m,5H),6.87–6.84(m,2H),4.12(t,J＝6.6Hz,2H),3.92(s,2H),3.08(t,J＝4.0Hz,2H),2.74(t,J＝6.6Hz,2H),2.69–2.66(m,2H)；13C NMR(100MHz,CDCl3)δ205.2,164.0,158.0,137.1,130.6,129.3,128.6,127.6,125.4,115.5,110.5,60.4,43.6,36.8,36.4,25.8。
Example 77
Figure BDA0002848711840000261
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-30, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, the mixture is cooled to room temperature, filtered, concentrated, 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 46%.
1H NMR(400MHz,CDCl3)δ8.98(dd,J＝4.2,1.7Hz,1H),8.16(dd,J＝8.2,1.7Hz,1H),7.77(dd,J＝8.1,1.4Hz,1H),7.60(dd,J＝7.0,1.5Hz,1H),7.51(dd,J＝8.1,7.1Hz,1H),7.43(dd,J＝8.2,4.2Hz,1H),7.31–7.23(m,3H),7.20–7.17(m,2H),4.39(s,2H),3.62(s,2H)；13C NMR(100MHz,CDCl3)δ149.6,146.0,137.4,136.4,135.8,130.2,129.3,128.5,128.4,127.7,127.3,126.0,121.2,43.5,39.1。
Example 78
Figure BDA0002848711840000262
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-31, 1.0mmol of thiourea, 1.0mmol of benzyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, filtering, concentrating the filtrate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 40%.
1H NMR(400MHz,CDCl3)δ7.80(d,J＝8.4Hz,2H),7.34(d,J＝8.0Hz,2H),5.34(d,J＝6.9Hz,1H),4.55(d,J＝6.9Hz,1H),3.74(s,3H),3.51(dd,J＝14.0,4.5Hz,1H),3.39(dd,J＝13.8,5.4Hz,1H),2.45(s,3H),1.43(s,9H)；13C NMR(100MHz,CDCl3)δ170.2,154.9,145.1,141.5,129.9,129.8,128.1,127.1,80.5,52.9,52.8,37.6,28.2,21.7。
Example 79
Figure BDA0002848711840000263
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate II-31, 1.0mmol of thiourea, 1.0mmol of cinnamyl bromide, 0.5mmol of potassium carbonate, and 3mL of toluene. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, filtering, concentrating the filtrate, and directly passing through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain the product with the yield of 32%.
1H NMR(400MHz,CDCl3)δ7.40–7.37(m,2H),7.32(t,J＝7.5Hz,2H),7.25–7.22(m,1H),6.54(d,J＝15.6Hz,1H),6.19(dt,J＝15.5,7.6Hz,1H),5.33(d,J＝8.4Hz,1H),4.60(dd,J＝8.3,5.1Hz,1H),3.73(s,3H),3.51(dd,J＝7.6,1.1Hz,2H),3.16–3.04(m,2H),1.45(s,9H)；13C NMR(100MHz,CDCl3)δ171.3,155.0,136.5,133.8,128.6,127.8,126.4,124.1,80.2,52.7,52.5,41.9,41.1,28.3。
Example 80
Figure BDA0002848711840000271
To a dry 25mL Schlenk reaction tube were added 0.5mmol of thiosulfonate I-31, 1.0mmol of thiourea, 1.0mmol of iodobutane, 0.5mmol of potassium carbonate, and 3mL of water. Stirred at 80 ℃ for 24 hours. After the reaction is finished, cooling to room temperature, extracting, concentrating the extract, and directly passing 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 22%.
1H NMR(400MHz,CDCl3)δ5.35(d,J＝7.4Hz,1H),4.60(q,J＝7.1,6.2Hz,1H),3.76(s,3H),3.17–3.04(m,2H),2.69(t,J＝6.0Hz,2H),1.67–1.60(m,2H),1.44(s,9H),1.43–1.37(m,2H),0.91(t,J＝7.4Hz,3H)；13C NMR(100MHz,CDCl3)δ171.3,80.2,52.9,52.5,41.1,38.6,31.1,28.3,21.6,13.6。

Claims (9)

1. A method for preparing an asymmetric organic persulfate compound, comprising the steps of: under the promotion of alkali, carrying out one-pot reaction on the compound of the formula (I), the compound of the formula (II) and thiourea to obtain an asymmetric organic persulfate compound shown in the formula (III); the reaction solvent is toluene, dimethyl sulfoxide, dimethyl formamide, acetonitrile, ethanol or 1, 4-dioxane;
Figure FDA0003233837220000011
wherein the content of the first and second substances,
R1is aryl, arylmethylene, heteroaryl, heteroarylmethylene, said R1Optionally substituted by 1, 2 or 3RaSubstitution;
Rais F, Cl, Br, I, OH, NH2、NO2CN, phenyl, C1-10Alkyl, -C (═ O) -O-C1～5Alkyl, said phenyl, C1-10Alkyl is optionally substituted by 1, 2 or 3 halogens or-C (═ O) -O-C1～5Alkyl substitution;
R2is alkyl, alkenyl, heteroalkyl, cycloalkyl, cycloalkylmethylene, heterocycloalkyl, heterocycloalkylmethylene, aryl, arylmethylene, heteroaryl or heteroarylmethylene, and R is2Optionally substituted by 1, 2 or 3RbSubstitution;
Rbis F, Cl, Br, I, OH,NH2、NO2、CN、C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -O-C1～5Alkyl, -NHBoc, -NH-C (═ O) -Ph, -Boc, aryl, heteroaryl, heterocycloalkyl, or-S (═ O)2-C1～5Alkyl, said RbOptionally substituted by 1, 2 or 3RdSubstitution;
Rdis F, Cl, Br, I, OH, NH2、NO2CN, phenyl, C1-10Alkoxy, -NHAc, -CHO, - (C)1-6Alkylene) -C (═ O) - (C)1-6Alkyl) or-C (═ O) -O-C1～5An alkyl group;
x is F, Cl, Br, I, OTs or OTf;
ring A is aryl, heteroaryl or heterocycloalkyl, said ring A optionally substituted with 1, 2 or 3RcSubstitution;
Rcis C1-10An alkyl group.
2. The method for preparing an asymmetric organic persulfate compound as claimed in claim 1, wherein R is1Is C6～14Aryl radical, C6～14Arylmethylene, 5-15 membered heteroaryl, 5-15 membered heteroarylmethylene, R1Optionally substituted by 1, 2 or 3RaSubstitution;
R2is C1-10Alkyl radical, C1-13Heteroalkyl group, C4-10Cycloalkyl radical, C4-10Cycloalkylmethylene, 4-15 heterocycloalkyl, 4-15 heterocycloalkylmethylene, C6～14Aryl radical, C6～14Arylmethylene, 5-15 membered heteroaryl, 5-15 membered heteroarylmethylene, R2Optionally substituted by 1, 2 or 3RbSubstitution;
ring A is C6～12A meta aryl, 5-12 membered heteroaryl or 4-10 membered heterocycloalkyl, said ring A optionally substituted with 1, 2 or 3RcAnd (4) substitution.
3. The method for preparing an asymmetric organic persulfate compound as claimed in claim 2, wherein R is1Is phenyl, benzyl,
Figure FDA0003233837220000012
Said R1Optionally substituted by 1, 2 or 3RaSubstitution;
R2is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
Figure FDA0003233837220000013
Figure FDA0003233837220000021
Phenyl, benzyl, or a salt thereof,
Figure FDA0003233837220000022
Said R2Optionally substituted by 1, 2 or 3RbSubstitution;
ring A is phenyl optionally substituted with 1, 2 or 3RcAnd (4) substitution.
4. The method for preparing an asymmetric organic persulfate compound according to any one of claims 1 to 3, wherein R isaIs F, Cl, Br, I, OH, NH2、NO2CN, phenyl, CF3、C1-4Alkyl, -C (═ O) -O-C1～5Alkyl, aryl, heteroaryl, and heteroaryl,
Figure FDA0003233837220000023
RbIs F, Cl, Br, I, OH, NH2、NO2、CN、C1～5Alkyl radical, C1～5Alkoxy, -C (═ O) -O-C1～5Alkyl, -NHBoc, -NH-C (═ O) -Ph, -Boc, phenyl, Ph,
Figure FDA0003233837220000024
Figure FDA0003233837220000025
or-S (═ O)2-C1～5Alkyl radical ofR of (A) to (B)bOptionally substituted by 1, 2 or 3RdSubstitution;
Rcis CH3。
5. The method for preparing an asymmetric organic persulfate compound as claimed in claim 1, wherein the base is an organic base or an inorganic base.
6. The method of claim 5, wherein the base is cesium carbonate, potassium carbonate, sodium carbonate, potassium dihydrogen phosphate, potassium hydroxide, triethylamine or diisopropylethylenediamine.
7. The method for preparing an asymmetric organic persulfate according to claim 1, wherein the reaction temperature of the one-pot reaction is 60 to 120 ℃ and the reaction time is 10 to 30 hours.
8. The process for the preparation of asymmetric organic peroxosulfur compounds as claimed in claim 1, wherein the molar ratio of base to compound of formula (II) is 1:1 to 2.
9. The process for the preparation of asymmetric organic peroxosulfur compounds as claimed in claim 1, wherein the molar ratio of the compound of formula (II), the compound of formula (I) and thiourea is 1: 1.5-2.5: 1.5 to 2.5.
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