CN117466790A - Preparation method of alpha-sulfinylated carbonyl compound - Google Patents

Preparation method of alpha-sulfinylated carbonyl compound Download PDF

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CN117466790A
CN117466790A CN202311479760.0A CN202311479760A CN117466790A CN 117466790 A CN117466790 A CN 117466790A CN 202311479760 A CN202311479760 A CN 202311479760A CN 117466790 A CN117466790 A CN 117466790A
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prop
thiophenol
phenyl
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sulfinylated
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CN117466790B (en
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杜正银
牟丹
王林达
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Northwest Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—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
    • 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
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/34—Sulfur atoms

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a preparation method of an alpha-sulfinylated carbonyl compound, which comprises the steps of sequentially adding a propargyl alcohol compound, a thiophenol compound and an oxidant into a container, adding a solvent under argon atmosphere, and carrying out sealing reaction for 24 hours at 50-90 ℃ to obtain a reaction solution after the reaction is completed; the reaction liquid is sequentially washed, concentrated and separated by column chromatography to obtainαSulfinated carbonyl compounds. The invention has the advantages of no need of metal catalysis, mild and simple conditions, convenient operation and costLow cost, good stability, strong compatibility and wide substrate universality, and can realize large-scale production, and the preparation method comprises the following stepsαThe sulfinylated carbonyl skeleton has better industrial application prospect in the aspects of the synthesis of bioactive compounds and medicines.

Description

Preparation method of alpha-sulfinylated carbonyl compound
Technical Field
The invention relates to the field of organic synthetic chemistry, in particular to a preparation method of an alpha-sulfinylated carbonyl compound.
Background
Elemental sulfur is one of the important elements in the life system, often in the form of proteins and amino acids, and sulfur-containing compoundsAre widely found in natural products, pesticides and pharmaceutical molecules, e.g.αThe sulfinylated carbonyl skeleton is a chemical building block present in the molecules of drugs having anti-inflammatory, anti-cancer, anti-tumor properties. At the same time, the method comprises the steps of,αsulfinated carbonyl compounds and their derivatives are also of great importance in agrochemicals and pharmaceuticals. Thus, efficient synthesisαSulfinated carbonyl compounds are highly favored by chemists.
Presently disclosedαThe synthesis method of the sulfinylated carbonyl compound mainly comprises the following steps: (1) Synthesized by conventional methodsαSulfinylated carbonyl compounds, e.g. Trost problem group, by substitution of the corresponding sulfide anionsαHalocarbonyl compounds, multistep synthesisαHalogenated carbonyl compoundsChem. Rev., 1978, 78, 363-382；Acc. Chem. Res., 1978, 11, 453-461) The method comprises the steps of carrying out a first treatment on the surface of the While Wlabislaw and Yadav are synthesized by reacting carbonyl compounds with sulfinylating reagentsαSulfinylated carbonyl compounds [ ]Org. Prep. Proced. Int., 2007, 39, 447-494； Tetrahedron Lett., 2008, 49, 3015-3018). (2) Synthesis under the action of transition metal catalystα-sulfinylated carbonyl compounds; as reported in the Samec group, a synthesis using gold catalyst in 1, 2-dichloroethaneαProcess for sulfinylation of carbonyl compoundsChem. Commun., 2012, 48, 6586-6588) The method comprises the steps of carrying out a first treatment on the surface of the In 2013, their subject group proposed the use of nitromethane (Meno 2 ) Is solvent and can be synthesized with high efficiency by gold chloride catalysisαSulfinylated carbonyl compounds [ ]Chem. Eur. J., 2013, 19, 17939-17950) The method comprises the steps of carrying out a first treatment on the surface of the The Samec group of subjects reported one-step synthesis of propargyl alcohol and arylthiophenols using water as solvent, copper catalysisαProcess for sulfinylation of carbonyl compoundsGreen Chem., 2013, 15, 3176-3179). However, the methods for synthesizing the target compounds reported in the above documents are mostly complex, and the reaction conditions are severe, so that the general application cannot be achieved.
The thiophenol compound is easy to generate sulfur free radical, and the sulfur free radical can generate free radical coupling and free radical addition reaction. At present, no thiophenol compound is available to generate sulfur free radical, and no transition metal existsSulfur free base regioselective attack of propargyl alcohol compounds in the presence of a catalytic, oxidizing agent aloneβThe triple bond of the position, thereby constructing a C-S bond and a C=O bond simultaneously in one step, generatingαReport of the reaction of the sulfinated carbonyl compounds.
Disclosure of Invention
The invention aims to solve the technical problem of providing the preparation method of the alpha-sulfinylated carbonyl compound, which has the advantages of low cost, simple condition, economy, high efficiency, strong compatibility and wide applicability.
In order to solve the problems, the preparation method of the alpha-sulfinylated carbonyl compound is characterized by comprising the following steps: the method comprises the steps of sequentially adding a propargyl alcohol compound, a thiophenol compound and an oxidant into a container, adding a solvent under argon atmosphere, and carrying out sealing reaction at 50-90 ℃ for 24 hours to obtain a reaction solution after the reaction is completed; the reaction liquid is sequentially washed, concentrated and separated by column chromatography to obtainα-sulfinylated carbonyl compounds; the molar ratio of the propargyl alcohol compound to the thiophenol compound is 1: 1-2: 1, a step of; the molar ratio of the propargyl alcohol compound to the oxidant is 4: 1-5: 1.
the propargyl alcohol compound refers to 3-phenyl-2-propyn-1-ol, 3- (p-tolyl) prop-2-yn-1-ol, 3- (4-ethylphenyl) prop-2-yn-1-ol, 3- (4-methoxyphenyl) prop-2-yn-1-ol, 3- (4- (tert-butyl) phenyl) prop-2-yn-1-ol, 3- ([ 1,1' -biphenyl ] -4-yl) prop-2-yn-1-ol, 3- (m-tolyl) prop-2-yn-1-ol, 3- (3-methoxyphenyl) prop-2-yn-1-ol, 3- (o-tolyl) prop-2-yn-1-ol, 3- (2-methoxyphenyl) prop-2-yn-1-ol, 3- (2-isopropylphenyl) prop-2-yn-1-ol, 3- (4-fluorophenyl) prop-2-yn-1-ol, 3- (4-chlorophenyl) prop-2-ol, 3- (4-bromophenyl) prop-1-ol, any one of 3- (4- (trifluoromethyl) phenyl) propan-2-yn-1-ol, 3- (4-cyanophenyl) propan-2-yn-1-ol, 3- (4-nitrophenyl) propan-2-yn-1-ol, 3- (2-fluorophenyl) propan-2-yn-1-ol, 3- (2-chlorophenyl) propan-2-yn-1-ol, 3- (2-bromophenyl) propan-2-yn-1-ol, 4-phenyl-3-butyn-2-ol, 1-phenyl-1-pentyn-3-ol, 1-phenyl-1-hexyn-3-ol, 4-hexyn-3-ol, 3-hexyn-2-ol, 2-propyn-1-ol, 2-butyn-1-ol, 2-pentyn-1-ol.
The thiophenol compound is any one of 4-methyl thiophenol, 4-methoxy thiophenol, 4-isopropyl thiophenol, 3-methyl thiophenol, 3-methoxy thiophenol, 2-methoxy thiophenol, 3, 4-dimethyl thiophenol, 4-fluoro thiophenol, 4-chlorobenzenesulfide, 4-bromo thiophenol, 3-chlorobenzenesulfide, 2-naphthalene thiophenol, 2-thiophene thiol and 2-pyridine thiol.
The oxidant is N-hydroxyphthalimide (NHPI), tert-butyl hydroperoxide (TBHP), di-tert-butyl peroxide (DTBP), tert-butyl peroxybenzoate (TBPB), hydrogen peroxide (H) 2 O 2 ) Sodium peroxide (Na) 2 O 2 ) Potassium persulfate (K) 2 S 2 O 8 ) Any one of Benzoyl Peroxide (BPO).
The solvent is any one of dichloroethane, dichloromethane, tetrahydrofuran, dioxane, acetonitrile, N-dimethylformamide, N-methyl-2-pyrrolidone and toluene.
Compared with the prior art, the invention has the following advantages:
1. in the invention, the thiophenol compound generates sulfur free radicals which can regioselectively attack propargyl alcohol compoundβThe three bonds at the position simultaneously construct a C-S bond and a C=O bond in one step, and have the characteristics of good stability, strong compatibility and wide substrate universality.
2. The invention has the advantages of no need of metal catalysis, mild and simple condition, convenient operation and low cost, can realize large-scale production, and containsαThe sulfinylated carbonyl skeleton has better industrial application prospect in the aspects of the synthesis of bioactive compounds and medicines.
Detailed Description
The preparation process of alpha-sulfinylated carbonyl compound includes adding propargyl alcohol compound, thiophenol compound and oxidant into container, adding solvent in argon atmosphere, sealing at 50-90 deg.c for reaction for 24 hr to obtain reaction liquid; the reaction solution isWashing, concentrating, and separating by column chromatography to obtainαSulfinated carbonyl compounds.
Wherein: the molar ratio of propargyl alcohol compound to thiophenol compound is 1: 1-2: 1, a step of; the molar ratio of the propargyl alcohol compound to the oxidant is 4: 1-5: 1.
propargyl alcohol refers to 3-phenyl-2-propen-1-ol, 3- (p-tolyl) propan-2-yn-1-ol, 3- (4-ethylphenyl) propan-2-yn-1-ol, 3- (4-methoxyphenyl) propan-2-yn-1-ol, 3- (4- (tert-butyl) phenyl) propan-2-yn-1-ol, 3- ([ 1,1' -biphenyl ] -4-yl) propan-2-yn-1-ol, 3- (m-tolyl) propan-2-yn-1-ol, 3- (3-methoxyphenyl) propan-2-yn-1-ol, 3- (o-tolyl) propan-2-yn-1-ol, 3- (2-methoxyphenyl) propan-2-yn-1-ol, 3- (2-isopropylphenyl) propan-2-yn-1-ol, 3- (4-chlorophenyl) propan-2-ol, 3- (4-bromophenyl) propan-1-ol, any one of 3- (4- (trifluoromethyl) phenyl) propan-2-yn-1-ol, 3- (4-cyanophenyl) propan-2-yn-1-ol, 3- (4-nitrophenyl) propan-2-yn-1-ol, 3- (2-fluorophenyl) propan-2-yn-1-ol, 3- (2-chlorophenyl) propan-2-yn-1-ol, 3- (2-bromophenyl) propan-2-yn-1-ol, 4-phenyl-3-butyn-2-ol, 1-phenyl-1-pentyn-3-ol, 1-phenyl-1-hexyn-3-ol, 4-hexyn-3-ol, 3-hexyn-2-ol, 2-propyn-1-ol, 2-butyn-1-ol, 2-pentyn-1-ol.
The thiophenol compound is any one of 4-methylphenylsulfiol, 4-methoxyphenylthiophenol, 4-isopropylthiophenol, 3-methylphenylsulfiol, 3-methoxyphenylthiophenol, 2-methoxyphenylthiophenol, 3, 4-dimethylphenylsulfiol, 4-fluorophenylthiophenol, 4-chlorophenylthiol, 4-bromophenylthiophenol, 3-chlorophenylthiol, 2-thiophenol and 2-pyridinethiol.
The oxidizing agent is N-hydroxyphthalimide (NHPI), tert-butyl hydroperoxide (TBHP), di-tert-butyl peroxide (DTBP), tert-butyl peroxybenzoate (TBPB), hydrogen peroxide (H) 2 O 2 ) Sodium peroxide (Na) 2 O 2 ) Potassium persulfate (K) 2 S 2 O 8 ) In Benzoyl Peroxide (BPO)Any one of them.
The solvent is any one of dichloroethane, dichloromethane, tetrahydrofuran, dioxane, acetonitrile, N-dimethylformamide, N-methyl-2-pyrrolidone and toluene.
Example 1AαA process for preparing the sulfinylated carbonyl compound, which comprises adding 3-phenyl-2-propyn-1-ol, 4-methyl thiophenol and N-hydroxy phthalimide (NHPI) to Schlenk tube, adding dichloromethane under argon atmosphere, and sealing at 60 deg.C for 24 hr.
Wherein: the molar ratio of 3-phenyl-2-propyn-1-ol to 4-methyl thiophenol is 1:1, a step of; the molar ratio of 3-phenyl-2-propyn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by a thin layer chromatography, namely sampling is carried out every 1 hour, a capillary is used for respectively dripping reaction liquid sample application and raw material propargyl alcohol compound sample application on a silica gel plate, the two sample application are positioned on the same straight line, and then the silica gel plate is put into a container with the volume ratio (mL/mL) of 20:1 in a display bottle of petroleum ether-ethyl acetate mixed solution. After the walking plate is completed, the silica gel plate is placed under an ultraviolet lamp or in an iodine bottle for observation, and if the reaction liquid does not have a point flush with the propargyl alcohol of the raw material liquid, the reaction is completely indicated, and the reaction liquid is obtained at the moment.
Pouring the reaction solution into a 50 mL round-bottom flask, washing a Schlenk tube three times by using ethyl acetate, and pouring the washing solution into the round-bottom flask; then, a RE-52AA rotary evaporator manufactured by Shanghai Asia Biochemical Co., ltd is used for carrying out reduced pressure evaporation to remove the solvent at 40 ℃ to obtain concentrated solution; adding silica gel with the mass of 2-3 times of the concentrated solution into the concentrated solution for sample mixing, placing the mixed sample into a chromatographic column, and adding the silica gel with the volume ratio (mL/mL) of 20:1, and finally collecting eluent, placing the eluent into a rotary evaporator, and concentrating at 40 ℃ to obtain the 3-phenyl-2- (p-toluenesulfonyl) propanal with the yield of 84%.
Example 2AαProcess for the preparation of a sulfinated carbonyl compound by sequential addition of 3-phenyl-2-propyn-1-ol, 4-isopropylthiophenol, N-hydroxyphthalodimethylImide (NHPI) was added to Schlenk tube, dichloroethane was added under argon atmosphere, and the reaction was sealed at 60℃for 24 hours.
Wherein: the molar ratio of 3-phenyl-2-propyn-1-ol to 4-isopropylthiophenol was 1:1, a step of; the molar ratio of 3-phenyl-2-propyn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to give 2- ((4-isopropylphenyl) thio) -3-phenylpropionaldehyde with a yield of 78%.
Example 3A kind ofαA process for the preparation of a sulfinated carbonyl compound, which comprises the sequential addition of 3-phenyl-2-propyn-1-ol, 2-methoxyphenylthiophenol, di-tert-butyl peroxide (DTBP) to a Schlenk tube, addition of dichloroethane under argon atmosphere and a sealed reaction at 60℃for 24 hours.
Wherein: the molar ratio of 3-phenyl-2-propyn-1-ol to 2-methoxyphenylthiophenol is 1:1, a step of; the molar ratio of 3-phenyl-2-propyn-1-ol to di-tert-butyl peroxide (DTBP) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as described in example 1 to obtain 2- ((2-methoxyphenyl) thio) -3-phenylpropionaldehyde with a yield of 77%.
Example 4AαA process for preparing the sulfinylated carbonyl compound, which comprises adding 3-phenyl-2-propyn-1-ol, 3, 4-dimethylbenzenesulfide and N-hydroxyphthalimide (NHPI) to Schlenk tube in sequence, adding dichloroethane under argon atmosphere, and sealing at 60 deg.C for 24 hr.
Wherein: the molar ratio of 3-phenyl-2-propyn-1-ol to 3, 4-dimethylbenzenesulfide is 1:1, a step of; the molar ratio of 3-phenyl-2-propyn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as described in example 1 to give 2- ((3, 4-dimethylphenyl) thio) -3-phenylpropionaldehyde in 74% yield.
Example 5AαA process for producing a sulfinylated carbonyl compound, which comprises sequentially reacting 3-phenyl-2-propyn-1-ol, 4-fluorobenzene thiophenol, potassium persulfate (K) 2 S 2 O 8 ) Into a Schlenk tube, dichloroethane was added under argon atmosphere, and the reaction was sealed at 60℃for 24 hours.
Wherein: the molar ratio of 3-phenyl-2-propyn-1-ol to 4-fluorobenzene thiophenol is 1:1, a step of; 3-phenyl-2-propyn-1-ol and potassium persulfate (K) 2 S 2 O 8 ) The molar ratio of (2) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as described in example 1 to give 2- ((4-fluorophenyl) thio) -3-phenylpropionaldehyde in 62% yield.
Example 6AαA process for the preparation of a sulfinated carbonyl compound, which comprises the sequential addition of 3-phenyl-2-propyn-1-ol, 3-chlorophenylthiol, N-hydroxyphthalimide (NHPI) to a Schlenk tube, the addition of dichloroethane under argon atmosphere and the sealed reaction at 60℃for 24 hours.
Wherein: the molar ratio of 3-phenyl-2-propyn-1-ol to 3-chlorophenylthiol is 1:1, a step of; the molar ratio of 3-phenyl-2-propyn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as described in example 1 to give 2- ((3-chlorophenyl) thio) -3-phenylpropionaldehyde with a yield of 68%.
Example 7AαA process for the preparation of a sulfinated carbonyl compound, which comprises the sequential addition of 3-phenyl-2-propyn-1-ol, 2-chlorophenylthiol, N-hydroxyphthalimide (NHPI) to a Schlenk tube, the addition of dichloroethane under argon atmosphere and the sealed reaction at 60℃for 24 hours.
Wherein: the molar ratio of 3-phenyl-2-propyn-1-ol to 2-chlorophenylthiol is 1:1, a step of; the molar ratio of 3-phenyl-2-propyn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as described in example 1 to obtain 2- ((2-chlorophenyl) thio) -3-phenylpropionaldehyde with a yield of 65%.
Example 8AαA process for preparing the sulfinated carbonyl compounds, which comprises adding 3-phenyl-2-propyn-1-ol, 2-naphthalenethiol and N-hydroxyphthalimide (NHPI) into Schlenk tube, adding dichloromethane under argon atmosphere, and sealing at 60deg.C for 24 hr.
Wherein: the molar ratio of 3-phenyl-2-propyn-1-ol to 2-naphthalene thiophenol is 1:1, a step of; the molar ratio of 3-phenyl-2-propyn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was subjected to washing, concentration and column chromatography separation as described in example 1 to obtain 2- (2-naphthylthio) -3-phenylpropionaldehyde with a yield of 53%.
Example 9AαA process for preparing the sulfinylated carbonyl compound, which comprises adding 3- (p-tolyl) prop-2-yn-1-ol, 3-methyl thiophenol, N-hydroxy phthalimide (NHPI) to Schlenk tube, adding dichloroethane under argon atmosphere, and sealing at 60 deg.C for 24 hr.
Wherein: the molar ratio of 3- (p-tolyl) prop-2-yn-1-ol to 3-methylthiophenol is 1:1, a step of; the molar ratio of 3- (p-tolyl) prop-2-yn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to obtain 3- (p-tolyl) -2- (m-tolylthio) propanal in 78% yield.
Example 10AαProcess for the preparation of sulfinated carbonyl compounds by sequential reaction of 3- (4-ethylphenyl) prop-2-yn-1-ol, 4-methylOxophenylthiophenol, t-butyl hydroperoxide (TBHP) and acetonitrile were added to Schlenk tube under argon atmosphere, and the reaction was sealed at 60℃for 24 hours.
Wherein: the molar ratio of 3- (4-ethylphenyl) prop-2-yn-1-ol to 4-methoxyphenylthiophenol is 1:1, a step of; the molar ratio of 3- (4-ethylphenyl) prop-2-yn-1-ol to t-butylhydroperoxide (TBHP) was 5:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as described in example 1 to give 3- (4-ethylphenyl) -2- ((4-methoxyphenyl) thio) propanal in 77% yield.
Example 11AαA process for preparing the sulfinated carbonyl compounds, which comprises adding 3- (4-methoxyphenyl) prop-2-yn-1-ol, 3, 4-dimethylbenzenesulfide and di-tert-butyl peroxide (DTBP) into a Schlenk tube in sequence, adding methylene chloride under argon atmosphere, and sealing at 60 ℃ for reaction for 24 hours.
Wherein: the molar ratio of 3- (4-methoxyphenyl) prop-2-yn-1-ol to 3, 4-dimethylbenzenesulfide is 1:1, a step of; the molar ratio of 3- (4-methoxyphenyl) prop-2-yn-1-ol to di-tert-butyl peroxide (DTBP) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as described in example 1 to give 2- ((3, 4-dimethylphenyl) thio) -3- (4-methoxyphenyl) propanal in 70% yield.
Example 12A method ofαA process for the preparation of a sulfinated carbonyl compound, which comprises adding 3- (4- (tert-butyl) phenyl) prop-2-yn-1-ol, 4-methylphenylsulfiol, N-hydroxyphthalimide (NHPI) to a Schlenk tube in sequence, adding tetrahydrofuran under argon atmosphere, and sealing at 60℃for 24 hours.
Wherein: the molar ratio of 3- (4- (tert-butyl) phenyl) prop-2-yn-1-ol to 4-methylphenylsulfiol is 1:1, a step of; the molar ratio of 3- (4- (tert-butyl) phenyl) prop-2-yn-1-ol to N-hydroxyphthalimide (NHPI) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as in example 1 to give 3- (4- (tert-butyl) phenyl) -2- (p-toluenesulfonyl) propanal in 79% yield.
Example 13AαProcess for the preparation of a sulfinylated carbonyl compound by sequential reaction of 3- ([ 1,1' -biphenyl)]-4-yl) prop-2-yn-1-ol, 4-methylphenylsulfate, potassium persulfate (K) 2 S 2 O 8 ) Toluene was added to the Schlenk tube and the reaction was sealed at 60℃for 24 hours under argon atmosphere.
Wherein: 3- ([ 1,1' -biphenyl)]-4-yl) prop-2-yn-1-ol to 4-methylphenylsulfiol in a molar ratio of 1:1, a step of; 3- ([ 1,1' -biphenyl)]-4-yl) prop-2-yn-1-ol and potassium persulfate (K) 2 S 2 O 8 ) The molar ratio of (2) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to give 3- ([ 1,1' -biphenyl ] -4-yl) -2- (p-toluenesulfonyl) propanal in 73% yield.
Example 14AαA process for preparing sulfinylated carbonyl compounds, which comprises adding 3- (m-tolyl) prop-2-yn-1-ol, 2-thiophenethiol, N-hydroxyphthalimide (NHPI) to Schlenk tube, adding dichloroethane under argon atmosphere, and sealing at 60 deg.C for 24 hr.
Wherein: the molar ratio of 3- (m-tolyl) prop-2-yn-1-ol to 2-thiophenethiol is 1:1, a step of; the molar ratio of 3- (m-tolyl) prop-2-yn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to obtain 2- (thiophene-2-thio) -3- (m-tolyl) propanal in 62% yield.
Example 15AαProcess for the preparation of sulfinylated carbonyl compounds, the processThe method is to add 3- (3-methoxy phenyl) prop-2-yn-1-ol, 4-bromothiophenol and N-hydroxy phthalimide (NHPI) into a Schlenk tube in sequence, add dichloromethane under argon atmosphere, and carry out sealing reaction for 24 hours at 60 ℃.
Wherein: the molar ratio of 3- (3-methoxyphenyl) prop-2-yn-1-ol to 4-bromothiophenol is 1:1, a step of; the molar ratio of 3- (3-methoxyphenyl) prop-2-yn-1-ol to N-hydroxyphthalimide (NHPI) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as described in example 1 to give 2- ((4-bromophenyl) thio) -3- (3-methoxyphenyl) propanal in 71% yield.
Example 16AαA process for preparing sulfinated carbonyl compounds, which comprises adding 3- (o-tolyl) prop-2-yn-1-ol, 2-pyridinethiol, N-hydroxyphthalimide (NHPI) into Schlenk tube, adding dichloromethane under argon atmosphere, and sealing at 60deg.C for 24 hr.
Wherein: the molar ratio of 3- (o-tolyl) prop-2-yn-1-ol to 2-pyridinethiol is 1:1, a step of; the molar ratio of 3- (o-tolyl) prop-2-yn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to obtain 2- (pyridine-2-thio) -3- (o-tolyl) propanal in 60% yield.
Example 17AαA process for preparing the sulfinylated carbonyl compound, which comprises adding 3- (2-methoxyphenyl) prop-2-yn-1-ol, 4-methyl thiophenol, N-hydroxy phthalimide (NHPI) to Schlenk tube, adding N, N-dimethylformamide under argon atmosphere, and sealing at 50 deg.C for 24 hr.
Wherein: the molar ratio of 3- (2-methoxyphenyl) prop-2-yn-1-ol to 4-methyl thiophenol is 1:1, a step of; the molar ratio of 3- (2-methoxyphenyl) prop-2-yn-1-ol to N-hydroxyphthalimide (NHPI) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as in example 1 to give 3- (2-methoxyphenyl) -2- (p-toluenesulfonyl) propanal in a yield of 76%.
Example 18AαA process for producing a sulfinated carbonyl compound, which comprises sequentially reacting 3- (2-isopropylphenyl) prop-2-yn-1-ol, 4-chlorophenylthiol, sodium peroxide (Na) 2 O 2 ) N, N-dimethylformamide was added to the Schlenk tube and the reaction was sealed at 60℃for 24 hours.
Wherein: the molar ratio of 3- (2-isopropylphenyl) prop-2-yn-1-ol to 4-chlorophenylthiol is 1:1, a step of; 3- (2-isopropylphenyl) prop-2-yn-1-ol and sodium peroxide (Na 2 O 2 ) The molar ratio of (2) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as described in example 1 to give 2- ((4-chlorophenyl) thio) -3- (2-isopropylphenyl) propanal in 69% yield.
Example 19AαA process for preparing the sulfinylated carbonyl compound, which comprises adding 3- (4-fluorophenyl) prop-2-yn-1-ol, 4-methyl thiophenol and tert-butyl peroxybenzoate (TBPB) to Schlenk tube, adding dichloroethane under argon atmosphere, and sealing at 70 deg.C for 24 hr.
Wherein: the molar ratio of 3- (4-fluorophenyl) prop-2-yn-1-ol to 4-methyl thiophenol is 1:1, a step of; the molar ratio of 3- (4-fluorophenyl) prop-2-yn-1-ol to tert-butyl peroxybenzoate (TBPB) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to obtain 3- (4-fluorophenyl) -2- (p-toluenesulfonyl) propanal in 66% yield.
Example 20AαProcess for the preparation of sulfinylated carbonyl compoundsThe method is to add 3- (4-chlorophenyl) prop-2-yn-1-ol, 4-methyl thiophenol and N-hydroxy phthalimide (NHPI) into a Schlenk tube in turn, add dioxane under argon atmosphere, and react for 24 hours under the sealing at 60 ℃.
Wherein: the molar ratio of 3- (4-chlorophenyl) prop-2-yn-1-ol to 4-methyl thiophenol is 1:1, a step of; the molar ratio of 3- (4-chlorophenyl) prop-2-yn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as in example 1 to give 3- (4-chlorophenyl) -2- (p-toluenesulfonyl) propanal in 69% yield.
Example 21AαA process for preparing the sulfinylated carbonyl compound, which comprises adding 3- (4-bromophenyl) prop-2-yn-1-ol, 4-fluorobenzene thiophenol and di-tert-butyl peroxide (DTBP) to Schlenk tube in sequence, adding methylene chloride under argon atmosphere, and sealing at 60 ℃ for reaction for 24 hours.
Wherein: the molar ratio of 3- (4-bromophenyl) prop-2-yn-1-ol to 4-fluorophenylthiophenol is 1:1, a step of; the molar ratio of 3- (4-bromophenyl) prop-2-yn-1-ol to di-tert-butyl peroxide (DTBP) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as described in example 1 to give 3- (4-bromophenyl) -2- ((4-fluorophenyl) thio) propanal in 61% yield.
Example 22AαA process for preparing sulfinated carbonyl compounds, which comprises adding 3- (4- (trifluoromethyl) phenyl) prop-2-yn-1-ol, 2-methoxyphenylthiophenol, N-hydroxyphthalimide (NHPI) to Schlenk tube, adding tetrahydrofuran under argon atmosphere, and sealing at 60 deg.C for 24 hr.
Wherein: the molar ratio of 3- (4- (trifluoromethyl) phenyl) prop-2-yn-1-ol to 2-methoxyphenylthiophenol is 1:1, a step of; the molar ratio of 3- (4- (trifluoromethyl) phenyl) prop-2-yn-1-ol to N-hydroxyphthalimide (NHPI) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as described in example 1 to give 2- ((2-methoxyphenyl) thio) -3- (4- (trifluoromethyl) phenyl) -propanal in 60% yield.
Example 23AαA process for preparing the sulfinated carbonyl compounds, which comprises adding 3- (4-cyanophenyl) prop-2-yn-1-ol, 4-methyl thiophenol, N-hydroxy phthalimide (NHPI) into Schlenk tube, adding dichloromethane under argon atmosphere, and sealing at 80deg.C for 24 hr.
Wherein: the molar ratio of 3- (4-cyanophenyl) prop-2-yn-1-ol to 4-methylphenylsulfiol is 1:1, a step of; the molar ratio of 3- (4-cyanophenyl) prop-2-yn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as in example 1 to give 3- (4-cyanophenyl) -2- (p-toluenesulfonyl) propanal in 61% yield.
Example 24AαA process for preparing sulfinated carbonyl compounds, which comprises adding 3- (4-nitrophenyl) prop-2-yn-1-ol, 4-methyl thiophenol, N-hydroxy phthalimide (NHPI) into Schlenk tube, adding dichloromethane under argon atmosphere, and sealing at 90 deg.C for 24 hr.
Wherein: the molar ratio of 3- (4-nitrophenyl) prop-2-yn-1-ol to 4-methyl thiophenol is 1:1, a step of; the molar ratio of 3- (4-nitrophenyl) prop-2-yn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to obtain 3- (4-nitrophenyl) -2- (p-toluenesulfonyl) propanal in 52% yield.
Example 25AαProcess for the preparation of sulfinylated carbonyl compoundsThe method is to add 3- (2-fluorophenyl) prop-2-yn-1-ol, 4-methyl thiophenol and tert-butyl peroxybenzoate (TBPB) into a Schlenk tube, add N-methyl-2-pyrrolidone under argon atmosphere, and carry out sealing reaction for 24 hours at 70 ℃.
Wherein: the molar ratio of 3- (2-fluorophenyl) prop-2-yn-1-ol to 4-methyl thiophenol is 1:1, a step of; the molar ratio of 3- (2-fluorophenyl) prop-2-yn-1-ol to tert-butyl peroxybenzoate (TBPB) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to obtain 3- (2-fluorophenyl) -2- (p-toluenesulfonyl) propanal in 65% yield.
Example 26AαA process for preparing sulfinylated carbonyl compounds, which comprises adding 3- (2-chlorophenyl) prop-2-yn-1-ol, 3-methoxythiophenol, benzoyl Peroxide (BPO) to Schlenk tube in sequence, adding methylene chloride under argon atmosphere, and sealing at 60 ℃ for reaction for 24 hours.
Wherein: the molar ratio of 3- (2-chlorophenyl) prop-2-yn-1-ol to 3-methoxyphenylthiophenol is 1:1, a step of; the molar ratio of 3- (2-chlorophenyl) prop-2-yn-1-ol to Benzoyl Peroxide (BPO) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as described in example 1 to give 3- (2-chlorophenyl) -2- ((3-methoxyphenyl) thio) propanal in 63% yield.
Example 27AαA process for the preparation of a sulfinated carbonyl compound, which comprises adding 3- (2-bromophenyl) prop-2-yn-1-ol, 4-isopropylthiophenol, tert-butyl peroxybenzoate (TBPB) into a Schlenk tube, adding methylene chloride under argon atmosphere, and hermetically reacting at 60 ℃ for 24 hours.
Wherein: the molar ratio of 3- (2-bromophenyl) prop-2-yn-1-ol to 4-isopropylthiophenol was 1:1, a step of; the molar ratio of 3- (2-bromophenyl) prop-2-yn-1-ol to tert-butyl peroxybenzoate (TBPB) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as described in example 1 to give 3- (2-bromophenyl) -2- ((4-isopropylphenyl) thio) propanal in 60% yield.
Example 28AαA process for producing a sulfinylated carbonyl compound, which comprises sequentially reacting 4-phenyl-3-butyn-2-ol, 4-methylphenylsulfanyl, hydrogen peroxide (H) 2 O 2 ) Into a Schlenk tube, dichloroethane was added under argon atmosphere, and the reaction was sealed at 90℃for 24 hours.
Wherein: the molar ratio of 4-phenyl-3-butyn-2-ol to 4-methyl thiophenol is 1:1, a step of; 4-phenyl-3-butyn-2-ol and hydrogen peroxide (H) 2 O 2 ) The molar ratio of (2) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to give 4-phenyl-3- (p-toluenesulfonyl) -2-butanone in 78% yield.
Example 29AαA process for the preparation of a sulfinated carbonyl compound, which comprises the sequential addition of 1-phenyl-1-pentyn-3-ol, 2-chlorophenylthiol, N-hydroxyphthalimide (NHPI) to a Schlenk tube, the addition of dichloroethane under argon atmosphere and the sealed reaction at 80℃for 24 hours.
Wherein: the molar ratio of 1-phenyl-1-pentyn-3-ol to 2-chlorophenylthiol is 1:1, a step of; the molar ratio of 1-phenyl-1-pentyn-3-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as described in example 1 to give 2- ((2-chlorophenyl) thio) -1-phenyl-3-pentanone in 67% yield.
Example 30AαA process for the preparation of a sulfinylated carbonyl compound by the sequential addition of 1-phenyl-1-hexyn-3-ol, 4-methylbenzothiool, N-hydroxyphthalimide (NHPI) to a Schlenk tube under argon atmosphereDichloroethane was added and the reaction was sealed at 80℃for 24 hours.
Wherein: the molar ratio of 1-phenyl-1-hexyn-3-ol to 4-methyl thiophenol is 1:1, a step of; the molar ratio of 1-phenyl-1-hexyn-3-ol to N-hydroxyphthalimide (NHPI) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to obtain 1-phenyl-2- (p-toluenesulfonyl) -3-hexanone with a yield of 65%.
Example 31AαA process for the preparation of a sulfinated carbonyl compound, which comprises the sequential addition of 4-hexyn-3-ol, 4-methylphenylsulfiol, N-hydroxyphthalimide (NHPI) to a Schlenk tube, the addition of dichloroethane under argon atmosphere and the sealed reaction at 70℃for 24 hours.
Wherein: the molar ratio of 4-hexyn-3-ol to 4-methyl thiophenol is 2:1, a step of; the molar ratio of 4-hexyn-3-ol to N-hydroxyphthalimide (NHPI) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to obtain 3- (p-toluenesulfonyl) -2-hexanone with a yield of 61%.
Example 32AαA process for the preparation of a sulfinated carbonyl compound, which comprises the sequential addition of 3-hexyn-2-ol, 4-methylphenylsulfiol, N-hydroxyphthalimide (NHPI) to a Schlenk tube, the addition of dichloroethane under argon atmosphere and the sealed reaction at 70℃for 24 hours.
Wherein: the molar ratio of 3-hexyn-2-ol to 4-methyl thiophenol is 2:1, a step of; the molar ratio of 3-hexyn-2-ol to N-hydroxyphthalimide (NHPI) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was washed, concentrated and separated by column chromatography as in example 1 to obtain 4- (p-toluenesulfonyl) -3-hexanone with a yield of 60%.
Example 33AαSulfinylated carbonyl compoundsThe preparation method is that 2-propyn-1-alcohol, 4-methyl thiophenol and N-hydroxy phthalimide (NHPI) are added into a Schlenk tube in sequence, dichloroethane is added under argon atmosphere, and the sealing reaction is carried out for 24 hours at 70 ℃.
Wherein: the molar ratio of 2-propyn-1-ol to 4-methyl thiophenol is 2:1, a step of; the molar ratio of 2-propyn-1-ol to N-hydroxyphthalimide (NHPI) is 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was subjected to washing, concentration and column chromatography separation as described in example 1 to obtain 2- (p-toluenesulfonyl) propanal in 50% yield.
Example 34AαA process for the preparation of a sulfinated carbonyl compound, which comprises the sequential addition of 2-butyn-1-ol, 4-methylphenylsulfiol, N-hydroxyphthalimide (NHPI) to a Schlenk tube, the addition of methylene chloride under argon atmosphere and the sealed reaction at 70℃for 24 hours.
Wherein: the molar ratio of 2-butyn-1-ol to 4-methyl thiophenol is 2:1, a step of; the molar ratio of 2-butyn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction mixture was washed, concentrated and separated by column chromatography as in example 1 to give 2- (p-toluenesulfonyl) butanal in 58% yield.
Example 35AαA process for the preparation of a sulfinated carbonyl compound, which comprises adding 2-pentyn-1-ol, 4-methylphenylsulfiol, N-hydroxyphthalimide (NHPI) in sequence to a Schlenk tube, adding methylene chloride under argon atmosphere, and hermetically reacting at 70℃for 24 hours.
Wherein: the molar ratio of 2-pentyn-1-ol to 4-methylphenylsulfiol is 2:1, a step of; the molar ratio of 2-pentyn-1-ol to N-hydroxyphthalimide (NHPI) was 4:1.
the whole reaction process is tracked by thin layer chromatography as described in example 1 to obtain a reaction solution; the reaction solution was subjected to washing, concentration and column chromatography separation as described in example 1 to obtain 2- (p-toluenesulfonyl) valeraldehyde with a yield of 53%.

Claims (5)

1. A process for the preparation of an α -sulfinylated carbonyl compound characterized by: the method comprises the steps of sequentially adding a propargyl alcohol compound, a thiophenol compound and an oxidant into a container, adding a solvent under argon atmosphere, and carrying out sealing reaction at 50-90 ℃ for 24 hours to obtain a reaction solution after the reaction is completed; the reaction liquid is sequentially washed, concentrated and separated by column chromatography to obtainα-sulfinylated carbonyl compounds; the molar ratio of the propargyl alcohol compound to the thiophenol compound is 1: 1-2: 1, a step of; the molar ratio of the propargyl alcohol compound to the oxidant is 4: 1-5: 1.
2. a process for the preparation of an α -sulfinylated carbonyl compound according to claim 1 wherein: the propargyl alcohol compound refers to 3-phenyl-2-propyn-1-ol, 3- (p-tolyl) prop-2-yn-1-ol, 3- (4-ethylphenyl) prop-2-yn-1-ol, 3- (4-methoxyphenyl) prop-2-yn-1-ol, 3- (4- (tert-butyl) phenyl) prop-2-yn-1-ol, 3- ([ 1,1' -biphenyl ] -4-yl) prop-2-yn-1-ol, 3- (m-tolyl) prop-2-yn-1-ol, 3- (3-methoxyphenyl) prop-2-yn-1-ol, 3- (o-tolyl) prop-2-yn-1-ol, 3- (2-methoxyphenyl) prop-2-yn-1-ol, 3- (2-isopropylphenyl) prop-2-yn-1-ol, 3- (4-fluorophenyl) prop-2-yn-1-ol, 3- (4-chlorophenyl) prop-2-ol, 3- (4-bromophenyl) prop-1-ol, any one of 3- (4- (trifluoromethyl) phenyl) propan-2-yn-1-ol, 3- (4-cyanophenyl) propan-2-yn-1-ol, 3- (4-nitrophenyl) propan-2-yn-1-ol, 3- (2-fluorophenyl) propan-2-yn-1-ol, 3- (2-chlorophenyl) propan-2-yn-1-ol, 3- (2-bromophenyl) propan-2-yn-1-ol, 4-phenyl-3-butyn-2-ol, 1-phenyl-1-pentyn-3-ol, 1-phenyl-1-hexyn-3-ol, 4-hexyn-3-ol, 3-hexyn-2-ol, 2-propyn-1-ol, 2-butyn-1-ol, 2-pentyn-1-ol.
3. A process for the preparation of an α -sulfinylated carbonyl compound according to claim 1 wherein: the thiophenol compound is any one of 4-methyl thiophenol, 4-methoxy thiophenol, 4-isopropyl thiophenol, 3-methyl thiophenol, 3-methoxy thiophenol, 2-methoxy thiophenol, 3, 4-dimethyl thiophenol, 4-fluoro thiophenol, 4-chlorobenzenesulfide, 4-bromo thiophenol, 3-chlorobenzenesulfide, 2-naphthalene thiophenol, 2-thiophene thiol and 2-pyridine thiol.
4. A process for the preparation of an α -sulfinylated carbonyl compound according to claim 1 wherein: the oxidant is any one of N-hydroxyphthalimide, tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, hydrogen peroxide, sodium peroxide, potassium persulfate and benzoyl peroxide.
5. A process for the preparation of an α -sulfinylated carbonyl compound according to claim 1 wherein: the solvent is any one of dichloroethane, dichloromethane, tetrahydrofuran, dioxane, acetonitrile, N-dimethylformamide, N-methyl-2-pyrrolidone and toluene.
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WO2013112104A1 (en) * 2012-01-27 2013-08-01 Kat2Biz Ab Preparation of [alpha]-sulfenylated carbonyl compounds from propargylic alcohols in one step

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Publication number Priority date Publication date Assignee Title
WO2013112104A1 (en) * 2012-01-27 2013-08-01 Kat2Biz Ab Preparation of [alpha]-sulfenylated carbonyl compounds from propargylic alcohols in one step

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Title
BISWAS, SRIJIT 等: "A gold(I)-catalyzed route to α-sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols", 《CHEMICAL COMMUNICATIONS》, 31 December 2012 (2012-12-31), pages 6586 - 6588, XP055081977, DOI: 10.1039/c2cc32042h *
BISWAS, SRIJIT 等: "Atom-Efficient Gold(I)-Chloride-Catalyzed Synthesis of α-Sulfenylated Carbonyl Compounds from Propargylic Alcohols and Aryl Thiols: Substrate Scope and Experimental and Theoretical Mechanistic Investigation", 《CHEMISTRY - A EUROPEAN JOURNAL》, 31 December 2013 (2013-12-31), pages 17939 - 17950 *
DAN MOU 等: "Synthesis of α-sulfenylated carbonyl compounds under metal-free conditions", 《ORG. BIOMOL. CHEM.》, 29 November 2023 (2023-11-29), pages 274 *
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