WO2024031242A1 - 一种合成芳基苄基硫醚类化合物的方法 - Google Patents

一种合成芳基苄基硫醚类化合物的方法 Download PDF

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WO2024031242A1
WO2024031242A1 PCT/CN2022/110855 CN2022110855W WO2024031242A1 WO 2024031242 A1 WO2024031242 A1 WO 2024031242A1 CN 2022110855 W CN2022110855 W CN 2022110855W WO 2024031242 A1 WO2024031242 A1 WO 2024031242A1
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himxy
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arylbenzyl
febr
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孙宏枚
李蓓
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苏州大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
    • C07C323/02—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/07—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
    • C07C323/09—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • 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
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/38—One sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/74—Sulfur atoms substituted by carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members 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

Definitions

  • the invention belongs to the technical field of organic synthesis and preparation, and specifically relates to a new method for synthesizing arylbenzyl sulfide compounds.
  • Arylbenzyl sulfide compounds have important synthetic value in the field of organic synthesis and are widely used in medicine, agricultural chemicals, polymer materials and other fields because of their diverse biological activities.
  • chlorfenac and pyridafen are important components of acaricides
  • omeprazole sulfide is an important intermediate used to synthesize drugs for the treatment of acid reflux disease. Therefore, research on the synthesis methods of arylbenzyl sulfide has received widespread attention.
  • Their traditional synthesis method is the coupling reaction of organic halides or organic boronic acids with sulfur sources such as thiols in the presence of strong bases and catalysts.
  • the present invention does not require existing The heating required by the technology especially avoids high-temperature conditions, shortens the reaction time, has wider substrate applicability, and the catalyst is an iron (III) complex that is simple, easy to obtain, air-stable and has a clear structure.
  • the present invention adopts the following technical solution: a method for synthesizing arylbenzyl sulfide compounds, including the following steps: in an inert gas, using sulfur phenol compounds and toluene compounds as raw materials, in an iron (III) complex [ In the presence of HIMXy Me ][FeBr 4 ] catalyst, oxidant, photosensitizer and solvent, aryl benzyl sulfide compounds are obtained through light reaction; the iron (III) complex [HIMXy Me ][FeBr 4 ] is used in the synthesis of aryl benzyl Application in thioether compounds.
  • the iron (III) complex [HIMXy Me ] [FeBr 4 ] contains 1,3-bis(4methoxy-2,6-dimethylphenyl)-4,5-dimethylimidazole
  • the chemical structural formula of the cationic iron (III) complex is as follows: .
  • the sulfur phenolic compound is represented by the following chemical formula: ,
  • Ar is an aryl group or a substituted aryl group, a heterocyclic group or a substituted heterocyclic group.
  • the thiophenol compounds are arylthiophenols and heteroarylthiophenols; such as 2-naphthylthiophenol, 4-methoxythiophenol, 4-methylthiophenol, and 4-nitrothiophenol. , 4-bromothiophenol, 2-mercaptopyrimidine, 2-mercaptopyridine, 2-mercaptothiazole, 2-mercaptobenzothiazole, 3-mercapto-1,2,4-triazole.
  • toluene compounds are expressed by the following chemical formula: .
  • R 1 is hydrogen, ortho-substituted fluorine, chlorine, bromine, methyl, meta-substituted methyl, para-substituted fluorine, chlorine, bromine, trifluoromethyl, methyl, methoxy, or disubstituted of 3,5-dimethyl.
  • arylbenzyl sulfide compounds are expressed by the following chemical structural formula: .
  • the Ar substituent is derived from a thiophenol compound, and R 1 is derived from a toluene compound.
  • the reaction temperature is room temperature and the reaction time is 6 to 18 hours. Preferably, the reaction time is 8 to 18 hours. 12 hours.
  • the light is visible light.
  • the reaction light source is an LED lamp with a power of 14 W. ⁇ 50W.
  • the preferred light source is a 28 W ⁇ 38 W white LED lamp.
  • the inert gas is argon; the solvent is acetonitrile, dichloromethane, etc.
  • the molar ratio of catalyst, photosensitizer, sulfur phenolic compound, and oxidant is 0.05 ⁇ 0.1:0.01 ⁇ 0.02:1:0.5 ⁇ 2.
  • it is 0.1:0.01:1: (1.7 ⁇ 1.8).
  • the dosage ratio of sulfur phenol compounds and toluene compounds is 0.25 mmol: 1 to 3 ml, preferably 0.25 mmol: 1.5 ml.
  • the product is extracted with ethyl acetate, and the product is purified by column chromatography to obtain arylbenzyl sulfide compounds.
  • reaction process of the present invention can be expressed as follows: .
  • the present invention uses iron (III) complex as the catalyst and uses visible light as the energy source to realize the oxidative dehydrogenation coupling of sulfur phenolic compounds and toluene compounds at room temperature for the first time.
  • the combined reaction provides a new synthesis method for arylbenzyl sulfide compounds. Compared with existing synthesis methods, the technology of the present invention can be carried out smoothly at room temperature, has better environmental friendliness and safety, and also has wider substrate applicability.
  • the iron (III) complex used in the present invention has a clear structure and air stability, and the reactants and other raw materials used are cheap and easy to obtain, which is conducive to large-scale synthesis applications and is also in line with the development concept of sustainable green synthetic chemistry.
  • Example 1 Iron (III) complex containing 1,3-bis(4methoxy-2,6-dimethylphenyl)-4,5-dimethylimidazole cation [HIMXy Me ][FeBr 4 ]Synthesis.
  • the iron(III) complex [HIMxy Me ][FeBr 4 ] exists in the form of an ion pair, in which the anion [FeBr 4 ] - was characterized by Raman spectroscopy and found to have a characteristic peak at 204 cm -1 , Consistent with what was reported in the literature (Melissa, SS; Eric, RS; Eric, VP; Freeman, RG, Inorg. Chem. , 2001 , 40, 2298).
  • the cation [HIMXy Me ] + of the iron (III) complex was characterized by high-resolution mass spectrometry, and it was found that it has a molecular ion peak at 365.2224.
  • the theoretical molecular ion peak of [HIMXy Me ] + is at 365.2224.
  • the actual measurement is consistent with the theory . It was proved that the obtained compound was the target iron(III) complex.
  • Example 2 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 2-naphthylthiol and toluene was used.
  • Example 3 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 4-methylthiophenol and toluene was used.
  • Example 4 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 4-bromothiophenol and toluene was used.
  • Example 5 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 4-chlorothiophenol and toluene was used.
  • Example 6 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 4-methoxythiophenol and toluene was used.
  • Example 7 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 2-mercaptobenzothiazole and toluene was used.
  • reaction product was extracted with ethyl acetate, separated and purified by column chromatography (using a mixed solvent with a volume ratio of ethyl acetate/petroleum ether of 1:50 as the developing agent), and the yield was 75%.
  • Example 8 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 2-mercaptopyrimidine and toluene was used.
  • the product was extracted with ethyl acetate, separated and purified by column chromatography (using a mixed solvent with a volume ratio of ethyl acetate/petroleum ether of 1:10 as the developing solvent), and the yield was 32%.
  • Example 9 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 2-mercaptopyridine and toluene was used.
  • the product was extracted with ethyl acetate, separated and purified by column chromatography (using a mixed solvent with a volume ratio of ethyl acetate/petroleum ether of 1:10 as the developing agent), and the yield was 21%.
  • Example 10 Using [HIMXy Me ][FeBr 4 ] as the catalyst, the photocatalytic oxidative dehydrogenation coupling reaction of 2-naphthylthiol and 4-tert-butyltoluene was used.
  • Example 11 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 2-naphthylthiol and 4-chlorotoluene was used.
  • Example 12 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 2-naphthylthiophenol and ethylbenzene was used.
  • Example 13 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 2-naphthylthiophenol and 2-methyltoluene was used.
  • Example 14 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 2-naphthylthiol and 4-methyltoluene was used.
  • Example 15 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 2-naphthylthiol and 3-methyltoluene was used.
  • Example 16 Using [HIMXy Me ][FeBr 4 ] as the catalyst, the photocatalytic oxidative dehydrogenation coupling reaction of 2-naphthylthiol and 2-chlorotoluene was used.
  • Example 17 Using [HIMXy Me ][FeBr 4 ] as the catalyst, photocatalytic oxidative dehydrogenation coupling reaction of 2-naphthylthiol and tetrahydrofuran was used.
  • reaction product was extracted with ethyl acetate, separated and purified by column chromatography (using a mixed solvent with a volume ratio of ethyl acetate/petroleum ether of 1:10 as the developing solvent), and the yield was 54%.
  • the present invention uses an iron (III) complex as a catalyst and uses visible light as an energy source to realize the oxidative dehydrogenation coupling reaction of sulfur phenol compounds and toluene compounds at room temperature for the first time, providing aryl benzyl sulfide compounds.
  • a new synthesis method Compared with existing synthesis methods, the technology of the present invention can be carried out smoothly at room temperature, has better environmental friendliness and safety, and also has wider substrate applicability.

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Abstract

一种利用光催化合成芳基苄基硫醚类化合物的方法，仅在可见光照射下，以铁(III)配合物[HIMXy Me][FeBr 4]([HIMXy Me]=l,3-二(4-甲氧基-2,6-二甲基苯基)-4,5-二甲基咪唑阳离子)为催化剂、以fac-Ir(ppy) 3(ppy=2-苯基吡啶基)为光敏剂、DTBP(过氧化二叔丁基)为氧化剂，通过硫酚类化合物与甲苯类化合物的氧化脱氢偶联反应合成相应的芳基苄基硫醚类化合物。由铁系催化剂在光照条件下通过S-H键和C-H键的活化而实现的芳基苄基硫醚类化合物的合成，在室温下即可顺利进行，同时所用的铁(III)配合物具有明确的结构和空气稳定性，所用的反应原料价廉易得，有利于大规模合成应用。

Description

一种合成芳基苄基硫醚类化合物的方法 技术领域
本发明属于有机合成制备技术领域，具体涉及到一种合成芳基苄基硫醚类化合物的新方法。
 背景技术
芳基苄基硫醚类化合物在有机合成领域中具有重要的合成价值，因其多样的生物活性被广泛应用于医药、农用化学品、高分子材料等领域。例如，氯杀螨、哒螨酮是除螨剂的重要成分，奥美拉唑硫醚是用来合成治疗胃酸反流性疾病药物的重要中间体。因此，对于芳基苄基硫醚合成方法的研究受到了广泛关注。它们的传统合成方法是有机卤化物或者有机硼酸与硫醇等硫源在强碱和催化剂存在下的偶联反应，这些方法具有明显的局限性，如反应温度高、官能团耐受性差、含卤废弃物排放等。近年来，过渡金属催化的S-H键和C-H键的氧化脱氢偶联反应开始收到了关注，在构建C-S键时显示出明显的优势（ Chem. Soc. Rev. 2015, 44, 291）。目前，相关的研究工作主要集中在S-H键与C(sp 2)-H键或C(sp)-H键之间氧化脱氢偶联，但涉及S-H键和C(sp 3)-H键的氧化脱氢偶联反应的报道还是很少的。2019年，徐大振课题组以FeCl 3为催化剂，将空气作为氧化剂，采用硫酚类化合物为硫源，实现了2-吲哚酮苄位C(sp 3)-H键的硫醚化，但反应仅适用于吲哚酮类化合物；2021年，黄汉民课题组通过Ni(OAc) 2·4H 2O催化实现了芳基苄基硫醚类化合物的构建，但是反应仅适用于苄位仲C(sp3)-H键的硫醚化，而且反应温度高达140℃。由此可见，目前报道的过渡金属催化的S-H键和苄位C(sp 3)-H键的氧化脱氢偶联反应往往需要贵金属催化剂（Pd(OAc) 2（OAc = CH 3COO -））、很高的反应温度或者底物适用性较差。因此，开发这类化合物的新合成方法是极具创新性和应用价值的。
技术问题
本发明的目的是提供一种合成芳基苄基硫醚类化合物的新方法，仅在可见光照射下，铁(Ⅲ)配合物[HIMXy Me][FeBr 4]（[HIMXy Me] = 1,3-二(4­甲氧基-2,6-二甲基苯基)-4,5-二甲基咪唑阳离子）为催化剂、以 fac-Ir(ppy) 3（ppy = 2-苯基吡啶基)为光敏剂，DTBP（过氧化二叔丁基）为氧化剂，通过硫酚类化合物与甲苯类化合物的氧化脱氢偶联反应来合成相应的芳基苄基硫醚类化合物，本发明无需现有技术所必须的加热，尤其避免了高温条件，也缩短了反应时间，具有更广的底物适用性，且催化剂是一种简单易得、具有空气稳定和明确结构的铁(Ⅲ)配合物。
技术解决方案
本发明采用如下技术方案：一种合成芳基苄基硫醚类化合物的方法，包括以下步骤，在惰性气体中，以硫酚类化合物与甲苯类化合物为原料，在铁(Ⅲ)配合物[HIMXy Me][FeBr 4]催化剂、氧化剂、光敏剂和溶剂存在下，光照反应，得到芳基苄基硫醚类化合物；铁(Ⅲ)配合物[HIMXy Me][FeBr 4]在合成芳基苄基硫醚类化合物中的应用。
本发明中，铁(Ⅲ)配合物[HIMXy Me][FeBr 4]为含1,3-二(4­甲氧基-2,6-二甲基苯基)-4,5-二甲基咪唑阳离子的铁(Ⅲ)配合物，其化学结构式如下： 。
本发明中，硫酚类化合物由下列化学式表示： ，Ar为芳基或者取代芳基、杂环基或者取代杂环基。
优选的，硫酚类化合物为芳基硫酚、杂芳基硫酚；比如2-萘硫酚、4-甲氧基苯硫酚、4-甲基苯硫酚、4-硝基苯硫酚、4-溴苯硫酚、2-巯基嘧啶、2-巯基吡啶、2-巯基噻唑、2-巯基苯并噻唑、3-巯基-1,2,4-三唑。
本发明中，甲苯类化合物由下列化学式表达： 。
R 1为氢、邻位取代的氟、氯、溴、甲基，间位取代的甲基，对位取代的氟、氯、溴、三氟甲基、甲基、甲氧基， 或者二取代的3,5-二甲基。
本发明中，芳基苄基硫醚类化合物由下列化学结构式表达： 。
式中Ar取代基源自硫酚类化合物、R 1源自甲苯类化合物。
上述技术方案中，反应温度为室温，时间为6 ~ 18小时，优选的，时间为8 ~ 12小时。
上述技术方案中，光照为可见光照，具体的，反应光源为LED灯，功率为14 W ~ 50 W。优选的光源为28 W~ 38 W的白色LED灯。
上述技术方案中，所述惰性气体为氩气；所述溶剂为乙腈、二氯甲烷等。
上述技术方案中，催化剂、光敏剂、硫酚类化合物、氧化剂的摩尔比为0.05 ~ 0.1 ∶0.01 ~ 0.02 ∶1∶0.5 ~ 2。优选为0.1∶0.01∶1∶（1.7~1.8）。硫酚类化合物、甲苯类化合物的用量比0.25 毫摩尔∶1~3毫升，优选0.25 毫摩尔∶1.5毫升。
上述技术方案中，反应结束后，用乙酸乙酯萃取，产物通过柱层析提纯，得到芳基苄基硫醚类化合物。
本发明的反应过程可表示如下： 。
有益效果
由于上述技术方案运用，本发明具有以下优点：1. 本发明以铁(Ⅲ)配合物为催化剂，首次在室温下以可见光为能量来源实现了硫酚类化合物与甲苯类化合物的氧化脱氢偶联反应，为芳基苄基硫醚类化合物提供了一种新合成方法。相对于现有的合成方法，本发明技术可在室温下件下顺利实行，具有更好的环境友好性和安全性，同时还具有更广的底物适用性。
2. 本发明所采用铁(Ⅲ)配合物具有明确的结构和空气稳定性，所用的反应物等原料价廉易得，有利于大规模合成应用，也符合可持续绿色合成化学的发展理念。
 本发明的实施方式
本发明所有原料都是市售产品，具体制备方法以及测试方法为本领域常规技术，收率为分离收率（特殊指出除外）。
实施例一：含1,3-二(4­甲氧基-2,6-二甲基苯基)-4,5-二甲基咪唑阳离子的铁(III)配合物[HIMXy Me][FeBr 4]的合成。
将含1,3-二(4­甲氧基-2,6-二甲基苯基)-4,5-二甲基咪唑氯盐（0.40克，1.0毫摩尔）加入到三溴化铁（0.27克，0.9毫摩尔）的四氢呋喃溶液中，60 oC下反应24小时，真空抽去溶剂，用超干正己烷洗涤，抽干，用四氢呋喃萃取，离心清液转移，在清液中加入己烷重结晶，室温下析出红棕色固体粉末，产率87%。
化学结构式如下： 。
对产物进行元素分析，结果如下所示： 。
铁(III)配合物[HIMxy Me][FeBr 4]是以离子对的形式存在的，其中阴离子[FeBr 4] -通过拉曼光谱进行了表征，发现其在204 cm -1处有特征峰，与文献报道的相符合（Melissa, S. S.; Eric, R. S.; Eric, V. P.; Freeman, R. G., Inorg. Chem., 2001, 40, 2298）。铁(III)配合物的阳离子[HIMXy Me] +通过高分辨质谱进行了表征，发现其在365.2224处有一个分子离子峰，理论上[HIMXy Me] +的分子离子峰在365.2224，实测与理论一致。证明所得化合物为目标铁(III)配合物。
实施例二：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-萘硫酚与甲苯的氧化脱氢偶联反应。
。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-萘硫酚（40.1毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应11小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以石油醚为展开剂），产率为91%。
将产物溶于CDCl 3中（0.4 mL），封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 7.70 – 7.59 (m, 4H), 7.34 (q, J = 6.7, 5.5 Hz, 3H), 7.28 – 7.13 (m, 5H), 4.12 (s, 2H)。
如将上述反应中的乙腈更换为同体积的THF、DMF或者DMSO，都得不到产物。
拓展实施例。
。
a反应条件: 1 (0.25 mmol), 2 (2.5 mL), DTBP (0.375 mmol), catalyst (10 mol%), 光敏剂 (1 mol%), 乙腈 2.5 mL，50 W 蓝光 LED, 室温反应24 h. GC收率， n-dodecane 为内标。
。
以[HIMXy Me][FeBr 4]为催化剂，乙腈用量为2.5 mL，不同光敏剂得到的产物收率如下。
 以。[HIMXy Me][FeBr 4]为催化剂，不同比例混合溶剂得到的产物收率如下。
。
a 反应条件: 1 (0.25 mmol), 2, DTBP (0.375 mmol), [HIMXy Me][FeBr 4] (10 mol%), 光敏剂 (1 mol%), 乙腈，50 W 蓝光 LED, 室温反应24 h. GC收率， n-dodecane 为内标。
。
以[HIMXy Me][FeBr 4]为催化剂，乙腈用量为1.5 mL，不同氧化剂用量得到的产物收率如下。
。
a反应条件: 1 (0.25 mmol), 2 (1.5 mL), DTBP, [HIMXy Me][FeBr 4] (10 mol%), 光敏剂 (1 mol%), 乙腈1.5 mL，50 W 蓝光 LED, 室温反应24 h. GC收率， n-dodecane 为内标。
。
以[HIMXy Me][FeBr 4]为催化剂，不同光照得到的产物收率如下。
。
a反应条件: 1 (0.25 mmol), 2 (1.5 mL), DTBP (0.44 mmol), [HIMXy Me][FeBr 4] (10 mol%), 光敏剂 (1 mol%), 乙腈1.5 mL，室温反应24 h. GC收率， n-dodecane 为内标。
b 分离收率。
实施例三：以[HIMXy Me][FeBr 4]为催化剂，利用光催化4-甲基苯硫酚与甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克，0.0025 毫摩尔）、4-甲基苯硫酚（31.1毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应8小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以石油醚为展开剂），产率为67%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 7.28 – 7.18 (m, 7H), 7.05 (d, J = 8.0 Hz, 2H), 4.06 (s, 2H), 2.29 (s, 3H)。
实施例四：以[HIMXy Me][FeBr 4]为催化剂，利用光催化4-溴苯硫酚与甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、4-溴苯硫酚（47.3毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应11小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以石油醚为展开剂），产率为85%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 7.80 (d, J = 8.1 Hz, 1H), 7.61 (d, J = 7.9 Hz, 1H), 7.47 – 7.10 (m, 7H), 4.48 (s, 2H)。
实施例五：以[HIMXy Me][FeBr 4]为催化剂，利用光催化4-氯苯硫酚与甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、4-氯苯硫酚（36.2毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应11小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以石油醚为展开剂），产率为86%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 7.80 (d, J = 8.1 Hz, 1H), 7.61 (d, J = 7.9 Hz, 1H), 7.47 – 7.10 (m, 7H), 4.48 (s, 2H)。
实施例六：以[HIMXy Me][FeBr 4]为催化剂，利用光催化4-甲氧基苯硫酚与甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、4-甲氧基苯硫酚（31微升，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应10小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以乙酸乙酯/石油醚体积比为1：50的混合溶剂为展开剂），产率为66%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 7.28 – 7.19 (m, 7H), 6.81 (d, J = 8.8 Hz, 2H), 4.01 (s, 2H), 3.80 (s, 3H)。
实施例七：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-巯基苯并噻唑与甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-巯基苯并噻唑（41.8 毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应12小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以乙酸乙酯/石油醚体积比为1：50的混合溶剂为展开剂），产率为75%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 7.89 (d, J = 8.1 Hz, 1H), 7.71 (d, J = 7.9 Hz, 1H), 7.46 – 7.37 (m, 3H), 7.34 – 7.21 (m, 4H), 4.58 (s, 2H)。
实施例八：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-巯基嘧啶与甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-巯基嘧啶（28.0 毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应12小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以乙酸乙酯/石油醚体积比为1：10的混合溶剂为展开剂），产率为32%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 8.55 (d, J = 4.8 Hz, 2H), 7.47 (dd, J = 7.2, 1.8 Hz, 2H), 7.36 – 7.24 (m, 4H), 6.99 (t, J = 4.8 Hz, 1H), 4.45 (s, 2H)。
实施例九：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-巯基吡啶与甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-巯基吡啶（27.8 毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应12小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以乙酸乙酯/石油醚体积比为1：10的混合溶剂为展开剂），产率为 21%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 8.42 (ddd, J = 5.0, 1.9, 1.0 Hz, 1H), 7.45 – 7.34 (m, 3H), 7.29 – 7.17 (m, 3H), 7.12 (dt, J = 8.1, 1.1 Hz, 1H), 6.94 (ddd, J = 7.4, 5.0, 1.1 Hz, 1H), 4.41 (s, 2H)。
实施例十：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-萘硫酚与4-叔丁基甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-萘硫酚（40.1 毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和4-叔丁基甲苯（1.5 毫升）作为混合溶剂，室温下，用28W白色LED灯照射反应10小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以石油醚为展开剂），产率为  81%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 7.74 (dt, J = 18.4, 9.1 Hz, 4H), 7.42 (ddd, J = 11.8, 6.6, 1.9 Hz, 3H), 7.30 (t, J = 8.5 Hz, 3H), 7.24 (s, 1H), 4.21 (s, 2H), 1.29 (s, 9H)。
实施例十一：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-萘硫酚与4-氯甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-萘硫酚（40.1 毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和4-氯甲苯（1.5 毫升）作为混合溶剂，室温下，用28W白色LED灯照射反应10小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以石油醚为展开剂），产率为  85%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 7.85 – 7.71 (m, 4H), 7.53 – 7.41 (m, 3H), 7.28 (d, J = 4.7 Hz, 4H), 4.20 (s, 2H)。
实施例十二：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-萘硫酚与乙苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-萘硫酚（40.1 毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和乙苯（1.5 毫升）作为混合溶剂，在38W白色LED灯照射下室温反应12小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以石油醚为展开剂），产率为  47%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 7.74 (q, J = 4.8, 3.7 Hz, 2H), 7.66 (d, J = 8.4 Hz, 2H), 7.40 (td, J = 6.6, 6.0, 3.2 Hz, 2H), 7.34 (ddd, J = 13.5, 8.4, 2.3 Hz, 3H), 7.25 (td, J = 7.4, 1.1 Hz, 2H), 7.21 – 7.16 (m, 1H), 4.44 (q, J = 7.0 Hz, 1H), 1.65 (d, J = 7.0 Hz, 3H)。
实施例十三：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-萘硫酚与2-甲基甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-萘硫酚（40.1 毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和2-甲基甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应10小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以石油醚为展开剂），产率为  88%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl 3) δ 7.82 – 7.65 (m, 4H), 7.48 – 7.36 (m, 3H), 7.21 – 7.14 (m, 3H), 7.09 (d, J = 5.6 Hz, 1H), 4.19 (s, 2H), 2.41 (s, 3H)。
实施例十四：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-萘硫酚与4-甲基甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-萘硫酚（40.1 毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和2-甲基甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应10小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以石油醚为展开剂），产率为  82%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl3) δ 7.71 (dq, J = 8.8, 6.1, 5.3 Hz, 4H), 7.52 – 7.32 (m, 3H), 7.26 – 7.16 (m, 2H), 7.06 (s, 2H), 4.18 (s, 2H), 2.30 (s, 3H)。
实施例十五：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-萘硫酚与3-甲基甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-萘硫酚（40.1 毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和3-甲基甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应10小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以石油醚为展开剂），产率为  74%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl3) δ 7.77 – 7.63 (m, 4H), 7.46 – 7.33 (m, 3H), 7.20 – 7.07 (m, 3H), 7.02 (d, J = 7.2 Hz, 1H), 4.15 (s, 2H), 2.27 (s, 3H)。
实施例十六：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-萘硫酚与2-氯甲苯的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-萘硫酚（40.1 毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和2-氯甲苯（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应11小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以石油醚为展开剂），产率为  82%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl3) δ 7.85 – 7.66 (m, 4H), 7.56 – 7.32 (m, 4H), 7.28 (d, J = 1.7 Hz, 1H), 7.16 (dtd, J = 24.8, 7.5, 1.5 Hz, 2H), 4.33 (s, 2H)。
实施例十七：以[HIMXy Me][FeBr 4]为催化剂，利用光催化2-萘硫酚与四氢呋喃的氧化脱氢偶联反应。
氮气保护下，在反应瓶中依次加入催化剂（18.4 毫克，0.025毫摩尔）、 fac-Ir(ppy) 3（1.6 毫克， 0.0025 毫摩尔）、2-萘硫酚（40.1 毫克，0.25 毫摩尔）、过氧化二叔丁基（80微升，0.44毫摩尔）、以乙腈（1.5 毫升）和四氢呋喃（1.5 毫升）作为混合溶剂，室温下，用38W白色LED灯照射反应12小时，用水淬灭反应，反应产物用乙酸乙酯萃取，通过柱层析分离提纯（以乙酸乙酯/石油醚体积比为1：10的混合溶剂为展开剂），产率为54%。
将产物溶于CDCl 3中（0.4 mL）, 封管，室温下于Unity Inova-400型NMR仪上测定表征： 1H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 1.8 Hz, 1H), 7.85 – 7.76 (m, 3H), 7.60 (dd, J = 8.7, 1.8 Hz, 1H), 7.48 (tt, J = 8.1, 5.9 Hz, 2H), 5.79 (dd, J = 7.2, 3.7 Hz, 1H), 4.21 – 3.93 (m, 2H), 2.44 (dtd, J = 12.1, 7.3, 4.6 Hz, 1H), 2.17 – 2.01 (m, 2H), 2.01 – 1.87 (m, 1H)。
本发明以铁(Ⅲ)配合物为催化剂，首次在室温下以可见光为能量来源实现了硫酚类化合物与甲苯类化合物的氧化脱氢偶联反应，为芳基苄基硫醚类化合物提供了一种新合成方法。相对于现有的合成方法，本发明技术可在室温下件下顺利实行，具有更好的环境友好性和安全性，同时还具有更广的底物适用性。

Claims (10)

  1. 一种合成芳基苄基硫醚类化合物的方法，包括以下步骤，在惰性气体中，以硫酚类化合物与甲苯类化合物为原料，在铁(Ⅲ)配合物[HIMXy Me][FeBr 4]催化剂、氧化剂、光敏剂和溶剂存在下，光照反应，得到芳基苄基硫醚类化合物。
  2. 根据权利要求1所述合成芳基苄基硫醚类化合物的方法，其特征在于，铁(Ⅲ)配合物[HIMXy Me][FeBr 4]的化学结构式如下：
    。
  3. 根据权利要求1所述合成芳基苄基硫醚类化合物的方法，其特征在于，硫酚类化合物由下列化学式表示： ，Ar为芳基或者取代芳基、杂环基或者取代杂环基。
  4. 根据权利要求1所述合成芳基苄基硫醚类化合物的方法，其特征在于，甲苯类化合物由下列化学式表达：
    R 1为氢、邻位取代的氟、氯、溴、甲基，间位取代的甲基，对位取代的氟、氯、溴、三氟甲基、甲基、甲氧基， 或者二取代的3,5-二甲基。
  5. 根据权利要求1所述合成芳基苄基硫醚类化合物的方法，其特征在于，反应温度为室温，时间为6～18小时。
  6. 根据权利要求1所述合成芳基苄基硫醚类化合物的方法，其特征在于，光照为可见光照。
  7. 根据权利要求1所述合成芳基苄基硫醚类化合物的方法，其特征在于，催化剂、光敏剂、硫酚类化合物、氧化剂的摩尔比为0.05～0.1∶0.01～0.02 ∶1∶0.5～2。
  8. 根据权利要求1所述合成芳基苄基硫醚类化合物的方法制备的芳基苄基硫醚类化合物，其特征在于，所述芳基苄基硫醚类化合物由下列化学结构式表达：
    式中Ar取代基源自硫酚类化合物、R 1源自甲苯类化合物。
  9. 铁(Ⅲ)配合物[HIMXy Me][FeBr 4] ，其特征在于，铁(Ⅲ)配合物[HIMXy Me][FeBr 4]的化学结构式如下：
    。
  10. 权利要求9所述铁(Ⅲ)配合物[HIMXy Me][FeBr 4]在合成芳基苄基硫醚类化合物中的应用。
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