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WO2018133473A1 - 一种可见光催化的饱和碳氢键直接氧化方法 - Google Patents

一种可见光催化的饱和碳氢键直接氧化方法 Download PDF

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WO2018133473A1
WO2018133473A1 PCT/CN2017/107760 CN2017107760W WO2018133473A1 WO 2018133473 A1 WO2018133473 A1 WO 2018133473A1 CN 2017107760 W CN2017107760 W CN 2017107760W WO 2018133473 A1 WO2018133473 A1 WO 2018133473A1
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visible light
organic compound
direct oxidation
saturated hydrocarbon
reaction
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左智伟
胡安华
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ShanghaiTech University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B33/00—Oxidation in general
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C281/02—Compounds containing any of the groups, e.g. carbazates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups

Definitions

  • the invention relates to the field of organic synthesis, in particular to a visible light catalyzed method for efficiently oxidizing saturated hydrocarbon bonds in an organic compound by using a ruthenium complex.
  • Visible light catalysis is a catalytic mode that utilizes the energy of visible light to activate a photocatalyst, thereby promoting organic reactions.
  • visible light catalysis uses only clean light energy, low catalyst dosage and mild reaction conditions, and it is expected to develop a more efficient and environmentally friendly synthesis method.
  • How to use visible light catalysis to achieve efficient saturated carbon-hydrogen bond oxidation reaction, while developing a more economical and environmentally friendly photocatalyst, in order to achieve industrial application is a great challenge.
  • the method of discharge of matter is an object of the present invention to provide a catalyst and a reagent which are inexpensive and readily available under mild conditions, to achieve high-efficiency oxidation of saturated hydrocarbon bonds in an organic compound under visible light irradiation, to obtain an oxidation product in a high yield, and to reduce waste.
  • the present invention provides a visible light catalyzed direct oxidation of a saturated hydrocarbon bond, characterized by comprising: the action of an organic compound and an oxidizing agent in a ruthenium complex and an additive under the condition of visible light irradiation.
  • the reaction is carried out to oxidize a saturated hydrocarbon bond in the organic compound to obtain an oxidation product.
  • the organic compound is a paraffin, a cycloalkane, an aromatic hydrocarbon or a saturated hydrocarbon bond Other compounds.
  • the oxidizing agent is oxygen, a halogenating agent or an azo reagent.
  • the halogenating agent is N-chlorosuccinimide, N-bromosuccinimide, p-toluenesulfonyl chloride, methanesulfonyl chloride, N-fluoropyridine, N-fluorodiphenyl At least one of a sulfonimide, 1-chloromethyl-4-fluoro-1,4-diazonium dicyclo 2.2.2 octane bis(tetrafluoroborate) salt and elemental iodine.
  • the azo reagent is at least one of azodicarbonate, azobenzene, azoformamide and azobisisobutyronitrile.
  • the metal cation of the ruthenium complex is any one of Ce 4+ and Ce 3+ , preferably ruthenium tetrachloride hydrate, ruthenium tetrachloride, ruthenium trichloride hydrate, trichlorination ⁇ , at least one of cerium nitrate hydrate, cerium triflate, cerium tetrafluoromethanesulfonate, cerium sulfate, cerium acetate, cerium oxalate and cerium tetraisopropoxide.
  • the anion of the additive is any one of Cl - , Br - , preferably tetrabutylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, tetraethylammonium bromide, At least one of tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, sodium chloride, potassium chloride, cesium chloride, sodium bromide, potassium bromide and cesium bromide.
  • the molar ratio of the organic compound to the ruthenium complex is 1:0.0000001-0.2.
  • the molar ratio of the rhodium complex to the additive is 1:0.2 - 1:10.
  • the reaction conditions are from room temperature to 80 °C.
  • the visible light is light having a wavelength of 300-800 nm.
  • the ruthenium complex functions to activate a hydrocarbon bond of an alkane under visible light irradiation to produce a highly reactive alkyl radical, and further reacts with an oxidizing reagent to obtain an oxidation product.
  • the effect of the additive is to increase the catalytic efficiency of the ruthenium complex.
  • the reaction of the invention only needs to be carried out at a relatively low temperature, the reaction time is short, and the reaction efficiency is high; at the same time, only visible light is required to provide the energy required for the activation reaction, which is a milder, green activation mode.
  • the ruthenium catalyst used in the invention is low in cost, simple and efficient, the oxidizing agent used is more stable in nature, low in industrial use cost, and can avoid environmental pollution caused by heavy transition metals and peroxides.
  • reaction raw materials ruthenium complexes, and additives in the following examples are all commercially available products.
  • Ethylbenzene and p-toluenesulfonyl chloride are reacted under the action of ruthenium complexes and additives for 12 hours to oxidize the saturated carbon-hydrogen bond of ethylbenzene to obtain an oxidation product.
  • the reaction equation is as follows:
  • Oxygen was added to a solution of 10 mL of methyl valerate (116 mg, 1 mmol) in acetonitrile for 20 min. Oxygen saturation, adding 2 mol% ruthenium complex ruthenium trichloride (4.8 mg, 0.02 mmol) and 5 mol% of the additive tetrabutylammonium chloride (14 mg, 0.05 mmol), at room temperature (25 ° C), at ( Under the condition of blue LED lamp with wavelength of 380nm-550nm, methyl valerate and oxygen are reacted under the action of ruthenium complex and additive for 12h to oxidize the saturated carbon-hydrogen bond of methyl valerate to obtain oxidation.
  • Product the reaction equation is as follows:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明提供了一种有机化合物中饱和碳氢键的直接氧化方法，其特征在于，包括：在可见光照射的条件下，使有机化合物与氧化试剂在铈复合物的存在下进行反应，使有机化合物的饱和碳氢键氧化得到氧化产物。本发明反应仅需在室温下进行，催化效率高，仅依靠可见光来提供活化反应所需的能量，是一种更加温和、绿色的活化模式；同时所用的催化剂成本低廉，所用氧化试剂性质更加稳定，在工业上利用成本低，催化体系实用性强；同时能避免重过渡金属，过氧化物等对环境的污染。

Description

一种可见光催化的饱和碳氢键直接氧化方法 技术领域
本发明是有机合成领域，特别涉及一种可见光催化的，利用铈复合物高效氧化有机化合物中的饱和碳氢键的方法。
背景技术
有机化合物中的碳氢键直接氧化反应一直是催化领域中的研究热点。该合成策略能够将广泛存在的碳氢键直接构建成预期的官能团(羟基，羰基，胺基等)，在合成高附加值的药物分子或其中间体中，能够使用廉价的起始原料，显著缩短合成路线，在工业上有着广泛的应用前景。由于这类碳氢键的键能较高，使得其活性较低，现有的方法通常需要贵重过渡金属催化，并使用性质不太稳定的过氧化物，也通常需要较高温度和压力。如何能在温和、绿色的条件下，仅使用廉价的催化剂和试剂，高效氧化碳氢键是化学合成领域一直追逐的目标。可见光催化是利用可见光的能量来活化光催化剂，进而促进有机反应的一种催化模式。与传统催化模式相比，可见光催化仅利用清洁的光能，催化剂的用量低，反应条件温和，有望发展出更高效，对环境更加友好的合成方法。如何利用可见光催化来实现高效的饱和碳氢键氧化反应，同时发展出更加经济环保的光催化剂，以期实现工业化应用是一个极大的挑战。
发明内容
本发明的目的是提供一种能够在温和的条件下，采用廉价易得的催化剂和试剂，在可见光照射下实现有机化合物中饱和碳氢键的高效氧化，高产率的得到氧化产物，同时减少废弃物排放的方法。
为了达到上述目的，本发明提供了一种可见光催化的饱和碳氢键直接氧化方法，其特征在于，包括：在可见光照射的条件下，使有机化合物与氧化试剂在铈的配合物及添加剂的作用下进行反应，使有机化合物中的饱和碳氢键氧化得到氧化产物。
优选地，所述的有机化合物为链烷烃、环烷烃、芳香烃或含有饱和碳氢键的 其它化合物。
优选地，所述的氧化试剂为氧气，卤代试剂或偶氮类试剂。
更优选地，所述的卤代试剂为N-氯代丁二酰亚胺，N-溴代丁二酰亚胺，对甲苯磺酰氯，甲磺酰氯，N-氟吡啶，N-氟二苯磺酰亚胺，1-氯甲基-4-氟-1,4-重氮化二环2.2.2辛烷双(四氟硼酸)盐和单质碘中的至少一种。
更优选地，所述的偶氮类试剂为偶氮二碳酸酯,偶氮苯，偶氮甲酰胺和偶氮二异丁腈中的至少一种。
优选地，所述的铈的配合物的金属阳离子为Ce4+,Ce3+中的任一种，优选四氯化铈水合物，四氯化铈，三氯化铈水合物，三氯化铈，硝酸铈水合物，三氟甲磺酸铈，四氟甲磺酸铈，硫酸铈，醋酸铈，草酸铈和四异丙醇铈中的至少一种。
优选地，所述的添加剂的阴离子为Cl-,Br-中的任一种，优选四丁基氯化铵，四乙基氯化铵，四丁基溴化铵，四乙基溴化铵，四丁基氯化磷，四丁基溴化磷，氯化钠，氯化钾，氯化铯，溴化钠，溴化钾和溴化铯中的至少一种。
优选地，所述的有机化合物与铈的配合物的摩尔比为1：0.0000001-0.2。
优选地，所述的铈的配合物与添加剂的摩尔比为1：0.2–1：10。
优选地，所述的反应条件为室温–80℃。
优选地，所述的可见光为波长为300-800nm的光。
所述的铈复合物的作用是在可见光照射下活化烷烃的碳氢键产生高活性的烷基自由基，进而和氧化试剂反应得到氧化产物。所述的添加剂的作用是提高铈复合物的催化效率。
与现有技术相比，本发明的有益效果是：
本发明反应仅需在较低温度下进行，反应时间短，反应效率高；同时仅需可见光来提供活化反应所需的能量，是一种更加温和、绿色的活化模式。本发明所用的铈催化剂成本低廉，简单高效，所用氧化试剂性质更加稳定，在工业上利用成本低，同时能避免重过渡金属，过氧化物等对环境的污染。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之 后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
以下实施例中的各反应原料、铈的配合物以及添加剂均为市售产品。
实施例1
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向2mL乙苯(106mg,1mmol)的乙腈溶液中通入氧气20min至氧气饱和，加入1mol％铈的配合物三氯化铈(2.4mg,0.01mmol)和2mol％的添加剂四丁基氯化铵(5.5mg,0.02mmol)之后，在室温(25℃)下，在(波长为380nm-550nm的)蓝色LED灯照射的条件下，使乙苯与氧气在铈的配合物和添加剂的作用下进行反应2h，使乙苯的碳氢键氧化得到氧化产物苯乙酮，反应方程式如下：
Figure PCTCN2017107760-appb-000001
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品苯乙酮(108mg,90％收率),核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：7.96(d,2H),7.68(t,1H),7.46(d,2H),2.50(s,3H)。
实施例2
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向2mL环己烷(85mg,1mmol)的乙腈溶液中通入氧气20min至氧气饱和，加入1mol％铈的配合物三氯化铈(2.4mg,0.01mmol)和2mol％的添加剂四丁基氯化铵(5.5mg,0.02mmol)之后，在室温(25℃)下，在(波长为380nm-550nm的)蓝色LED灯照射的条件下，使环己烷与氧气在铈的配合物和添加剂的作用下进行反应5h，使环己烷的碳氢键氧化得到氧化产物环己醇，反应方程式如下：
Figure PCTCN2017107760-appb-000002
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品环己醇(88mg,88％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：4.80(brs,1H),3.54(m,1H),1.59(m,4H),1.45-1.5 (m,6H)。
实施例3
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向2mL环己烷(85mg,1mmol)的乙腈溶液中通入氧气20min至氧气饱和，加入2mol％铈的配合物硝酸铈(8.7mg,0.02mmol)和4mol％的添加剂四丁基溴化铵(12.9mg,0.04mmol)之后，在室温(25℃)下，在(波长为380nm-550nm的)蓝色LED灯照射的条件下，使环己烷与氧气在铈的配合物和添加剂的作用下进行反应48h，使环己烷的碳氢键氧化得到氧化产物环己酮，反应方程式如下：
Figure PCTCN2017107760-appb-000003
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品环己酮(80mg,82％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：2.33(t,4H),1.86(m,4H),1.73(m,2H)。
实施例4
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向2mL乙苯(106mg,1mmol)的乙腈溶液中，加入对甲苯磺酰氯(286mg,1.5mmol),1mol％铈的配合物三氯化铈(2.4mg,0.01mmol)和2mol％的添加剂四丁基氯化铵(5.5mg,0.02mmol)之后，通入氩气鼓泡20min，在室温(25℃)下，在(波长为(380nm-550nm)的)蓝色LED灯照射的条件下，使乙苯和对甲苯磺酰氯在铈的配合物和添加剂的作用下进行反应12h，使乙苯的饱和碳氢键氧化得到氧化产物，反应方程式如下：
Figure PCTCN2017107760-appb-000004
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品1-氯乙基苯(122mg,87％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：7.45-7.22(m,5H),5.07(q,1H),1.82(d,3H)。
实施例5
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向10mL乙苯(106mg,1mmol)的乙腈溶液中，加入偶联碳酸二异丁酯(0.3ml,1.5mmol),1mol％铈的配合物三氯化铈(2.4mg,0.01mmol)和5mol％的添加剂四丁基氯化铵(14mg,0.05mmol)之后，通入氩气鼓泡20min，在室温(25℃)下，在(波长为(380nm-550nm)的)蓝色LED灯照射的条件下，使乙苯和偶联碳酸二异丁酯在铈的配合物和添加剂的作用下进行反应10h,使乙苯的饱和碳氢键氧化得到氧化产物，反应方程式如下：
Figure PCTCN2017107760-appb-000005
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品(283mg,92％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：7.36(m,5H),6.16(brs,1H),5.5(q,1H),5.0(m,2H),1.55(d,3H),1.23(d,12H)。
实施例6
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向5mL戊酸甲酯(116mg,1mmol)的乙腈溶液中，加入N-氟二苯磺酰亚胺(473mg,1.5mmol),2mol％铈的配合物三氯化铈(4.8mg,0.02mmol)和4mol％的添加剂四丁基氯化铵(11mg,0.04mmol)之后，通入氩气鼓泡20min，在室温(25℃)下，在(波长为(380nm-550nm)的)蓝色LED灯照射的条件下，使戊酸甲酯和N-氟二苯磺酰亚胺在铈的配合物和添加剂的作用下进行反应20h,使戊酸甲酯的饱和碳氢键氧化得到氧化产物，反应方程式如下：
Figure PCTCN2017107760-appb-000006
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品(110mg,82％收率)。核磁共振氢谱表征的数据为(500MHz,氘代乙腈为溶剂)：4.72(dm,1H),3.66(s,3H),2.47-2.42(m,2H),1.95-1.84(m,2H),1.32(dd,3H)。
实施例7
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向10mL戊酸甲酯(116mg,1mmol)的乙腈溶液中溶液中通入氧气20min至 氧气饱和，加入2mol％铈的配合物三氯化铈(4.8mg,0.02mmol)和5mol％的添加剂四丁基氯化铵(14mg,0.05mmol)之后，在室温(25℃)下，在(波长为380nm-550nm的)蓝色LED灯照射的条件下，使戊酸甲酯和氧气在铈的配合物和添加剂的作用下进行反应12h,使戊酸甲酯的饱和碳氢键氧化得到氧化产物，反应方程式如下：
Figure PCTCN2017107760-appb-000007
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品(100mg,77％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：3.64(s,3H),2.73(t,2H),2.54(t,2H),2.16(s,3H)。
实施例8
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向20mL茚满(119mg,1mmol)的乙腈溶液中溶液中通入氧气20min至氧气饱和，加入2mol％铈的配合物硝酸铈(8.7mg,0.02mmol)和4mol％的添加剂四丁基溴化铵(13mg,0.04mmol)之后，在室温(25℃)下，在(波长为380nm-550nm的)蓝色LED灯照射的条件下，使茚满和氧气在铈的配合物和添加剂的作用下进行反应2h,使茚满的饱和碳氢键氧化得到氧化产物，反应方程式如下：
Figure PCTCN2017107760-appb-000008
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品(106mg,80％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：7.41-7.0(m,4H),2.94(t,2H),2.61(t,2H)。
实施例9
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向10mL茚满(119mg,1mmol)的乙腈溶液中，加入N-溴代丁二酰亚胺(356mg,2mmol)，2mol％铈的配合物硝酸铈(8.7mg,0.02mmol)和4mol％的添加剂四丁基溴化铵(13mg,0.04mmol)之后，在室温(25℃)下，在(波长为(380nm-550nm)的)蓝色LED灯照射的条件下，使茚满和N-溴代丁二酰亚胺在铈的配合物和添 加剂的作用下进行反应12h,使茚满的饱和碳氢键氧化得到氧化产物，反应方程式如下：
Figure PCTCN2017107760-appb-000009
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品(165mg,84％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：7.18-7.16(m,1H),7.01-6.98(m,3H),5.33(dd,1H),2.99(m,1H),2.67(m,1H),2.39(m,2H)。

Claims (10)

  1. 一种可见光催化的饱和碳氢键直接氧化方法，其特征在于，包括：在可见光照射的条件下，使有机化合物与氧化试剂在铈的配合物及添加剂的作用下进行反应，使有机化合物中的饱和碳氢键氧化得到氧化产物。
  2. 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的有机化合物为链烷烃、环烷烃、芳香烃或含有饱和碳氢键的其它化合物。
  3. 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的氧化试剂为氧气，卤代试剂或偶氮类试剂。
  4. 如权利要求3所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的卤代试剂为N-氯代丁二酰亚胺，N-溴代丁二酰亚胺，对甲苯磺酰氯，甲磺酰氯，N-氟吡啶，N-氟二苯磺酰亚胺，1-氯甲基-4-氟-1,4-重氮化二环2.2.2辛烷双(四氟硼酸)盐和单质碘中的至少一种。
  5. 如权利要求3所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的偶氮类试剂为偶氮二碳酸酯,偶氮苯，偶氮甲酰胺和偶氮二异丁腈中的至少一种。
  6. 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的铈配合物的金属阳离子为Ce4+和Ce3+中的任一种。
  7. 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的添加剂的阴离子为Cl-和Br-中的任一种。
  8. 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的有机化合物与铈的配合物的摩尔比为1：0.0000001-0.2。
  9. 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的反应条件为室温–80℃。
  10. 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的可见光为波长为300-800nm的光。
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