CN108059593A - 一种芳香仲醇氧化裂解制备有机酸的方法 - Google Patents

一种芳香仲醇氧化裂解制备有机酸的方法 Download PDF

Info

Publication number
CN108059593A
CN108059593A CN201610976718.3A CN201610976718A CN108059593A CN 108059593 A CN108059593 A CN 108059593A CN 201610976718 A CN201610976718 A CN 201610976718A CN 108059593 A CN108059593 A CN 108059593A
Authority
CN
China
Prior art keywords
secondary alcohol
method described
oxygen
copper
mantoquita
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610976718.3A
Other languages
English (en)
Other versions
CN108059593B (zh
Inventor
王峰
王敏
李利花
刘慧芳
罗能超
李宏基
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201610976718.3A priority Critical patent/CN108059593B/zh
Publication of CN108059593A publication Critical patent/CN108059593A/zh
Application granted granted Critical
Publication of CN108059593B publication Critical patent/CN108059593B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/08—Formation or introduction of functional groups containing oxygen of carboxyl groups or salts, halides or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/803—Processes of preparation
    • 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
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • 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
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D333/40—Thiophene-2-carboxylic acid

Abstract

本发明涉及到一种芳香仲醇氧化制备有机酸的方法。以空气或氧气为氧源，以铜盐和有机配体为催化剂，加入无机碱，芳香仲醇发生碳碳键氧化裂解，得到有机酸。本发明氧化效率高，产品收率高；以空气或氧气作为氧源，经济、环保，具有很好的应用前景。

Description

一种芳香仲醇氧化裂解制备有机酸的方法
技术领域
本发明涉及到一种芳香仲醇氧化裂解制备有机酸的方法。
背景技术
有机酸是一种重要的化合物，广泛应用于食品、溶剂、医药合成中间体等。传统有机酸主要是通过伯醇氧化，或者烃类氧化，或者醛类的氧化得到。脂肪醇氧化制备脂肪酸是有机合成中非常重要的反应之一，同时也非常具有挑战性。传统的伯醇氧化方法制备酸，使用计量的高锰酸钾、二氧化锰、三氧化铬、次氯酸钠等氧化剂氧化，该方法会副产大量的无机氧化物或盐，污染严重。
芳香仲醇是一类容易得到的原料。目前芳香仲醇氧化主要生成酮。本发明的目的是发展一种芳香仲醇氧化裂解直接制备有机酸的方法。本方法采用氧气为氧源，在铜基催化剂作用下，芳香仲醇高效的转化到有机酸，具有很好的应用前景。
发明内容
本发明提供一种芳香仲醇氧化裂解制备酸的方法。
本发明所采用的技术方案为：
一种芳香仲醇氧化裂解制备有机酸的方法：
以空气或氧气为氧源，以铜盐和有机配体为催化剂，加入无机碱，芳香仲醇发生碳碳键氧化裂解，得到有机酸。
为了使得催化剂与底物充分接触，需要加入溶剂，使催化剂和底物溶解，使其能够充分的接触与反应。有些醇室温为固体，需加入有机溶剂使其溶解。所用溶剂为甲苯、邻二甲苯、乙腈、二氯甲烷、二甲基亚砜中的一种或者两种以上；反应过程中进行搅拌。
所述芳香仲醇的结构式为产物有机酸的结构式为
其中，R为苯基、萘基、吡啶、噻吩、呋喃，或含有取代基的苯基、萘基、吡啶、噻吩、呋喃；
所述取代基为OCH3、F、Cl、Br、I、NO2、CH3中的一种、两种或三种以上，取代基的个数为1-7个。
所述铜盐中铜离子的价态为一价或者二价，阴离子为醋酸跟、硫酸根、硝酸根、氯、溴或碘；
铜盐选自醋酸铜、硫酸铜、硝酸铜、氯化铜、氯化亚铜、溴化铜、溴化亚铜、碘化亚铜。
为了调控铜金属的催化性能，需要引入一些有机配体来调控其电子性质，所述有机配体为含氧和氮的化合物；
优选的有机配体结构如下：
本体系需要加入一定量的无机碱来促进该反应，所述无机碱为KOH、NaOH、LiOH、LiOH、K2CO3、Na2CO3或Cs2CO3中的一种或两种以上。
所述芳香仲醇氧化所用氧源为空气或氧气，氧源中氧气分压为0.1-2MPa。
反应温度为30-150℃；反应时间为0.5-48h。
无机碱与底物芳香仲醇的摩尔比为0.5-2。
以金属铜计，铜盐为底物芳香仲醇的0.1-10mol％；有机配体与铜盐的摩尔比为0.5-2。
本发明将上述催化剂用于芳香仲醇氧化制备有机酸，具体操作过程如下：将催化剂和醇加入到反应釜中，再加入适量溶剂，密闭反应釜，通入一定压力的空气或氧气，搅拌下升至一定温度，反应一定时间后，冷却。
本发明的有益效果为：
催化剂体系简单、高效，副产物少，副产物为苯乙酮，催化剂用量少。
具体实施方式
下面通过具体实施例对本发明进行说明，但本发明实施不局限于这些实施例：
实施例1-18：将0.5mmol 1-苯乙醇，0.025mmol硝酸铜，0.025mmol邻菲罗琳配体，1mmol KOH,2mL溶剂加入到30mL反应釜中，密闭反应釜，通入一定压力的空气或氧气，搅拌下升至一定温度，反应一定时间后，冷却，离心分离催化剂。所得样品定性分析采用气相色谱-质谱联用技术，定量分析由气相色谱实现，结果见表1。
表1反应条件优化
分析表1中结果可知，催化分子氧氧化1-苯乙醇到苯甲酸的较佳溶剂二甲基亚砜，优化条件为0.8MPa氧气分压，90℃，12h，1-苯乙醇的转化率为96％，苯甲酸的选择性为97％。
实施例19-29，将0.5mmol 1-苯乙醇，一定量的催化剂和邻菲罗琳配体，1mmolKOH,2mL二甲基亚砜加入到30mL反应釜中，密闭反应釜，通入0.8MPa氧气，搅拌下升至90℃，反应12h后，冷却。所得样品定性分析采用气相色谱-质谱联用技术，定量分析由气相色谱实现，结果见表2。
表2不同铜盐对催化反应的影响
分析表2中结果可知，随着硝酸铜的增加，1-苯乙醇的转化率和苯甲酸的选择性先增加后减小，优化值5mol％。其它铜盐也有较好的催化效果。
实施例30-34，将0.5mmol 1-苯乙醇，0.01mol硝酸铜，一定量的有机配体，1mmolKOH,2mL二甲基亚砜苯加入到30mL反应釜中，密闭反应釜，通入0.8MPa氧气，搅拌下升至90℃，反应12h后，冷却。所得样品定性分析采用气相色谱-质谱联用技术，定量分析由气相色谱实现，结果见表3。
表3有机配体对催化反应的影响
分析表3中结果可知，有机配体对反应的有着重要影响，影响催化活性和反应的选择性。
实施例35-41，将0.5mmol 1-苯乙醇，0.025mol硝酸铜，0.025mol的邻菲罗琳，一定量的碱，2mL二甲基亚砜加入到30mL反应釜中，密闭反应釜，通入0.8MPa氧气，搅拌下升至90℃，反应12h后，冷却。所得样品定性分析采用气相色谱-质谱联用技术，定量分析由气相色谱实现，结果见表4。
表4碱对催化反应的影响
分析表4中结果可知，碱对反应有明显的促进作用，强键KOH,NaOH表现出更好的效果。
实施例42-53，将0.5mmol芳香仲醇，0.025mol硝酸铜，0.025mol的邻菲罗琳，1mmolKOH,2mL二甲基亚砜加入到30mL反应釜中，密闭反应釜，通入0.8MPa氧气，搅拌下升至90℃，反应12h后，冷却。所得样品定性分析采用气相色谱-质谱联用技术，定量分析由气相色谱实现，结果见表5。
表5不同芳香仲醇氧化
分析表5中结果可知，其它芳香仲醇也能实现高效率的转化为相应的有机酸。
产品的定性采用气相色谱-质谱分析，并和标准样品的保留时间进行比对；定量用内标法气相色谱分析。
转化率＝(转化醇的摩尔数/投入醇的摩尔数)×100％
选择性＝(酸的摩尔数/转化醇的摩尔数)×100％
本发明方法氧化效率高，所用氧源为分子氧，环保、绿色、成本低，具有很好的应用前景。

Claims (10)

1.一种芳香仲醇氧化裂解制备有机酸的方法，其特征在于：
以空气或氧气为氧源，以铜盐和有机配体为催化剂，加入无机碱，芳香仲醇发生碳碳键氧化裂解，得到有机酸。
2.根据权利要求1所述的方法，其特征在于：反应中加入溶剂，所用溶剂为甲苯、邻二甲苯、乙腈、二氯甲烷、二甲基亚砜中的一种或者两种以上；反应过程中进行搅拌。
3.根据权利要求1所述的方法，其特征在于：
所述芳香仲醇的结构式为产物有机酸的结构式为
其中，R为苯基、萘基、吡啶、噻吩、呋喃，或含有取代基的苯基、萘基、吡啶、噻吩、呋喃；
所述取代基为OCH3、F、Cl、Br、I、NO2、CH3中的一种、两种或三种以上，取代基的个数为1-7个。
4.根据权利要求1所述的方法，其特征在于：所述铜盐中铜离子的价态为一价或者二价，阴离子为醋酸跟、硫酸根、硝酸根、氯、溴或碘；
铜盐选自醋酸铜、硫酸铜、硝酸铜、氯化铜、氯化亚铜、溴化铜、溴化亚铜、碘化亚铜。
5.根据权利要求1所述的方法，其特征在于：
所述有机配体为含氧和氮的化合物；
优选的有机配体结构如下：
6.根据权利要求1所述的方法，其特征在于：
所述无机碱为KOH、NaOH、LiOH、LiOH、K2CO3、Na2CO3或Cs2CO3中的一种或两种以上。
7.根据权利要求1所述的方法，其特征在于：所述芳香仲醇氧化所用氧源为空气或氧气，氧源中氧气分压为0.1-2MPa。
8.根据权利要求1所述的方法，其特征在于：反应温度为30-150℃；反应时间为0.5-48h。
9.根据权利要求1所述的方法，其特征在于：无机碱与底物芳香仲醇的摩尔比为0.5-2。
10.根据权利要求1所述的方法，其特征在于：以金属铜计，铜盐为底物芳香仲醇的0.1-10mol％；有机配体与铜盐的摩尔比为0.5-2。
CN201610976718.3A 2016-11-07 2016-11-07 一种芳香仲醇氧化裂解制备有机酸的方法 Active CN108059593B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610976718.3A CN108059593B (zh) 2016-11-07 2016-11-07 一种芳香仲醇氧化裂解制备有机酸的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610976718.3A CN108059593B (zh) 2016-11-07 2016-11-07 一种芳香仲醇氧化裂解制备有机酸的方法

Publications (2)

Publication Number Publication Date
CN108059593A true CN108059593A (zh) 2018-05-22
CN108059593B CN108059593B (zh) 2020-09-08

Family

ID=62136524

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610976718.3A Active CN108059593B (zh) 2016-11-07 2016-11-07 一种芳香仲醇氧化裂解制备有机酸的方法

Country Status (1)

Country Link
CN (1) CN108059593B (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110483356A (zh) * 2019-08-28 2019-11-22 上海克琴科技有限公司 一种铜配合物促进的视黄醛的合成方法
CN114907196A (zh) * 2021-02-09 2022-08-16 赣南医学院 通过芳基取代邻二醇氧化裂解制备羰基化合物的方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110483356A (zh) * 2019-08-28 2019-11-22 上海克琴科技有限公司 一种铜配合物促进的视黄醛的合成方法
CN114907196A (zh) * 2021-02-09 2022-08-16 赣南医学院 通过芳基取代邻二醇氧化裂解制备羰基化合物的方法
CN114907196B (zh) * 2021-02-09 2024-01-05 赣南医学院 通过芳基取代邻二醇氧化裂解制备羰基化合物的方法

Also Published As

Publication number Publication date
CN108059593B (zh) 2020-09-08

Similar Documents

Publication Publication Date Title
Jha et al. Mixed Co–Mn Oxide‐Catalysed Selective Aerobic Oxidation of Vanillyl Alcohol to Vanillin in Base‐Free Conditions
CN101678333B (zh) 制备羟基芳醛的方法
Fernandes et al. Mild alkane C–H and O–H oxidations catalysed by mixed-N, S copper, iron and vanadium systems
Bikas et al. Electronic effects of aromatic rings on the catalytic activity of dioxidomolybdenum (VI)–hydrazone complexes
Tamizh et al. Ruthenium (II) carbonyl complexes containing ‘pincer like’ONS donor Schiff base and triphenylphosphine as catalyst for selective oxidation of alcohols at room temperature
Cuenca et al. Water Compatible Gold (III)‐Catalysed Synthesis of Unsymmetrical Ethers from Alcohols
Ballistreri et al. Oxidation of alkynes catalyzed by molybdenum (VI) and tungsten (VI) polyoxometalates
CN103086838B (zh) 一种四甲基联苯的制备方法
Yuan et al. Transition-metal-free, chemoselective aerobic oxidations of sulfides and alcohols with potassium nitrate and pyridinium tribromide or bromine
Hosseini‐Monfared et al. Syntheses, Structures, and Catalytic Activity of Copper (II)‐Aroylhydrazone Complexes
Giorgi et al. Selective Oxidation of Activated Alcohols by Supported Gold Nanoparticles under an Atmospheric Pressure of O2: Batch and Continuous‐Flow Studies
Zhu et al. Copper-mediated fluoroalkylation reactions with [(phenylsulfonyl)-difluoromethyl] trimethylsilane: synthesis of PhSO2CF2-containing allenes and alkynes
CN108059593A (zh) 一种芳香仲醇氧化裂解制备有机酸的方法
Motsch et al. Systematic evaluation of sulfoxides as catalysts in nucleophilic substitutions of alcohols
CN114716371B (zh) 一种用于合成环状碳酸酯的含n活性中心金属有机催化剂及其制备方法和应用
Hierso et al. Ultra‐Low Catalyst Loading as a Concept in Economical and Sustainable Modern Chemistry: The Contribution of Ferrocenylpolyphosphane Ligands
CN106800492A (zh) 一种铁催化醇氧化制备醛或铜的绿色方法
Mecozzi et al. Oxidation of Vicinal Diols to α‐Hydroxy Ketones with H2O2 and a Simple Manganese Catalyst
CN104292106B (zh) 一种一锅法制备有机羧酸酯的方法
Lapa et al. C-scorpionate Au (III) complexes as pre-catalysts for industrially significant toluene oxidation and benzaldehyde esterification reactions
CN108002968A (zh) 一种酮类化合物氧化断裂碳碳键制备羧酸类化合物的方法
Puzari et al. An unsymmetrical Schiff-base derived recyclable Pd-catalyst for Suzuki–Miyaura and Sonogashira reactions in aqueous media
Weerasiri et al. Cu (II) 2-quinoxalinol salen catalyzed oxidation of propargylic, benzylic, and allylic alcohols using tert-butyl hydroperoxide in aqueous solutions
Chakrabarty et al. Epoxidation of α-pinene catalysed by tetrameric cobalt (III) complexes
CN101830783B (zh) 一种希夫碱配合物催化氧气氧化醇制备醛的方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant