CN103570493A - Method for synthesizing 1,2-orthodiol through immobilized type heteropolyacid phase-transfer catalytic oxidation - Google Patents

Method for synthesizing 1,2-orthodiol through immobilized type heteropolyacid phase-transfer catalytic oxidation Download PDF

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CN103570493A
CN103570493A CN 201310527788 CN201310527788A CN103570493A CN 103570493 A CN103570493 A CN 103570493A CN 201310527788 CN201310527788 CN 201310527788 CN 201310527788 A CN201310527788 A CN 201310527788A CN 103570493 A CN103570493 A CN 103570493A
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catalytic oxidation
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李斌栋
吴绪巍
靳垒
王普军
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江苏紫奇化工科技有限公司
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C07C29/103Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
    • C07C29/106Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • C07D301/02Synthesis of the oxirane ring
    • C07D301/03Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/14Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
    • C07D301/16Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof formed in situ, e.g. from carboxylic acids and hydrogen peroxide
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/58Recycling
    • Y02P20/584Recycling of catalysts

Abstract

The invention discloses a method for synthesizing 1,2-orthodiol through immobilized type heteropolyacid phase-transfer catalytic oxidation. The method comprises the following steps: 1, sequentially adding an acid, terminal alkene, hydrogen peroxide and a polystyrene resin immobilized type heteropolyacid phase-transfer catalyst into a reactor, stirring, reacting a mixture liquid at 40-80 DEG C, after the reaction is accomplished, filtering and recycling the catalyst so as to obtain an epoxy mixture liquid; 2, dropwisely adding an alkali solution into the epoxy mixture liquid so as to adjust the pH value to be 10-12, keeping the temperature of 30-70 DEG C to react so as to obtain a target product mixture liquid; 3, after the reaction is accomplished, extracting the target product mixture liquid by using an ester solution, washing, drying, and distilling under reduced pressure so as to obtain 1,2-orthodiol. The 1,2-orthodiol is widely applied to production of polyesters and surfactants and can also be used as a raw material for pharmacy.

Description

固载型杂多酸相转移催化氧化合成1 ' 2-邻二醇的方法 Supported heteropolyacid phase transfer catalysis method of synthesis of 2-oxidizing vicinal diols of 1 '

技术领域 FIELD

[0001] 本发明属于精细有机合成领域,涉及1,2-邻二醇的合成,具体涉及一种利用固载型杂多酸相转移催化剂,催化端烯发生氧化反应合成1,2-邻二醇的方法。 [0001] The present invention belongs to the field of fine organic synthesis, it involves the synthesis of 1,2-vicinal diols, particularly, to a solid carrier heteropolyacid use of a phase transfer catalyst, the catalytic oxidation of a terminal alkene occurs Synthesis of 1,2-o- methods alcohol.

背景技术 Background technique

[0002] 1,2-邻二醇是重要的化工原料,常用来生产聚酯、表面活性剂,也可用作制药的原料。 [0002] o-1,2-diol is an important chemical raw material used to produce a polyester, a surfactant, can be used as pharmaceutical raw materials. 直链1,2-邻二醇特别是C2-C4的邻二醇,大多数是由环氧化物在高温高压或者碱性或者酸性下水合法制得,现有1,2-邻二醇的合成方法存在的缺点是生产成本相对较高,环境污染比较严重。 1,2-linear vicinal diol is a vicinal diol in particular C2-C4, most of the water is made valid in basic or acidic, or high temperature and pressure from epoxides, 1,2 vicinal diol conventional synthetic disadvantage that the production method is relatively high cost, environmental pollution is serious.

[0003] James P.Morken 等《J.AM.CHEM.S0C.,2009,131:13210_13211》研究组成员利用联硼酸新戊二醇酯催化端烯合成1,2-邻二醇,此研究过程对于工业生产不切实际,催化剂太昂贵;黎林清等人《应用化学,2011,28 (11): 1256-1262》研究了金属四羧酸酞菁对烯烃的催化环氧化,合成了4种金属的四羧酸酞菁金属,以其作为催化剂,开展了以分子氧为氧源的烯烃环氧化的研究,此研究中1-辛烯的转化率和选择性比较低;Venturello等人《J Org Chem,1988,53:1553-1557 J Org Chem,1983,48:3831_3833》使用双氧水作为氧化剂,此反应的副产物只是水,他们使用的Na2WO4-H3PO4-季铵盐作为催化剂,反应过程中必须加入I,2- 二氯乙烷与水形成两相,双氧水作为氧源,氧化性不够强,其产率只有53%,产率比较低。 [0003] James P.Morken like "J.AM.CHEM.S0C, 2009,131:. 13210_13211" study group members using the acid with neopentyl glycol Catalytic Synthesis of 1,2-vicinal diols ethylenically end, this study for industrial production impractical, too expensive catalysts; Lilin Qing et al., "applied Chemistry, 2011,28 (11): 1256-1262," Study of metal phthalocyanine tetracarboxylic acid catalytic epoxidation of olefins, 4 kinds of metals were synthesized metal phthalocyanine tetracarboxylic acid, as its catalyst, carried out research molecular oxygen as an oxygen source olefin epoxidation, in this study, the 1-octene conversion and selectivity is relatively low; Venturello et al., "J Org Chem, 1988,53: 1553-1557 J Org Chem, 1983,48: 3831_3833 "using hydrogen peroxide as the oxidant, the reaction by-product is only water, Na2WO4-H3PO4- their quaternary ammonium salt as a catalyst used during the reaction must be was added I, 2- dichloroethane with water to form a two-phase, hydrogen peroxide as the oxygen source, oxidation is not strong enough, the yield is only 53%, the yield is relatively low. 刘敏申请的专利中《CN200610050149.6》没有运用到催化剂,由于像1_辛烯这种的端烯,没有催化剂的情况下很难发生反应,产率必然很低,不能用于工业生产。 Liu Minshen Please patent "CN200610050149.6" not to use a catalyst, since this image 1_ end octene alkenyl, absence of a catalyst reaction is difficult, yield is low inevitably, it can not be used in industrial production.

发明内容 SUMMARY

[0004] 本发明的目的在于:提供一种固载型杂多酸相转移催化氧化合成1,2-邻二醇的方法,由末端烯烃经氧化制备1,2-邻二醇,广泛应用在生产聚酯、表面活性剂,也可用作制药的原料。 [0004] The object of the present invention is: providing a heteropoly acid having a solid phase-transfer catalytic oxidation of o-1,2-diol carrier type synthesis method, the terminal olefin prepared by oxidation of 1,2-vicinal diols, widely used in producing a polyester, a surfactant, can be used as pharmaceutical raw materials.

[0005] 本发明的技术解决方案为:固载型杂多酸相转移催化氧化合成1,2-邻二醇的方法包括以下步骤: [0005] The technical solutions of the present invention is: a method of synthesis of 1,2-catalytic oxidation of vicinal diols Supported heteropolyacid phase transfer comprising the steps of:

第一步,向反应器中依次加入酸、端烯、双氧水、聚苯乙烯树脂固载型杂多酸相转移催化剂,搅拌,反应混合液在4(T8(TC反应,反应结束后,过滤回收催化剂,得环氧化物混合液; The first step, followed by an acid added to the reactor, a terminal alkene, hydrogen peroxide, polystyrene Supported heteropolyacid phase-transfer catalyst resin, stirring the reaction mixture 4 (T8 (TC reaction, after the reaction was recovered by filtration The catalyst to give the epoxide mixture;

第二步,向环氧化物混合液中滴加碱溶液调节PH值为10-12,保持3(T70°C反应,得目标产物混合液; The second step, the epoxide was added dropwise to the mixture an alkali solution to adjust the PH value of 10-12, holding 3 (T70 ° C reaction to give a mixture of the desired product;

第三步,反应结束后,目标产物混合液用酯溶液萃取,洗涤,干燥,减压蒸馏,得1,2_邻二醇。 The third step, after the reaction, the desired product was extracted with a mixture of ester solution, washed, dried and distilled under reduced pressure to give 1,2_ vicinal diol.

[0006] 其中,第一步中,酸选用甲酸、乙酸。 [0006] wherein, in a first step, selection of formic acid, acetic acid.

[0007] 其中,第一步中,端烯指1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十二烯或 [0007] wherein, in a first step, a terminal alkene refers to 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, or

1-十四烯。 1-tetradecene. [0008] 其中,第一步中,双氧水与酸的摩尔比为I 17,端烯与双氧水的摩尔比为1:1~3。 [0008] wherein the molar ratio of the first step, hydrogen peroxide and the acid is I 17, the molar ratio of a terminal alkene and hydrogen peroxide is 1: 1 ~ 3.

[0009] 其中,第一步中,聚苯乙烯树脂固载型杂多酸相转移催化剂选用[31 -C5H5N(CH2) 15CH3]3[PMo W3O24]、[ (C4H9) 4N] 3PMo1204(l、[ (C4H9) 4N] 3PW12040、(Bu4N) 3{P04 [WO (0) 2] 4}、(Bu4N)3 {P04[Mo 0(0)2]4} , [(C18H37)2N(CH3)2J3 [PW4O16]、(^ -C5H5NC16H33) 3 [Pff4O16]、[C16H33N(CH3) 3] [Pff4O16]、Bu4NPff4O160 催化剂用量为端烯质量的1%~10%。 [0009] wherein, in a first step, the polystyrene resin by supported heteropolyacid phase transfer catalyst selected [31 -C5H5N (CH2) 15CH3] 3 [PMo W3O24], [(C4H9) 4N] 3PMo1204 (l, [ (C4H9) 4N] 3PW12040, (Bu4N) 3 {P04 [WO (0) 2] 4}, (Bu4N) 3 {P04 [Mo 0 (0) 2] 4}, [(C18H37) 2N (CH3) 2J3 [ PW4O16], (^ -C5H5NC16H33) 3 [Pff4O16], [C16H33N (CH3) 3] [Pff4O16], Bu4NPff4O160 catalyst in an amount of 1% to 10% by mass of a terminal alkene.

[0010] 其中,第一步中,反应时间维持在:T6h。 [0010] wherein, in a first step, the reaction time was maintained at: T6h.

[0011] 其中,第二步中,反应时间维持在疒5h。 [0011] wherein, in the second step, the reaction time was maintained at epileptic 5h.

[0012] 其中,第三步中,萃取溶剂选用乙酸乙酯或乙酸丁酯。 [0012] wherein, in the third step, the choice of extraction solvent ethyl acetate or butyl acetate.

[0013] 本发明与现有技术相比,其显著优点是:(I)通过有机酸和过氧化氢自催化作用生成比双氧水氧化性更强的有机过氧酸,更有利于进行环氧化反应;(2)利用固载型杂多酸相转移催化剂,解决了均相催化剂不易于回收利用的难题;(3)制得的1,2-邻二醇产品不需要提纯处理,纯度达98.0%以上;(4)反应条件温和,反应操作简单,降低了生产成本。 [0013] Compared with the prior art, which are significant advantages: (I) an organic acid and hydrogen peroxide by autocatalysis to generate more hydrogen peroxide than the oxidation of organic peroxy acids, more conducive epoxidation reaction; (2) using Supported heteropolyacid phase transfer catalyst, a heterogeneous catalyst is not easy to solve the problem in recycling; (3) the 1,2 vicinal diol obtained product does not require purification treatment, the purity of 98.0 % or more; (4) mild reaction conditions, the reaction operation is simple, reduces the production cost.

附图说明 BRIEF DESCRIPTION

[0014] 图1是固载型杂多酸相转移催化氧化合成1,2-邻二醇的流程框图。 [0014] FIG. 1 is a Supported heteropolyacid phase transfer catalyzed Oxidation of 1,2-diols synthesized block flow diagram.

具体实施方式 detailed description

[0015] 下面结合具体实施例进一步说明本发明的技术解决方案,实施例可以使本专业技术人员更全面地理解本发明,但这些实施例不能理解为是对技术方案的限制。 [0015] The following specific examples further illustrate the technical solutions in conjunction with the present invention, embodiments may enable those skilled in the art will more fully understand the invention, but these examples should not be construed as limiting the technical solutions.

[0016] 实施例1: [0016] Example 1:

第一步:向四口烧瓶中加入甲酸46g,双氧水3.4g,聚苯乙烯树脂催化剂[^ -C5H5N(CH2)15CH3]3[PMoff3O24] 0.07g, 1-己烯7g,控制反应温度在50°C,反应混合物溶液继续保持4h,反应后过滤回收催化剂,得环氧化物混合液; Step: To a four-necked flask acid 46g, hydrogen peroxide 3.4g, polystyrene resin catalyst [^ -C5H5N (CH2) 15CH3] 3 [PMoff3O24] 0.07g, 1- hexene 7g, controlling the reaction temperature at 50 ° C, the reaction mixture was maintained 4h, the reaction catalyst was recovered by filtration to give the epoxide mixture;

第二步:向环氧化物混合液中滴加碱溶液使混合溶液的pH值呈10,40°C反应2h,得目标产物混合液; Step Two: To a solution of the epoxide was added dropwise a mixture of alkali the pH of the mixed solution in the reactor was 10,40 ° C 2h, to give a mixture of the desired product;

第三步:反应结束后,目标产物混合液用乙酸乙酯进行萃取,萃取液用饱和食盐水洗涤2次,洗涤后的萃取液用无水Na2SO4干燥脱水,真空过滤后减压蒸馏,蒸出产品1,2-己二醇 Third step: After completion of the reaction, the desired product mixture was extracted with ethyl acetate, the extract was washed with saturated brine twice, the extract was dried over anhydrous Na2SO4 dehydration after washing, vacuum filtration after distillation under reduced pressure, evaporated product 1,2-hexanediol

9.2g,收率94%,经气相色谱检测,I, 2-己二醇纯度98.2%。 9.2 g of, 94% yield by gas chromatography, I, 2- hexanediol purity of 98.2%.

[0017] 实施例2: [0017] Example 2:

第一步:向四口烧瓶中加入甲酸46g,双氧水34g,聚苯乙烯树脂催化剂[(C4H9)4N]3PMo120« 4.9g,1-庚烯98g,控制反应温度在80°C,反应混合物溶液继续保持3h,反应后过滤回收催化剂,得环氧化物混合液; Step: To a four-necked flask acid 46g, hydrogen peroxide 34g, polystyrene resin catalyst [(C4H9) 4N] 3PMo120 «4.9g, 1- heptene 98g, controlling the reaction temperature at 80 ° C, the reaction mixture was continued holding 3h, the reaction catalyst was recovered by filtration to give the epoxide mixture;

第二步:向环氧化物混合液中滴加碱溶液使混合溶液的pH值呈12,70°C反应2h,得目标产物混合液; Step Two: To a solution of the epoxide was added dropwise a mixture of alkali the pH of the mixed solution in the reactor was 12,70 ° C 2h, to give a mixture of the desired product;

第三步:反应结束后,目标产物混合液用乙酸乙酯进行萃取,萃取液用饱和食盐水洗涤2次,洗涤后的萃取液用无水Na2SO4干燥脱水,真空过滤后减压蒸馏,蒸出产品1,2-庚二醇115g,收率87.1% ;经气相色谱检测,I, 2-庚二醇纯度98.7%。 Third step: After completion of the reaction, the desired product mixture was extracted with ethyl acetate, the extract was washed with saturated brine twice, the extract was dried over anhydrous Na2SO4 dehydration after washing, vacuum filtration after distillation under reduced pressure, evaporated product 1,2-heptanediol 115g, a yield of 87.1%; by gas chromatography, I, 2- heptanediol purity of 98.7%. [0018] 实施例3: [0018] Example 3:

第一步:向四口烧瓶中加入甲酸46g,双氧水2g,聚苯乙烯树脂催化剂[(C4H9)4N]3PW120« 0.5g,1-辛烯6.6g,控制反应温度在40°C,反应混合物溶液继续保持6h,反应后过滤回收催化剂,得环氧化物混合液; Step: formic acid was added to the four-necked flask 46g, hydrogen peroxide 2g, polystyrene resin catalyst [(C4H9) 4N] 3PW120 «0.5g, 1- octene 6.6g, controlling the reaction temperature at 40 ° C, the reaction mixture solution remain 6h, the reaction catalyst was recovered by filtration to give the epoxide mixture;

第二步:向环氧化物混合液中滴加碱溶液使混合溶液的pH值呈11,60°C反应4h,得目标产物混合液; Step Two: To a solution of the epoxide was added dropwise a mixture of alkali the pH of the mixed solution in the reactor was 11,60 ° C 4h, to give a mixture of the desired product;

第三步:反应结束后,目标产物混合液用乙酸乙酯进行萃取,萃取液用饱和食盐水洗涤2次,洗涤后的萃取液用无水Na2SO4干燥脱水,真空过滤后减压蒸馏,蒸出产品1,2-辛二醇 Third step: After completion of the reaction, the desired product mixture was extracted with ethyl acetate, the extract was washed with saturated brine twice, the extract was dried over anhydrous Na2SO4 dehydration after washing, vacuum filtration after distillation under reduced pressure, evaporated product 1,2-octanediol

7.3g,收率84.9% ;经气相色谱检测,I, 2-辛二醇纯度99.0%。 7.3g, yield 84.9%; by gas chromatography, I, 2- octanediol a purity of 99.0%.

[0019] 实施例4: [0019] Example 4:

第一步:向四口烧瓶中加入甲酸46g,双氧水3.4g,聚苯乙烯树脂催化剂(Bu4N)3{P04[W0(0)2]4} 0.56g,1-辛烯5.6g,控制反应温度在60°C,反应混合物溶液继续保持4h,反应后过滤回收催化剂,得环氧化物混合液; Step: To a four-necked flask acid 46g, hydrogen peroxide 3.4g, polystyrene resin catalyst (Bu4N) 3 {P04 [W0 (0) 2] 4} 0.56g, 1- octene 5.6g, control of the reaction temperature at 60 ° C, the reaction mixture was maintained 4h, the reaction catalyst was recovered by filtration to give the epoxide mixture;

第二步:向环氧化物混合液中滴加碱溶液使混合溶液的pH值呈10,60°C反应5h,得目标产物混合液;第三步:反应结束后,目标产物混合液用乙酸乙酯进行萃取,萃取液用饱和食盐水洗涤2次,洗涤后的萃取液用无水Na2SO4干燥脱水,真空过滤后减压蒸馏,蒸出产品1,2-辛二醇 Step Two: To a solution of the epoxide was added dropwise a mixture of alkali the pH of the mixed solution in the reactor was 10,60 ° C 5h, to give the desired product mixture; Third step: After completion of the reaction, the desired product mixture was neutralized with acetic acid ethyl ester, and the extract was washed with saturated brine twice, the extracts were washed dried over anhydrous Na2SO4 dehydration, filtration and vacuum distillation under reduced pressure, the product was distilled 1,2-octanediol

6.6g,收率90.4% ;经气相色谱检测,I, 2-辛二醇纯度99.2%。 6.6g, 90.4% yield; by gas chromatography, I, 2- octanediol 99.2% purity.

[0020] 实施例5: [0020] Example 5:

第一步:向四口烧瓶中加入乙酸60g,双氧水17g,聚苯乙烯树脂催化剂(Bu4N)3 (PO4[MoO(O)2J4I 0.21g,1-壬烯21g,控制反应温度在70°C,反应混合物溶液继续保持6h,反应后过滤回收催化剂,得环氧化物混合液; Step: Into a four-necked flask were added 60g acetic acid, hydrogen peroxide 17g, polystyrene resin catalyst (Bu4N) 3 (PO4 [MoO (O) 2J4I 0.21g, 1- nonene 21g, controlling the reaction temperature at 70 ° C, the reaction mixture was maintained 6h, the reaction catalyst was recovered by filtration to give the epoxide mixture;

第二步:向环氧化物混合液中滴加碱溶液使混合溶液的pH值呈11,70°C反应5h,得目标产物混合液; Step Two: To a solution of the epoxide was added dropwise a mixture of alkali the pH of the mixed solution in the reactor was 11,70 ° C 5h, to give the desired product mixture;

第三步:反应结束后,目标产物混合液用乙酸乙酯进行萃取,萃取液用饱和食盐水洗涤2次,洗涤后的萃取液用无水Na2SO4干燥脱水,真空过滤后减压蒸馏,蒸出产品1,2-壬二醇24.3g,收率91.4% ;经气相色谱检测,I, 2-壬二醇纯度99.1%。 Third step: After completion of the reaction, the desired product mixture was extracted with ethyl acetate, the extract was washed with saturated brine twice, the extract was dried over anhydrous Na2SO4 dehydration after washing, vacuum filtration after distillation under reduced pressure, evaporated 1,2-nonanediol product 24.3g, 91.4% yield; by gas chromatography, I, 2- nonanediol 99.1% purity.

[0021] 实施例6: [0021] Example 6:

第一步:向四口烧瓶中加入乙酸60g,双氧水6.Sg,聚苯乙烯树脂催化剂[(C18H37)2N(CH3)2J3 [PW4O16] 1.(^,1_癸烯18.68,控制反应温度在80°C,反应混合物溶液继续保持3h,反应后过滤回收催化剂,得环氧化物混合液; Step: Into a four-necked flask were added 60g acetic acid, hydrogen peroxide 6.Sg, polystyrene resin catalyst [(C18H37) 2N (CH3) 2J3 [PW4O16] 1 (^, 1_ decene 18.68, control of the reaction temperature. 80 ° C, the reaction mixture was maintained 3h, the reaction catalyst was recovered by filtration to give the epoxide mixture;

第二步:向环氧化物混合液中滴加碱溶液使混合溶液的pH值呈11,50°C反应2h,得目标产物混合液; Step Two: To a solution of the epoxide was added dropwise a mixture of alkali the pH of the mixed solution in the reactor was 11,50 ° C 2h, to give a mixture of the desired product;

第三步:反应结束后,目标产物混合液用乙酸丁酯进行萃取,萃取液用饱和食盐水洗涤2次,洗涤后的萃取液用无水Na2SO4干燥脱水,真空过滤后减压蒸馏,蒸出产品1,2-癸二醇20.6g,收率89.2% ;经气相色谱检测,I, 2-癸二醇纯度99.3%。 Third step: After completion of the reaction, the desired product is carried out with a mixture of butyl acetate, and the extract was washed with saturated brine twice, the extract was dried over anhydrous Na2SO4 dehydration after washing, vacuum filtration after distillation under reduced pressure, evaporated 1,2-decanediol product 20.6g, 89.2% yield; by gas chromatography, I, 2- decanediol 99.3% purity.

[0022] 实施例7: [0022] Example 7:

第一步:向四口烧瓶中加入乙酸60g,双氧水2.3g,聚苯乙烯树脂催化剂(^ -C5H5NC16H33) 3 [PW4O16] 1.0g, 1-十二烯11.2g,控制反应温度在80°C,反应混合物溶液继续保持4h,反应后过滤回收催化剂,得环氧化物混合液; Step: Into a four-necked flask were added 60g acetic acid, hydrogen peroxide 2.3g, polystyrene resin catalyst (^ -C5H5NC16H33) 3 [PW4O16] 1.0g, 1- dodecene 11.2 g, controlling the reaction temperature at 80 ° C, the reaction mixture was maintained 4h, the reaction catalyst was recovered by filtration to give the epoxide mixture;

第二步:向环氧化物混合液中滴加碱溶液使混合溶液的pH值呈11,50°C反应4h,得目标产物混合液; Step Two: To a solution of the epoxide was added dropwise a mixture of alkali the pH of the mixed solution in the reactor was 11,50 ° C 4h, to give a mixture of the desired product;

第三步:反应结束后,目标产物混合液用乙酸丁酯进行萃取,萃取液用饱和食盐水洗涤2次,洗涤后的萃取液用无水Na2SO4干燥脱水,真空过滤后减压蒸馏,蒸出产品1,2-十二碳二醇11.9g,收率89.2% ;经气相色谱检测,I, 2-癸二醇纯度99.0%。 Third step: After completion of the reaction, the desired product is carried out with a mixture of butyl acetate, and the extract was washed with saturated brine twice, the extract was dried over anhydrous Na2SO4 dehydration after washing, vacuum filtration after distillation under reduced pressure, evaporated 1,2-dodecanediol product 11.9g, 89.2% yield; by gas chromatography, I, 2- decanediol purity of 99.0%.

[0023] 实施例8: [0023] Example 8:

第一步:向四口烧瓶中加入乙酸60g,双氧水3.4g,聚苯乙烯树脂催化剂[C16H33N(CH3)3][PW4O16] 0.6g,1-十二烯11.2g,控制反应温度在80°C,反应混合物溶液继续保持4h,反应后过滤回收催化剂,得环氧化物混合液; Step: Into a four-necked flask were added 60g acetic acid, hydrogen peroxide 3.4g, polystyrene resin catalyst [C16H33N (CH3) 3] [PW4O16] 0.6g, 1- dodecene 11.2 g, controlling the reaction temperature at 80 ° C , the reaction mixture was maintained 4h, the reaction catalyst was recovered by filtration to give the epoxide mixture;

第二步:向环氧化物混合液中滴加碱溶液使混合溶液的pH值呈10,50°C反应5h,得目标产物混合液; Step Two: To a solution of the epoxide was added dropwise a mixture of alkali the pH of the mixed solution in the reactor was 10,50 ° C 5h, to give the desired product mixture;

第三步:反应结束后,目标产物混合液用乙酸丁酯进行萃取,萃取液用饱和食盐水洗涤2次,洗涤后的萃取液用无水Na2SO4干燥脱水,真空过滤后减压蒸馏,蒸出产品1,2-十二碳二醇12.8g,收率94.8% ;经气相色谱检测,I, 2-癸二醇纯度99.5%。 Third step: After completion of the reaction, the desired product is carried out with a mixture of butyl acetate, and the extract was washed with saturated brine twice, the extract was dried over anhydrous Na2SO4 dehydration after washing, vacuum filtration after distillation under reduced pressure, evaporated 1,2-dodecanediol product 12.8g, 94.8% yield; by gas chromatography, I, 2- decanediol 99.5% purity.

[0024] 实施例9: [0024] Example 9:

第一步:向四口烧瓶中加入乙酸60g,双氧水17g,聚苯乙烯树脂催化剂Bu4NPW4O161.0g, 1-十四烯32.6g,控制反应温度在80°C,反应混合物溶液继续保持4h,反应后过滤回收催化剂,得环氧化物混合液; After a four-necked flask were added 60g acetic acid, hydrogen peroxide 17g, a polystyrene resin catalyst Bu4NPW4O161.0g, 1- tetradecene 32.6 g, controlling the reaction temperature at 80 ° C, the reaction mixture was maintained 4h, reaction: a first step The catalyst was recovered by filtration to give the epoxide mixture;

第二步:向环氧化物混合液中滴加碱溶液使混合溶液的pH值呈10,50°C反应5h,得目标产物混合液; Step Two: To a solution of the epoxide was added dropwise a mixture of alkali the pH of the mixed solution in the reactor was 10,50 ° C 5h, to give the desired product mixture;

第三步:反应结束后,目标产物混合液用乙酸丁酯进行萃取,萃取液用饱和食盐水洗涤2次,洗涤后的萃取液用无水Na2SO4干燥脱水,真空过滤后减压蒸馏,蒸出产品1,2_十四碳二醇35.2g,收率92.0% ;经气相色谱检测,I, 2-癸二醇纯度99.6%。 Third step: After completion of the reaction, the desired product is carried out with a mixture of butyl acetate, and the extract was washed with saturated brine twice, the extract was dried over anhydrous Na2SO4 dehydration after washing, vacuum filtration after distillation under reduced pressure, evaporated 1,2_ fourteen carbon diol product 35.2g, 92.0% yield; by gas chromatography, I, 2- decanediol 99.6% purity.

Claims (8)

  1. 1.固载型杂多酸相转移催化氧化合成1,2-邻二醇的方法,其特征在于:它包括以下步骤:第一步,向反应器中依次加入酸、端烯、双氧水、聚苯乙烯树脂固载型杂多酸相转移催化剂,搅拌,反应混合液在4(T8(TC反应,反应结束后,过滤回收催化剂,得环氧化物混合液;第二步,向环氧化物混合液中滴加碱溶液调节PH值为10-12,保持3(T70°C反应,得目标产物混合液;第三步,反应结束后,目标产物混合液用酯溶液萃取,洗涤,干燥,减压蒸馏,得1,2_邻二醇。 The method of synthesis of 1,2-diols catalyzed oxidation of o 1. Supported heteropolyacid phase transfer, characterized in that: it comprises: a first step, successively added to the reactor an acid end-ene, hydrogen peroxide, poly Supported heteropolyacid styrene resin phase transfer catalyst, stirring the reaction mixture 4 (T8 (TC reaction, after the completion of the reaction, the catalyst was recovered by filtration to give the epoxide mixture; a second step, mixing the epoxide base solution was added dropwise to adjust the PH value of 10-12, holding 3 (T70 ° C reaction to give a mixture of the desired product; a third step, after the reaction, the desired product mixture was extracted, washed with ester solution, drying under reduced pressure distillation to yield 1,2_ vicinal diol.
  2. 2.根据权利要求1所述的固载型杂多酸相转移催化氧化合成1,2-邻二醇的方法,其特征在于:第一步中,酸选用甲酸、乙酸。 The Supported heteropolyacid A method according to claim 1 Synthesis of 1,2-catalytic oxidation of vicinal diols phase transition, wherein: in a first step, selection of formic acid, acetic acid.
  3. 3.根据权利要求2所述的固载型杂多酸相转移催化氧化合成1,2-邻二醇的方法,其特征在于:第一步中,端烯指1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十二烯或1-十四烯。 The Supported heteropolyacid A method according to claim 2 Synthesis of 1,2-catalytic oxidation of vicinal diols phase transition, wherein: in a first step, a terminal alkene refers to 1-hexene, 1-heptanol pentene, 1-octene, 1-nonene, 1-decene, 1-dodecene or 1-tetradecene.
  4. 4.根据权利要求1所述的固载型杂多酸相转移催化氧化合成1,2-邻二醇的方法,其特征在于:第一步中,双氧水与酸的摩尔比为1:广17,端烯与双氧水的摩尔比为1:广3。 The Supported heteropolyacid A method according to claim 1 Synthesis of 1,2-catalytic oxidation of vicinal diols phase transfer, wherein: the first step in a molar ratio of hydrogen peroxide to acid is 1: wide 17 the molar ratio of a terminal alkene and hydrogen peroxide is 1: 3 wide.
  5. 5.根据权利要求1所述的固载型杂多酸相转移催化氧化合成1,2-邻二醇的方法,其特征在于:第一步中,聚苯乙烯树脂固载型杂多酸相转移催化剂选用[π -C5H5N (CH2)15CH3] 3 [PMo W3O2J、[ (C4H9) 4N] 3PMo1204。 The Supported heteropolyacid A method according to claim 1 Synthesis of 1,2-catalytic oxidation of vicinal diols phase transition, wherein: in a first step, the resin immobilized polystyrene phase heteropolyacid transfer catalyst selected [π -C5H5N (CH2) 15CH3] 3 [PMo W3O2J, [(C4H9) 4N] 3PMo1204. 、[ (C4H9) 4N] 3PW12040、(Bu4N) 3{P04 [WO (0) 2] 4}、(Bu4N)3 {P04[Mo 0(0)2]4} , [(C18H37)2N(CH3)2J3 [PW4O16]、(^ -C5H5NC16H33) 3 [Pff4O16]、[C16H33N(CH3) 3] [Pff4O16]、Bu4NPff4O16;催化剂用量为端烯质量的1%~10%。 , [(C4H9) 4N] 3PW12040, (Bu4N) 3 {P04 [WO (0) 2] 4}, (Bu4N) 3 {P04 [Mo 0 (0) 2] 4}, [(C18H37) 2N (CH3) 2J3 [PW4O16], (^ -C5H5NC16H33) 3 [Pff4O16], [C16H33N (CH3) 3] [Pff4O16], Bu4NPff4O16; catalyst in an amount of 1% to 10% by mass of a terminal alkene.
  6. 6.根据权利要求1所述的固载型杂多酸相转移催化氧化合成1,2-邻二醇的方法,其特征在于:第一步中,反应时间维持在3~6h。 The Supported heteropolyacid A method according to claim 1 Synthesis of 1,2-catalytic oxidation of vicinal diols phase transfer, wherein: the first step, the reaction time was maintained at 3 ~ 6h.
  7. 7.根据权利要求1所述的固载型杂多酸相转移催化氧化合成1,2-邻二醇的方法,其特征在于:第二步中,反应时间维持在2~5h。 The Supported heteropolyacid A method according to claim 1 Synthesis of 1,2-catalytic oxidation of vicinal diols phase transfer, wherein: the second step, the reaction time was maintained at 2 ~ 5h.
  8. 8.根据权利要求1所述的固载型杂多酸相转移催化氧化合成1,2-邻二醇的方法,其特征在于:第三步中,萃取溶剂选用乙酸乙酯或乙酸丁酯。 8. The method of synthesis of 1,2-catalytic oxidation of vicinal diols in accordance with a phase transfer Supported heteropolyacid according to claim 1, wherein: the third step, the extraction solvent is selected ethyl acetate or butyl acetate.
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CN105772085A (en) * 2016-04-06 2016-07-20 上海应用技术学院 Cr-Anderson type heteropolyacid catalyst modified by (S)-1-(1-ethoxyl-1-isopropyl) thiourea, and preparation method and application thereof
CN105772101A (en) * 2016-04-06 2016-07-20 上海应用技术学院 1-phenethyl thiourea modified Mn-Anderson type heteropolyacid catalyst and preparation method and application thereof
CN105772086A (en) * 2016-04-06 2016-07-20 上海应用技术学院 (S)-1-(1-hydroxyethyl-1-isopropyl) thiourea modified Mn-Anderson type heteropoly acid catalyst, and preparation method and application thereof
CN105772100A (en) * 2016-04-06 2016-07-20 上海应用技术学院 (R)-1-(1-(2-naphthyl) ethyl) thiourea modified Cr-Anderson type heteropolyacid catalyst and preparation method and application thereof
CN105797769A (en) * 2016-04-06 2016-07-27 上海应用技术学院 (R)-1-(2-hydroxy-1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as preparation method and application thereof
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CN105854940A (en) * 2016-04-06 2016-08-17 上海应用技术学院 (R)-1-(1-phenethyl) thiourea modified Cr-Anderson type heteropolyacid catalyst as well as preparation method and application thereof

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CN105772085A (en) * 2016-04-06 2016-07-20 上海应用技术学院 Cr-Anderson type heteropolyacid catalyst modified by (S)-1-(1-ethoxyl-1-isopropyl) thiourea, and preparation method and application thereof
CN105772101A (en) * 2016-04-06 2016-07-20 上海应用技术学院 1-phenethyl thiourea modified Mn-Anderson type heteropolyacid catalyst and preparation method and application thereof
CN105772086A (en) * 2016-04-06 2016-07-20 上海应用技术学院 (S)-1-(1-hydroxyethyl-1-isopropyl) thiourea modified Mn-Anderson type heteropoly acid catalyst, and preparation method and application thereof
CN105772100A (en) * 2016-04-06 2016-07-20 上海应用技术学院 (R)-1-(1-(2-naphthyl) ethyl) thiourea modified Cr-Anderson type heteropolyacid catalyst and preparation method and application thereof
CN105797769A (en) * 2016-04-06 2016-07-27 上海应用技术学院 (R)-1-(2-hydroxy-1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as preparation method and application thereof
CN105797770A (en) * 2016-04-06 2016-07-27 上海应用技术学院 (S)-1-(3-hydroxyl-1-phenylpropyl) thiourea modified Cr-Anderson type heteropolyacid catalyst as well as preparation method and application thereof
CN105833909A (en) * 2016-04-06 2016-08-10 上海应用技术学院 (S)-1-(2-hydrox-1-phenethyl)thiourea modified Cr-Anderson heteropolyacid catalyst, and preparation method and application thereof
CN105854952A (en) * 2016-04-06 2016-08-17 上海应用技术学院 (S)-1-(2-hydroxyl-1-phenethyl) thiourea modified Mn-Anderson type heteropolyacid catalyst as well as a preparation method and application thereof
CN105854940A (en) * 2016-04-06 2016-08-17 上海应用技术学院 (R)-1-(1-phenethyl) thiourea modified Cr-Anderson type heteropolyacid catalyst as well as preparation method and application thereof
CN105797770B (en) * 2016-04-06 2018-03-30 上海应用技术学院 (S) -1- (3- hydroxy-1-phenylpropyl) thiourea modified Cr-Anderson heteropolyacid catalyst preparation method and application
CN105772086B (en) * 2016-04-06 2018-03-30 上海应用技术学院 (S) -1- (1- hydroxyethyl-1-isopropyl-yl) thiourea modified Mn-Anderson heteropolyacid catalyst preparation method and application
CN105797769B (en) * 2016-04-06 2018-03-30 上海应用技术学院 (R) -1- (2- hydroxy-1-phenylethyl) thiourea modified Mn-Anderson heteropolyacid catalyst preparation method and application
CN105772085B (en) * 2016-04-06 2018-04-13 上海应用技术学院 (S) -1- (1- hydroxyethyl-1-isopropyl-yl) thiourea modified Cr-Anderson heteropolyacid catalyst preparation method and application
CN105772100B (en) * 2016-04-06 2018-05-15 上海应用技术学院 (R) -1- (1- (2- naphthyl) ethyl) thiourea modified Cr-Anderson heteropolyacid catalyst preparation method and application
CN105854952B (en) * 2016-04-06 2018-05-15 上海应用技术学院 (S) -1- (2- hydroxy-1-phenylethyl) thiourea modified Mn-Anderson heteropolyacid catalyst preparation method and application
CN105854940B (en) * 2016-04-06 2018-05-15 上海应用技术学院 (R) -1- (1- phenylethyl) thiourea modified Cr-Anderson heteropolyacid catalyst preparation method and application

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