CN103732800B - 电化学生产γ‑羟基羧酸酯和γ‑内酯的方法 - Google Patents
电化学生产γ‑羟基羧酸酯和γ‑内酯的方法 Download PDFInfo
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- CN103732800B CN103732800B CN201280040196.6A CN201280040196A CN103732800B CN 103732800 B CN103732800 B CN 103732800B CN 201280040196 A CN201280040196 A CN 201280040196A CN 103732800 B CN103732800 B CN 103732800B
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- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- ZXUCBXRTRRIBSO-UHFFFAOYSA-L tetrabutylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC ZXUCBXRTRRIBSO-UHFFFAOYSA-L 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229940094989 trimethylsilane Drugs 0.000 description 1
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Abstract
本发明涉及一种通过α,β‑不饱和酯与羰基化合物在无分隔电解池中电化学还原交叉偶联而生产适合作为芳香物质的γ‑羟基羧酸酯和γ‑内酯的方法,所述池具有由铅、铅合金、镉、镉合金、汞、钢、玻璃碳或硼掺杂金刚石组成的阴极,并使用包含抑制阴极氢形成的导电盐的碱性水性电解质。
Description
本申请通过引用并入2011年8月24日提交的临时申请US61/526722。
本发明涉及一种通过α,β-不饱和酯与羰基化合物在无分隔电解池中还原交叉偶联而电化学制备γ-羟基羧酸酯和γ-内酯的方法,其中使用由铅、铅合金、镉、镉合金、汞、钢、玻璃碳或硼掺杂金刚石组成的阴极和包含选自双季铵盐和多季铵盐以及盐的电解质盐的碱性水性电解质。
本发明还涉及式I的γ-丁内酯衍生物:
其可通过本发明方法制备,且其也用作调料。
本发明也涉及式VII的γ-羟基羧酸或γ-羟基羧酸酯:
其同样可通过本发明方法制备。
工业上最重要的γ-内酯是γ-丁内酯。工业上通过在气相中1,4-丁二醇脱氢环化或通过马来酸酐氢化制备。另一制备γ-内酯的经典方法是γ-卤代羧酸的加碱水解。
上述方法都是由现有的双取代C4骨架出发,以致环上的取代方式不能集中实现。然而,仅借助C,C-键偶联构建其他内酯环的方法也为已知。这些包括例如乙酸与烯烃(C2+C2)的氧化偶联或氢过氧化叔丁基辅助的丙烯酸与醇(C3+C1)环化。在这些情况下,环的取代可通过在环化中灵活使用合适原料控制。
该类型内酯合成也包括根据以下反应方案的丙烯酸酯和羰基化合物的还原偶联(二氢化二聚):
丙烯酸衍生物与羰基化合物的还原偶联可借助还原剂如镁或钐(II)的碘化物进行。避免化学计量使用化学还原剂的电化学方法也已描述。该领域的基本金属研究在分隔电化学池中在硫酸电解质中在汞槽阴极上以至多为2.8A/dm2的阴极电流密度进行。在研究中,观察到丙烯腈与丙酮的还原偶联,因此其还未得到内酯。
由此出发,Shono等(Tetrahedron Lett.1980,21,5029-5032)描述了在分隔电化学池中α,β-不饱和酯与醛或酮的还原偶联。所用电解质基于作为电解质盐的N,N-二甲基甲酰胺(DMF)和N,N,N,N-四乙基甲苯磺酸铵(Et4NOTs)。此外,加入化学计量量的氯硅烷(氯化三甲基硅烷,TMSCl)活化羰基组分。电解在0.4A/dm2的电流密度下进行,其与>1A/dm2的工业上相关的电流密度相差甚远。Nobuya等(JP57108274A)通过使用水基电解质向工业实施更近一步。该内酯的制备在电流密度为10A/dm2的分隔电解池中进行。在此,使用酸性阳极电解液(如浓度为10%的H2SO4)和KH2PO4-缓冲阴极电解液。在分隔池中,两电极空间通过膜分隔。无分隔池更便宜且工业上更易实现。特别是在有机方法的情况下,膜的快速老化且因此令人不满意的操作寿命是可预期的。
US4,414,079描述了在无分隔池中α,β-不饱和酯与醛的反应,其使用如四正丁基硫酸铵作为电解质盐。在另一方法中,Bürger(Katrin Bürger,Thesis2003,Münster)在无分隔池中进行α,β-不饱和酯与醛或酮的反应。所用电解质为醇(如甲醇或乙醇)与水或二烷的二元混合物以及高浓度电解质盐(如四丁基四氟硼酸铵Bu4NBF4)。令人感兴趣的是在所述体系中使用石墨电极,由于其相对高的氢过电压,因此其可替代铅、汞和镉电极使用。尽管α,β-不饱和酯的均相偶联(homo-kopplung)可通过大过量的羰基化合物对抗,然而由于相应均相偶联的产物和还原的羰基组分(即相应的醇)很大程度上作为副产物形成,因此可通过该方法得到的内酯的产率令人不满意。此外,该方法基于使用基于二元有机溶剂(醇和水或醇和二烷)的电解质,其使得产物在电解后从溶剂中的复杂分离成为必需。由于醇在电解中氧化(成为醛和其他),因此含醇溶剂的使用也是不利的。因此,昂贵溶剂损失以及形成的醛必须以复杂的方式分离。
因此,本发明的目的是提供通过α,β-不饱和酯与羰基化合物交叉偶联而电化学制备γ-内酯和γ-羟基羧酸酯的方法,其中避免了低电流密度(<1A/dm2)的现有技术的缺点,特别是分隔电化学池的使用和降低产率的副反应的发生。该目的通过下述所要求保护的实施方案实现。
因此,本发明提供通过在无分隔电解池中α,β-不饱和酯与羰基化合物的还原交叉偶联而电化学制备γ-羟基羧酸酯和/或γ-内酯的方法,其中阴极材料选自铅、铅合金、镉、镉合金、汞、钢、玻璃碳和硼掺杂金刚石,并使用包含至少一种选自双季铵盐和多季铵盐以及盐的电解质盐的碱性水性电解质。
对本发明而言,羰基化合物为醛或酮,优选醛。本发明羰基化合物在每种情况下在20℃下优选在水中具有低于100g/l,更优选低于50g/l,特别优选低于30g/l的低溶解度。优选键于羰基化合物的羰基的烷基和/或芳基也可包含其他官能团(例如醇、醚、羰基、羧酸基团等)且可为被氧、硫或氮间隔的烷基、亚烷基或亚芳基。特别优选除羰基外不具有任何其他杂原子的脂族羰基化合物。合适的羰基化合物为例如戊醛、2-甲基戊醛、己醛、2-乙基己醛、庚醛、4-甲酰基四氢吡喃、4-甲氧基苯甲醛、4-叔丁基苯甲醛、4-甲基苯甲醛、乙二醛、戊二醛、甲基乙二醛、环己烯酮、环己酮、二乙基甲酮。特别优选羰基化合物为戊醛、2-甲基戊醛、己醛和庚醛。
对本发明而言,α,β-不饱和酯为可在2和3位上独立取代的丙烯酸酯衍生物,其中两个取代基也可位于3位上。取代基优选为烷基、卤原子、C1-C20烷氧基,被氧、硫或氮间隔的烷基、亚烷基或亚芳基,腈基和硝基。取代基优选选自甲基、乙基、正丙基、异丙基、正丁基、叔丁基、三氟甲基、氟、氯、溴、碘、甲氧基、乙氧基、亚甲基、亚乙基、亚丙基、亚异丙基、亚苄基、腈基和硝基。特别优选取代基选自甲基、乙基、甲氧基、乙氧基。α,β-不饱和酯优选为C1-C12烷基酯,特别优选C1-C5烷基酯,非常特别优选甲基或乙基酯。根据本发明所用α,β-不饱和酯优选在每种情况下在20℃下在水中具有低于100g/l,优选低于50g/l,特别优选低于20g/l的低溶解度。
根据本发明,α,β-不饱和酯和羰基化合物为还原偶联的原料。
对本发明而言,水性电解质包含原料与水、至少一种电解质盐和至少一种缓冲剂作为组分。此外,电解质也优选包含至少一种络合剂和/或至少一种阳极腐蚀抑制剂作为其他组分。全部的水性电解质与包括原料的所有组分一起在下文中也称为反应电解质。对应于不含原料的反应电解质的水性组合物在下文中也称为支持电解质。水性反应电解质具有基于总水性反应电解质优选为至少20重量%,特别优选至少50重量%,特别是至少75重量%的水含量。
本发明反应电解质包含至少一种选自双季铵盐和多季铵盐以及盐的电解质盐,其抑制阴极形成氢。除这些双季铵盐和多季铵盐以及盐外,优选不使用其他电解质盐。一般来说,电解质盐以基于总水性反应电解质为0.01-2.5重量%,优选0.01-1.5重量%,优选0.01-0.5重量%,特别优选0.05-0.25重量%的量。特别合适的电解质盐为双季铵盐和盐(EP635587A)。特别优选使用双(二丁基乙基)六亚甲基氢氧化二铵作为电解质的电解质盐。抗衡离子可为例如硫酸盐、硫酸氢盐、烷基硫酸盐、芳基硫酸盐、烷基磺酸盐、芳基磺酸盐、卤化物、磷酸盐、碳酸盐、烷基磷酸盐、烷基碳酸盐、硝酸盐、醇盐、氢氧化物、四氟硼酸盐或高氯酸盐。衍生自上述阴离子的酸也可作为电解质盐,即例如硫酸、磺酸和羧酸。离子液体也适合作为电解质盐。合适的离子液体描述于“Ionic Liquids in Synthesis”,PeterWasserscheid编辑,Tom Welton,Verlag Wiley VCH,2003,第1-3章和DE102004011427A。
反应电解质还包含至少一种缓冲范围为pH7至11,优选8至10的用于缓冲在阳极形成氧中形成的质子的缓冲剂。合适的缓冲剂为例如磷酸氢盐或碳酸氢盐,优选呈其钠盐形式。特别优选使用磷酸氢二钠作为电解质的缓冲剂。一般来说,缓冲剂以基于总水性反应电解质为0.9-8重量%,优选4-7重量%的量使用。
此外,反应电解质优选包含一种或多种阳极腐蚀抑制剂如对于该目的已知的硼酸盐,优选二硼酸二钠和原硼酸,其量基于总水性反应电解质为0.4-3重量%,优选1-2重量%。
此外,反应电解质优选包含一种或多种络合剂以避免铁和铅离子沉淀。可例如提及乙二胺四乙酸盐(EDTA)、三乙醇胺(TEA)、三乙基胺、次氮基三乙酸盐,优选基于总水性反应电解质为0-1重量%,优选0.1-0.5重量%的量的EDTA,和/或基于总水性反应电解质为0-0.5重量%,优选0.05-0.2重量%的量的TEA。替代TEA可使用基于总水性反应电解质为0-0.5重量%,优选0.05-0.2重量%的量的三乙胺。
作为阳极材料可使用已知的阳极材料;在无分隔池的情况下,通常使用具有低氧过电压的材料,例如碳钢、玻璃碳、钢、汞、镉、铂、铁、镍、磁铁矿、铅、铅合金或二氧化铅。优选使用由钢、铁、铅或铅合金组成的阳极。
作为阴极使用铅、铅合金、镉、镉合金、汞、钢、玻璃碳或硼掺杂金刚石电极。优选使用铅、铅合金、镉、钢和玻璃碳作为阴极材料。特别优选使用铅和铅合金作为阴极材料。
在本发明水性反应电解质中,有机原料(α,β-不饱和酯和羰基化合物)及形成的产物(γ-羟基羧酸酯和γ-内酯)作为乳液的有机相存在。在电解期间通过机械搅动如电解质在电解池中的搅拌或泵送循环,或通过加入合适的稳定乳液的乳化剂维持乳液。在电解期间优选通过机械搅动如电解质的搅拌或泵循环维持乳液。电解后,可例如通过停止搅动或通过加入合适的絮凝剂完成乳液分层。乳液分层为水相和有机相后,产物和任何未反应的原料可易与有机相一起由水性电解质分离出来。这简化了产物与电解质的分离。
在本发明的电解中,原料α,β-不饱和酯和羰基化合物优选以基本等摩尔比使用。所用α,β-不饱和酯和所用羰基化合物的摩尔比通常在0.25至4,优选0.5至2,特别优选0.8至1.2的范围内。当过量羰基化合物在先前已知方法中用于α,β-不饱和酯与羰基化合物的还原偶联以抑制酯的均相偶联时,本发明方法显示了对α,β-不饱和酯和羰基化合物交叉偶联产物的高选择性。当使用基本等摩尔比的原料时,可借助本发明方法得到特别良好产率的交叉偶联产物。α,β-不饱和酯优选以基于总水性反应电解质为1-25重量%,特别优选5-10重量%的量使用。
电解通常在至少1A/dm2,优选1-4A/dm2的电流密度下进行。然而,也可在高达20A/dm2的较高电流密度下进行。
本发明电解通常在20-60℃的温度和大气压力下进行。
电解可连续或间歇且在所有常见无分隔电解池中,例如在玻璃烧杯池或板式池(plattenzellen)以及框架池(rahmenzellen)或具有固定床或移动床电极的池中进行。单极和双极连接的电极都可使用。电解池中的电解质优选通过泵送循环或搅拌,结果是维持其作为乳液存在。非常特别合适的池为以双极形式连接的毛细管池或叠板式池,其中电极构造为板且彼此平行排列(Ullmann's Encyclopedia of Industrial Chemistry,2009电子版,VCH-Verlag Weinheim,Volume Electrochemistry,第3章,Electrochemical Cells和第5章,Organic Electrochemistry,第5.4.3.子章节Electrochemical Cells)。
在无分隔电解池中,阳极空间和阴极空间不通过膜彼此分开。这种无分隔池较便宜且技术上易于实现。特别是在有机方法情况下,使用分隔池可使膜快速老化,其导致令人不满意的操作寿命。
在本发明方法中对于α,β-不饱和酯与羰基化合物的电化学还原交叉偶联,γ-内酯或相应的γ-羟基羧酸酯可在每种情况下单独或作为混合物形成。如果需要,形成的任何γ-羟基羧酸酯可在电化学还原交叉偶联后通过酯交换转化为γ-内酯。酯交换形成γ-内酯可例如通过在酸存在下加热γ-羟基羧酸酯进行。如果需要,所释放的醇可由反应混合物中除去以使反应向γ-内酯方向转移。相反,形成的任何γ-内酯可在电化学还原交叉偶联后通过酯交换(醇解),例如通过在碱性非水性醇溶液中加热γ-内酯,转化为γ-羟基羧酸酯。γ-羟基羧酸酯随后可通过水解进一步转化为游离酸或羧酸盐。为此,将γ-羟基羧酸酯例如与水性碱性溶液一起加热。作为替换,游离的γ-羟基羧酸或其盐还可直接由γ-内酯通过水解制备。这可例如通过在水性碱性溶液中加热γ-内酯进行。
本发明还提供通式I的γ-丁内酯衍生物:
其中
R1、R2和R3各自彼此独立为氢或具有1至5个碳原子的烷基,优选氢、甲基或乙基,和
R4和R5为具有1至4个碳原子,优选1至3个碳原子的烷基,其中R4和R5为相同基团,
其可通过本发明方法制备。
式I化合物可通过式II的α,β-不饱和酯与式III的2-烷基链烷醛的本发明电化学交叉偶联而制备:
其中R1至R5具有与在式I化合物中相同的含义,且R为烷基,通常为具有1至12个碳原子,优选1至5个碳原子的烷基,非常特别优选甲基或乙基。
本发明优选提供通式IV的γ-丁内酯衍生物:
其中
R2为氢或具有1至5个碳原子的烷基,优选氢、甲基基团或乙基,且R4和R5为具有1至4个碳原子,优选1至3个碳原子的烷基,其中R4和R5为相同基团,
其可通过本发明方法制备。
式IV化合物可通过式II(其中R1和R3在每种情况下为氢)的α,β-不饱和酯与式III的2-烷基链烷醛根据本发明电化学交叉偶联而制备。
式III的2-烷基链烷醛可例如通过具有3至6个碳原子的链烷醛(丙醛、丁醛、戊醛或己醛)的羟醛缩合制备。
特别优选γ-丁内酯衍生物4-(2-戊基)丁内酯
和3-甲基-4-(2-戊基)丁内酯(VI),其可通过丙烯酸酯或巴豆酸酯与2-甲基戊醛根据本发明电化学交叉偶联而制备。
本发明还提供通式VIII的γ-羟基羧酸和γ-羟基羧酸酯:
其中
R1、R2、R3和R7各自彼此独立为氢或具有1至5个碳原子的烷基,优选氢、甲基或乙基。R为氢或烷基,通常为氢或具有1至5个碳原子的烷基,且R8为具有3至10个碳原子的支化烷基,
其可通过本发明方法制备。
本发明优选提供通式VIII的γ-羟基羧酸和γ-羟基羧酸酯,其中R1、R2和R3各自彼此独立为氢或具有1至5个碳原子的烷基,优选氢、甲基或乙基,R为氢或烷基,通常为氢或具有1至5个碳原子的烷基,R7为氢且R8为具有3至10个碳原子的支化烷基,其可通过本发明方法制备。
式VIII化合物可通过式II的α,β-不饱和酯与式VIII的羰基化合物根据本发明电化学交叉偶联而制备:
其中R7和R8具有与式VIII化合物相同的含义。
对本发明而言,烷基原则上可为支化或未支化的、线性或环状的以及饱和或不饱和的(包括多级不饱和的)。其优选具有1至20,特别优选1至6个碳原子。其优选不具有任何杂原子。
对本发明而言,芳基为具有优选5至20个碳原子的芳基。
本发明还提供本发明的式I的γ-丁内酯衍生物,优选式IV的γ-丁内酯衍生物,特别优选4-(2-戊基)丁内酯或3-甲基-4-(2-戊基)丁内酯作为香料或调料的用途。4-(2-戊基)丁内酯具有梨的香气,且3-甲基-4-(2-戊基)丁内酯具有木质的香气。
实施例
现在本发明将通过以下非限制性实施例说明。
实施例1
使用过量己醛通过丙烯酸乙酯与己醛的还原交叉偶联而电化学制备γ-羟基壬酸乙酯和4-戊基丁内酯
将丙烯酸乙酯(1.7重量%)和己醛(29.7重量%)在水性电解质(0.16重量%双(二丁基乙基)六亚甲基氢氧化二铵(双季铵盐),0.38重量%EDTA,0.14重量%TEA,1.45重量%Na2B4O7和5.84重量%Na2HPO4,在水中,pH为10)(所有重量%基于总水性反应电解质)中乳化,且在罐式池(topfzelle)中在2.23A/dm2的电流密度和20℃的温度下进行恒电流电解。现有生产量为2F/mol的酯。钢阳极和铅阴极用作电极(电极面积为0.1dm2且间距为1cm)。为监测反应,将电解输出的样品的甲基三丁基甲基硫酸铵提取物(MTBE提取物)通过气相色谱分析。得到产率为0.1%的4-戊基丁内酯和产率为2.9%的相应的γ-羟基壬酸乙酯。这对应于目标产物的总产率为理论产率的3.0%。
实施例2
使用等摩尔比原料通过丙烯酸乙酯与己醛的还原交叉偶联而电化学制备γ-羟基壬酸乙酯和4-戊基丁内酯
使丙烯酸乙酯(5.9重量%)和己醛(6.0重量%)如实施例1中所述反应(所有重量%基于总水性反应电解质)和分析。得到产率为23.7%的4-戊基丁内酯和产率为48.0%的相应γ-羟基壬酸乙酯。这对应于目标产物的总产率为理论产率的71.7%。
对比实施例1
使用过量己醛通过丙烯酸乙酯与己醛的还原交叉偶联而电化学制备γ-羟基壬酸乙酯和4-戊基丁内酯
对应于Bürger描述的还原偶联,将丙烯酸乙酯(1.7重量%)和己醛(29.7重量%)溶于电解质(在3:1的二烷和乙醇混合物中的17.0重量%四丁基四氟硼酸胺(Bu4NBF4))(所有重量%基于总水性反应电解质),且在罐式电解池中在初始2.23A/dm2的电流密度和21℃的温度下进行恒电流电解。现有生产量为2F/mol的酯。在电解过程中,电流密度降至0.73A/dm2。铂阳极和石墨阴极用作电极(电极面积为0.1dm2且间距为1cm)。为监测反应,将电解输出的样品的甲基三丁基甲基硫酸铵提取物通过气相色谱分析。得到产率为2.0%的4-戊基丁内酯和产率为0.2%的相应的γ-羟基壬酸乙酯。这对应于目标产物的总产率为理论产率的2.2%。
对比实施例2
使用等摩尔比原料通过丙烯酸乙酯与己醛的还原交叉偶联而电化学制备γ-羟基壬酸乙酯和4-戊基丁内酯
使丙烯酸乙酯(5.9重量%)和己醛(6.0重量%)如对比实施例1中所述在22oC下反应(所有重量%基于总水性反应电解质)且随后如对比实施例1中所述分析,其中电流密度在实验期间保持恒定。得到产率为16.5%的4-戊基丁内酯和产率为0.7%的相应的γ-羟基壬酸乙酯。这对应于目标产物的总产率为理论产率的17.2%。
实施例3
威士忌内酯(whiskeylacton)的制备
将巴豆酸乙酯(6.9重量%)和戊醛(5.2重量%)在水性电解质(0.16重量%双(二丁基乙基)六亚甲基氢氧化二铵(双季铵盐),0.38重量%EDTA,0.14重量%TEA,1.45重量%Na2B4O7和5.84重量%Na2HPO4,在水中,pH为10)(所有重量%基于总水性反应电解质)中乳化,且在框架电解池中在2.23A/dm2的电流密度和25℃的温度下进行恒电流电解。现有生产量为2F/mol的酯。钢阳极和铅阴极用作电极(电极面积为0.1dm2且间距为1cm)。为监测反应,将电解输出的样品的MTBE提取物通过气相色谱分析。得到产率为68.5%的3-甲基-4-丁基丁内酯(威士忌内酯)和产率为24.2%的相应的γ-羟基羧酸乙酯。这对应于目标产物的总产率为理论产率的92.7%。
实施例4
4-(2-戊基)丁内酯的制备
使丙烯酸乙酯(5.9重量%)和2-甲基戊醛(6.0重量%)利用类似于实施例3的方法电化学反应(所有重量%基于总水性反应电解质)。得到产率为88.4%的4-(2-戊基)丁内酯。
实施例5
3-甲基-4-(2-戊基)丁内酯
使巴豆酸乙酯(6.7重量%)和2-甲基戊醛(5.9重量%)通过类似于实施例3的方法电化学反应(所有重量%基于总水性反应电解质)。得到产率为66.7%的4-(2-戊基)丁内酯和产率为26.6%的相应的γ-羟基羧酸乙酯。这对应于目标产物的总产率为理论产率的93.2%。
实施例6
3,3-二甲基-4-戊基丁内酯的制备
使3,3-二甲基丙烯酸甲酯(4.9重量%)和己醛(4.3重量%)通过类似于实施例3的方法电化学反应(所有重量%基于总水性反应电解质)。得到产率为37.2%的3,3-二甲基-4-戊基丁内酯。
实施例7
2-甲基-4-丁基丁内酯的制备
使甲基丙烯酸乙酯(6.7重量%)和戊醛(5.2重量%)利用类似于实施例3的方法电化学反应(所有重量%基于总水性反应电解质)。得到产率为81.0%的2-甲基-4-丁基丁内酯。
实施例8
2-甲基-4-(2-戊基)丁内酯的制备
使甲基丙烯酸乙酯(6.7重量%)和甲基戊醛(5.9重量%)利用类似于实施例3的方法电化学反应(所有重量%基于总水性反应电解质)。得到产率为70.9%的2-甲基-4-(2-戊基)丁内酯。
Claims (15)
1.一种通过α,β-不饱和酯与羰基化合物在无分隔电解池中还原交叉偶联而电化学制备γ-羟基羧酸酯和/或γ-内酯的方法,其中阴极材料选自铅、铅合金、镉、镉合金、汞、钢、玻璃碳和硼掺杂金刚石,并使用包含选自双季铵盐、多季铵盐、双季盐以及多季盐的至少一种电解质盐的碱性水性电解质,其中所用α,β-不饱和酯与所用羰基化合物的摩尔比为0.5-2。
2.根据权利要求1的方法,其中原料α,β-不饱和酯和羰基化合物以及这些原料的还原交叉偶联产物在水性电解质中作为乳液存在。
3.根据权利要求1的方法,其中电解质盐为双季铵盐或双季盐。
4.根据权利要求2的方法,其中电解质盐为双季铵盐或双季盐。
5.根据权利要求1-4中任一项的方法,其中阴极材料选自铅、铅合金、镉、钢和玻璃碳。
6.根据权利要求1-4中任一项的方法,其中阳极材料选自玻璃碳、钢、汞、镉、铂、铁、镍、磁铁矿、铅、铅合金和二氧化铅。
7.根据权利要求1-4中任一项的方法,其中阳极材料为碳钢。
8.根据权利要求1-4中任一项的方法,其中水性电解质包含至少一种缓冲范围为pH 7至11的缓冲剂。
9.根据权利要求1-4中任一项的方法,其中水性电解质额外包含一种或多种阳极腐蚀抑制剂。
10.根据权利要去1-4中任一项的方法,其中水性电解质额外包含一种或多种络合剂。
11.根据权利要求1-4中任一项的方法,其中所用α,β-不饱和酯和羰基化合物的摩尔比在0.8至1.2的范围内。
12.根据权利要求1-4中任一项的方法,其中羰基化合物为醛。
13.根据权利要求1-4中任一项的方法,其中形成的γ-羟基羧酸酯在随后的工艺步骤中酯交换为γ-内酯。
14.根据权利要求1-4中任一项的方法,其中形成的γ-内酯在随后的工艺步骤中酯交换为γ-羟基羧酸酯。
15.根据权利要求1-4中任一项的方法,其中形成的γ-内酯和/或形成的γ-羟基羧酸酯在随后的工艺步骤中水解为γ-羟基羧酸。
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US20140100376A1 (en) | 2014-04-10 |
WO2013026737A9 (de) | 2013-10-17 |
WO2013026737A3 (de) | 2013-05-23 |
EP2748353B1 (de) | 2017-04-26 |
US20130053582A1 (en) | 2013-02-28 |
CN103732800A (zh) | 2014-04-16 |
WO2013026737A2 (de) | 2013-02-28 |
JP6100779B2 (ja) | 2017-03-22 |
MX2014001914A (es) | 2014-04-14 |
ES2634561T3 (es) | 2017-09-28 |
JP2014524517A (ja) | 2014-09-22 |
EP2748353A2 (de) | 2014-07-02 |
US8617376B2 (en) | 2013-12-31 |
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