CN101233263A - 制备1,1,4,4-四烷氧基丁-2-烯衍生物的方法 - Google Patents
制备1,1,4,4-四烷氧基丁-2-烯衍生物的方法 Download PDFInfo
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- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
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- SOZRYPUHONTBPJ-UHFFFAOYSA-L ethyl(tripropyl)azanium sulfate Chemical compound S(=O)(=O)([O-])[O-].C(C)[N+](CCC)(CCC)CCC.C(C)[N+](CCC)(CCC)CCC SOZRYPUHONTBPJ-UHFFFAOYSA-L 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/30—Compounds having groups
- C07C43/303—Compounds having groups having acetal carbon atoms bound to acyclic carbon atoms
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Abstract
本发明涉及制备通式(I)的1，1，4，4－四烷氧基丁－2－烯衍生物的方法，其中基团R1和R2各自相互独立地为氢，C1－C6烷基，C6－C12芳基如苯基，或C5－C12环烷基，或R1和R2与它们连接的双键一起形成C6－C12芳基如苯基，由1个或多个C1－C6烷基、卤原子或烷氧基取代的苯基，或单不饱和或多不饱和C5－C12环烷基，R3、R4各自相互独立地为氢、甲基、三氟甲基或腈，所述方法包括在C1－C6烷基醇的存在下电化氧化式II的1，4－二烷氧基－1，3－丁二烯，其中R1、R3和R4具有如式I中相同的含义。
Description
本发明涉及一种在C1-C6烷基醇的存在下通过电化氧化而由1，4-二烷氧基-1，3-丁二烯制备1，1，4，4-四烷氧基丁-2-烯的电化方法。
已知合成1，1，4，4-四烷氧基丁-2-烯的各种非电化方法。
因此，EP-A 581 097描述了使用脱水试剂并在酸的存在下由2，5-二甲氧基二氢呋喃制备1，1，4，4-四甲氧基丁-2-烯。EP-A 581 097中使用的2，5-二氢-2，5-二甲氧基呋喃起始原料的电化合成为已知的。在此阳极甲氧基化中，起始于呋喃，溴化物尤其用作有利的氧化催化剂(媒介物)。因此，DE-A-27 10 420和DE-A-848 501描述了呋喃在溴化钠或溴化铵作为电解质盐的存在下的阳极氧化。1，1，4，4-四甲氧基丁-2-烯的这种两级合成的缺点是难以处理的呋喃、溴化物用作媒介物、脱水剂的使用和副产物1，1，2，5，5-五甲氧基丁烷的形成。
起始于呋喃和溴的合成公开于US-A3240818中。在此方法中，也必须处理呋喃。溴不仅为非常昂贵的氧化剂，而且难以且高费用地正确除去。
因此，本发明的目的是提供一种经济的并且以高收率和良好选择性得到所需产物的制备1，1，4，4-四烷氧基丁-2-烯衍生物的电化方法。
因此，我们发现一种制备通式(I)的1，1，4，4-四烷氧基丁-2-烯衍生物的方法：
其中基团R1和R2各自相互独立地为氢，C1-C6烷基，C6-C12芳基如苯基，或C5-C12环烷基，或R1和R2与它们连接的双键一起形成C6-C12芳基如苯基，由1个或多个C1-C6烷基、卤原子或烷氧基取代的苯基或单不饱和或多不饱和C5-C12环烷基，R3、R4各自相互独立地为氢、甲基、三氟甲基或腈，所述方法包括在C1-C6烷基醇的存在下电化氧化式II的1，4-二烷氧基-1，3-丁二烯：
其中基团R1、R3和R4具有如式I中相同的含义。基团R1优选甲基。
意欲包括所有可能的式I和II的化合物的非对映体、对映体和反式/顺式异构体、立体异构体及其混合物，因此，尤其不仅是纯非对映体、对映体和异构体，而且还有相应混合物。
1，4-二烷氧基-1，3-丁二烯显著比在现有技术方法中用作起始原料的呋喃便宜。由于1，4-二烷氧基-1，3-丁二烯的更高的沸点，反应期间所需的冷却也降低并且更高的反应温度成为可能。这种起始原料的其他重要优点是它显著更低的毒性。1，4-二甲氧基-1，3-丁二烯为本身已知的。1，4-二甲氧基-1，3-丁二烯可通过将1，4-丁二醇甲基化成1，4-二甲氧基-2-丁炔并将其重排而制备，例如如L.Brandsma在Synthesis of Acetylenes，Allenes andCumulenes，Elesevier Ltd.2004，第204页，和P.E.van Rijn等，J.R.Neth.Chem.Soc.100，198，372-375所述。如H.Hiranuma等，J.Org.Chem.1982，47，5083-5088所述，在后处理之后得到顺，顺/顺，反/反，反(59±5)：(35±5)：(6±3)-1，4-二烷氧基-1，3-丁二烯，并且这优选用于本发明方法中。在2和3位上取代的1，4-二烷氧基-1，3-丁二烯的制备类似地进行。
在电解质中，C1-C6烷基醇以基于通式(II)的1，4-二烷氧基-1，3-丁二烯衍生物等摩尔量，或以至多1∶20过量使用，然后同时用作溶剂或稀释剂以产生通式(I)的化合物。优选使用C1-C6烷基醇，非常特别优选甲醇。
如果合适的话，将常规助溶剂加入电解溶液中。这些为通常在有机化学中惯用的具有高氧化电势的惰性溶剂。可提到的实例为二甲基甲酰胺、碳酸二甲酯、乙腈和碳酸亚丙酯。
包含在电解溶液中的电解质盐通常为至少一种选自钾、钠、锂、铁、碱金属、碱土金属、四(C1-C6烷基)铵盐的化合物，优选三(C1-C6烷基)甲基铵盐。可能的抗衡离子为硫酸根、硫酸氢根、烷基硫酸根、芳基硫酸根、卤离子、磷酸根、碳酸根、烷基磷酸根、烷基碳酸根、硝酸根、醇盐、四氟硼酸根或高氯酸根。
此外，衍生于上述阴离子的酸可作为电解质盐。
优选甲基三丁基甲基硫酸铵(MTBS)、甲基三乙基甲基硫酸铵或甲基三丙基甲基甲基硫酸铵。
另外，离子液体也适用作电解质盐。适合的离子液体描述于“IonicLiquids in Synthesis”，Peter Wasserscheid，Tom Welton编辑，Verlag WileyVCH出版，2003，第3.6章，第103-126页中。
本发明方法可在所有常规类型的电解池中进行。优选使用未分隔的流通池中连续进行。
特别有用的电解池为其中阳极区通过膜或膈膜与阴极分隔开的那些。非分隔的双极毛细池或电极配置成板并以平行方式排列的板堆积池(platestack cell)(参看Ullmann’s Encyclopedia of Industrial Chemistry，1999电子版，第6版，VCH-Verlag Weinheim，Electrochemistry卷，第3.5.章特别池设计和第5章，Organic Electrochemistry，子章节5.4.3.2Cell Design)非常特别有用。这种电解池还例如描述于DE-A-19533773中。
进行本方法的电流密度通常为1-20mA/cm2，优选3-5mA/cm2。温度通常为-20至55℃，优选20-40℃。本方法通常在大气压力下进行。当本方法在更高的温度下进行时，优选使用更高的压力以避免起始化合物或助溶剂沸腾。
适合的阳极材料例如为石墨材料、贵金属如铂或金属氧化物如氧化钌或氧化铬或RuOxTiOx型混合氧化物、金属如铅或镍或掺杂有硼的金刚石。优选石墨和铂。还优选具有金刚石表面的阳极。
可能的阴极材料例如为铁、钢、不锈钢、镍、铅、汞或贵金属如铂、掺杂有硼的金刚石以及石墨或碳材料，优选石墨。
非常特别优选石墨系作为阳极和阴极。
反应完成之后，将电解溶液通过通常已知的分离方法后处理。为此，电解溶液通常首先得到8-9的pH，随后蒸馏，各个化合物分别以各种馏分的形式得到。进一步提纯可例如通过结晶、蒸馏或层析进行。
实施例
实施例1-1，1，4，4-四甲氧基丁-2-烯
设备：具有6个石墨电极的非分隔板堆积池(直径：65mm，间隔：1mm，5间隙)
阳极和阴极：石墨
电解质：47g反，反-、反，顺-和顺，顺-1，4-二甲氧基丁二烯
20g甲基三丁基甲基硫酸铵(MTBS)
717g甲醇
使用2.5F/摩尔1，4-二甲氧基-1，3-丁二烯电解
电流密度：3.4Adm-2
温度：24℃
在所述条件下的电解中，电解质借助换热器以250l/h的流动速率泵送通过池5小时。
在电解完成后，电解溶液通过蒸馏而除去甲醇并将残余物在54-64℃和2毫巴下蒸馏。这得到46g1，1，4，4-四甲氧基丁-2-烯，相当于收率为62％。选择性为84％。
Claims (5)
1.一种制备通式(I)的1，1，4，4-四烷氧基丁-2-烯衍生物的方法：
其中基团R1和R2各自相互独立地为氢，C1-C6烷基，C6-C12芳基或C5-C12环烷基，或R1和R2与它们连接的双键一起形成C6-C12芳基，由1个或多个C1-C6烷基、卤原子或烷氧基取代的苯基或单不饱和或多不饱和C5-C12环烷基，R3、R4各自相互独立地为氢、甲基、三氟甲基或腈，所述方法包括在C1-C6烷基醇的存在下电化氧化式II的1，4-二烷氧基-1，3-丁二烯：
其中R1、R3和R4具有如式I中相同的含义。
2.根据权利要求1的方法，其中所述脂族C1-C6烷基醇为甲醇。
3.根据权利要求1或2的方法，其中每摩尔式(II)的1，4-二烷氧基-1，3-丁二烯，使用至少1摩尔烷基醇。
4.根据权利要求1-3中任一项的方法，其在包括钠、钾、锂、铁、四(C1-C6烷基)铵盐的电解质中用硫酸根、硫酸氢根、烷基硫酸根、芳基硫酸根、卤离子、磷酸根、碳酸根、烷基磷酸根、烷基碳酸根、硝酸根、醇盐、四氟硼酸根、六氟磷酸根或高氯酸根作为抗衡离子或离子液体作为电解质盐进行。
5.根据前述权利要求1-4中任一项的方法，其在双极毛细池或板堆积池或在分隔的电解池中进行。
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| DE102005036687A DE102005036687A1 (de) | 2005-08-04 | 2005-08-04 | Verfahren zur Herstellung von 1,1,4,4,-Tetraalkoxy-but-2-enderivaten |
| DE102005036687.2 | 2005-08-04 |
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| EP (1) | EP1913178A1 (zh) |
| JP (1) | JP2009503266A (zh) |
| KR (1) | KR20080044257A (zh) |
| CN (1) | CN101233263A (zh) |
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| CN109518211A (zh) * | 2019-01-08 | 2019-03-26 | 合肥工业大学 | 一种芳香偶酰类化合物的电化学合成方法 |
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| DE4223889A1 (de) * | 1992-07-21 | 1994-01-27 | Basf Ag | Verfahren zur Herstellung von E,Z-Butendial-bis-dialkylacetalen |
| DE19944989A1 (de) * | 1999-09-20 | 2001-03-22 | Basf Ag | Verfahren zur elektrolytischen Umwandlung von Furanderivaten |
| DE10324192A1 (de) * | 2003-05-28 | 2004-12-23 | Basf Ag | Verfahren zur Herstellung von alkoxylierten 2,5-Dihydrofuran-oder tetra-1,1,4,4-alkoxylierten But-2-enderivaten |
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| US20080228009A1 (en) | 2008-09-18 |
| KR20080044257A (ko) | 2008-05-20 |
| CA2617556A1 (en) | 2007-02-08 |
| DE102005036687A1 (de) | 2007-02-08 |
| WO2007014932A1 (de) | 2007-02-08 |
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