CN101137635A - 制备烷氧基化2,5-二氢呋喃丁-2-烯衍生物或四-1,1,4,4-烷氧基化的丁-2-烯衍生物的方法 - Google Patents
制备烷氧基化2,5-二氢呋喃丁-2-烯衍生物或四-1,1,4,4-烷氧基化的丁-2-烯衍生物的方法 Download PDFInfo
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- LNYJYVGUHXQWLO-UHFFFAOYSA-M methyl sulfate;triethyl(methyl)azanium Chemical compound COS([O-])(=O)=O.CC[N+](C)(CC)CC LNYJYVGUHXQWLO-UHFFFAOYSA-M 0.000 description 1
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- 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
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D307/32—Oxygen atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/88—Benzo [c] furans; Hydrogenated benzo [c] furans with one oxygen atom directly attached in position 1 or 3
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- C07—ORGANIC CHEMISTRY
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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Abstract
本发明涉及一种在C1-C6单烷基醇存在下通过电化学氧化由通式(I)的2-丁烯-1,4-二醇衍生物或者由该2-丁烯-1,4-二醇衍生物与在3-或4-位被取代的且在2-或5-位携带C1-C6烷氧基的2,5-二氢呋喃衍生物的混合物制备在3-或4-位被取代的且在2-或在5-位或在这两个位置都各携带C1-C6烷氧基的2,5-二氢呋喃衍生物(DHF烷氧基衍生物)或者制备在3-或4-位被取代的1,1,4,4-四烷氧基-丁-2-烯衍生物的方法,在式(I)中基团R1和R2彼此独立地代表氢、C1-C6烷基、C6-C12芳基或者C5-C12环烷基,或者R1和R2与它们所连接的双键一起形成C6-C12芳基或者单-或多不饱和的C5-C12环烷基。
Description
本发明涉及一种制备在3-或4-位被取代的并且在2-或在5-位或在这两个位置都各携带C1-C6烷氧基的2,5-二氢呋喃衍生物或者制备在3-或4-位被取代的1,1,4,4-四烷氧基-丁-2-烯(DHF烷氧基衍生物)的新颖方法。
在二氢呋喃的情况下,环中原子位置的命名根据通常的命名原则进行,即如式(V)所示。
在稠合二氢呋喃的情况下,属于呋喃环的原子的原子位置的命名根据通常的命名原则改变,以异苯并呋喃为例,其原子位置如下式(VI)所示:
在本文中,为了更清楚,与稠合环体系和尤其是异苯并呋喃的上述原则相反,在呋喃环以稠合形式存在的化合物中,也保留如非稠合呋喃环中通常那样的原子位置的命名。在本文中,苯并-稠合二氢呋喃环体系中原子位置的命名因此按照式VII中这样进行。
从呋喃开始的2,5-二氢-2,5-二甲氧基呋喃的电化学合成已经已知。
因此,DE-A-2710420和DE-A-848501描述了在用作导电盐的溴化钠或溴化氨存在下呋喃的阳极氧化。
此外,由Bull.Chem.Soc.Jpn.60,229-240,1987已知呋喃的氰化物催化的阳极氧化。EP-A-078004公开了使用醇盐、卤化物和磺酸盐作为导电盐的呋喃的阳极氧化,然而WO2004/85710描述了在特殊的掺硼的金刚石电极上直接阳极氧化呋喃。
未取代的2,5-二氢呋喃采用电化学氧化的烷氧基化作用公开于EP-A-78004中。在DE10324192中将被取代的呋喃电化学氧化。二氢呋喃衍生物的沸点引起的更高的原材料价格和在冷却上增加的费用导致了该方法不令人满意的经济效果。
因此,本发明目的是获得制备烷氧基化的2,5-二氢呋喃或四-1,1,4,4烷氧基丁-2-烯衍生物的可行的电化学方法,该方法是经济的并且以高产率和良好的选择性得到所需产物。
因而,现在已发现一种在C1-C6单烷基醇存在下通过电化学氧化由通式(I)的2-丁烯-1,4-二醇衍生物或者由该式(I)的2-丁烯-1,4-二醇衍生物与式(II)的在3-或4-位被取代的并且在2-或5-位携带C1-C6烷氧基的2,5-二氢呋喃衍生物的混合物制备在3-或4-位被取代的并且在2-或在5-位或在这两个位置都各携带C1-C6烷氧基的2,5-二氢呋喃衍生物或者制备在3-或4-位被取代的1,1,4,4-四烷氧基-丁-2-烯衍生物(DHF烷氧基衍生物)的方法,
其中基团R1和R2彼此独立地为氢、C1-C6烷基、C6-C12芳基例如苯基或者C5-C12环烷基,或者R1和R2与它们所键合的双键一起形成C6-C12芳基,例如苯基,单-或多C1-C6烷基-、卤素-或烷氧基取代的苯基,或者单-或多不饱和的C5-C12环烷基。
优选使用的C1-C6单烷基醇是甲醇或异丙醇。
特别优选使用本发明方法用于:
1.由式(I)的2-丁烯二醇衍生物在C1-C6单烷基醇存在下通过电化学氧化而制备通式(II)的DHF烷氧基衍生物
其中基团R1、R2和R3具有下述含意:R1、R2彼此独立地为氢、C1-C6烷基、C6-C12芳基或者C5-C12环烷基,或者R1和R2与它们所键合的双键一起形成C6-C12芳基或者单-或多不饱和的C5-C12环烷基,R3是C1-C6烷基;
2.由式(I)的2-丁烯二醇衍生物或它们与通式(II)的DHF-烷氧基衍生物的混合物制备通式(III)的DHF-烷氧基衍生物,
其中基团R1、R2和R3具有与在通式(II)中同样的含意;
或者
3.由式(I)的2-丁烯二醇衍生物制备通式(IV)的在3-或4-位被取代的1,1,4,4-四烷氧基-丁-2-烯衍生物,
其中基团R1、R2和R3具有与在通式(II)中所述同样的意义。
本发明方法尤其适合用于:
1a.由通式(I)的丁烯-1,4-二醇(其中式(I)中的R1和R2为氢)制备通式(IIIa)的DHF烷氧基衍生物
其中R3是C1-C6烷基。
与在现有技术方法中用作原料的呋喃比较,2-丁烯-1,4-二醇费用明显地更少。此外,由于2-丁烯-1,4-二醇的沸点更高,在反应期间冷却时的费用将减少并且更高的反应温度是可行的。这种原料更进一步的显著优点是它明显更低的毒性。在本发明方法中优选使用顺-丁烯-1,4-二醇或者至少含有20%重量的顺-丁烯-1,4-二醇的非对映体混合物。
2a.本发明方法尤其适合由通式(Ia)的在3或4-位被取代的2-丁烯-1,4-二醇衍生物或者由该通式(Ia)的在3或4-位被取代的2-丁烯-1,4-二醇衍生物与通式(II)的DHF烷氧基衍生物的混合物制备通式(IIIb)的DHF烷氧基衍生物,
其中基团R4、R5、R6和R7为氢、C1-C4烷基、C1-C6烷氧基或者卤素,并且R3具有通式(II)中所述的含意,
其中基团R4、R5、R6和R7为氢、C1-C4烷基、C1-C6烷氧基或者卤素,或者
3a.由通式(Ia)的丁烯-1,4-二醇衍生物或由它们与通式(II)的DHF烷氧基衍生物的混合物制备通式(IVa)的1,1,4,4-四烷氧基-丁-2-烯衍生物,
其中基团R4、R5、R6和R7为氢、C1-C4烷基、C1-C6烷氧基或者卤素,并且R3具有通式(II)中所述的含意。
在通式(Ia)、(IIIb)和(IVa)的化合物中,基团R4、R5、R6和R7尤其特别优选为氢。
一般来说,通式(II)、(III)和(IV)的化合物将以它们的混合物形式获得。可以将这些混合物借助于通常已知的分离方法进行后处理。
如果想得到的目标产物是通式(III)或(IV)的化合物,还优选的是由通式(I)的2-丁烯-1,4-二醇衍生物开始。从此处得到的反应混合物,将不期望的通式(II)的化合物送回到电解槽,然后与对应的通式(I)的2-丁烯-1,4-二醇衍生物一起用作制备具有所需更高烷氧基数的目标产物的初产物。
在电解质中,基于通式(I)的2-丁烯-1,4-二醇衍生物,使用等摩尔量或过量不超过1∶20的C1-C6单醇,于是该单醇同时用作所形成的通式(II)化合物和通式(I)化合物的溶剂或稀释剂。优选使用C1-C6单烷基醇,非常特别优选使用甲醇。
合适的话,将惯常的共溶剂加入电解溶液中。这些共溶剂是在有机化学中通常常见的具有高氧化电位的惰性溶剂。作为实例,可以提及二甲基甲酰胺、碳酸二甲酯或碳酸亚丙酯。
一般而言,包含于电解溶液中的导电盐是至少一种选自钾盐、钠盐、锂盐、铁盐、碱金属盐、碱土金属盐和四(C1-C6烷基)铵盐,优选三(C1-C6烷基)甲铵盐中的化合物。合适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、醇盐离子、四氟硼酸根或者高氯酸根。
此外,合适的导电盐为来自于上述阴离子的酸。
优选甲基三丁基铵甲基硫酸盐(MTBS)、甲基三乙基铵甲基硫酸盐或者甲基三丙基铵甲基硫酸盐。
另外,合适的导电盐也是离子液体。合适的离子液体描述于“IonicLiquids in Synthesis”中,编辑:Peter Wasserscheid,Tom Welton,VerlagWiley VCH,2003,第3.6章,103-126。
电解质的pH值通过加有机和无机酸例如柠檬酸、酒石酸、硫酸、磷酸、磺酸、C1-C6羧酸如甲酸、乙酸、丙酸或通过使用本身已知的缓冲体系调节到pH2-7,优选2.5-5。
本发明方法可以在所有的通常类型的电解槽中进行。优选的是使用无分格流的槽(ungeteilten Durchflusszellen)连续进行。
尤其特别合适的是双极-转换毛细管缝隙槽或堆积板槽,其中将电极设计为平板并且平面平行排列(参见,Ullmann’s Encyclopedia of IndustrialChemistry,1999电子版,第六版,VCH-Verlag Weinheim,电化学卷,第3.5章“特殊槽设计”和第5章“有机电化学”第5.4.3.2节“槽设计”)。这样的电解槽例如也描述于DE-A-19533773中。
进行上述方法的电流密度通常为1-20mA/cm3、优选3-5mA/cm3。温度通常为-20至55℃、优选20-40℃。通常而言,该方法在常压下进行。如果希望在较高的温度下工作的话,为了避免起始的化合物或共溶剂沸腾,优选使用更高的压力。
合适的阳极材料例如是贵金属如铂,或金属氧化物如钌或铬的氧化物,或RuoxTiOx类型的混合氧化物。优选石墨或碳电极。进一步优选具有金刚石表面的阳极。
在阴极,不同的电化学还原将在有机化合物上进行。这类还原尤其描述于DE-A-10058304中。然而,一般而言,因质子或醇的电化学还原而在阴极有氢气逸出。
合适的阴极材料例如是铁、钢、不锈钢、镍或贵金属如铂以及还有石墨或碳材料,优选石墨。进一步优选具有金刚石表面的阴极。
特别优选石墨作阳极和阴极以及石墨作阳极和镍、不锈钢或钢作阴极的体系。进一步优选具有金刚石表面的阳极。
反应完成之后,按照通常的分离方法将电解溶液进行后处理。为此,通常首先使电解溶液产生8-9的pH值,然后将其蒸馏,并且以不同馏分形式分别得到各化合物。还可例如通过结晶、蒸馏或通过色谱法将上述电解溶液进一步提纯。如果需由2,5-二氢-2,5-二甲氧基呋喃制备2,5-二甲氧基四氢呋喃,则提纯不是必要的,并且可以使用通过本发明方法获得的粗产物。
实验部分
实施例1-2,5-二甲氧基-2,5-二氢呋喃
装置:具有6个石墨电极的无分格堆积板槽(UngeteiltePlattenstapelzelle)(65mm,缝隙:1mm)
阳极和阴极:石墨
电解质:72.6g的2-丁烯-1,4-二醇
25.7g的甲基三丁基铵甲基硫酸盐(MTBS)
1.4g的H3PO4,浓度96%
660.0g的甲醇
阴极:石墨
使用4.8F/mol的2-丁烯-1,4-二醇进行电解
电流密度:3.4A dm-2
温度:22℃
在于上述条件下的电解期间,将电解质以200L/h的流速泵送经由换热器通过槽达19小时。
在电解完成之后,通过加1.89g的甲醇钠(甲醇中,浓度30%)将电解的排出物调节到pH值8-9,通过蒸馏除去甲醇,并且在70℃和1毫巴下将残余物蒸馏。在该方法中,得到47.9g的2,5-二甲氧基-2,5-二氢呋喃,这对应于46%的收率。选择性是51%。
实施例2-1,3-二甲氧基-1,3-二氢异苯并呋喃
装置:具有6个石墨电极的无分格堆积板槽(65mm???,缝隙:1mm)
阳极:石墨
电解质:35.0g的1,2-苯二甲醇
2.3g的MTBS(甲醇中,浓度为60%)
2.2g的H2SO4,浓度96%
660.5g的甲醇
阴极:在石墨上的不锈钢箔
使用9.5F/mol的1,2-苯二甲醇进行电解
电流密度:3.4A dm-2
温度:20℃
在于上述条件下的电解期间,将电解质以200L/h的流速泵送经由换热器通过槽达12小时。
在电解完成之后,通过加4.3g的甲醇钠(甲醇中,浓度30%)将电解的排出物调节到pH值8-9,通过蒸馏除去MeOH,用150ml的甲基·叔丁基醚进行处理,通过压力吸滤器空吸将沉淀的导电盐滤出并且将滤液在70℃和1毫巴下蒸馏。在该方法中,得到3.4g(对应于9%收率)的1-甲氧基-1,3-二氢异苯并呋喃、14.4g(对应于31.7%收率)的1,3-二甲氧基-1,3-二氢异苯并呋喃和4.1g(对应于20.4%收率)的邻苯二甲醛缩四甲醇缩醛。所述1-甲氧基-1,3-二氢异苯并呋喃可再次用于电解。
Claims (10)
1.一种在C1-C6单烷基醇存在下通过电化学氧化由通式(I)的2-丁烯-1,4-二醇衍生物或者由该式(I)的2-丁烯-1,4-二醇衍生物与在3-或4-位被取代的且在2-或5-位携带C1-C6烷氧基的2,5-二氢呋喃衍生物的混合物制备在3-或4-位被取代的且在2-或在5-位或在这两个位置都各携带C1-C6烷氧基的2,5-二氢呋喃衍生物(DHF烷氧基衍生物)或者制备在3-或4-位被取代的1,1,4,4-四烷氧基-丁-2-烯衍生物的方法,
其中基团R1和R2彼此独立地为氢、C1-C6烷基、C6-C12芳基或者C5-C12亚环烷基,或者R1和R2与它们所键合的双键一起形成C6-C12芳基或者单-或多不饱和的C5-C12环烷基。
3.根据权利要求1所述的方法,其中由式(I)的2-丁烯-1,4-二醇衍生物或它们与通式(II)的DHF-烷氧基衍生物的混合物制备通式(III)的DHF-烷氧基衍生物,
其中基团R1、R2和R3具有与在通式(II)中所述的含意。
5.根据权利要求1-4之一所述的方法,其中脂族C1-C6单烷基醇为甲醇或异丙醇。
6.根据权利要求1-5之一所述的方法,其中每摩尔通式(I)的丁烯-1,4-二醇衍生物使用至少1摩尔的单烷基醇。
7.根据权利要求1-6之一所述的方法,其中该方法在电解质中进行,该电解质包含含有硫酸根、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、醇盐离子、四氟硼酸根、六氟磷酸根或者高氯酸根作为抗衡离子的钠盐、钾盐、锂盐、铁盐和四(C1-C6烷基)铵盐,或离子液体作为导电盐。
8.根据权利要求1-7之一所述的方法,其中使用的电解质包含少于20重量%的水。
9.根据权利要求1-8之一所述的方法,其中电解质的pH值通过添加硫酸、磷酸、磺酸、C1-C6羧酸或通过使用缓冲体系而保持为2.5-5。
10.根据上述权利要求1-8之一所述的方法,其在双极-转换毛细管缝隙槽或堆积板槽或在分格的电解槽(geteilten Elektrolysezelle)中进行。
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CN102633754A (zh) * | 2012-03-28 | 2012-08-15 | 南开大学 | 用改性纳米氧化铝催化剂制备高纯度2,5-二氢呋喃的方法 |
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 |
CN109983162A (zh) * | 2016-11-24 | 2019-07-05 | 阿凡田知识中心有限公司 | 处理呋喃-2,5-二羧酸组合物的方法 |
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DE19962102A1 (de) * | 1999-12-22 | 2001-06-28 | Basf Ag | Verfahren zur elektrochemischen Oxidation von organischen Verbindungen |
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CN102633754A (zh) * | 2012-03-28 | 2012-08-15 | 南开大学 | 用改性纳米氧化铝催化剂制备高纯度2,5-二氢呋喃的方法 |
CN102633754B (zh) * | 2012-03-28 | 2014-02-05 | 南开大学 | 用改性纳米氧化铝催化剂制备高纯度2,5-二氢呋喃的方法 |
CN109983162A (zh) * | 2016-11-24 | 2019-07-05 | 阿凡田知识中心有限公司 | 处理呋喃-2,5-二羧酸组合物的方法 |
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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