CN1184801A - 乙二醛单缩醛的制备 - Google Patents
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
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Abstract
一种分子式Ⅰ所示的乙二醛单缩醛的制备方法,其中R1和R2可以相同或不同,是C1~C4的烷基或C2~C4的链烯基,是由乙二醛和分子式Ⅱ所示的乙二醇双缩醛的混合物与过量的醇在一种酸性催化剂的存在下反应直至达到反应平衡,其中R1和R2与上述的R1、R2具有相同的含义;醇可以使用R1OH或R2OH或者二者的混合物。
Description
本发明涉及一种制备乙二醛单缩醛的新方法。
乙二醛与醇类,如甲醇的反应已久为人知,例如,在J.Org.Chem.38,(1973)556;J.Am.Chem.Soc.77,(1955)1285及美国专利2,360,959号中有过报道。然而,按照以上参考文献,只能得到相应的乙二醛双缩醛;乙二醛单缩醛,如乙二醛二甲基缩醛的分离并未见报道。
在Synth.Comm.1343(1988);Bull.Soc.Chim.Fr95(1988)及EP-B-0249530等文献中曾报道过乙二醛单缩醛的靶向合成及分离,是使乙二醛在酸性催化剂存在的条件下与过量的醇反应,当反应介质中所要得到的单缩醛的浓度开始下降,有利于生成双缩醛时就中止反应。反应通过经常地分析从反应介质中得到的样品来加以监控。
然而,这条路线的不足之处在于反应必须不断地用气相色谱来检测;用旋带精馏塔进行蒸馏过于复杂;而副产物乙二醛双缩醛,如1,1,2,2-四甲氧基乙烷显然要被除去。
此外,EP-B-0316672报道了一条制备乙二醛单缩醛的路线,但只局限于乙二醛与取代的1,3-丙二醇反应得到环状单缩醛。
因此,本发明的目的在于提供一种没有上述种种缺陷的制备乙二醛单缩醛的方法。
我们发现这一目的可以通过下述路线以一种在工艺上非常有利的方式得以实现,分子式I所示的乙二醛单缩醛可以通过乙二醛同分子式II所示的乙二醛双缩醛的混合物在一种酸性催化剂存在下与过量的醇反应直至反应达到平衡来制备,
式I中,R1、R2可以相同或不同,表示C1-C4的烷基或C2-C4的链烯基,式II中,R1、R2含义同上,醇的分子式为R1OH和/或R2OH。
分子式I和II中的基团R1和R2可直接由所用的R1OH和/或R2OH得到,因此具有相似的含义。R1和R2是支链或无支链的C1-C4的烷基和/或支链和无支链的C2-C4的链烯基。C1-C4的烷基例如:甲基,乙基,丙基,异丙基和丁基;C2-C4链烯基例如乙烯基,丙烯基,异丙烯基。R1和R2特别优选基团是甲基和乙基。
本发明中,乙二醛的缩醛化可用相对每摩尔乙二醛,过量5到20摩尔、优选10到15摩尔的醇来进行。
乙二醛优选以水溶液的形式进行反应,可以用市售的乙二醛的含量在20%-60重量%之间的工业用水溶液,优选含量在30%-50重量%之间的。不过也可以使用结晶乙二醛--含有两分子结晶水的三聚体进行缩醛化反应。
分子式II所示的乙二醛双缩醛的投料量或回收量一方面是平衡状态时各个反应物浓度的函数,另一方面又是乙二醛双缩醛在蒸馏后处理步骤时所能达到的产率的函数。一般来说,相对于每摩尔乙二醛加入0.4到1摩尔,优选0.4到0.7摩尔的分子式II所示的乙二醛双缩醛。
反应可以在常压、减压或加压下进行。通常反应是在常压下在反应混合物的沸点进行,或者在封闭系统内以系统内压相应的沸点温度下进行。
本发明的新方法可适用于连续式或批式操作过程;可使用各种反应器,如:连续式或批式搅拌反应釜、管状反应器和反应塔。
适用的酸性催化剂不仅有Lewis酸还包括Brnstedt(质子)酸。因此,可以应用如硫酸锆,硫酸,甲磺酸,对甲苯磺酸,三氯醋酸,草酸以及优选酸性离子交换剂,特别是包在大孔膜中的离子交换树脂。大孔酸性离子交换剂例如市售的LewatitS100,BayKatK2611(Bayer公司),AmberliteIR-120(Rohm&Haas公司)及Dowex50(Dow Chemicals公司)。在优选的具体操作过程中,酸性离子交换树脂作为固定床装入柱中,反应混合物在泵的驱动下循环通过交换柱。一般,在反应过程中,每摩尔乙二醛需要0.01摩尔到0.25摩尔的催化剂。
在EP-B-0249530报道的制备方法中,缩醛化在反应达到平衡即乙二醛单缩醛含量达到最大之前就被中止了,本发明方法与之不同的是,反应一直进行到体系达到平衡状态。达到平衡状态所需的时间可以通过一个反应动力学的预实验很快地测量出来。通常在上面提到的反应条件下,这个时间为3至8小时,优选4至6小时。
在反应结束时或者反应达到平衡以后,向反应混合物中加入一种适当的碱,如碱金属或碱土金属的氢氧化物或碳酸盐中和酸性催化剂使之失活。而对于离子交换树脂,可将其从反应混合物中滤除以使其在下一个反应批次中再利用。如果使用的是离子交换固定床,当反应完毕时可以很方便地从循环体系中拆解下来。
在酸性催化剂失活或被分离出去之后,过量的醇可以通过蒸馏除去,同样可以投入到下一个反应周期中进行再循环。形成的乙二醛双缩醛可通过与加入的水形成共沸物除去。为了完全除去生成的副产物,需在反应混合物中加入足量的水,使得乙二醛双缩醛形成一个浓度为20%~50重量%,优选为30%的水溶液;而乙二醛单缩醛形成一个浓度为30%~50重量%,优选40%的粗品溶液分离出来。副产物乙二醛双缩醛再利用之前,优选先将乙二醛双缩醛与水的共沸物进行脱水处理,这可以通过大家所熟知的在夹带剂,如:己烷、环己烷、庚烷、辛烷、甲苯或二甲苯的存在下的共沸蒸馏来完成。
分离出的乙二醛单缩醛粗品可通过水蒸汽蒸馏及接下来的分馏加以纯化,如果合适的话,在减压下进行,为了避免有价值的产品分解,优选在蒸馏之前加入碱,如Na2CO3,将粗液的pH值调整至6.5~8.5之间。
令人惊讶的是,为了完善再循环过程,水蒸汽蒸馏的残余物也可以投入到以后的制备过程中得到再利用。在这种情况下,为了避免酸性催化剂失活,一定不能用碱,如Na2CO3中和蒸馏的残余物。
在本发明提供的乙二醛单缩醛的制备方法中,对反应的有时是较为复杂的分析是不必要的,而且由于上述的包括再循环,尤其是环境和资源保护等方面的优点,使得本发明也具有经济上的应用价值。
下面以实施例来说明本项说明。
一般的工作程序:
725克40重量%的乙二醛水溶液(5摩尔),2400克(75摩尔)甲醇和约450克(3摩尔)四甲氧基乙烷的混合物通过泵的驱动在体系的固有压力下在填有酸性离子交换剂(BayKatK2611)的3个串联的管形反应器(催化剂体积:1.14升)中进行循环,反应温度为70℃,泵输出量为14~15升/小时。反应5小时后加入20重量%Na2CO3水溶液中和反应混合物,过量的甲醇在350毫巴下通过一根填充有19个纤维填料(Sulzer型)的分馏柱蒸出(柱长100厘米,直径3厘米,塔板数约为20),回流比为10∶1,塔顶馏出物温度41℃。在经过气相色谱分析之后,在馏出的甲醇中加入新的甲醇至75摩尔投入下一批反应,进行再循环。
向反应液中加入水,四甲氧基乙烷与水形成共沸物通过上述的蒸馏柱在350毫巴下从反应液中蒸出,塔顶馏出物温度72℃。向四甲氧基乙烷/水的共沸物中加入500克辛烷,在600毫巴下蒸馏脱水。四甲氧基乙烷从底部放出并再循环利用,辛烷相也可以再循环利用。
四甲氧基乙烷分离出去之后,放出含有乙二醛二甲缩醛的蒸馏残液,并通过蒸馏进行纯化。
下面的表格总结了五个实验包括四次再循环过程的结果:
实验 | 再循环 | 乙二醛[摩尔] | 四甲氧基乙烷[克;摩尔] | 乙二醛二甲缩醛[克] | 粗产率*[%] |
1 | 5 | 450;3 | 390 | 74.8 | |
2 | 1 | 5 | 450*;3 | 367 | 70.4 |
3 | 2 | 5 | 434*;2.9 | 395 | 75.8 |
4 | 3 | 5 | 456*;3 | 407 | 78.2 |
5 | 4 | 5 | 464*;3.1 | 410 | 78.8 |
*再循环的四甲氧基乙烷 | *以所用的乙二醛计 |
Claims (9)
1.一种制备分子式I所示的乙二醛单缩醛的方法,其特征在于,其中R1和R2可以相同或不同,是C1~C4的烷基或C2~C4的链烯基,是由乙二醛和分子式II所示的乙二醛二缩醛的混合物与过量的醇在一种酸性催化剂存在下反应直至达到反应平衡得到的,式II中R1和R2与上述的R1、R2含义相同;醇可以使用R1OH或R2OH或者二者的混合物。
2.如权利要求1所述的制备方法,其中酸性催化剂是一种酸性离子交换剂。
3.如权利要求1或2所述的制备方法,其中酸性离子交换剂以固定床形式催化反应。
4.如权利要求1至3任一项所述的制备方法,其中分子式II所示的乙二醛二缩醛与水形成共沸物通过蒸馏除去。
5.如权利要求1至4任一项所述的制备方法,其中分子式II所示的乙二醛二缩醛与水形成的共沸物通过一种合适的夹带剂来脱水。
6.如权利要求1至5任一项所述的制备方法,其中分子式II所示的副产物乙二醛二缩醛可在反应过程中再循环利用。
7.如权利要求1至6任一项所述的制备方法,其中酸性催化剂可再循环利用。
8.如权利要求1至7任一项所述的制备方法,其中过量的醇和蒸馏底相可投回到反应中再循环利用。
9.如权利要求1至8任一项所述的制备方法,其中分子式R1OH或R2OH所示的醇是甲醇。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19651325.1 | 1996-12-11 | ||
DE19651325A DE19651325A1 (de) | 1996-12-11 | 1996-12-11 | Verfahren zur Herstellung von Glyoxalmonoacetalen |
Publications (2)
Publication Number | Publication Date |
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CN1184801A true CN1184801A (zh) | 1998-06-17 |
CN1094921C CN1094921C (zh) | 2002-11-27 |
Family
ID=37836816
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN97125380A Expired - Fee Related CN1094921C (zh) | 1996-12-11 | 1997-12-10 | 乙二醛单缩醛的制备 |
Country Status (5)
Country | Link |
---|---|
US (1) | US6013842A (zh) |
EP (1) | EP0847976B1 (zh) |
JP (1) | JPH10182540A (zh) |
CN (1) | CN1094921C (zh) |
DE (2) | DE19651325A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100349843C (zh) * | 2003-05-22 | 2007-11-21 | 科莱恩(法国)股份公司 | 采用液-液逆流萃取分离乙二醛的二缩醛 |
CN103242145A (zh) * | 2013-04-27 | 2013-08-14 | 南京工业大学 | 乙二醛制备乙二醛单缩醛和二缩醛的方法 |
CN105481667A (zh) * | 2016-01-12 | 2016-04-13 | 西安近代化学研究所 | 一种提纯2,2-二甲氧基乙醛的方法 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0987261A4 (en) * | 1998-02-17 | 2003-02-05 | Daicel Chem | METHOD FOR PRODUCING THE MONOACETALS OF DIALDEHYDES |
DE10149063A1 (de) * | 2001-10-05 | 2003-04-17 | Basf Ag | Verfahren zur Herstellung von Diacetalen des Glyoxals |
DE10340738A1 (de) * | 2003-09-04 | 2005-03-31 | Basf Ag | Verfahren zur Herstellung von 1,1,2,2-Tetramethoxyethan- und/oder Glyoxaldimethylacetal |
DE102005011720A1 (de) * | 2005-03-15 | 2006-09-21 | Clariant Produkte (Deutschland) Gmbh | Neue amphiphile Acetale |
DE102005011722B4 (de) * | 2005-03-15 | 2010-04-08 | Clariant Produkte (Deutschland) Gmbh | Verfahren zur chemischen Reinigung von Textilmaterial |
DE102005011719A1 (de) * | 2005-03-15 | 2006-09-28 | Clariant Produkte (Deutschland) Gmbh | Wasch- und Reinigungsmittel enthaltend Acetale als organische Lösemittel |
DE102005021444A1 (de) * | 2005-05-10 | 2006-11-16 | Clariant Produkte (Deutschland) Gmbh | Glyoxal-Alkylpolyglykolether-Acetale |
WO2014162761A1 (ja) * | 2013-04-06 | 2014-10-09 | 三菱樹脂株式会社 | 塗布フィルム |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2360959A (en) * | 1944-10-24 | Process of making tetra-acetals | ||
US4835320A (en) * | 1986-06-03 | 1989-05-30 | Societe Francaise Hoechst | Process for the preparation of glyoxal monoactals |
DE3738535A1 (de) * | 1987-11-13 | 1989-05-24 | Basf Ag | Verfahren zur herstellung von glyoxalmonoacetalen und neue glyoxalmonoacetale |
US4835920A (en) * | 1988-08-01 | 1989-06-06 | Carole Posner | Guardrail window assembly with movable crossheader |
FR2700535B1 (fr) * | 1993-01-19 | 1995-04-14 | Hoechst France | Procédé continu de fabrication industrielle du diméthoxyéthanal. |
-
1996
- 1996-12-11 DE DE19651325A patent/DE19651325A1/de not_active Withdrawn
-
1997
- 1997-11-25 US US08/978,010 patent/US6013842A/en not_active Expired - Fee Related
- 1997-12-03 EP EP97121242A patent/EP0847976B1/de not_active Expired - Lifetime
- 1997-12-03 DE DE59703903T patent/DE59703903D1/de not_active Expired - Fee Related
- 1997-12-09 JP JP9338752A patent/JPH10182540A/ja not_active Withdrawn
- 1997-12-10 CN CN97125380A patent/CN1094921C/zh not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100349843C (zh) * | 2003-05-22 | 2007-11-21 | 科莱恩(法国)股份公司 | 采用液-液逆流萃取分离乙二醛的二缩醛 |
CN103242145A (zh) * | 2013-04-27 | 2013-08-14 | 南京工业大学 | 乙二醛制备乙二醛单缩醛和二缩醛的方法 |
CN105481667A (zh) * | 2016-01-12 | 2016-04-13 | 西安近代化学研究所 | 一种提纯2,2-二甲氧基乙醛的方法 |
CN105481667B (zh) * | 2016-01-12 | 2017-12-22 | 西安近代化学研究所 | 一种提纯2,2‑二甲氧基乙醛的方法 |
Also Published As
Publication number | Publication date |
---|---|
DE59703903D1 (de) | 2001-08-02 |
EP0847976A1 (de) | 1998-06-17 |
JPH10182540A (ja) | 1998-07-07 |
EP0847976B1 (de) | 2001-06-27 |
DE19651325A1 (de) | 1998-06-18 |
US6013842A (en) | 2000-01-11 |
CN1094921C (zh) | 2002-11-27 |
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