CN105985313B - 用于制备氯乙醛乙缩醛的方法 - Google Patents
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 27
- -1 chloroacetaldehyde acetal Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
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- 239000002904 solvent Substances 0.000 claims abstract description 19
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- 239000003377 acid catalyst Substances 0.000 claims abstract description 9
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- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract 2
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
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- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
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- AVIYEYCFMVPYST-UHFFFAOYSA-N hexane-1,3-diol Chemical compound CCCC(O)CCO AVIYEYCFMVPYST-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/04—Seven-membered rings not condensed with other rings
- C07D321/06—1,3-Dioxepines; Hydrogenated 1,3-dioxepines
-
- 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
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/16—Radicals substituted by halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种用于制备单羟基、二羟基或更高官能度脂肪醇的氯乙醛乙缩醛的方法,其中在待乙缩醛化的醇和酸催化剂的存在下,借助于溶剂,通过共沸移除水,由氯乙醛水溶液获得氯乙醛乙缩醛,其中所述溶剂为卤化溶剂。
Description
本发明涉及一种用于由氯乙醛水溶液通过适当溶剂辅助共沸移除水来制备无环和环状氯乙醛乙缩醛的方法。
已知氯乙醛乙缩醛可通过乙烯基化合物(乙酸乙烯酯、氯乙烯、乙烯基醚)在醇介质中的氯化制备。对于该现有技术的讨论可见于US4440959。
EP0456157B1描述了由氯乙醛的三聚体以良好的质量和产率制备氯乙醛乙缩醛。用于制备的氯乙醛的三聚体描述于EP0368613B1。用于制备所需氯乙醛的三聚体的该方法非常复杂,需要大量的溶剂和浓硫酸并得到较差产率(约50%),以致该方法无法工业化。
还已知乙缩醛可通过Fischer乙缩醛化的方法制备,即醛与醇在酸催化剂的存在下直接反应,并且通过共沸蒸馏移除反应水(Meskens,Synthesis 501-522(1981)),但该方法对于低沸醛无效,因为除水不完全或无法进行并因此不得不加入干燥剂(例如氯化钙等)。如DE1235880B中所描述的由80%浓度氯乙醛和醇的制备方法相类似,其中仅通过水结合剂实现除水。然而,这些水结合剂不仅使得制备昂贵而且形成大量的废物,所述废物在氯化醛的情况下因其氯化成分的含量而难以处置。另外,80%浓度氯乙醛难以制备并且也因可能分解而不易操作。
Xuezheng Liang,Chunqing Li,Chenze Qi,J.Mater Sci(2011)46:5345-5349描述了由氯乙醛和相应的二醇在Dean-Stark设备中通过环己烷辅助共沸蒸馏制备环状氯乙醛乙缩醛,产率为99%。然而,在其中使用了氯乙醛的情况下无形成迹象,并且所描述的最大批量仅为0.1mol的氯乙醛和仅10ml的环己烷作为水夹带剂(entrainer)。根据我们自己的知识,环己烷不适用于氯乙醛的共沸乙缩醛化,因为其易于从反应混合物移除氯乙醛(参见对比实施例3)。
氯乙醛易于在水溶液中以高纯度获得(高达45%氯乙醛)。然而,不存在已知的适用于由氯乙醛水溶液制备氯乙醛乙缩醛的工业相关方法。仅已知由氯乙醛半水化合物作为原料的方法,氯乙醛半水化合物难以制备并且因可能分解而有处理危险。
本发明的目的在于提供一种用于由氯乙醛制备单羟基、二羟基或更高官能度脂肪醇的氯乙醛乙缩醛的方法。
该目的通过以下方法实现:其中在待乙缩醛化的醇和酸催化剂的存在下,借助于溶剂,通过共沸移除水,由氯乙醛水溶液获得氯乙醛乙缩醛,其中溶剂为卤化溶剂。
在更高官能度醇(对于本发明的目的其优选为3-至5-羟基醇)的情况下,游离羟基可保留于氯乙醛乙缩醛中或者可在分子中形成两个或更多个氯乙醛乙缩醛基团。
卤化溶剂优选为单卤化或多卤化,特别优选氯化或氟化的烃,其具有1-5个碳原子并在大气压力(101.3kPa)下与水形成沸点在25℃-80℃范围内的共沸物。对于本发明的目的,多卤化烃优选为二卤化至四卤化的烃。
卤化溶剂特别优选为三氯甲烷。
氯乙醛水溶液优选为含5重量%-70重量%,优选30重量%-50重量%的氯乙醛的水溶液。该溶液易于以高纯度获得。
待乙缩醛化的醇优选为具有1-12个碳原子的单羟基、二羟基或更高官能度脂肪醇;其特别优选为具有1-12个碳原子的单羟基或二羟基脂肪醇。
具有1-12个碳原子的单羟基脂肪醇可为饱和或不饱和的并含有芳基或在反应条件下稳定的取代基(例如醚)。
具有1-12个碳原子的二羟基脂肪醇可为饱和或不饱和的并含有芳基或在反应条件下稳定的取代基,例如醚。羟基可相对于彼此位于α、β或γ位置。具有1-12个碳原子的更高官能度脂肪醇可为饱和或不饱和的并含有芳基或在反应条件下稳定的取代基(例如醚)。
单羟基脂肪醇优选为甲醇、乙醇、正丙醇、异丙醇、1-丁醇、2-丁醇、异丁醇、叔丁醇、1-戊醇、环己醇、环戊醇。
二羟基脂肪醇优选为1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、2,2-丁二醇、1,3-己二醇、顺-1,3-环己二醇、顺-1,2-环己二醇。
更高官能度脂肪醇优选为甘油、季戊四醇、木糖醇。
酸催化剂优选为无机或有机酸,例如氢氯酸、硫酸、磷酸、甲磺酸、甲苯磺酸、三氟甲磺酸、三氟乙酸、苯膦酸或强酸性离子交换树脂。对于本发明的目的,强酸性离子交换树脂优选为具有磺酸基团的离子交换树脂。这种强酸性离子交换树脂可以商标名或商购。
特别优选的是磷酸、甲苯磺酸、硫酸或
氯乙醛乙缩醛优选为具有1-12个碳原子的无环或环状氯乙醛乙缩醛。
溶剂优选以溶剂与氯乙醛溶液体积比1∶10-5∶1存在于反应混合物中。
基于所用的氯乙醛,所述酸催化剂优选以0.01mol%-2mol%的量使用。由于氯乙醛溶液的酸性pH,反应也可无催化剂,但反应速率对于工业方法而言会太慢。
氯乙醛乙缩醛可令人惊讶地以简单的方式通过卤化溶剂在待乙缩醛化的醇和酸催化剂的存在下使氯乙醛水溶液脱水而以高产率高纯度获得。甚至在低沸醇的情况下这也是可能的。在酸敏氯乙醛乙缩醛的情况下,酸催化剂必须在蒸馏之前中和。这优选通过沸点显著高于产物沸点的胺实现。也可使用碱金属或碱土金属碳酸盐、碳酸氢盐或氧化物。
已发现使用脂肪烃例如己烷、戊烷、环己烷作为溶剂是不适合的,因为在这种情况下大量的氯乙醛在水分离器中排出,因此氯乙醛乙缩醛的产率大大降低。特别是在低沸醇(对于本发明的目的其优选为在标准条件下具有65℃-80℃沸点范围的醇)的情况下,已发现用作夹带剂的溶剂仅从反应混合物移除少量醇是有利的,对于本发明的目的其优选为小于20重量%的量。与本发明相关的实验已令人惊讶地显示具有1-5个碳原子并在大气压力下与水形成25℃-80℃沸点范围的共沸物的单卤化或多卤化烃优选用作溶剂。已发现三氯甲烷特别有用。由于氯化分子之间的相互作用,这将反应混合物的氯乙醛移除至相当小程度。
本发明方法的优点在于溶剂或在较低级醇例如甲醇、乙醇或异丙醇的情况下,溶剂和相应醇(其用于移除水)的混合物可在本发明方法中再次使用而无需进一步纯化。进一步的优点在于除少量蒸馏残渣外,几乎无废物产生(例如在实施例1和6中,<2%的所用量)。
以下实施例用以阐明本发明。
实施例1:2-氯甲基-1,3-二氧杂环庚烷(dioxepane)的制备
将1744.4g 45%浓度氯乙醛水溶液(10mol氯乙醛)、919.0g(10.2mol)1,4-丁二醇、1l三氯甲烷和2g对甲苯磺酸置于4l四颈烧瓶中,所述烧瓶装有水分离器、回流冷凝器、精密玻璃搅拌器和内部温度计。将两相混合物在水分离器上在回流下加热,同时搅拌直至再无水分离出(约10小时)。此处反应混合物变为单一相。随后减压蒸馏反应混合物(15mbar,80℃)。产率:1459.3g(96.9%),纯度>99%(GC)。
对比实施例1
如实施例1所述进行实验,区别在于使用正己烷代替三氯甲烷。产率873.5g(58%),纯度>99%(GC)。
实施例2:氯乙醛二乙基乙缩醛的制备
将2442g 45%浓度氯乙醛水溶液(14mol氯乙醛)、1612g(35mol)乙醇、1500ml三氯甲烷和2.8g对甲苯磺酸置于6l四颈烧瓶中,所述烧瓶装有水分离器、回流冷凝器、填充柱、精密玻璃搅拌器和内部温度计以及计量单元。将两相混合物在水分离器上在回流下加热,同时搅拌直至再无水分离出(7小时)。此处反应混合物变为单一相。然后在回流下引入另外的322.5g(7mol)乙醇并与水分离。随后加入另外的253.7g(4.35mol)乙醇以及500g三氯甲烷,并且将混合物在水分离器上在回流下加热直至再无水分离出。随后加入31.2g三丁基胺以实现中和,并且将反应混合物减压分馏(100mbar,90℃)。产率1987g(理论量的93.0%),纯度>99%(GC)。
实施例3:2-氯甲基-1,3-二氧杂环戊烷的制备
将174.44g 45%浓度氯乙醛水溶液(1mol氯乙醛)、68.28g(1.1mol)乙二醇、200ml三氯甲烷和0.2g对甲苯磺酸置于1l四颈烧瓶中,所述烧瓶装有水分离器、回流冷凝器、精密玻璃搅拌器和内部温度计以及计量单元。将两相混合物在水分离器上在回流下加热同时搅拌,直至再无水分离出(总计约7小时)。此处反应混合物变为单一相。然后加入2.2g三丁基胺以中和对甲苯磺酸并减压蒸馏反应混合物(75mbar,85℃)。产率111.6g(91%),纯度>99%(GC)。
实施例4:氯乙醛二甲基乙缩醛的制备
将174.44g 45%浓度氯乙醛水溶液(1mol氯乙醛)、16.02g(0.5mol)甲醇、200ml三氯甲烷和0.2g对甲苯磺酸置于1l四颈烧瓶中,所述烧瓶装有水分离器、回流冷凝器、精密玻璃搅拌器和内部温度计以及计量单元。将两相混合物在水分离器上在回流下加热同时搅拌,直至再无水分离出。随后在回流下引入另外的48g(1.5mol)甲醇并与水分离(总计约7小时)。此处反应混合物变为单一相。然后加入2.2g三丁基胺以中和对甲苯磺酸并减压蒸馏反应混合物(100mbar,90℃)。产率99.7g(80%),纯度>99%(GC)。
对比实施例2
如实施例4所述进行实验,区别在于使用正己烷代替三氯甲烷。4小时后实验停止,因为在水分离器中大部分甲醇和氯乙醛已由反应混合物进入水相。
对比实施例3
如实施例4所述进行实验,区别在于使用环己烷代替三氯甲烷。4小时后实验停止,因为在水分离器中大部分甲醇和氯乙醛已由反应混合物进入水相。
实施例5:氯乙醛二甲基乙缩醛的制备
如实施例4所述进行实验,区别在于使用4mol甲醇(初始加入1.5mol并计量加入2.5mol)代替2mol甲醇。产率:109.1g(87.6%),纯度>99%(GC)。
实施例6:氯乙醛二甲基乙缩醛的制备
将200ml三氯甲烷和0.2g甲苯磺酸置于1l四颈烧瓶中,所述烧瓶装有水分离器、回流冷凝器、精密玻璃搅拌器和内部温度计以及计量单元。将混合物在水分离器上加热至回流同时搅拌,并且当开始回流时,经6小时计量加入348.9g 45%浓度氯乙醛水溶液(2mol氯乙醛)、96.12g(3mol)甲醇的混合物。然后经2小时计量加入另外的96.12g(3mol)甲醇。产率:209.6g(84.1%),纯度>99%(GC)。
实施例7:氯乙醛二甲基乙缩醛的制备
将3140g 45%浓度氯乙醛水溶液(18mol氯乙醛)、865g(27mol)甲醇、1500ml三氯甲烷和3.6g对甲苯磺酸置于6l四颈烧瓶中,所述烧瓶装有水分离器、回流冷凝器、填充柱、精密玻璃搅拌器和内部温度计以及计量单元。将两相混合物在水分离器上在回流下加热同时搅拌。在除水期间,计量加入另外的1153g(36mol)甲醇和500ml三氯甲烷,反应混合物变为单一相。一旦再无水分离出便加入40.14g三丁基胺以实施中和并减压分馏反应混合物(80mbar,63℃)。产率1900g(理论量的88.8%),纯度>99%(GC)。
Claims (4)
1.用于制备单羟基、二羟基或更高官能度脂肪醇的氯乙醛乙缩醛的方法,其中在待乙缩醛化的醇和酸催化剂的存在下,借助于溶剂,通过共沸移除水,由氯乙醛水溶液获得氯乙醛乙缩醛,其中所述溶剂为三氯甲烷。
2.如权利要求1所述的方法,其中所述待乙缩醛化的醇为具有1-12个碳原子的单羟基、二羟基或更高官能度脂肪醇。
3.如权利要求1所述的方法,其中所述酸催化剂为无机或有机酸或含磺酸基团的强酸性离子交换树脂。
4.如权利要求1所述的方法,其中基于所用的氯乙醛,所述酸催化剂以0.01mol%-2mol%的量存在。
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