CN1117483A - 2，3，6-三甲基苯酚的制备 - Google Patents
2，3，6-三甲基苯酚的制备 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种制备2，3，6-三甲基苯酚的方法，其中将二乙基酮与1-氨基-乙烯基甲基酮在碱存在下在50至200℃温度范围内反应。
Description
本发明涉及制备2，3，6-三甲基苯酚的方法，该化合物是制备维生素E的必需的原料。
根据DE 2415930，2，3，6-三甲基苯酚可以通过n-甲苯酚在气相催化烷基化得到。该方法具有缺陷，即该方法产生异构体混合物，从该混合物中很难以纯的形式得到所需异构体并且损失产率。
其他的工业方法是基于二乙基酮与C4单元结构，如巴豆醛(参考DE1793037)或甲基乙烯基酮(参考DE1668874)的缩合。这种在其他方面优越的方法的一个缺陷是其不能直接得到2，3，6-三甲基苯酚，而是首先得到三甲基环己酮，该化合物必须在后续步骤中脱水形成三甲基苯酚。
因此，本发明的目的是提供一种从二乙基酮和容易得到的C4单元结构仅需一步反应即可制备2，3，6，-三甲基苯酚的方法。
本发明涉及制备2，3，6-三甲基苯酚的方法，该方法将二乙基酮与1-氨基-乙烯基甲基酮在50至200℃，优选70—150℃温度范围内反应。
该反应根据下列反应式进行：
使用的1-氨基-乙烯基甲基酮理论上可以是所有1-氨基乙烯基甲基酮，其具有伯、仲或叔氨基基团。出于经济上的原因，这些氨基化合物优选使用廉价易得的和/或处理或分离特别方便的氨基化合物。其实例是1-二甲氨基-，1-二乙氨基-，1-二丙氨基-，1-二环己基氨基-，1-二乙醇氨基-，1-哌嗪基-，1-N-甲基哌嗪基-，或1-吗啉代氨基-乙烯基甲基酮。但是，理论上所有具有前面提到的结构式的1-氨基-乙烯基甲基酮都可以使用，其中取代基R1和R2具有下列含义：a)R1和R2分别是氢或C1-C20烷基，优选C1-C8烷基，尤其是C1-C4烷基如甲基，乙基，正丙基，异丙基，正丁基，异丁基和叔丁基；C3-C8的环烷基，优选C5-C8环烷基如环戊基，环己基，环庚基和环辛基，尤其是环戊基和环己基；C1-C20羟基烷基，优选C2-C8羟基烷基，尤其是C2-C4羟基烷基如2-羟乙基和3-羟丙基；苯基和C7-C12烷基苯基如2-甲苯基，3-甲苯基，4-甲苯基，2，4-二甲苯基，2，5-二甲苯基，2，6-二甲苯基，3，5-二甲苯基和2，3，4-三甲基苯基；或C7-C12苯基烷基如苄基，苯乙基，1-苯丙基，2-苯丙基，1-苯丁基，2-苯丁基，3-苯丁基，优选苄基和苯乙基；或另一方面b)R1和R2一起形成C2-C7亚烷基链，其可以被一个至四个C1-C4烷基取代和/或被氧，氮或硫插入。其实例是下列基团：-(CH2)2-，-(CH2)3-，-(CH2)4-，-(CH2)5-，-(CH2)6-，-(CH2)7-，-(CHCH3)-，-(CH2)2-O-(CH2)2-，-(CH2)2-N-(CH2)2-和-(CH2)2-S-(CH2)2-
最近发现(参考德国专利申请DE4308080.4)一种简单的制备1-氨基-乙烯基甲基酮的方法，该方法是将含有联乙炔的并且是在乙炔产生中形成的裂化气与仲胺和水在0至150℃温度范围内反应，由此可以得到一种非常优越的方法，在该方法中所需的2，3，6-三甲基苯酚可以从容易得到的原料直接得到。
而且，1-氨基-乙烯基甲基酮可以通过，例如，如US3141880中所述的将单胺与酮反应制备，或如US3285915中描述的将仲胺与3-烷氧基环丁酮反应制备。
本发明的方法在碱试剂存在下成功地进行。
使用的碱试剂可以是任何具有去质子作用的较强碱。其实例是碱金属或碱土金属的氢氧化物，氧化物，醇盐，氨化物或氢化物，金属有机化合物，如丁基锂或苯基锂或季铵氢氧化物，如苄基三甲基铵氢氧化物。
碱试剂通常以化学计算量或，如果需要，以稍过量的形式使用。
本发明的方法可以在有或无溶剂存在下进行。当没有溶剂存在时，该方法优选在作为稀释剂的过量的二乙基酮中进行。
适合的溶剂是，例如：脂族石油醚，烃如石油醚或汽油混合物；环脂族烃如环己烷；芳族烃如苯，甲苯，二甲苯，枯烯和对二异丙基苯；氯代烃如氯苯，氯代甲苯和二氯苯；醚如甲基叔丁基醚，四氢呋喃和二噁烷；亚砜如二甲亚砜，酰胺如二甲基甲酰胺和N-甲基吡咯烷酮，和较高级醇如戊醇。
当使用与水不混溶溶剂时该反应特别成功。
当使用这种与水不混溶的溶剂时，该反应优选在不断除去水的条件下进行。
本发明的方法的特别的优点是也可以使用仲胺与水的混合物，这样就可以直接使用从联乙炔制得的氨基乙烯基酮，即不用分离，在DE 4,308080,4中所述的仲胺水溶液直接用于制备三甲基苯酚。
缩合通常在50至200℃，优选70至150℃温度范围内进行。
反应时间通常为20至40小时，优选25至30小时，反应时间取决于反应温度和反应物。
反应通常在常压下进行，但反应可以在减压或加压下进行。
使用的二乙基酮和氨基乙烯基甲基酮的摩尔比率较好的是1∶1至50∶1，优选1∶1至20∶1。
为了有效的纯化反应混合物，通常采用的方法是首先中和得到的酚盐，然后通过分馏分离反应混合物。
通过蒸馏或从底物转得到的胺可以重新用于制备1-氨基-乙烯基甲基酮。
使用本发明的方法可以得到作为所需的维生素E前体的2，3，6-三甲基苯酚，该方法只用一个简单的反应步骤并且具有非常好的收率，其原料是容易得到的二乙基酮和容易用简单的方式得到的式iii的氨基乙烯基甲基酮。实施例
在容量为250ml安装有搅拌器和分水装置的玻璃烧瓶中将16.99(0.1mol)二丙基氨基乙烯基甲基酮，172.39(2mol)二乙基酮和11.29 50％的浓KOH水溶液(相当于0.lmol)混合，将该混合物回流29小时并除水。在此期间分出6.7ml水(预计：5.6ml来自苛性钾溶液，1.8ml来自反应)。将得到的深黑棕色反应溶液用乙酸中和后用气相色谱分析。基于转化了的氨基乙烯基甲基酮(转化率为89％)，对三甲基苯酚的选择性是63％。一个非常重要的付产物是3-乙基-4-甲基苯酚，其选择性是26％(根据通过气相色谱测量的峰面积确定)。
Claims (5)
1.一种制备2，3，6-三甲基苯酚的方法，包括在50至200℃温度范围内将二乙基酮与1-氨基-乙烯基甲基酮反应。
2.根据权利要求1的方法，其中在70至150℃温度范围内将二乙基酮与1-氨基-乙烯基甲基酮反应。
3.根据权利要求1的方法，其中在具有去质子作用的碱存在下将二乙基酮与1-氨基-乙烯基甲基酮反应。
4.根据权利要求3的方法，其中使用的碱是碱金属或碱土金属的氢氧化物，氧化物，醇盐，氨化物或氢化物。
5.根据权利要求1的方法，其中使用的1-氨基-乙烯基甲基酮是1-二甲基氨基-，1-二乙基氨基-，1-吗啉代氨基-，1-二丙基氨基-，1-二环己基氨基-，1-二乙醇氨基-，1-哌嗪基-，或1-N-甲基哌嗪基-乙烯基甲基酮。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19944414877 DE4414877A1 (de) | 1994-04-28 | 1994-04-28 | Verfahren zur Herstellung von 2,3,6-Trimethyl-phenol |
| DEP4414877.1 | 1994-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1117483A true CN1117483A (zh) | 1996-02-28 |
Family
ID=6516698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95105783 Pending CN1117483A (zh) | 1994-04-28 | 1995-04-28 | 2，3，6-三甲基苯酚的制备 |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0679625A2 (zh) |
| JP (1) | JPH07300438A (zh) |
| CN (1) | CN1117483A (zh) |
| CA (1) | CA2147913A1 (zh) |
| DE (1) | DE4414877A1 (zh) |
| RU (1) | RU95106463A (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108264450A (zh) * | 2016-12-30 | 2018-07-10 | 浙江省诸暨合力化学对外贸易有限公司 | 一种多取代苯酚的制备方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1668874C2 (de) * | 1968-03-08 | 1975-11-20 | Basf Ag | Verfahren zur Herstellung von 2,3,6-Trimethylphenol |
| DE1793037B1 (de) * | 1968-07-26 | 1971-07-15 | Basf Ag | Verfahren zur Herstellung von 2,3,6-Trimethylphenol |
| US3833673A (en) * | 1971-11-09 | 1974-09-03 | Eastman Kodak Co | Synthesis of alkylated phenols from carbonyl compounds |
-
1994
- 1994-04-28 DE DE19944414877 patent/DE4414877A1/de not_active Withdrawn
-
1995
- 1995-04-19 EP EP95105849A patent/EP0679625A2/de not_active Withdrawn
- 1995-04-21 JP JP9728995A patent/JPH07300438A/ja not_active Withdrawn
- 1995-04-26 CA CA002147913A patent/CA2147913A1/en not_active Abandoned
- 1995-04-27 RU RU95106463/04A patent/RU95106463A/ru unknown
- 1995-04-28 CN CN 95105783 patent/CN1117483A/zh active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108264450A (zh) * | 2016-12-30 | 2018-07-10 | 浙江省诸暨合力化学对外贸易有限公司 | 一种多取代苯酚的制备方法 |
| CN108264450B (zh) * | 2016-12-30 | 2021-04-30 | 浙江省诸暨合力化学对外贸易有限公司 | 一种多取代苯酚的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4414877A1 (de) | 1995-11-02 |
| CA2147913A1 (en) | 1995-10-29 |
| EP0679625A2 (de) | 1995-11-02 |
| EP0679625A3 (zh) | 1995-12-06 |
| RU95106463A (ru) | 1997-02-10 |
| JPH07300438A (ja) | 1995-11-14 |
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