CN1615290A - 植胨的制备方法 - Google Patents
植胨的制备方法 Download PDFInfo
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- CN1615290A CN1615290A CNA038021471A CN03802147A CN1615290A CN 1615290 A CN1615290 A CN 1615290A CN A038021471 A CNA038021471 A CN A038021471A CN 03802147 A CN03802147 A CN 03802147A CN 1615290 A CN1615290 A CN 1615290A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C45/69—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 addition to carbon-to-carbon double or triple bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
- C07C49/24—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种用于制备植胨和维生素E的新颖中间体化合物的制备方法。
Description
本发明涉及一种用于制备植胨和/或维生素E的中间体化合物的制备方法。
长期以来,人们已经会用许多化学方法制备维生素E。这种维生素一般由已知为植胨的中间体化合物制备,植胨具有如下化学结构
植胨。
欧洲专利0544588介绍了通过多不饱和烯丙醇衍生物的缩合制备维生素E的方法。美国专利3867408介绍了可用来制备植胨的新颖缩酮化合物的制备方法,而植酮又是制备维生素E的中间体。
我们现在合成了一种新颖化合物,它可用作合成植胨的中间体化合物,如果需要,可进一步用作合成维生素E的中间体化合物。
因此,本发明提供化学式(I)所示化合物的制备方法,
该方法包括化学式(II)所示化合物
在催化剂和极性溶剂存在下与化学式(III)所示化合物反应
化合物(I)是新颖化合物,因而其构成本发明的另一方面。
制备化合物(I)的方法是在极性溶剂存在下进行的。合适的溶剂包括非质子极性溶剂,如二甲基乙酰胺、二甲基甲酰胺、N-甲基吡咯烷酮和二甲基亚砜。溶剂优选二甲基乙酰胺。溶剂浓度可以是0.01-5mol/l,宜为0.1-1mol/l。
虽非必需,但可以在溶剂中加水。如果在溶剂中加水,则水的浓度宜为10-50体积%。
所述方法在催化剂存在下实施。合适的催化剂包括二价钌阳离子配合物。所述催化剂优选三乙腈六氟磷酸环戊二烯合钌。
本发明的优选实施方式包括向催化剂溶液中加入反应物。为防止反应物降解,优选此加料方法。
所述方法也可在不与极性溶剂混溶的第二种溶剂的存在下实施。符合此条件的溶剂包括非极性溶剂。合适的非极性溶剂包括芳烃,如甲苯、苯和二甲苯。脂肪烃,如戊烷、庚烷、己烷和辛烷;烃溶剂与醚的单相混合物。第二种溶剂相对于催化剂极性相的体积比为0.01-10,宜为0.5-2。
该方法可在20-100℃,宜在20-60℃的温度和常压或高压下实施。该反应宜在常压下进行。
化合物(III)宜缓慢加入反应介质中,以免形成副反应产物。
通过本发明方法获得的化学式(I)所示化合物特别适合用作合成植胨的原料。因此,本发明另一方面提供一种制备植胨的方法,该方法包括(a)第一步水解下式所示化合物
得到水解产物;(b)第二步氢化所述水解产物。
本方法第一步,即水解步骤适合使用酸性催化剂,如磺酸、硫酸或盐酸实施。催化剂的用量相对于化学式(I)所示化合物为0.001-0.5摩尔当量,宜为0.05-0.1摩尔当量。
水解还适宜在有机溶剂如甲苯或醚,例如二乙醚或四氢呋喃的存在下进行。反应温度可在-50到+150℃之间,宜在20-100℃之间。
然后氢化水解步骤此产物。氢化宜在氢气和金属或金属盐存在下进行。合适的金属和金属盐包括任选地在铁、锰、钴、铜、锌或铬存在下的Raney镍(镍/铝合金);乙酸存在下的锌;氯化锡;钼(III)盐。该反应可在钯或铂存在下进行,钯或铂可负载在合适的惰性载体,如炭上。氢化宜在负载于惰性载体如炭上的钯的存在下进行。所用金属或金属盐一般为0.01-3摩尔当量,宜为0.05-2摩尔当量。
氢化步骤一般在溶剂中进行,所述溶剂可选自醇,如甲醇或乙醇;直链醚或环醚,例如四氢呋喃;以及芳烃。溶剂优选醚,特别是四氢呋喃。
氢化步骤的反应温度一般为20-150℃,宜为20-90℃;所用气体压力一般为1-50巴,宜为5-10巴。
水解和氢化可分两步进行,或者可在反应体系中合并成一步进行。
在前述反应条件下,植胨的制备过程宜进行30分钟-24小时,更宜为30分钟-6小时,以便于反应化合物反应完全。
维生素E可由本发明方法制备的植胨合成。
下面结合实施例对本发明进行阐述。
实施例1:化合物(I)的制备
在氩气下,将22mg催化剂溶解于750微升二甲基乙酰胺和250微升水的混合物(又所谓极性相溶液)。将所得溶液在60℃下加热。然后在90分钟时间里缓慢加入1ml含63mg化合物(II)和77mg化合物(III)的庚烷溶液。在60℃再搅拌该溶液3小时,然后冷却到20℃。从极性相分离庚烷相,向极性相加入1ml纯庚烷。在20℃搅拌所得混合物15分钟,分离庚烷相。重复该步骤四次:收集四次得到的庚烷相;蒸馏除去庚烷,用硅胶色谱法(洗脱剂:戊烷/二乙醚=2/1(体积比))纯化留下的油状残留物。所得纯化合物(I)为黄色油,产量:84毫克(60%)。
实施例2:植胨的制备
用实施例1所得化合物按下述用量分两步制备植胨:
化合物 | 用量 | 摩尔质量 | 毫摩尔 |
化合物I | 0.689g | 280 | 2.46 |
甲苯 | 30ml | 92 | - |
APTS.H2O | 0.01g | 190.22 | 0.053(0.02当量) |
乙醇 | 15ml | 46 | - |
Pd/c;5%重量/重量 | 0.117g | 106.42 | 0.055(0.02当量) |
APTS.H2O是一水合对甲苯硫酸。
将化合物(I)、甲苯和一水合APTS置于25ml圆底烧瓶中,在平稳的甲苯回流下反应3小时。然后加入10ml碳酸钠饱和水溶液,所得产物用醚萃取3次。蒸馏除去醚之后,在氩气气氛下将所得残留物立即放入含有钯黑和乙醇的玻璃小瓶中。将小瓶放入不锈钢高压釜中。密闭高压釜,用氢气吹扫,将氢压固定在5±0.2巴,搅拌内容物。氢化反应在室温下持续6小时,然后高压釜脱气,将内容物倒入含有过滤硅藻土的小柱中。用乙醇洗涤该柱,浓缩滤液,得到0.587g植胨。产率为89%,纯度95%。
实施例3:植胨的制备
用实施例1所得化合物按下述用量一步制备植胨:
化合物 | 用量 | 摩尔质量 | 毫摩尔 |
化合物I | 138mg | 280 | 0.493 |
四氢呋喃 | 2ml | 72 | - |
硫酸(96%水溶液) | 7mg | 98 | 0.07(0.14当量) |
Pd/C;5%w/w | 105mg | 106.42 | 0.049(0.1当量Pd) |
反应在位于不锈钢高压釜中的5ml玻璃烧瓶中进行,氢气压力为5巴,反应温度为65℃(对高压釜进行外部加热),反应时间持续1.5小时。高压釜减压,用氩气吹扫,然后打开。粗样品过滤并用醚和水处理后,经分析可知植胨产率超过95%。
Claims (13)
2.权利要求1所述的方法,其特征在于所述极性溶剂选自二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜和N-甲基吡咯烷酮。
3.权利要求1或2所述的方法,其特征在于所述催化剂选自二价钌阳离子配合物,如三乙腈六氟磷酸环戊二烯合钌或三乙腈六氟磷酸五甲基环戊二烯合钌。
4.前述权利要求中任何一项所述的方法,其特征在于该方法在第二种溶剂存在下实施,所述第二种溶剂不与第一种溶剂混溶。
5.权利要求4所述的方法,其特征在于所述第二种溶剂是非极性溶剂,选自脂肪烃或芳烃。
6.前述权利要求中任何一项所述的方法,其特征在于该方法在20-100℃的温度和常压下实施。
8.一种制备植胨的方法,该方法包含(a)第一步水解权利要求6所述的化合物,生成水解产物;(b)第二步氢化步骤(a)的水解产物。
9.权利要求8所述的方法,其特征在于第一步在酸性催化剂存在下实施,所述催化剂选自磺酸、硫酸或盐酸。
10.权利要求8或9所述的方法,其特征在于第一步在有机溶剂存在下实施,所述有机溶剂选自烃和醚。
11.权利要求8-10中任一项所述的方法,其中第二步在氢气和金属或金属盐存在下实施,所述金属或金属盐选自钯或铂,任选地在铁、锰、钴、铜、锌或铬存在下的Raney镍;乙酸存在下的锌;氯化锡;及钼(III)盐。
12.权利要求11所述的方法,其特征在于所述催化剂为负载在炭上的钯。
13.由植胨制备的维生素E,其特征在于植胨由权利要求8-12中任一项所述的方法制备。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02356006A EP1327620A1 (en) | 2002-01-14 | 2002-01-14 | Process for the preparation of phytone |
EP02356006.3 | 2002-01-14 |
Publications (1)
Publication Number | Publication Date |
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CN1615290A true CN1615290A (zh) | 2005-05-11 |
Family
ID=8185732
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNA038021471A Pending CN1615290A (zh) | 2002-01-14 | 2003-01-13 | 植胨的制备方法 |
Country Status (14)
Country | Link |
---|---|
US (1) | US6987203B2 (zh) |
EP (2) | EP1327620A1 (zh) |
JP (1) | JP2005514416A (zh) |
KR (1) | KR20040083075A (zh) |
CN (1) | CN1615290A (zh) |
AU (1) | AU2003235760A1 (zh) |
BR (1) | BR0306702A (zh) |
CA (1) | CA2473367A1 (zh) |
MX (1) | MXPA04006772A (zh) |
PL (1) | PL369647A1 (zh) |
RU (1) | RU2305091C2 (zh) |
UA (1) | UA78754C2 (zh) |
WO (1) | WO2003057654A1 (zh) |
ZA (1) | ZA200404978B (zh) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3867408A (en) | 1972-08-23 | 1975-02-18 | Eastman Kodak Co | 1,2-Epoxy-2-methyl-6-heptanone ketals |
US3917710A (en) * | 1974-05-23 | 1975-11-04 | Eastman Kodak Co | Preparation of phytone via the addition of dimethylketene to 4,8-dimethyl-12-oxotridecanal |
US4292459A (en) * | 1975-07-16 | 1981-09-29 | Scm Corporation | Coupling reaction involving a Grignard and allylic halide |
FR2555170B1 (fr) * | 1983-11-18 | 1986-07-18 | Rhone Poulenc Sante | Nouveaux derives insatures, leur preparation et leur emploi |
FR2684373A1 (fr) * | 1991-11-28 | 1993-06-04 | Rhone Poulenc Nutrition Animal | Nouveaux intermediaires de preparation de vitamines a et e et des carotenouides. |
DE19513840A1 (de) * | 1995-04-12 | 1996-10-17 | Basf Ag | Verfahren zur Herstellung von acetylenisch ungesättigten Verbindungen |
US5955636A (en) * | 1996-07-05 | 1999-09-21 | Kuraray Co., Ltd. | Process for producing 6-methyl-3-hepten-2-one and 6-methyl-2-heptanone analogues, and process for producing phyton or isophytol |
EP1179520A1 (en) * | 2000-08-11 | 2002-02-13 | Aventis Animal Nutrition S.A. | Process for the preparation of phytone and novel intermediates thereof |
-
2002
- 2002-01-14 EP EP02356006A patent/EP1327620A1/en not_active Withdrawn
-
2003
- 2003-01-13 EP EP03729248A patent/EP1465853A1/en not_active Withdrawn
- 2003-01-13 JP JP2003557973A patent/JP2005514416A/ja active Pending
- 2003-01-13 MX MXPA04006772A patent/MXPA04006772A/es active IP Right Grant
- 2003-01-13 US US10/500,285 patent/US6987203B2/en not_active Expired - Fee Related
- 2003-01-13 RU RU2004124826/04A patent/RU2305091C2/ru not_active IP Right Cessation
- 2003-01-13 AU AU2003235760A patent/AU2003235760A1/en not_active Abandoned
- 2003-01-13 UA UA20040806768A patent/UA78754C2/uk unknown
- 2003-01-13 WO PCT/EP2003/000231 patent/WO2003057654A1/en not_active Application Discontinuation
- 2003-01-13 PL PL03369647A patent/PL369647A1/xx unknown
- 2003-01-13 CN CNA038021471A patent/CN1615290A/zh active Pending
- 2003-01-13 KR KR10-2004-7010398A patent/KR20040083075A/ko not_active Application Discontinuation
- 2003-01-13 BR BR0306702-5A patent/BR0306702A/pt not_active IP Right Cessation
- 2003-01-13 CA CA002473367A patent/CA2473367A1/en not_active Abandoned
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2004
- 2004-06-23 ZA ZA200404978A patent/ZA200404978B/xx unknown
Also Published As
Publication number | Publication date |
---|---|
WO2003057654A1 (en) | 2003-07-17 |
EP1327620A1 (en) | 2003-07-16 |
RU2004124826A (ru) | 2006-01-27 |
UA78754C2 (en) | 2007-04-25 |
KR20040083075A (ko) | 2004-09-30 |
MXPA04006772A (es) | 2004-11-10 |
PL369647A1 (en) | 2005-05-02 |
ZA200404978B (en) | 2006-06-28 |
BR0306702A (pt) | 2004-12-28 |
RU2305091C2 (ru) | 2007-08-27 |
EP1465853A1 (en) | 2004-10-13 |
US6987203B2 (en) | 2006-01-17 |
AU2003235760A1 (en) | 2003-07-24 |
CA2473367A1 (en) | 2003-07-17 |
US20050065380A1 (en) | 2005-03-24 |
JP2005514416A (ja) | 2005-05-19 |
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