CN100448830C - 用于制备甲基庚烯酮的方法 - Google Patents
用于制备甲基庚烯酮的方法 Download PDFInfo
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- CN100448830C CN100448830C CNB2005800039960A CN200580003996A CN100448830C CN 100448830 C CN100448830 C CN 100448830C CN B2005800039960 A CNB2005800039960 A CN B2005800039960A CN 200580003996 A CN200580003996 A CN 200580003996A CN 100448830 C CN100448830 C CN 100448830C
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- 238000000034 method Methods 0.000 title claims description 18
- JPTOCTSNXXKSSN-UHFFFAOYSA-N methylheptenone Chemical compound CCCC=CC(=O)CC JPTOCTSNXXKSSN-UHFFFAOYSA-N 0.000 title 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 15
- UHEPJGULSIKKTP-UHFFFAOYSA-N sulcatone Chemical compound CC(C)=CCCC(C)=O UHEPJGULSIKKTP-UHFFFAOYSA-N 0.000 claims description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 239000007983 Tris buffer Substances 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 abstract 2
- BZAZNULYLRVMSW-UHFFFAOYSA-N 2-Methyl-2-buten-3-ol Natural products CC(C)=C(C)O BZAZNULYLRVMSW-UHFFFAOYSA-N 0.000 abstract 1
- YOWQWFMSQCOSBA-UHFFFAOYSA-N 2-methoxypropene Chemical compound COC(C)=C YOWQWFMSQCOSBA-UHFFFAOYSA-N 0.000 abstract 1
- YKQSPKJDNQDIRX-UHFFFAOYSA-N CCCC=CC(=O)CC.CC(C)=CCCC(C)=O Chemical compound CCCC=CC(=O)CC.CC(C)=CCCC(C)=O YKQSPKJDNQDIRX-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
-
- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种用于制备甲基庚烯酮(2-甲基-2-庚烯-6-酮)的方法，所述方法包括将2-甲基-3-丁烯-2-醇与异丙烯基甲基醚在氢化三(草酸根合)磷酸盐或氢化双(草酸根合)硼酸盐的存在下反应。
Description
本发明涉及一种新型的用于制备2-甲基-2-庚烯-6-酮(此后，也被称为甲基庚烯酮)的方法。现有技术已知通过将2-甲基-3-丁烯-2-醇与异丙烯基甲基醚在例如磷酸(见DE 1193490)或有机磷酸盐或膦酸盐(见DE19649564)的催化剂的存在下反应来制备甲基庚烯酮。
发现，氢化双(草酸根合)硼酸盐(hydrogen bis(oxalao)borate)和氢化三(草酸根合)磷酸盐(hydrogen tris(oxalato)phosphate)特别适于催化该反应。因此，本发明涉及一种用于制备2-甲基-2-庚烯-6-酮的方法，所述方法包括将2-甲基-3-丁烯-2-醇与异丙烯基甲基醚在氢化三(草酸根合)磷酸盐或氢化双(草酸根合)硼酸盐的存在下反应。
本发明的方法可以在常压或高压下实施。优选地，该反应在高压下实施，例如，在约105至约20×105帕斯卡(Pa)下，优选地在5×105至15×105下实施。而且，根据本发明的反应优选在无溶剂下实施。添加的催化剂可以是纯催化剂形式或溶解形式的，优选地，添加的催化剂是溶于丙酮或甲醇的溶解形式。该反应适于在高温下实施，例如，在约373K至约450K的温度下。反应物的摩尔比适当的是1∶1至1∶3，优选的是1∶2至1∶2.5，但是，其中一种反应物可以过量(例如，廉价的反应物异丙烯基甲基醚过量)，并如果希望的话，该过量的反应物可以在将所希望的反应产物从反应混合物中分离后循环使用。
根据本发明的反应可以分批或以连续方式(例如，在两个或更多个串联排列的搅拌罐中或在管式反应器中)实施。
催化剂(氢化三(草酸根合)磷酸盐或氢化双(草酸根合)硼酸盐)在反应混合物中的用量基于2-甲基-3-丁烯-2-醇基质计算可提供约1000∶1至约100∶1，优选的是约900∶1至约300∶1的基质/催化剂比。氢化三(草酸根合)磷酸盐可以通过如EP 1227089所公开的过程制备。氢化双(草酸根合)硼酸盐可以通过如EP 784042所公开的过程制备。
本发明通过以下实施例进一步阐述。
实施例
反应采用主要部件是具有1.0升名义体积、最高493K操作温度和20bar最高压力的不绣钢间歇反应器(Medimex-High Pressure)的装置来实施。反应器装有加热系统(安装在护套上的电加热螺旋管)、冷却系统(流过反应器护套的乙二醇-水混合物)、用于测量内部反应器、护套和冷却温度的温度控制仪和搅拌器。反应器与实验室用真空泵连接以从反应器中除去空气。通过不锈钢毛细管和连接到取样瓶上的细螺旋不绣钢管进行取样。催化剂使用氢化双(草酸根合)硼酸盐的约12wt％或5.5wt％的甲醇溶液，或6.5wt％的丙酮溶液，或使用氢化三(草酸根合)磷酸盐的约12wt％、10wt％或8wt％的甲醇溶液或6wt％的丙酮溶液。
将195g MBE(2.22mol)、催化剂(见表1)和342g IPM(4.6mol＝2.1eq)混合并加到反应器中。将反应器采用真空泵抽空很短一段时间。将反应混合物加热到423K并搅拌且维持在所述温度。将样品通过样品阀和毛细管以适当时间间隔取出，并直接用乙酸钠中和。通过气相色谱分析样品(NORM％)。在将反应混合物冷却到室温后，将剩余的反应混合物样品取出(无气相)并用气相色谱分析(NORM％)。
结果示于下列表1、2和3中。
表1
| 催化剂(mol％)<sup>1</sup> | 催化剂溶液 | T(K) | 反应时间(h) | MBE的转化率(％) | MH产率(％) |
| HOB(0.15) | 5.5％甲醇 | 423 | 21.7 | 25.0 | 23.9 |
| HOB(0.10) | 5.5％甲醇 | 423 | 24 | 29.9 | 29.5 |
| HOB(0.10) | 6.5％丙酮 | 423 | 24 | 48.0 | 23.3 |
| HOB(0.05) | 6.5％丙酮 | 423 | 24 | 35.7 | 20.1 |
| HOB(0.01) | 6.5％丙酮 | 423 | 24 | 16.6 | 14.4 |
| HOP(0.15) | 10.0％甲醇 | 423 | 21.3 | 96.3 | 91.0 |
| HOP(0.15) | 11.7％甲醇 | 423 | 24 | 97.7 | 92.5 |
| HOP(0.15) | 11.7％甲醇 | 423 | 24 | 97.9 | 97.7<sup>3</sup> |
| HOP(0.15) | 11.7％甲醇 | 423 | 24 | 97.6 | 97.6<sup>4</sup> |
| HOP(0.12) | 10.0％甲醇 | 423 | 21.5 | 96.7 | 80.6 |
| HOP(0.09) | 10.0％甲醇 | 423 | 17 | 81.5 | 80.8 |
| HOP(0.23) | 10.0％甲醇 | 398 | 25 | 87.1 | 80.2 |
| HOP(0.17) | 10.0％甲醇 | 398 | 22 | 77.5 | 77.3<sup>2</sup> |
| HOP(0.15) | 6.1％丙酮 | 423 | 24 | 94.9 | 56.4 |
表2
| HOB(0.9) | 11.6％甲醇 | 423 | 24 | 50.3 | 43.2 |
| HOB(0.3) | 11.6％甲醇 | 423 | 24 | 22.0 | 20.3<sup>4</sup> |
| HOB(0.3) | 11.6％甲醇 | 423 | 24 | 28.5 | 26.1<sup>3</sup> |
| HOB(0.3) | 11.6％甲醇 | 448 | 24 | 39.2 | 37.6 |
| HOB(0.3) | 5.5％甲醇 | 423 | 24 | 29.8 | 28.0 |
表3
| HOP(0.14) | 6.1％丙酮 | 423 | 24 | 98.6 | 98.4<sup>4</sup> |
| HOP(0.30) | 11.7％甲醇 | 423 | 8.5 | 94.0 | 90.1 |
| HOP(0.30) | 7.9％甲醇 | 398 | 24 | 88.3 | 83.4 |
| HOP(0.30) | 11.7％甲醇 | 423 | 24 | 99.0 | 81.1 |
HOB：氢化双(草酸根合)硼酸盐；HOP：氢化三(草酸根合)磷酸盐；
MH：甲基庚烯酮；MBE：2-甲基-3-丁烯-2-醇；IPM：异丙烯基甲基醚
1基于MBE
2IPM/MBE比＝3.3/1(其它情况下为2.1/1)，3IPM/MBE比＝2.5/1，
4IPM/MBE比＝3.0/1
Claims (9)
1.用于制备2-甲基-2-庚烯-6-酮的方法，所述方法包括将2-甲基-3-丁烯-2-醇与异丙烯基甲基醚在氢化三(草酸根合)磷酸盐或氢化双(草酸根合)硼酸盐的存在下反应。
2.如权利要求1所述的方法，其中，所述反应在氢化三(草酸根合)磷酸盐的存在下实施。
3.如权利要求1所述的方法，其中，所述反应在105至20×105Pa下实施。
4.如权利要求3所述的方法，其中，所述反应在5×105至约15×105Pa下实施。
5.如权利要求1至4中任意一项所述的方法，其中，催化剂的用量基于2-甲基-3-丁烯-2-醇基质计算提供1000∶1至100∶1的基质/催化剂摩尔比。
6.如权利要求1至4中任意一项所述的方法，其中，催化剂的用量基于2-甲基-3-丁烯-2-醇基质计算提供900∶1至300∶1的基质/催化剂摩尔比。
7.如权利要求1至4中任意一项所述的方法，其中，所述2-甲基-3-丁烯-2-醇与异丙烯基甲基醚的摩尔比为1∶1至1∶3。
8.如权利要求1至4中任意一项所述的方法，其中，所述2-甲基-3-丁烯-2-醇与异丙烯基甲基醚的摩尔比为1∶1至1∶2.5。
9.如权利要求1至4中任意一项所述的方法，其中，所述反应以连续方式实施。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04002422.6 | 2004-02-04 | ||
| EP04002422 | 2004-02-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1914143A CN1914143A (zh) | 2007-02-14 |
| CN100448830C true CN100448830C (zh) | 2009-01-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005800039960A Expired - Fee Related CN100448830C (zh) | 2004-02-04 | 2005-01-27 | 用于制备甲基庚烯酮的方法 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US7319172B2 (zh) |
| EP (1) | EP1711451B1 (zh) |
| JP (1) | JP4733057B2 (zh) |
| KR (1) | KR101128256B1 (zh) |
| CN (1) | CN100448830C (zh) |
| AT (1) | ATE505451T1 (zh) |
| DE (1) | DE602005027439D1 (zh) |
| ES (1) | ES2364272T3 (zh) |
| WO (1) | WO2005075400A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0920620A2 (pt) * | 2008-10-21 | 2015-12-22 | Dsm Ip Assets Bv | fabricação de cetonas gama-delta insaturadas |
| CN103570516B (zh) * | 2013-10-31 | 2015-03-11 | 广西科伦制药有限公司 | 头孢噻肟钠生产中丙酮的回收工艺 |
| CN105218339B (zh) * | 2015-11-03 | 2017-03-22 | 山东新和成药业有限公司 | 一种由异戊烯醛制备甲基庚烯酮的方法 |
| CN108299171B (zh) * | 2018-02-11 | 2021-03-16 | 浙江新和成股份有限公司 | 一种由2-甲基-3-丁烯-2-醇合成甲基庚烯酮的方法 |
| CN113999100B (zh) * | 2021-10-29 | 2023-10-13 | 万华化学集团股份有限公司 | 一种甲基庚烯酮的制备及原料套用方法 |
| CN114933518B (zh) * | 2022-06-16 | 2023-11-28 | 山东新和成药业有限公司 | 一种乙基庚烯酮的合成方法及杂多酸催化剂的应用 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3453317A (en) * | 1962-07-11 | 1969-07-01 | Hoffmann La Roche | Unsaturated carbonyl compounds and processes |
| CN1365977A (zh) * | 2001-01-18 | 2002-08-28 | 罗切维他命股份公司 | (全－rac)α－生育酚的生产方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL295084A (zh) * | 1962-07-11 | 1900-01-01 | ||
| US5886196A (en) * | 1996-01-12 | 1999-03-23 | Roche Vitamins Inc. | Method of catalyzing condensation reactions |
| DE19649564A1 (de) * | 1996-11-29 | 1998-06-04 | Basf Ag | Verfahren zur Herstellung von gamma,delta-ungesättigter Ketone durch Umsetzung tertiärer Allylalkohole mit Alkenylalkylethern |
-
2005
- 2005-01-27 KR KR1020067015352A patent/KR101128256B1/ko not_active IP Right Cessation
- 2005-01-27 EP EP05707037A patent/EP1711451B1/en not_active Not-in-force
- 2005-01-27 ES ES05707037T patent/ES2364272T3/es active Active
- 2005-01-27 WO PCT/EP2005/000795 patent/WO2005075400A1/en active Application Filing
- 2005-01-27 JP JP2006551772A patent/JP4733057B2/ja not_active Expired - Fee Related
- 2005-01-27 DE DE602005027439T patent/DE602005027439D1/de active Active
- 2005-01-27 CN CNB2005800039960A patent/CN100448830C/zh not_active Expired - Fee Related
- 2005-01-27 AT AT05707037T patent/ATE505451T1/de not_active IP Right Cessation
- 2005-01-27 US US10/588,035 patent/US7319172B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3453317A (en) * | 1962-07-11 | 1969-07-01 | Hoffmann La Roche | Unsaturated carbonyl compounds and processes |
| CN1365977A (zh) * | 2001-01-18 | 2002-08-28 | 罗切维他命股份公司 | (全－rac)α－生育酚的生产方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20070161823A1 (en) | 2007-07-12 |
| KR101128256B1 (ko) | 2012-03-26 |
| WO2005075400A1 (en) | 2005-08-18 |
| CN1914143A (zh) | 2007-02-14 |
| EP1711451B1 (en) | 2011-04-13 |
| JP2007520510A (ja) | 2007-07-26 |
| JP4733057B2 (ja) | 2011-07-27 |
| ES2364272T3 (es) | 2011-08-30 |
| US7319172B2 (en) | 2008-01-15 |
| KR20060134039A (ko) | 2006-12-27 |
| DE602005027439D1 (de) | 2011-05-26 |
| ATE505451T1 (de) | 2011-04-15 |
| EP1711451A1 (en) | 2006-10-18 |
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