WO1999045173A1 - Verfahren zur carboxylierung von terminalen alkinen - Google Patents
Verfahren zur carboxylierung von terminalen alkinen Download PDFInfo
- Publication number
- WO1999045173A1 WO1999045173A1 PCT/EP1999/001366 EP9901366W WO9945173A1 WO 1999045173 A1 WO1999045173 A1 WO 1999045173A1 EP 9901366 W EP9901366 W EP 9901366W WO 9945173 A1 WO9945173 A1 WO 9945173A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- terminal
- cathode
- carbon dioxide
- carboxylation
- anode
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Definitions
- the invention relates to a process for the carboxylation of terminal alkynes according to the preamble of the first claim.
- the Kataly ⁇ sator is m-situ generated by electrolysis of the corresponding ligand and Ni (II) salts.
- the electrodes of the electrolytic cell used a carbon fiber as a cathode and a magnesium anode.
- carboxylic acids are obtained in this carboxylation.
- Aromatic or cycloaliphatic carboxylic acids are formed in part by ring closure.
- those with secondary carboxyl groups are formed.
- all reaction products have in common that the term triple bond of the alkm, which is involved in the carboxylation, is converted into a double bond. It is therefore not possible to produce 2-alkcarboxylic acids from the terminal alkynes using this process.
- the invention is based on the object of proposing a method of the type mentioned at the outset, in which carbon dioxide is selectively installed between the terminal C-H bond, the triple bond being retained.
- a nickel complex catalyst should not be used.
- alkms are carboxylated with gaseous carbon dioxide in an aprotic solvent, the carboxylation being carried out in an undivided electrolysis cell without the use of a catalyst or a catalyst precursor.
- Suitable term alkme are in particular the alkme with 2 to 9 carbon atoms.
- Substituents of the terminal alk, but also ether functions and additional double or triple bonds generally do not interfere with the reaction, since the process according to the invention selectively onocarboxylates the terminal, triple bonded carbon atom.
- Alkme with non-terminal triple bond are not carboxylated according to the invention.
- the gaseous carbon dioxide is fed to the electrolysis under excess pressure, preferably at a pressure of 0.2 to 5 bar. Pressures of 0.5 to 1 bar are particularly preferred. Pressures above 1 bar, but in particular above 5 bar, reduce the yield and should therefore be avoided.
- the reaction temperature can be at room temperature. Higher or lower temperatures have no significant advantages.
- the carboxylation is carried out according to the invention in an aprotic solvent.
- Dimethylformamide is particularly suitable as solvent; however, acetonitrile and tetrahydrofuran can also be used.
- the method according to the invention is carried out in an undivided electrolysis cell with a cathode and an anode which is sufficiently pressure-tight and has a gas supply for the carbon dioxide.
- metals are suitable as the cathode, but not the carbon fibers used in the prior art. Particularly high reaction yields are achieved with silver cathodes. Easily oxidizable metals such as zinc and aluminum are suitable as the material for the anode; magnesium is preferred.
- the electrolysis is preferably carried out under galvanostatic conditions. Usually voltages of up to 20 V and currents in the range of 50 mA are set.
- Fig. 1 is a schematic representation of a device for
- Fig. 2 shows an embodiment of the electrolytic cell.
- Fig. 1 is a device for performing the method according to the invention.
- an electrolysis cell 2 e termmal Alkm is presented together with an aprotic solvent.
- the electrolysis cell 2 With the help of a carbon dioxide gas bottle 1, the electrolysis cell 2, the contents of which can be mixed with a magnetic stirrer 3, is subjected to a carbon dioxide overpressure.
- the electrodes m of the electrolytic cell are connected to a current source 4. The electrolysis takes place under galvanostatic conditions.
- the electrolytic cell forms an autoclave which can be acted upon by the gas supply 10 with the carbon dioxide pressure.
- Anode 11 and cathode 12 are connected to a current source (not shown).
- a magnetic stirrer rod 13 for mixing the reaction solution.
- the electrolysis cell was flushed with carbon dioxide to remove atmospheric oxygen from the cell.
- the dimethylformamide (DMF) used as solvent was dried over calcium hydroxide, freshly distilled off and used immediately. 3 mmol of the terminal alkm were dissolved in DMF and placed in the electrolytic cell. Carbon dioxide was injected at a pressure of 0.5 bar with constant stirring. The electrochemical reaction was started after 15 minutes to ensure that the solution equilibrium of carbon dioxide in DMF was established.
- the experiments were carried out under galvanostatic conditions, with current intensities of 50 i ⁇ A and voltages of up to 20 V being established. The tests were carried out with a silver cathode.
- terminal monoalkms were carboxylated according to this specification:
- the influence of the cathode material on the yield of the carboxylation was determined in further experiments.
- the experiments were carried out with CH ⁇ 5 -C ⁇ CH according to the instructions given above, the cathode material being varied.
- a Plat cathode provided product I with a 5% yield and product II with a 40% yield. 35 % of the terminal alkyne was not converted. In contrast, a cathode made from a carbon fiber produced almost exclusively product II, while 75% of the terminal alkyne was not converted.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Saccharide Compounds (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/623,418 US6342149B1 (en) | 1998-03-05 | 1999-03-03 | Method for carboxylating terminal alkynes |
EP99914466A EP1060294B1 (de) | 1998-03-05 | 1999-03-03 | Verfahren zur carboxylierung von terminalen alkinen |
JP2000534700A JP3325883B2 (ja) | 1998-03-05 | 1999-03-03 | 末端アルキンをカルボキシル化するための方法 |
AT99914466T ATE230040T1 (de) | 1998-03-05 | 1999-03-03 | Verfahren zur carboxylierung von terminalen alkinen |
DE59903829T DE59903829D1 (de) | 1998-03-05 | 1999-03-03 | Verfahren zur carboxylierung von terminalen alkinen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19809532.5 | 1998-03-05 | ||
DE19809532A DE19809532C1 (de) | 1998-03-05 | 1998-03-05 | Verfahren zur Carboxylierung von terminalen Alkinen |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999045173A1 true WO1999045173A1 (de) | 1999-09-10 |
Family
ID=7859868
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/001366 WO1999045173A1 (de) | 1998-03-05 | 1999-03-03 | Verfahren zur carboxylierung von terminalen alkinen |
Country Status (6)
Country | Link |
---|---|
US (1) | US6342149B1 (de) |
EP (1) | EP1060294B1 (de) |
JP (1) | JP3325883B2 (de) |
AT (1) | ATE230040T1 (de) |
DE (2) | DE19809532C1 (de) |
WO (1) | WO1999045173A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8889897B2 (en) | 2011-12-23 | 2014-11-18 | Air Products And Chemicals, Inc. | Electrocarboxylation synthesis for obtaining intermediates useful for the synthesis of SPAN derivatives |
CN113117713A (zh) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | 一种负载型羧化催化剂、其制备方法及应用 |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011075087A1 (en) * | 2009-12-17 | 2011-06-23 | Agency For Science, Technology And Research | Carboxylation of terminal alkynes |
MY161393A (en) * | 2010-08-20 | 2017-04-14 | Basf Se | Process for preparing a propiolic acid or a derivative thereof |
AU2013207783B2 (en) | 2012-01-13 | 2017-07-13 | Lummus Technology Llc | Process for providing C2 hydrocarbons via oxidative coupling of methane and for separating hydrocarbon compounds |
US9670113B2 (en) | 2012-07-09 | 2017-06-06 | Siluria Technologies, Inc. | Natural gas processing and systems |
WO2014089479A1 (en) | 2012-12-07 | 2014-06-12 | Siluria Technologies, Inc. | Integrated processes and systems for conversion of methane to multiple higher hydrocarbon products |
WO2015081122A2 (en) | 2013-11-27 | 2015-06-04 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
CN106068323B (zh) | 2014-01-08 | 2019-09-06 | 希路瑞亚技术公司 | 乙烯成液体的***和方法 |
US9701597B2 (en) | 2014-01-09 | 2017-07-11 | Siluria Technologies, Inc. | Oxidative coupling of methane implementations for olefin production |
US10377682B2 (en) | 2014-01-09 | 2019-08-13 | Siluria Technologies, Inc. | Reactors and systems for oxidative coupling of methane |
CN103789790B (zh) * | 2014-02-11 | 2016-09-14 | 华东师范大学 | 不对称合成具有光学活性的苯乙烯环状碳酸酯的方法 |
US10793490B2 (en) | 2015-03-17 | 2020-10-06 | Lummus Technology Llc | Oxidative coupling of methane methods and systems |
US9334204B1 (en) | 2015-03-17 | 2016-05-10 | Siluria Technologies, Inc. | Efficient oxidative coupling of methane processes and systems |
US20160289143A1 (en) | 2015-04-01 | 2016-10-06 | Siluria Technologies, Inc. | Advanced oxidative coupling of methane |
US9328297B1 (en) | 2015-06-16 | 2016-05-03 | Siluria Technologies, Inc. | Ethylene-to-liquids systems and methods |
US20170107162A1 (en) | 2015-10-16 | 2017-04-20 | Siluria Technologies, Inc. | Separation methods and systems for oxidative coupling of methane |
WO2017180910A1 (en) | 2016-04-13 | 2017-10-19 | Siluria Technologies, Inc. | Oxidative coupling of methane for olefin production |
CA3042940A1 (en) * | 2016-12-02 | 2018-06-07 | Siluria Technologies, Inc. | Ethylene-to-liquids systems and methods |
EP3554672A4 (de) | 2016-12-19 | 2020-08-12 | Siluria Technologies, Inc. | Verfahren und systeme für chemische abscheidungen |
PL3630707T3 (pl) | 2017-05-23 | 2024-02-19 | Lummus Technology Llc | Zintegrowanie sposobów utleniającego sprzęgania metanu |
RU2020102298A (ru) | 2017-07-07 | 2021-08-10 | Люммус Текнолоджи Ллс | Системы и способы окислительного сочетания метана |
CN113117757B (zh) * | 2019-12-31 | 2023-04-07 | 中国石油化工股份有限公司 | 一种合成苯丙炔酸的体相催化剂及其制备和工艺 |
CN113117726B (zh) * | 2019-12-31 | 2023-04-07 | 中国石油化工股份有限公司 | 一种合成苯丙炔酸的成型催化剂及其制备和应用 |
-
1998
- 1998-03-05 DE DE19809532A patent/DE19809532C1/de not_active Expired - Fee Related
-
1999
- 1999-03-03 WO PCT/EP1999/001366 patent/WO1999045173A1/de active IP Right Grant
- 1999-03-03 JP JP2000534700A patent/JP3325883B2/ja not_active Expired - Fee Related
- 1999-03-03 AT AT99914466T patent/ATE230040T1/de not_active IP Right Cessation
- 1999-03-03 DE DE59903829T patent/DE59903829D1/de not_active Expired - Fee Related
- 1999-03-03 US US09/623,418 patent/US6342149B1/en not_active Expired - Fee Related
- 1999-03-03 EP EP99914466A patent/EP1060294B1/de not_active Expired - Lifetime
Non-Patent Citations (2)
Title |
---|
DERIEN, SYLVIE ET AL: "Activation of carbon dioxide: nickel-catalyzed electrochemical carboxylation od diynes", J. ORG. CHEM., vol. 58, no. 9, 1993, pages 2578 - 2588, XP002108475 * |
DUNACH ELISABET ET AL: "Electrochemical carboxylation of terminal alkynes catalyzed by nickel complexes: unusual regioselectivity", J. ORGANOMET. CHEM., vol. 352, no. 1-2, 1988, pages 239 - 246, XP002108474 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8889897B2 (en) | 2011-12-23 | 2014-11-18 | Air Products And Chemicals, Inc. | Electrocarboxylation synthesis for obtaining intermediates useful for the synthesis of SPAN derivatives |
CN113117713A (zh) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | 一种负载型羧化催化剂、其制备方法及应用 |
CN113117713B (zh) * | 2019-12-31 | 2023-07-04 | 中国石油化工股份有限公司 | 一种负载型羧化催化剂、其制备方法及应用 |
Also Published As
Publication number | Publication date |
---|---|
DE19809532C1 (de) | 1999-04-15 |
US6342149B1 (en) | 2002-01-29 |
DE59903829D1 (de) | 2003-01-30 |
EP1060294A1 (de) | 2000-12-20 |
JP3325883B2 (ja) | 2002-09-17 |
EP1060294B1 (de) | 2002-12-18 |
JP2002506119A (ja) | 2002-02-26 |
ATE230040T1 (de) | 2003-01-15 |
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