EP0000885B1 - Verfahren zur Herstellung eines Cyclopentendions - Google Patents
Verfahren zur Herstellung eines Cyclopentendions Download PDFInfo
- Publication number
- EP0000885B1 EP0000885B1 EP78100596A EP78100596A EP0000885B1 EP 0000885 B1 EP0000885 B1 EP 0000885B1 EP 78100596 A EP78100596 A EP 78100596A EP 78100596 A EP78100596 A EP 78100596A EP 0000885 B1 EP0000885 B1 EP 0000885B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- manganese
- catalyst
- dione
- pyridine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
- C07C45/673—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 change of size of the carbon skeleton
Definitions
- the present invention relates to a process for the preparation of a cyclopentene dione, namely 2,2,4-trimethyl-cyclopent-4-ene-1,3-dione.
- This compound is a known substance which has certain olfactory properties and can also be used as an intermediate in various syntheses.
- a salt of manganese, cobalt or copper with a weak acid for example a lower alkane carboxylic acid such as formic acid, acetic acid or propionic acid, is expediently used as the catalyst.
- a manganese, cobalt or copper salt of an enol for example an acetylacetonate of these metals, is used as the catalyst.
- a particularly preferred embodiment consists in using manganese acetate or manganese acetylacetonate as the catalyst.
- pyridine or a homologue of pyridine that is to say a lower alkyl-substituted pyridine, such as collidine, picoline, lutidine or 2-methyl-5-ethyl-pyridine.
- the oxidation according to the invention is expediently carried out in an inert organic solvent which at least partially dissolves the catalyst.
- solvents examples include aromatic hydrocarbons, such as benzene, toluene or xylene, ether, in particular di-lower alkyl ether such as diethyl ether, or pyridine or a lower alkyl-substituted pyridine, in the latter case this solvent simultaneously acting as a co-catalyst.
- aromatic hydrocarbons such as benzene, toluene or xylene
- ether in particular di-lower alkyl ether such as diethyl ether, or pyridine or a lower alkyl-substituted pyridine, in the latter case this solvent simultaneously acting as a co-catalyst.
- the oxidation according to the invention can expediently be carried out in a temperature range between approximately 40 ° and 110 ° C., in particular between approximately 55 ° and approximately 70 ° C.
- a very particularly preferred temperature range is between 55 and 65 ° C.
- the oxidation can be carried out with oxygen or an oxygen-containing gas.
- oxygen or an oxygen-containing gas.
- the reaction is about half as fast as when using pure oxygen.
- reaction mixture is distilled (bp. - 30-180 0 C / 0.1 Torr).
- the condensate is fractionated on a 1.5 m column with Fenskering filling. 602 g of 2,2,4-trimethyl-4-cyclopentene-1,3-dione are obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
- Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines Cyclopentendions, nämlich von 2,2,4-Trimethyl-cyclopent-4-en-1,3-dion.
- Es handelt sich bei dieser Verbindung um eine bekannte Substanz, welche gewisse olfaktorische Eigenschaften aufweist und ausserdem als Zwischenprodukt in verschiedenen Synthesen verwendbar ist.
- Bisher war diese Verbindung nur auf umständlichem Wege, beispielsweise über das 3,3-Dimethyl-bicyclo[3.1.0.Ihexandion(2,4) und in niedrigen Ausbeuten zugänglich ("Chemische Berichte" 1967, Seiten 2837-2841). Das erfindungsgemasse Verfahren, welches eine leichte Zugänglichkeit dieser Verbindung in hohen Ausbeuten ermöglicht, ist dadurch gekennzeichnet, dass man 3,5,5-Trimethyl-cyclohex-2-en-1,4-dion mit Sauerstoff oder einem Sauerstoff enthaltenden Gas in Gegenwart eines Katalysators auf der Basis von Mangan, Kobalt oder Kupfer oxydiert.
- Als Katalysator wird hiebei zweckmässig ein Salz von Mangan, Kobalt oder Kupfer mit einer schwachen Säure, beispielsweise einer niederen Alkancarbonsäure, wie Ameisensäure, Essigsäure oder Propion säure verwendet.
- Gemäss einer anderen, bevorzugten Ausführung des erfindungsgemässen Verfahrens wird als Katalysator ein Mangan-, Kobalt- oder Kupfersalz eines Enols, beispielsweise ein Acetylacetonat dieser Metalle verwendet.
- Eine besonders bevorzugte Ausführungsform besteht darin, dass man als Katalysator Manganacetat oder Manganacetylacetonat verwendet.
- Es hat sich als vorteilhaft erwisen, die Oxydation in Gegenwart von Pyridin oder einem Homologen von Pyridin, also einem niederalkyl-substituierten Pyridin, wie Collidin, Picolin, Lutidin oder 2-Methyl-5-äthyl-pyridin durchzuführen.
- Die erfindungsgemässe Oxydation wird zweckmässig in einem inerten organischen Lösungsmittel durchgeführt, welches den Katalysator wenigstens, teilweise löst.
- Beispiele solcher Lösungsmittel sind aromatische Kohlenwasserstoffe, wie Benzol, Toluol oder Xylol, Aether, insbesondere Di-niederalkyl-äther wie Diäthyläther, oder Pyridin bzw. ein niederalkyl-substituiertes Pyridin, wobei in letzterem Falle dieses Lösungsmittel gleichzeitig die Funktion eines Co-Katalysators ausübt.
- Die erfindungsgemässe Oxydation kann zweckmässig in einem Temperaturbereich zwischen etwa 40° und 110°C durchgeführt werden, insbesondere zwischen etwa 55° und etwa 70°C. Ein ganz besonders bevorzugter Temperaturbereich liegt zwischen 55 und 65°C.
- Die Oxydation kann mit Sauerstoff oder einem sauerstoffhaltigen Gas durchgeführt werden. Wenn man Luft als Oxydationsmittel verwendet, verläuft die Reaktion etwa halb so schnell wie bei der Verwendung von reinem Sauerstoff.
- In einem 4-Liter-Kolben mit Rührer, Rückflusskühler, Gaseinleitrohr und Thermometer werden 220,5 g Mangan(11)acetat x 4H20 in 1800 ml Pyridin gelöst. Bei 60°C unter Sauerstoffbegasung und intensivem Rühren werden 1368 g Ketoisophoron zugegeben. 3-4 Minuten danach findet eine schwache exotherme Reaktion statt. Gleichzeitig nimmt das Reaktionsgemisch langsam Sauerstoff auf.
-
Claims (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH9910/77 | 1977-08-12 | ||
CH991077 | 1977-08-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000885A1 EP0000885A1 (de) | 1979-03-07 |
EP0000885B1 true EP0000885B1 (de) | 1981-06-10 |
Family
ID=4357017
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100596A Expired EP0000885B1 (de) | 1977-08-12 | 1978-08-07 | Verfahren zur Herstellung eines Cyclopentendions |
Country Status (9)
Country | Link |
---|---|
US (1) | US4157352A (de) |
EP (1) | EP0000885B1 (de) |
JP (1) | JPS5432440A (de) |
AT (1) | AT357139B (de) |
DE (2) | DE2834557A1 (de) |
FR (1) | FR2399995A1 (de) |
GB (1) | GB2002382A (de) |
IT (1) | IT1098369B (de) |
NL (1) | NL7807700A (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6427322A (en) * | 1988-04-21 | 1989-01-30 | Sony Corp | Arithmetic circuit for galois field |
DE3842547A1 (de) * | 1988-12-17 | 1990-06-21 | Huels Chemische Werke Ag | Verfahren zur herstellung von 2,6,6-trimethyl-cyclohex-2-en-1,4-dion |
US5407910A (en) * | 1993-10-12 | 1995-04-18 | Union Camp Corporation | Cyclopent-1-en-3,5-dione compounds and compositions |
CN106573081B (zh) * | 2014-07-18 | 2020-03-10 | 3M创新有限公司 | 用于空气过滤器的芳香剂分配器 |
-
1978
- 1978-07-18 NL NL787807700A patent/NL7807700A/xx not_active Application Discontinuation
- 1978-07-19 US US05/926,593 patent/US4157352A/en not_active Expired - Lifetime
- 1978-07-19 FR FR7821394A patent/FR2399995A1/fr active Granted
- 1978-08-07 DE DE19782834557 patent/DE2834557A1/de not_active Withdrawn
- 1978-08-07 EP EP78100596A patent/EP0000885B1/de not_active Expired
- 1978-08-07 DE DE7878100596T patent/DE2860753D1/de not_active Expired
- 1978-08-09 IT IT26632/78A patent/IT1098369B/it active
- 1978-08-10 JP JP9676878A patent/JPS5432440A/ja active Pending
- 1978-08-11 GB GB7833013A patent/GB2002382A/en not_active Withdrawn
- 1978-08-11 AT AT585878A patent/AT357139B/de not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
AT357139B (de) | 1980-06-25 |
JPS5432440A (en) | 1979-03-09 |
NL7807700A (nl) | 1979-02-14 |
EP0000885A1 (de) | 1979-03-07 |
ATA585878A (de) | 1979-11-15 |
US4157352A (en) | 1979-06-05 |
FR2399995B1 (de) | 1980-09-05 |
IT1098369B (it) | 1985-09-07 |
DE2860753D1 (en) | 1981-09-17 |
DE2834557A1 (de) | 1979-03-01 |
GB2002382A (en) | 1979-02-21 |
FR2399995A1 (fr) | 1979-03-09 |
IT7826632A0 (it) | 1978-08-09 |
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