DE1073476B - Process for the preparation of γ, δ-olefinically unsaturated ketones which are branched in the δ-position - Google Patents
Process for the preparation of γ, δ-olefinically unsaturated ketones which are branched in the δ-positionInfo
- Publication number
- DE1073476B DE1073476B DENDAT1073476D DE1073476DA DE1073476B DE 1073476 B DE1073476 B DE 1073476B DE NDAT1073476 D DENDAT1073476 D DE NDAT1073476D DE 1073476D A DE1073476D A DE 1073476DA DE 1073476 B DE1073476 B DE 1073476B
- Authority
- DE
- Germany
- Prior art keywords
- olefinically unsaturated
- branched
- reaction
- preheated
- preparation
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 6
- 150000002576 ketones Chemical class 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims description 17
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 5
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000009835 boiling Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- -1 alkyl acetoacetate Chemical compound 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N Ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 210000003932 Urinary Bladder Anatomy 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
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
- C07C45/676—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 by elimination of carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von in d-Stellung verzweigten, y,4-olefinisch-ungesättigten Ketonen Zusatz zur Patntanmeldung B 38242 IVb/l2 o (Auslegesdlrift 1 068 696) Die Hauptpatentanmeldung betrifft ein Verfahren zur Herstellung von in b-Stellung verzweigten, y,8-olefinisch-ungesättigten Ketonen durch Umsetzung von tertiären B,y-olefinisch-ungesättigten Alkoholen mit Alkylestern der Acetessigsäure bei 160 bis 2500 C in flüssiger Phase. Process for the preparation of γ, 4-olefinically unsaturated compounds which are branched in the d-position Ketones addendum to patent application B 38242 IVb / l2 o (Auslegesdlrift 1 068 696) Die The main patent application relates to a process for the production of branched in the b-position, y, 8-olefinically unsaturated ketones by reaction of tertiary B, y-olefinically unsaturated Alcohols with alkyl esters of acetoacetic acid at 160 to 2500 C in the liquid phase.
Die Ausführungsformen dieses Verfahrens bestehen darin, daß man unter 1400 C siedende, verzweigte tertiäre jB,y-olefinisch ungesättigte Alkohole in Acetessigsäurealkylester oder in ein Gemisch von Acetessigsäurealkylester mit einem Lösungsmittel oder ein Gemisch der Alkohole mit Acetessigsäurealkylester in ein Lösungsmittel einführt, wobei das jeweilige Reaktionsmedium auf die Reaktionstemperatur vorgewärmt ist. The embodiments of this method consist in that one under 1400 C boiling, branched tertiary jB, γ-olefinically unsaturated alcohols in alkyl acetoacetate or in a mixture of alkyl acetoacetate with a solvent or a Introduces mixture of alcohols with alkyl acetoacetate in a solvent, wherein the respective reaction medium is preheated to the reaction temperature.
Die niedrigsiedenden Komponenten werden laufend aus dem Reaktionsgemisch abdestilliert, damit die Reaktionstemperatur nicht unter 1600 C fällt. The low-boiling components are continuously removed from the reaction mixture distilled off so that the reaction temperature does not fall below 1600 C.
Es wurde nun gefunden, daß man bei dem Verfahren nach der Hauptpatentanmeldung auf die Verwendung eines Lösungsmittels verzichten kann, wenn man das Reaktionsgefäß selbst auf die Umsetzungstemperatur, d. h. auf 160 bis 2500 C, vorwärmt und die zweckmäßig ebenfalls vorgewärmten Ausgangsstoffe getrennt oder gemeinsam in das vorgewärmte Reaktionsgefäß einleitet und miteinander umsetzt. Als Reaktionsgefäß kann z. B. eine Destillierblase verwendet werden, die mit den nötigen Vorrichtungen zum Einbringen der Reaktionskomponenten und zum Abdestillieren der niedrigsiedenden Anteile versehen ist. It has now been found that in the process according to the main patent application can dispense with the use of a solvent if the reaction vessel itself on the reaction temperature, d. H. to 160 to 2500 C, preheated and the expediently also preheated starting materials separately or together in the Introduced preheated reaction vessel and reacted with each other. As a reaction vessel can e.g. B. a still can be used with the necessary devices for introducing the reaction components and for distilling off the low-boiling ones Shares is provided.
Eine weitere Ausführungsform des Verfahrens besteht darin, daß man die Reaktionskomponenten für sich oder gemeinsam in ein Rohr, das auf 160 bis 2500 C erhitzt und gegebenenfalls mit inertem Material gefüllt ist, einbringt. Eine solche Vorrichtung ist z. B. eine Füllkörperkolonne, über deren Kopf die niedrigsiedenden Anteile abdestilliert werden, während man gleichzeitig am unteren Ende die höhersiedenden Anteile abzieht. Another embodiment of the method is that one the reaction components individually or together in a tube that is 160 to 2500 C heated and optionally filled with inert material, introduces. Such Device is z. B. a packed column, over the top of the low boiling point Fractions are distilled off, while at the same time the higher-boiling at the lower end Subtracts shares.
In gleicher Weise wie bei dem Verfahren nach der Hauptpatentanmeldung werden nach Einführung der Ausgangs stoffe, das sind Alkylester der Acetessigsäure, insbesondere solche, die sich von Alkoholen mit 1 bis 5 Kohlenstoffatomen, vor allem von Methanol und Äthanol, ableiten und tertiäre ,B,r-olefinisch-ungesättigte Alkohole, die niedrigsiedenden Komponenten laufend aus dem Reaktionsgemisch abdestilliert. Es ist zweckmäßig, den ungesättigten Alkohol im Über schuß, z. B. im Molverhältnis 2 : 1, zu verwenden. Die Ausgangsstoffe kann man sowohl getrennt als auch im Gemisch in das vorgewärmte Reaktionsgefäß einleiten. Zweckmäßig werden die Ausgangsstoffe vorgewärmt. In the same way as with the procedure after the main patent application after the introduction of the starting materials, which are alkyl esters of acetoacetic acid, especially those that differ from alcohols with 1 to 5 carbon atoms, especially derived from methanol and ethanol, and tertiary, B, r-olefinically unsaturated alcohols, the low-boiling components are continuously distilled off from the reaction mixture. It is appropriate to use the unsaturated alcohol in excess, for. B. in the molar ratio 2: 1, to be used. The starting materials can be used either separately or as a mixture Introduce into the preheated reaction vessel. The starting materials are expedient preheated.
Die ungesättigten Ketone kann man nach Beendigung der Reaktion, die am Aufhören der Gasentwicklung erkennbar ist, z. B. durch fraktionierte Destillation, in reiner Form gewinnen. The unsaturated ketones can be obtained after the reaction has ended can be recognized by the cessation of gas evolution, e.g. B. by fractional distillation, win in pure form.
Beispiel In die auf 2200 C erwärmte Blase eines Destillierapparates wird im Laufe von 20 Stunden die Mischung von 520 g Acetessigsäureäthylester und 687 g 2-Methylbuten-3-ol-2 eingeführt. Gleichzeitig werden am Kopf der angeschlossenen Destillierkolonne die unter 1000 C siedenden Anteile des Reaktionsgemisches abdestilliert, so daß die Temperatur im Flüssigkeitsgemisch in der Blase nicht unter 1750 C absinkt. Die Destillatvorlage der Kolonne ist mit einer Gasuhr verbunden, wodurch die bei der Reaktion in Freiheit gesetzte Kohlensäure gemessen wird. Es entwickeln sich im Laufe der Umsetzung etwa 93 1 Kohlensäure. Example In the still heated to 2200 C pot is in the course of 20 hours, the mixture of 520 g of ethyl acetoacetate and 687 g of 2-methylbuten-3-ol-2 were introduced. At the same time are connected to the head of the The distillation column distills off the portions of the reaction mixture boiling below 1000 C, so that the temperature in the liquid mixture in the bladder does not drop below 1750 C. The distillate receiver of the column is connected to a gas meter, whereby the at The carbon dioxide released by the reaction is measured. It evolves in the course of the conversion about 93 l of carbonic acid.
Aus dem in der Kolonne verbleibenden Rückstand erhält man durch Destillation 296 g reines 2-Methylbepten-2-on-6. Die Ausbeute beträgt 59 O/o der Theorie. The residue remaining in the column is obtained by distillation 296 g of pure 2-methylbepten-2-one-6. The yield is 59% of theory.
Claims (1)
Publications (1)
Publication Number | Publication Date |
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DE1073476B true DE1073476B (en) | 1960-01-21 |
Family
ID=597731
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DENDAT1073476D Pending DE1073476B (en) | Process for the preparation of γ, δ-olefinically unsaturated ketones which are branched in the δ-position |
Country Status (1)
Country | Link |
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DE (1) | DE1073476B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1000922A1 (en) * | 1998-11-16 | 2000-05-17 | Basf Aktiengesellschaft | Process for the preparation of higher unsaturated ketones |
-
0
- DE DENDAT1073476D patent/DE1073476B/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1000922A1 (en) * | 1998-11-16 | 2000-05-17 | Basf Aktiengesellschaft | Process for the preparation of higher unsaturated ketones |
US6300524B1 (en) | 1998-11-16 | 2001-10-09 | Basf Aktiengesellschaft | Process for preparing higher unsaturated ketones |
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