DE1082257B - Process for the production of polyunsaturated alcohols - Google Patents
Process for the production of polyunsaturated alcoholsInfo
- Publication number
- DE1082257B DE1082257B DEB52539A DEB0052539A DE1082257B DE 1082257 B DE1082257 B DE 1082257B DE B52539 A DEB52539 A DE B52539A DE B0052539 A DEB0052539 A DE B0052539A DE 1082257 B DE1082257 B DE 1082257B
- Authority
- DE
- Germany
- Prior art keywords
- parts
- alcohols
- production
- reaction
- acetylene
- 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
- 150000001298 alcohols Chemical class 0.000 title claims description 9
- 238000000034 method Methods 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- -1 Propylene, butylene, isobutylene Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000001371 (5E)-3,5-dimethylocta-1,5,7-trien-3-ol Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZJIQIJIQBTVTDY-SREVYHEPSA-N dehydrolinalool Chemical compound CC(=C)\C=C/CC(C)(O)C=C ZJIQIJIQBTVTDY-SREVYHEPSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- YULMNMJFAZWLLN-UHFFFAOYSA-N methylenecyclohexane Chemical compound C=C1CCCCC1 YULMNMJFAZWLLN-UHFFFAOYSA-N 0.000 description 1
- WPHGSKGZRAQSGP-UHFFFAOYSA-N methylenecyclohexane Natural products C1CCCC2CC21 WPHGSKGZRAQSGP-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C35/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic
- C07C35/06—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring monocyclic containing a five-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von mehrfach ungesättigten Alkoholen Es wurde gefunden, daß man mehrfach ungesättigte Alkohole erhält, wenn man Olefine, die mehr als 2 Kohlenstoffatome enthalten und mindestens 1 Wasserstoffatom in Allylstellung besitzen, mit a-Acetylenalkoholen bei Temperaturen zwischen 100 und 3000 C, vorzugsweise zwischen 180 und 250"C, umsetzt. Process for the production of polyunsaturated alcohols Es it was found that polyunsaturated alcohols are obtained when olefins, which contain more than 2 carbon atoms and at least 1 hydrogen atom in the allyl position have, with α-acetylene alcohols at temperatures between 100 and 3000 C, preferably between 180 and 250 "C.
Die Umsetzung nach dem Verfahren läßt sich bei Verwendung von Isobuten und 2-Methylbutin-(3)-ol-(2) wie folgt formulieren: Es entsteht also in einer intermolekularen Reaktion 2-Methyl-3 ,5-dimethylenhexanol-(2). Besonders vorteilhaft lassen sich nach dem Verfahren a-Acetylenalkohole, die außer der Acetylenbindung in demselben Molekül mindestens noch eine olefinische Bindung enthalten, in einer intramolekularen Reaktion zu cyclischen, mehrfach ungesättigten Alkoholen umsetzen. Für den Fall der Verwendung von 2,6-Dimethylocten-(2)-in-(7)-ol-(6) (Dehydrolinalool) läßt sich die Umsetzung wie folgt wiedergeben: Es entsteht 1 -Methyl-2-methylen-3-isopropenylcyclo pentanol-(t).The reaction according to the process can be formulated as follows when using isobutene and 2-methylbutyn- (3) -ol- (2): So 2-methyl-3, 5-dimethylenehexanol- (2) is formed in an intermolecular reaction. According to the process, α-acetylene alcohols which, in addition to the acetylene bond, contain at least one olefinic bond in the same molecule, can be converted particularly advantageously in an intramolecular reaction to give cyclic, polyunsaturated alcohols. In the case of using 2,6-dimethylocten- (2) -in- (7) -ol- (6) (dehydrolinalool), the reaction can be reproduced as follows: The result is 1-methyl-2-methylene-3-isopropenylcyclo pentanol- (t).
Für das Verfahren geeignete Monoolefine sind z. B. Monoolefins suitable for the process are e.g. B.
Propylen, Butylen, Isobutylen, Tetramethyläthylen, Cyclopenten, Cyclohexen und Methylencyclohexan.Propylene, butylene, isobutylene, tetramethylethylene, cyclopentene, cyclohexene and methylenecyclohexane.
Geeignete a-Acetylenalkohole sind unter anderem Propargylalkohol, Butin- (1) -ol- (3), 2-Methylbutin- (3) -ol-(2), t-Äthinylcyclohexanol-(l), Phenyläthinylcarbinol und Butin-(2)-ol-(1). a-Acetylenalkohole, die außer der Acetylenverbindung noch mindestens eine olefinische Doppelbindung und gegebenenfalls indifferente Substituenten, wie Halogenatome oder Alkoxygruppen, enthalten, sind beispielsweise 2,6-Dimethylocten- (2)-in- (7) -ol- (6), 2, 3,6-Trimethylocten-(2)-in-(7)-ol-(6) und 2,4,5,6-Tetramethylocten-(2)-in-(7)-ol-(6). Suitable a-acetylene alcohols include propargyl alcohol, Butyn- (1) -ol- (3), 2-methylbutyn- (3) -ol- (2), t-ethynylcyclohexanol- (1), phenylethinylcarbinol and butyne- (2) -ol- (1). a-acetylene alcohols, which apart from the acetylene compound still at least one olefinic double bond and optionally indifferent substituents, such as halogen atoms or alkoxy groups, are for example 2,6-Dimethylocten- (2) -in- (7) -ol- (6), 2, 3,6-trimethylocten- (2) -in- (7) -ol- (6) and 2,4,5,6-tetramethylocten- (2) -in- (7) -ol- (6).
Zur Ausführung der Reaktion wird das Gemisch von Olefin und a-Acetylenalkohol bzw. der a-Acetylenalkohol, der außer der Acetylenbindung noch mindestens eine olefinische Bindung enthält, für sich oder in einem Lösungsmittel, wie Cyclohexan, n-Hexan, Benzol und Xylol, erhitzt. Die Umsetzung erfordert in der Regel einige Stunden, beispielsweise 2 bis 20 Stunden. Die Reaktionszeit hängt von der Reaktionsfähigkeit der Komponenten ab und läßt sich durch einen Vorversuch leicht ermitteln. In manchen Fällen ist es vorteilhaft, die Umsetzung unter der Atmosphäre eines Inertgases, wie Stickstoff, Kohlendioxyd und Argon, durchzuführen. The mixture of olefin and α-acetylene alcohol is used to carry out the reaction or the a-acetylene alcohol, which, in addition to the acetylene bond, has at least one olefinic Contains bond, by itself or in a solvent such as cyclohexane, n-hexane, Benzene and xylene, heated. The implementation usually takes a few hours, for example 2 to 20 hours. The response time depends on the responsiveness of the components and can easily be determined by a preliminary test. In some In some cases it is advantageous to carry out the reaction under the atmosphere of an inert gas, such as nitrogen, carbon dioxide and argon.
Wenn man Ausgangsstoffe oder Lösungsmittel anwendet, deren Siedepunkte unter der Reaktionstemperatur liegen, benutzt man zweckmäßig ein Druckgefäß. Man gewinnt die mehrfach ungesättigten Alkohole aus dem Reaktionsgemisch im allgemeinen durch Destillation unter vermindertem Druck.If starting materials or solvents are used, their boiling points are below the reaction temperature, it is advisable to use a pressure vessel. Man wins the polyunsaturated alcohols from the reaction mixture in general by distillation under reduced pressure.
Die nach dem neuen Verfahren erhaltenen Verbindungen eignen sich als Zwischenprodukte, z. B. für die Synthese von Riechstoffen. The compounds obtained by the new process are suitable as intermediates, e.g. B. for the synthesis of fragrances.
Die in den folgendert Beispielen genannten Teile sind Gewichtsteile. The parts mentioned in the following examples are parts by weight.
Beispiel 1 152 Teile 2,6-Dimethylocten-(2)-in-(7)-ol-(6) werden 6 Stunden-unter-Rückfluß etwa auf 185"C erhitzt. Man destilliert das Gemisch unter vermindertem Druck und erhält zunächst 136 Teile eines Destillats, das bei Kp., 60 bis 709C. übergeht und aus dem durch Rektifikation 124 Teile 1-Methyl-2-methylen-3-isopropenylcyclopentanol-(1) und 12 Teile Ausgangsstoff gewonnen werden.Example 1 152 parts of 2,6-dimethylocten- (2) -in- (7) -ol- (6) are heated under reflux for 6 hours to about 185 ° C. The mixture is distilled under reduced pressure and 136 is initially obtained Parts of a distillate, which passes over at b.p., 60 to 709C. And from which 124 parts of 1-methyl-2-methylene-3-isopropenylcyclopentanol- (1) and 12 parts of raw material are obtained.
Beispiel 2 304 Teile 2,6-Dimethylocten-(2)-in-(7)-ol-(6) werden in einem Druckgefäß 2 Stunden auf 220"C erhitzt. Durch Destillation des Reaktionsproduktes unter vermindertem Druck erhält man 273 Teile, entsprechend 9001, der Theorie, reines l-Methyl-2-methylen-3-isopropenylcyclopentanol-(l) vom Siedepunkt Kp.0,5 43 bis 45"C. Example 2 304 parts of 2,6-dimethylocten- (2) -in- (7) -ol- (6) are in heated in a pressure vessel to 220 ° C. for 2 hours. By distilling the reaction product under reduced pressure, 273 parts are obtained, corresponding to 9001, the theory, pure l-methyl-2-methylene-3-isopropenylcyclopentanol- (l) with a boiling point of bp 0.5 43 bis 45 "C.
Beispiel 3 In einem Druckgefäß wird ein Gemisch aus 112 Teilen Isobuten, 168 Teilen 2-Methylbutin-(3)-ol-(2) und 250 Teilen Cyclohexan unter einer Stickstoffatmosphäre 12 Stunden auf 240"C erhitzt. Nach dem Abkühlen entspannt man das Druckgefäß und destilliert das Reaktionsprodukt unter einer Stickstoffatmosphäre und, nachdem das Cyclohexan entfernt ist, unter vermindertem Druck Man erh; neben 127 Teilen nicht umgesetztem 2-Methylbutin- (3) -ol- 10 Teile 2-Methyl-3,5-dimethylenhexanol-(2) vom Siedepunkt Kp.l 58 bis 60"C.Example 3 A mixture of 112 parts of isobutene, 168 parts of 2-methylbutyn- (3) -ol- (2) and 250 parts of cyclohexane is heated in a pressure vessel to 240 ° C. for 12 hours under a nitrogen atmosphere. After cooling, the pressure vessel is let down and the reaction product is distilled under a nitrogen atmosphere and, after the cyclohexane has been removed, under reduced pressure. In addition to 127 parts of unreacted 2-methylbutyn- (3) -ol- 10 parts of 2-methyl-3,5-dimethylenehexanol- (2nd ) from boiling point bp 58 to 60 "C.
Beispiel 4 In einem Druckgefäß wird ein Gemisch aus 168 Teilen 2-Methylbutin-(3)-ol-(2) und 164 Teilen Cyclohexen unter einer Stickstoffatmosphäre 30 Stunden auf 240"C erhitzt. Durch Destillation des Reaktionsgemisches bei Normaldruck erhält man insgesamt 250 Teile der Ausgangsstoffe zurück. Durch Destillation des Rückstandes unter vermindertem Druck gewinnt man 18 Teile 2-[Cyclohexen-(2')-yl-(1')]-3-methylbuten-(1)-ol-(3) vom Siedepunkt Kp.l 60 bis 62"C.Example 4 In a pressure vessel, a mixture of 168 parts of 2-methylbutyn- (3) -ol- (2) and 164 parts of cyclohexene is heated under a nitrogen atmosphere to 240 ° C. for 30 hours. Distillation of the reaction mixture at normal pressure gives a total of 250 parts By distilling the residue under reduced pressure, 18 parts of 2- [cyclohexen- (2 ') - yl- (1')] - 3-methylbuten- (1) -ol- (3) are obtained with a boiling point of 60 to 62 "C.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB52539A DE1082257B (en) | 1959-03-19 | 1959-03-19 | Process for the production of polyunsaturated alcohols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB52539A DE1082257B (en) | 1959-03-19 | 1959-03-19 | Process for the production of polyunsaturated alcohols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1082257B true DE1082257B (en) | 1960-05-25 |
Family
ID=6969921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB52539A Pending DE1082257B (en) | 1959-03-19 | 1959-03-19 | Process for the production of polyunsaturated alcohols |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1082257B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4125484A (en) * | 1976-02-27 | 1978-11-14 | Shell Oil Company | Tertiary alcohols |
-
1959
- 1959-03-19 DE DEB52539A patent/DE1082257B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4125484A (en) * | 1976-02-27 | 1978-11-14 | Shell Oil Company | Tertiary alcohols |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1238906B (en) | Process for the preparation of cyclooctadiene-1, 5 | |
| US2501144A (en) | Unsaturated aldehydes and preparation thereof | |
| DE3633033A1 (en) | METHOD AND CATALYST SYSTEM FOR TRIMERIZING ACETYLENE AND ACETYLENE COMPOUNDS | |
| EP0314003B1 (en) | Process for the preparation of 1-aryl alkenes-1 | |
| DE1251296C2 (en) | METHOD FOR MANUFACTURING HIGHER PRIMARY ALCOHOLS | |
| DE1082257B (en) | Process for the production of polyunsaturated alcohols | |
| DE2103686C3 (en) | Process for the preparation of α-hydroxy-γ-lactones | |
| DE2411440A1 (en) | METHOD FOR PRODUCING METHACRYLIC ACID AND BUTYROLACTONE | |
| DE887644C (en) | Process for the production of carboxylic acids | |
| DE896638C (en) | Process for the preparation of n- and i-butyraldehyde or the corresponding alcohols | |
| DE879990C (en) | Process for the production of nitrogen compounds with two triple carbon-carbon bonds | |
| DE1618420C3 (en) | ||
| DE922585C (en) | Process for the production of alcohols | |
| EP0248422B1 (en) | Processing by distillation of mixtures containing cyclohexene, cyclohexane and benzene | |
| US2615055A (en) | Cyclic olefins | |
| DE943353C (en) | Process for the production of ª ‰ -Acylvinylalkyllaethern | |
| DE1443331C (en) | Process for the production of phenol | |
| DE859735C (en) | Process for the production of condensation products by reacting ethers with unsaturated organic compounds | |
| DE1643729C (en) | Process for the preparation of alkene- (3) -olen- (l) | |
| AT246721B (en) | Process for the preparation of the new cis, cis-cyclodecadiene- (1,6) | |
| DE947474C (en) | Process for the preparation of 1-methylcyclohexene (1) | |
| DE1068255B (en) | Process for the preparation of cyclic carboxylic acids and / or their esters from cyclododecatrienes (1,5,9) | |
| DE1157598B (en) | Process for the preparation of N-substituted carbamic acid esters | |
| DE824051C (en) | Process for the production of conversion products from unsaturated organic compounds and nitrogen oxide (NO) | |
| DE1643751C2 (en) | Process for the production of mono-beta-hydroxyketones and / or unsaturated ketones |