DEB0037755MA - - Google Patents
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- Publication number
- DEB0037755MA DEB0037755MA DEB0037755MA DE B0037755M A DEB0037755M A DE B0037755MA DE B0037755M A DEB0037755M A DE B0037755MA
- Authority
- DE
- Germany
- Prior art keywords
- cyclooctanediol
- ether
- parts
- mixture
- cold
- 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.)
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N Cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims 1
- 239000004914 cyclooctane Substances 0.000 claims 1
- SUGGJLOBTAREMB-UHFFFAOYSA-N cyclooctane-1,1-diol Chemical compound OC1(O)CCCCCCC1 SUGGJLOBTAREMB-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- 229960000583 Acetic Acid Drugs 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- URYYVOIYTNXXBN-UHFFFAOYSA-N cyclooctene Chemical compound [CH]1[CH]CCCCCC1 URYYVOIYTNXXBN-UHFFFAOYSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- MELPJGOMEMRMPL-UHFFFAOYSA-N 9-oxabicyclo[6.1.0]nonane Chemical compound C1CCCCCC2OC21 MELPJGOMEMRMPL-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Description
BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY
Tag der Anmeldung: 3. November 1955 Bekanntgemacht am 22. November 1956Registration date: November 3, 1955. Advertised on November 22, 1956
DEUTSCHES PATENTAMTGERMAN PATENT OFFICE
B· 37755 IVbIB 37755 IVbI y^jC'*"y ^ jC '* "
Bekanntlich lassen sich Cyclooctandiol-ii, 2) und Cyclooctandiol^i, 4), wie man sie beispielsweise durch Spaltung von 1, 2-Epoxycyclooctan mit Säuren oder durch Epoxydation von Cycloocten mit Perameisensäure erhält (vgl. J. Am. Chem. Soc, Bd. 74, 1952, S. 5884 ff.), nicht durch fraktionierte Destillation trennen. Man hat daher die Zerlegung solcher Gemische in der Weise durchgeführt, daß man auf das Gemisch Aceton in Gegenwart von wasserfreiem Kupfersulfat einwirken ließ. Durch Destillation des Umsetzungsgemisches läßt sich dann das Cyclooctandiol-(i, 2) in Form des Isopropylidenketais nach dem Entfernen des überschüssigen Acetons leicht von dem nicht mit Aceton in Reaktion getretenen Cyclooctandiol-(i, 4) trennen. Zur Gewinnung des Cyclooctandiols-(i, 2) muß danin das Isopropylidenketal noch in bekannter Weise, z. B. durch Säurehydrolyse, zerlegt werden. Dieses Verfahren ist umständlich und für die Technik bedeutungslos. ,It is known that cyclooctanediol-ii, 2) and Cyclooctanediol ^ i, 4), as can be obtained, for example, by cleavage of 1,2-epoxycyclooctane with acids or obtained by epoxidation of cyclooctene with performic acid (cf. J. Am. Chem. Soc, Vol. 74, 1952, pp. 5884 ff.), Not by fractionated Separate distillation. One has therefore carried out the decomposition of such mixtures in such a way that acetone was allowed to act on the mixture in the presence of anhydrous copper sulfate. Through Distillation of the reaction mixture can then be the cyclooctanediol (i, 2) in the form of isopropylidene ketais after removing the excess acetone slightly from the cyclooctanediol- (i, 4) which did not react with acetone separate. In order to obtain the cyclooctanediol (i, 2), the isopropylidene ketal must then be known Way, e.g. B. by acid hydrolysis, are broken down. This procedure is cumbersome and for the Technology meaningless. ,
Es wurde nun gefunden, daß sich die Trennung von Cyclooctandiol-(i, 2) und Cyclooctandiol-(i, 4) in einfacher Weise durchführen läßt, wenn man die Gemische mit Äther extrahiert. Dabei geht nur das Cyclooctandiol - (1,2) in die Ätherauszüge und kann durch Abdampfen des Extraktionsmittels rein erhalten werden, während das Cyclooctandiol-(1, 4) ungelöst bleibt und sich kristallin abscheidet.It has now been found that the separation of cyclooctanediol (i, 2) and cyclooctanediol (i, 4) can be carried out in a simple manner if the mixtures are extracted with ether. There is only that Cyclooctanediol - (1,2) in the ether extracts and can by evaporating the extractant can be obtained pure, while the cyclooctanediol- (1, 4) remains undissolved and precipitates in crystalline form.
609 708/367609 708/367
B 37755 IVb/12οB 37755 IVb / 12ο
Vorteilhaft wendet man den Äther in wasserfreier Form an, jedoch erzielt man auch mit Äther, der etwa.. 5 bis 7,5 % Wasser enthält, noch gute Ergebnisse.It is advantageous to use the ether in anhydrous form, but also with ether, which contains about .. 5 to 7.5% water, still good results.
Will man besonders reine Cyclooctandiole erhalten, so kann man dies beim Cyclooctandiol-(i, 4) durch Umkristallisieren des Extraktionsrückstandes aus Essigsäureäthylester oder anderen Lösungsmitteln, wie Chloroform, Äthylenchlorid oder Eisessig erreichen, während man das Cyclooctandiol-(i, 2) durch Destillation unter vermindertem Druck als farbloses, dickflüssiges Öl rein erhält.If you want to get particularly pure cyclooctanediols, you can do this with the cyclooctanediol- (i, 4) by recrystallizing the extraction residue from ethyl acetate or other solvents, such as chloroform, ethylene chloride or glacial acetic acid, while the cyclooctanediol (i, 2) obtained pure as a colorless, viscous oil by distillation under reduced pressure.
Die in den Beispielen angegebenen Teile sind Gewichtsteile.The parts given in the examples are parts by weight.
200 Teile eines sirupartigen Gemisches von Cyclooctandiol-(1, 2) und Cyclooctandiol-(1, 4), das durch Umsetzen von Cycloocten mit Perameisen-200 parts of a syrupy mixture of cyclooctanediol (1, 2) and cyclooctanediol (1, 4), the by reacting cyclooctene with performic iron
ao säure erhalten wurde, werden mit 400 Teilen wasserfreiem Äther bei gewöhnlicher Temperatur digeriert, bis sich aus dem sirupartigen Gemisch Kristalle abscheiden. Zur Vervollständigung der Kristallabscheidung läßt man das Gemisch einige Zeit, in der Kälte stehen. Dann saugt man die Kristalle ab und wäscht den auf der Nutsche zurückgebliebenen Rückstand mit kaltem Äther nach. Man erhält 61 Teile Cyclooctandiol-(1, 4). Nach dem Umkristallisieren aus Essigsäureäthylester schmilzt das Diol bei 85 bis 870. Die ätherische Lösung wird vom Äther befreit und der Rückstand im Vakuum destilliert. Man erhalt 135 Teile Cyclo- < Λ octandiol-(i, 2) vom Siedepunkt 160 bis 1720 bei einem Druck von 1,5 mm Hg.ao acid was obtained, are digested with 400 parts of anhydrous ether at ordinary temperature until crystals separate from the syrupy mixture. To complete the separation of crystals, the mixture is left to stand in the cold for some time. The crystals are then filtered off with suction and the residue left on the suction filter is washed with cold ether. 61 parts of cyclooctanediol- (1,4) are obtained. After recrystallization from ethyl acetate, the diol melts at 85 to 87 ° . The ethereal solution is freed from ether and the residue is distilled in vacuo. 135 parts of cyclo- <Λ octanediol- (i, 2) with a boiling point of 160 to 172 0 at a pressure of 1.5 mm Hg are obtained.
Cyclooctandiol-(i, 2) ist leicht löslich in Wasser, Alkoholen, Aceton, Äther, Tetrahydrofuran, Pyridin, Eisessig, Dioxan, Essigester, Chloroform, Äthylenchlorid, Acetonitril, sehr schwer löslich bis unlöslich in Petroläther, Cyclohexan, Benzol, Toluol.Cyclooctanediol- (i, 2) is easily soluble in water, alcohols, acetone, ether, tetrahydrofuran, pyridine, Glacial acetic acid, dioxane, ethyl acetate, chloroform, ethylene chloride, acetonitrile, very sparingly soluble to insoluble in petroleum ether, cyclohexane, benzene, toluene.
Cyclooctendiol-(i, 4) ist in der Kälte leicht löslich in Wasser, Alkoholen, Aceton, Tetrahydrofuran, in der Wärme leicht und in der Kälte schwer löslich in Eisessig, Dioxan, Essigester, . Chloroform, Äthylenchlorid, Acetonitril, sehr schwer löslich in der Wärme und in der Kälte in Petroläther, Cyclohexan, Benzol, Toluol und Äther.Cyclooctenediol- (i, 4) is easily soluble in the cold in water, alcohols, acetone, tetrahydrofuran, light in the heat and heavy in the cold soluble in glacial acetic acid, dioxane, ethyl acetate,. Chloroform, ethylene chloride, acetonitrile, very heavy soluble in hot and cold in petroleum ether, cyclohexane, benzene, toluene and ether.
B e i s ρ i e 1 2B e i s ρ i e 1 2
140 Teile eines Gemisches von gleichen Teilen Cyclooctandiol-(1, 2) und Cyclooctandiol-^, 4) werden, wie in Beispiel 1 beschrieben, mit 100 Teilen wasserfreiem Äther extrahiert. Man erhält 68 Teile Cyclooctandiol-(1, 4) und 70 Teile Cyclooctandiol-(i, 2).140 parts of a mixture of equal parts Cyclooctanediol- (1, 2) and Cyclooctanediol- ^, 4) are, as described in Example 1, with 100 parts extracted from anhydrous ether. 68 parts of cyclooctanediol (1, 4) and 70 parts of cyclooctanediol (i, 2).
Claims (1)
Family
ID=
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