DE1283836B - Process for the preparation of products mainly containing cyclododecatriene (1,5,9) by cyclooligomerization of 1,3-diolefins - Google Patents
Process for the preparation of products mainly containing cyclododecatriene (1,5,9) by cyclooligomerization of 1,3-diolefinsInfo
- Publication number
- DE1283836B DE1283836B DEST23133A DEST023133A DE1283836B DE 1283836 B DE1283836 B DE 1283836B DE ST23133 A DEST23133 A DE ST23133A DE ST023133 A DEST023133 A DE ST023133A DE 1283836 B DE1283836 B DE 1283836B
- Authority
- DE
- Germany
- Prior art keywords
- diolefins
- compounds
- cyclooligomerization
- cyclododecatriene
- 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
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052987 metal hydride Inorganic materials 0.000 claims description 6
- 150000004681 metal hydrides Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 4
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 24
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 3
- -1 aryl phosphites Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- HOMQMIYUSVQSHM-UHFFFAOYSA-N cycloocta-1,3-diene;nickel Chemical compound [Ni].C1CCC=CC=CC1.C1CCC=CC=CC1 HOMQMIYUSVQSHM-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical class O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
- C07C2/44—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion of conjugated dienes only
- C07C2/46—Catalytic processes
- C07C2/465—Catalytic processes with hydrides or organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/324—Cyclisations via conversion of C-C multiple to single or less multiple bonds, e.g. cycloadditions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Gegenstand des Patentes 1 140 569 ist ein Verfahren zur katalytischen Di- bzw. Trimerisation von 1,3-uiolefinen, wie Isopren, Piperylen oder vorzugsweise Butadien, zu cyclischen Verbindungen bei normalem oder erhöhtem Druck und bei erhöhten Temparaturen in Gegenwart von Katalysatoren, die durch Mischen von kohlenoxydfreien Verbindungen des Nickels mit metallorganischen Verbindungen, wie Metallalkylen, Metallarylen, Grignard-Verbindungen, oder mit Metallhydriden oder mit Metallhydridkomplexen und Elektronendonatoren entstehen. The subject of the patent 1 140 569 is a method for catalytic Dimerization or trimerization of 1,3-uiolefins, such as isoprene, piperylene or preferably Butadiene, to cyclic compounds at normal or elevated pressure and at elevated Temperatures in the presence of catalysts obtained by mixing carbon monoxide-free Compounds of nickel with organometallic compounds, such as metal alkyls, Metal aryls, Grignard compounds, or with metal hydrides or with metal hydride complexes and electron donors arise.
Als Elektronendonatoren werden hierbei Verbindungen eingesetzt, die sich allgemein als Lewis-Basen kennzeichnen lassen und die mit freien Elektronenpaaren an anderen Atomgruppierungen anteilig werden können. In diesem Sinne kommen Äther, insbesondere cyclische Äther, tert. Amine, insbesondere cyclische tert. Amine, Alkyl- oder Arylphosphine, insbesondere Triphenylphosphine, Alkyl- oder Arylphosphite, oder Verbindungen mit Kohlenstoff-dreifach-Bindungen in Frage. The electron donors used here are compounds which can generally be identified as Lewis bases and those with lone pairs of electrons can share in other atom groupings. In this sense ethers come especially cyclic ethers, tert. Amines, especially cyclic tert. Amines, alkyl or arylphosphines, especially triphenylphosphines, alkyl or aryl phosphites, or compounds with carbon triple bonds in question.
Es wurde nun gefunden, daß hauptsächlich Cyclododekatrien-(1,5,9) enthaltende Produkte durch Cyclooligomerisation von 1,3-Diolefinen in Gegenwart von Katalysatoren, die durch Mischen von kohlenoxydfreien Verbindungen des Nickels mit halogenfreien metallorganischen Verbindungen oder Metallhydriden oder Metallhydridkomplex-Verbindungen und Elektronendonatoren entstehen, nach Patent 1 140 569, hergestellt werden können, wenn man Katalysatoren verwendet, die unter Zusatz von Cyclododecen oder von Cyclooktadien-1,5 als Elektronendonatoren hergestellt worden sind. It has now been found that mainly cyclododecatriene (1,5,9) containing products by cyclooligomerization of 1,3-diolefins in the presence of catalysts made by mixing carbon-free compounds of nickel with halogen-free organometallic compounds or metal hydrides or metal hydride complex compounds and electron donors can be produced according to patent 1 140 569, when using catalysts which, with the addition of cyclododecene or of cyclooctadiene-1,5 as electron donors.
Hierbei kann auch Butadien in den Katalysator eingebaut werden und ebenso als weiterer Elektronendonator wirken (s. » Angewandte Chemie«, Bd. 75 (1963), S. 10 bis 20, insbesondere S. 15). Here, butadiene can also be incorporated into the catalyst and also act as a further electron donor (see "Angewandte Chemie", Vol. 75 (1963), P. 10 to 20, especially p. 15).
Vorzugsweise werden solche Verbindungen des Nickels zur Herstellung der Katalysatoren verwendet, in denen die Metallatome an organische Reste gebunden sind, wie Acetylacetonate, Acetatessigonolate, Alkoholate, Salze schwacher organischer Säuren oder Dimethylglyoxim-Verbindungen. Such compounds of nickel are preferably used for production of catalysts used in which the metal atoms are bound to organic residues are like acetylacetonate, acetate essigonolate, alcoholates, salts of weak organic Acids or dimethylglyoxime compounds.
Nach einer Ausführungsform der Erfindung, die mit dem Hauptpatent gemeinsam ist, werden die Katalysatoren nach ihrer Herstellung ohne Isolierung aus dem zur Herstellung angewandten Lösungsmittel verwendet. Es hat sich jedoch gezeigt, daß es gegebenenfalls auch von Vorteil sein kann, die Katalysatoren zunächst in fester, vorzugsweise kristalliner Form zu isolieren und sie zu einem späteren Zeitpunkt wieder in Lösung zu bringen und für die Herstellung von cyclischen Trimeren von 1,3-Diolefinen einzusetzen. Als Lösungsmittel werden beispielsweise aliphatische, aromatische oder halogenisierte Kohlenwasserstoffe verwendet. Man arbeitet bei Normaldruck oder geringem Überdruck von beispielsweise 1 bis 20 atü und bei Temperaturen von 20 bis 150° C. According to one embodiment of the invention, which with the main patent common, the catalysts are made after their preparation without isolation the solvent used for the production. However, it has been shown that it may also be advantageous to first run the catalysts in solid, preferably crystalline form and isolate them at a later date to be brought back into solution and for the preparation of cyclic trimers of Use 1,3-diolefins. Aliphatic, aromatic or halogenated hydrocarbons are used. One works at normal pressure or a slight overpressure of, for example, 1 to 20 atmospheres and at temperatures of 20 to 150 ° C.
Beispiel 1 1 g Nickelacetylacetonat wird zusammen mit 4 Mol Cyclododecen je Mol Nickel in 60ccm absolutem Benzol in der Wärme gelöst. Die Mischung wird mit Eiswasser gekühlt und langsam mit 35,5cm einer benzolischen Lösung von Äthoxy-dieäthyl-aluminium (422 mg/ccm) versetzt. Es entsteht eine rotbraune Lösung, die man unter Luftausschluß in einen mit einer magnetischen Rührvorrichtung ausgerüsteten 2-Liter-V4A-Autoklay einführt; zu der Mischung werden 125 g flüssiges Butadien aufgepreßt. Example 1 1 g of nickel acetylacetonate is used together with 4 moles of cyclododecene per mole of nickel dissolved in 60ccm of absolute benzene in the heat. The mixture is made with Ice water and cooled slowly with 35.5 cm of a benzene solution of ethoxy-di-ethyl-aluminum (422 mg / ccm) added. The result is a red-brown solution, which can be treated with the exclusion of air into one equipped with a magnetic stirrer 2 liter V4A autoklay introduces; 125 g of liquid butadiene are injected into the mixture.
Der Autoklav wird auf 80"C aufgeheizt und der Inhalt so lange gerührt, bis der Druck auf etwa 2 at gefallen ist. Dann werden weitere 125 g Butadien aufgepreßt. Nach insgesamt 2 Stunden ist die Reaktion beendet. Das Butadien ist quantitativ umgesetzt. Der Autoklavinhalt wird ausgefüllt, durch Wasserdampfdestillation vom Katalysator und nicht flüchtigen Anteilen befreit. Das Destillat wird durch Feinfraktionierung in die Komponenten getrennt. Die genaue Zusammensetzung des Wasserdampfdestillats wird durch gaschromatographische Analyse ermittelt. Die nicht flüchtigen Anteile werden in Benzol gelöst, vomKatalysatorrückstand abgetrennt und nach dem Abdestillieren des Benzols ausgewogen. Der Umsatz beträgt genau 92,30/0. Davon sind 4,6 0/o 4-Vinylcyclohexen 3,50/0 Cyclooktadien-(1,5) 78, 0°/o Cyclododekatrien-(1,5,9), insgesamt 86,1 °/o cyclische Produkte und 13,9 01o normale Cl2-Kohlenwasserstoffe. The autoclave is heated to 80 "C and the contents are stirred for so long until the pressure has dropped to about 2 at. Then a further 125 g of butadiene are pressed in. The reaction has ended after a total of 2 hours. The butadiene is quantitative implemented. The contents of the autoclave are filled out by steam distillation Catalyst and non-volatile components exempt. The distillate is made by fine fractionation separated into the components. The exact composition of the steam distillate is determined by gas chromatographic analysis. The non-volatile components are dissolved in benzene, separated from the catalyst residue and after distilling off of benzene balanced. The conversion is exactly 92.30 / 0. 4.6% of this is 4-vinylcyclohexene 3.50 / 0 cyclooctadiene- (1.5) 78.0% cyclododecatriene- (1.5.9), total 86.1% cyclic products and 13.9 01o normal Cl2 hydrocarbons.
Beispiel 2 100 g Nickel-acetylacetonat und 100 g Cyclooktadie(1,5) werden in 1 1 absolutem Benzol gelöst. Man reduziert bei 0 bis 5"C im Verlauf von 2 Stunden mit 115 g Monoäthoxydiäthylaluminium. Die Mischung wird 15 Stunden bei dieser Temperatur gerührt. Example 2 100 g of nickel acetylacetonate and 100 g of cyclooctadiene (1.5) are dissolved in 1 liter of absolute benzene. One reduces at 0 to 5 "C in the course of 2 hours with 115 g of monoethoxydiethylaluminum. The mixture will last for 15 hours stirred at this temperature.
Man erhält 100 g = 93, 5°/0 Bis-Cyclooktadien-Nickel-(O) = (Cl8Hl2) 2Ni-(O) in Form von schönen gelben Kristallen. 7 g des hergestellten Bis-Cyclooktadien-Nickel-(O)-Katalysators werden in 100 ccm absolutem Benzol gelöst, und 200 g Butadien werden innerhalb von 12 Stunden bei 100"C zur Reaktion gebracht. Durch Wasserdampfdestillation und anschließende Feinfraktionierung werden die flüchtigen Bestandteile abgetrennt, Die nicht flüchtigen Anteile werden in Benzol gelöst, vom Katalysatorrückstand abgetrennt und nach dem Abdestillieren des Benzols ausgewogen. 100 g = 93.5 ° / 0 bis-cyclooctadiene-nickel- (O) = (Cl8Hl2) are obtained 2Ni- (O) in the form of beautiful yellow crystals. 7 g of the bis-cyclooctadiene-nickel (O) catalyst prepared are dissolved in 100 cc of absolute benzene, and 200 g of butadiene are within Brought to reaction for 12 hours at 100 ° C. By steam distillation and then Fine fractionation separates the volatile components, the non-volatile Fractions are dissolved in benzene, separated from the catalyst residue and after Distilling off the benzene balanced.
Man erhält 94 g = 47,20/0 der Theorie eines Reaktionsproduktes, das 8,50/0 Vinylcyclohexen 17,40/0 Cyclooktadien 66,30/0 Cyclododekatrien, also insgesamt 92, 2°/o cyclische Produkte, 4,10/0 offenkettige C8-Kohlenwasserstoffe und 3,70/0 offenkettige Cl2-Kohlenwasserstoffe enthält. 94 g = 47.20 / 0 of the theory of a reaction product are obtained which 8.50 / 0 vinylcyclohexene 17.40 / 0 cyclooctadiene 66.30 / 0 cyclododecatriene, so in total 92.2% cyclic products, 4.10 / 0 open-chain C8 hydrocarbons and 3.70 / 0 Contains open-chain Cl2 hydrocarbons.
Beispiel 3 40 g des gemäß Beispiel 2 hergestellten Bis-Cyclooktadien-(1,5)-Nickel-(O) werden mit 400 ccm absolutem Benzol versetzt. Die Mischung sättigt man bei Normaldruck und unter Kühlung mit Butadien. Example 3 40 g of the bis-cyclooctadiene (1,5) -nickel (O) prepared according to Example 2 400 ccm of absolute benzene are added. The mixture is saturated at normal pressure and with cooling with butadiene.
Man erhält eine klare rotbraune Lösung, die man bei 20"C stehenläßt. Nach 24 Stunden sättigt man erneut mit Butadien. Ebenso nach weiteren 24 Stunden. Insgesamt werden 370 g Butadien aufgenommen. Nach 72 Stunden arbeitet man die Reaktionsmischung auf, indem man alle leicht flüchtigen Anteile in eine gekühlte Falle absaugt und höhersiedende Produkte im Hochvakuum abdestilliert. Man erhält neben Benzol 365 g Destillat, das sich laut gaschromatographischer Analyse aus 68 g = 18,6 °/o Butadien 35 g = 9,60/0 Cyclooktadien-(1,5) (davon 31 gaus dem angesetzten Komplex) 262 g = 71,80/0 Cyclododekatrien-(1,5,9) zusammensetzt.A clear red-brown solution is obtained, which is left to stand at 20 ° C. After 24 hours, it is again saturated with butadiene. Likewise after a further 24 hours. A total of 370 g of butadiene are absorbed. The reaction mixture is worked after 72 hours by sucking off all volatile components in a cooled trap and higher-boiling products distilled off in a high vacuum. In addition to benzene, 365 is obtained g of distillate, which, according to gas chromatographic analysis, consists of 68 g = 18.6% butadiene 35 g = 9.60 / 0 cyclooctadiene (1.5) (of which 31 g from the prepared complex) 262 g = 71.80 / 0 cyclododecatriene (1,5,9) composed.
Als Rückstand erhält man 42 g eines neuen Komplexes, der mit weiterem Butadien umgesetzt, wiederum Cyclododekatrien liefert. Bei einem Umsatz von etwa 80°/o wurden demnach 870/, des Butadiens in Cyclododekatrien, 1,5 5°/o in andere cyclische Produkte verwandelt, während 33,5 g = 11,50/, in dem neuen Komplex gefunden wurden. The residue obtained is 42 g of a new complex, which with further Butadiene implemented, in turn provides cyclododecatriene. With a turnover of about 80 per cent was accordingly 870 per cent, of the butadiene in cyclododecatriene, 1.5 5 per cent in others cyclic products transformed, while 33.5 g = 11.50 /, found in the new complex became.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEST23133A DE1283836B (en) | 1959-12-22 | 1961-02-01 | Process for the preparation of products mainly containing cyclododecatriene (1,5,9) by cyclooligomerization of 1,3-diolefins |
| DE19611643071 DE1643071B1 (en) | 1959-12-22 | 1961-06-30 | Process for the cyclodimerization of 1,3-diolefins |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEST15930A DE1140569B (en) | 1959-12-22 | 1959-12-22 | Process for the catalytic dimerization or trimerization of 1,3-diolefins |
| DEST23133A DE1283836B (en) | 1959-12-22 | 1961-02-01 | Process for the preparation of products mainly containing cyclododecatriene (1,5,9) by cyclooligomerization of 1,3-diolefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1283836B true DE1283836B (en) | 1968-11-28 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEST23133A Pending DE1283836B (en) | 1959-12-22 | 1961-02-01 | Process for the preparation of products mainly containing cyclododecatriene (1,5,9) by cyclooligomerization of 1,3-diolefins |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1283836B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1069098A1 (en) * | 1999-07-13 | 2001-01-17 | Degussa-Hüls Aktiengesellschaft | Process for the synthesis of cyclododecatrienes with recycling of the catalyst |
| US6407304B2 (en) | 2000-02-03 | 2002-06-18 | Degussa Ag | Process for the isolation of high boilers from the cyclooligomerization of 1,3-butadiene |
| WO2010086313A1 (en) | 2009-01-28 | 2010-08-05 | Basf Se | Method for isolating dodecatrienal and use thereof as a flavouring |
| WO2010086314A1 (en) | 2009-01-28 | 2010-08-05 | Basf Se | Method for producing pure cyclododecanone |
| WO2013186238A1 (en) | 2012-06-13 | 2013-12-19 | Basf Se | Method for producing macrocyclic ketones |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1086226B (en) * | 1959-03-10 | 1960-08-04 | Studiengesellschaft Kohle Mbh | Process for the preparation of cyclododecatriene (1, 5, 9) |
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1961
- 1961-02-01 DE DEST23133A patent/DE1283836B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1086226B (en) * | 1959-03-10 | 1960-08-04 | Studiengesellschaft Kohle Mbh | Process for the preparation of cyclododecatriene (1, 5, 9) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1069098A1 (en) * | 1999-07-13 | 2001-01-17 | Degussa-Hüls Aktiengesellschaft | Process for the synthesis of cyclododecatrienes with recycling of the catalyst |
| US6403851B1 (en) | 1999-07-13 | 2002-06-11 | Degussa Ag | Process for preparing cyclododecatrienes with recycling of the catalyst |
| US6407304B2 (en) | 2000-02-03 | 2002-06-18 | Degussa Ag | Process for the isolation of high boilers from the cyclooligomerization of 1,3-butadiene |
| WO2010086313A1 (en) | 2009-01-28 | 2010-08-05 | Basf Se | Method for isolating dodecatrienal and use thereof as a flavouring |
| WO2010086314A1 (en) | 2009-01-28 | 2010-08-05 | Basf Se | Method for producing pure cyclododecanone |
| US8188320B2 (en) | 2009-01-28 | 2012-05-29 | Basf Se | Process for preparing pure cyclododecanone |
| WO2013186238A1 (en) | 2012-06-13 | 2013-12-19 | Basf Se | Method for producing macrocyclic ketones |
| US8940940B2 (en) | 2012-06-13 | 2015-01-27 | Basf Se | Process for preparing macrocyclic ketones |
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