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DE1283838B - Process for the cyclooligomerization of 1,3-diolefins in the presence of a catalyst composed of carbon-oxide-free compounds of nickel and metal alkyls and triphenylphosphine - Google Patents

Process for the cyclooligomerization of 1,3-diolefins in the presence of a catalyst composed of carbon-oxide-free compounds of nickel and metal alkyls and triphenylphosphine

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Publication number
DE1283838B
DE1283838B DEST26895A DEST026895A DE1283838B DE 1283838 B DE1283838 B DE 1283838B DE ST26895 A DEST26895 A DE ST26895A DE ST026895 A DEST026895 A DE ST026895A DE 1283838 B DE1283838 B DE 1283838B
Authority
DE
Germany
Prior art keywords
nickel
triphenylphosphine
diolefins
cyclooligomerization
carbon
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
Application number
DEST26895A
Other languages
German (de)
Inventor
Dipl-Chem Dr Guenther
Mueller
Wilke
Dipl-Chem Dr Ernst Willi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Priority to DEST26895A priority Critical patent/DE1283838B/en
Publication of DE1283838B publication Critical patent/DE1283838B/en
Pending legal-status Critical Current

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Classifications

    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • 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
    • 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
    • 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
    • B01J2231/326—Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues
    • 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
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

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  • 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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Description

Gegenstand des Patentes 1 140 569 ist ein Verfahren zur katalytischen Di- bzw. Trimerisation von 1,3-Diolefinen, wie Isopren, Piperylen oder vorzugsweise Butadien, zu cyclischen Verbindungen bei normalem oder erhöhtem Druck und bei erhöhten Temperaturen 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, 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 Triphenyltert. Amine, Alkyl- oder Arylphosphine, insbesondere Triphenylphosphine, Alkyl- oder Arylphosphite, oder Verbindungen mit Kohlenstoff-dreifach-Bindungen in Frage. The subject of the patent 1 140 569 is a method for catalytic Dimerization or trimerization of 1,3-diolefins, 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 oxide-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, as electron donors here are compounds used, which can generally be characterized as Lewis bases and those with free Electron pairs on other atom groupings can be proportionate. In this Senses come ethers, especially cyclic ethers, tert. Amines, especially triphenyltert. Amines, alkyl or aryl phosphines, in particular triphenyl phosphines, alkyl or aryl phosphites, or compounds with carbon triple bonds in question.

Es wurde nun ein Verfahren zur Cyclooligomerisation von 1,3-Diolefinen in Gegenwart eines Katalysators aus kohlenoxydfreien Verbindungen des Nickels und Metallalkylen und Triphenylphosphin nach Patent 1 140 569 gefunden, bei welchem zur Herstellung von hauptsächlich Cyclooctadien-(1,5) enthaltenden Produkten in Gegenwart des zuvor isolierten Komplexes Ni[P(C6H5)3]4 oder C8H12NI[P(C6H5)2]2 gearbeitet wird. There has now been a process for the cyclooligomerization of 1,3-diolefins in the presence of a catalyst made from compounds of nickel and carbon free Metal alkyls and triphenylphosphine found in Patent 1,140,569, in which for the production of mainly cyclooctadiene (1,5) containing products in The presence of the previously isolated complex Ni [P (C6H5) 3] 4 or C8H12NI [P (C6H5) 2] 2 worked will.

Hierbei kann auch das 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). The butadiene can also be incorporated into the catalyst here and also act as a further electron donor (see »Angewandte Chemie», Vol. 75, (1963) pp. 10 to 20, especially p. 15).

Beispiel 1 Man löst 10 g Nickelacetylacetonat, 42 g Triphenylphosphin in 400 ccm absolutem - Äther und reduziert bei 0°C mit 16 ccm Äthoxydiäthylaluminium. Die entstehenden rotbraunen Kristalle werden isoliert. Example 1 10 g of nickel acetylacetonate and 42 g of triphenylphosphine are dissolved in 400 ccm of absolute ether and reduced at 0 ° C with 16 ccm of ethoxy diethylaluminum. The resulting red-brown crystals are isolated.

Man erhält 32 g = 80% der Theorie an Ni[P(C6H5)3]4. 32 g = 80% of theory of Ni [P (C6H5) 3] 4 are obtained.

Man löst 5, 75 g dieses Komplexes in 50 ccm absolutem Benzol und setzt 300 g Butadien bei 106°C in 1112 Stunden um. You dissolve 5, 75 g of this complex in 50 cc of absolute benzene and converts 300 g of butadiene at 106 ° C. in 1112 hours.

Das Butadien ist quantitativ umgesetzt Der Autoklavinhalt wird ausgefüllt durch Wasserdampfdestillation, von Katalysator und nicht flüchtigen Anteilen befreit. Das Destillat wird durch-Feinfraktionierung in die Komponenten getrennt. Die genaue Zusammensetzung des Wasserdampfdestillates wird durch gaschromatographische Analyse ermittelt.The butadiene has been converted quantitatively. The contents of the autoclave are filled freed from catalyst and non-volatile components by steam distillation. The distillate is separated into its components by fine fractionation. The exact The composition of the steam distillate is determined by gas chromatographic analysis determined.

Die nicht flüchtigen Anteile werden in Benzol gelöst, vom Katalysatorrückstand abgetrennt und nach dem Abdestillieren des Benzols ausgewogen. Man erhält 291 g = 970/o der Theorie mit 18,80/o Vinylcyclohexen 59, 3°/0 Cyclooctadien 10,0 % Cyclododecatrien-1,5,9 also insgesamt 88,1 01o cyclische Produkte und 3,90/, normale Cl2-Kohlenwasserstoffe und 8,0 01o nicht flüchtige Anteile.The non-volatile components are dissolved in benzene from the catalyst residue separated and weighed after distilling off the benzene. 291 g are obtained = 970 / o of theory with 18.80 / o vinylcyclohexene 59.3 ° / o cyclooctadiene 10.0% cyclododecatriene-1,5.9 so a total of 88.1 01o cyclic products and 3.90 /, normal Cl2 hydrocarbons and 8.0 01o non-volatile components.

Beispiel 2 Man löst 5 g Nickelacetylacetonat, 10,5 g Triphenylphosphin, 2,2 g Cyclooctadien in 150 ccm absolutem Äther und reduziert bei 0°C mit 8 ccm absolutem Äther und reduziert bei 0°C mit 8 com Äthoxydiäthylaluminium. Man erhält 7,6 g 50% der Theorie an C8H12Ni[P(C6H5)3]2 in Form rotbrauner Kristalle. Example 2 Dissolve 5 g of nickel acetylacetonate, 10.5 g of triphenylphosphine, 2.2 g cyclooctadiene in 150 ccm absolute ether and reduced at 0 ° C with 8 ccm absolute Ether and reduced at 0 ° C with 8 com Äthoxydiethylaluminium. 7.6 g of 50% are obtained the theory of C8H12Ni [P (C6H5) 3] 2 in the form of red-brown crystals.

Man arbeitet wie im Beispiel 1, verwendet jedoch 4 g bis-tri-Phenylphosphin-cyclooctadien-Nickel-0 in 50 ccm absolutem Benzol gelöst als Katalysator. Bei 100O C werden 200 g Butadien innerhalb einer Stunde umgesetzt. Es werden 200 g (100% der Theorie) Reaktionsprodukt mit 26,1 % Vinylcyclohexen, 62,20/0 Cyclooctadien, 7,6 % Cyclododecatrien, also insgesamt 95,9% cyclische Produkte und 4,1% normale Cl2-Kohlenwasserstoffe erhalten. The procedure is as in Example 1, but 4 g of bis-tri-phenylphosphine-cyclooctadiene-nickel-0 are used Dissolved in 50 cc of absolute benzene as a catalyst. At 100 ° C., 200 g of butadiene are produced implemented within an hour. There are 200 g (100% of theory) of reaction product with 26.1% vinylcyclohexene, 62.20 / 0 cyclooctadiene, 7.6% cyclododecatriene, i.e. a total of 95.9% cyclic products and 4.1% normal Cl2 hydrocarbons were obtained.

Claims (1)

Patentanspruch : Verfahren zur Cyclooligomerisation von 1, 3-Diolefinen in Gegenwart eines Katalysators aus kohlenoxydfreien Verbindungen des Nickels und Metallalkylen und Triphenylphosphin, nach Patent 1140569, dadurch gekennzeichnet, daß zur Herstellung von hauptsächlich Cyclooctadien-(1,5) enthaltenden Produkten in Gegenwart des zuvor isolierten Komplexes Ni [P (C6Hs) 3], oder C8H12Ni[P(C6H5)3]4 gearbeitet wird. Claim: Process for the cyclooligomerization of 1,3-diolefins in the presence of a catalyst made from compounds of nickel and carbon free Metal alkyls and triphenylphosphine, according to Patent 1140569, characterized in that that for the preparation of mainly cyclooctadiene (1,5) containing products in the presence of the previously isolated complex Ni [P (C6Hs) 3], or C8H12Ni [P (C6H5) 3] 4 is being worked on.
DEST26895A 1960-06-30 1960-06-30 Process for the cyclooligomerization of 1,3-diolefins in the presence of a catalyst composed of carbon-oxide-free compounds of nickel and metal alkyls and triphenylphosphine Pending DE1283838B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEST26895A DE1283838B (en) 1960-06-30 1960-06-30 Process for the cyclooligomerization of 1,3-diolefins in the presence of a catalyst composed of carbon-oxide-free compounds of nickel and metal alkyls and triphenylphosphine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEST26895A DE1283838B (en) 1960-06-30 1960-06-30 Process for the cyclooligomerization of 1,3-diolefins in the presence of a catalyst composed of carbon-oxide-free compounds of nickel and metal alkyls and triphenylphosphine

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DE1283838B true DE1283838B (en) 1968-11-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1643071B1 (en) * 1959-12-22 1972-05-31 Studiengesellschaft Kohle Mbh Process for the cyclodimerization of 1,3-diolefins

Citations (2)

* Cited by examiner, † Cited by third party
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)
DE1140569B (en) * 1959-12-22 1962-12-06 Studiengesellschaft Kohle Mbh Process for the catalytic dimerization or trimerization of 1,3-diolefins

Patent Citations (2)

* Cited by examiner, † Cited by third party
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)
DE1140569B (en) * 1959-12-22 1962-12-06 Studiengesellschaft Kohle Mbh Process for the catalytic dimerization or trimerization of 1,3-diolefins

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1643071B1 (en) * 1959-12-22 1972-05-31 Studiengesellschaft Kohle Mbh Process for the cyclodimerization of 1,3-diolefins

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