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DE1078108B - Process for the trimerization of 2,3-dimethylbutadiene- (1,3) to an open-chain trimer - Google Patents

Process for the trimerization of 2,3-dimethylbutadiene- (1,3) to an open-chain trimer

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Publication number
DE1078108B
DE1078108B DEST14119A DEST014119A DE1078108B DE 1078108 B DE1078108 B DE 1078108B DE ST14119 A DEST14119 A DE ST14119A DE ST014119 A DEST014119 A DE ST014119A DE 1078108 B DE1078108 B DE 1078108B
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Germany
Prior art keywords
dimethylbutadiene
trimerization
open
aluminum
halides
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Pending
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DEST14119A
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German (de)
Inventor
Dipl-Chem Dr Guenther Wilke
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Studiengesellschaft Kohle gGmbH
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Studiengesellschaft Kohle gGmbH
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Publication of DE1078108B publication Critical patent/DE1078108B/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/38Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes
    • C07C2/40Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of dienes or alkynes of conjugated dienes
    • C07C2/403Catalytic processes
    • C07C2/406Catalytic processes with hydrides or organic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06Halogens; Compounds thereof
    • C07C2527/132Compounds comprising a halogen and chromium, molybdenum, tungsten or polonium
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06Halogens; Compounds thereof
    • C07C2527/135Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
    • C07C2531/34Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of chromium, molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
    • C07C2531/38Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of titanium, zirconium or hafnium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Trimerisation von 2,3-Dimethylbutadien- ,3) zu einem offenkettigen Trimeren In den belgischen Patentschriften 555 180 und 564 175 werden Verfahren geschildert, nach denen Diolefine, wie Butadien, Isopren und Piperylen mit Hilfe von metallorganischen Mischkatalysatoren in ringförmige Kohlenwasserstoffe mit mindestens 8 Kohlenstoffatomen, d. h. in Cyclododecatriene-(1,5,9) verwandelt werden können. Die ringförmigen Verbindungen dienen als wichtige Ausgangsprodukte zur Gewinnung bifunktioneller Derivate des n-Dodecans, z B. Dodecan-1,12-disäure und des 12-Aminododecansäurelactams. Process for the trimerization of 2,3-dimethylbutadiene, 3) to one open-chain trimers In the Belgian patents 555 180 and 564 175 are Process described by which diolefins such as butadiene, isoprene and piperylene with the help of organometallic mixed catalysts into ring-shaped hydrocarbons with at least 8 carbon atoms, d. H. converted into cyclododecatriene- (1,5,9) can be. The ring-shaped connections serve as important starting products to obtain bifunctional derivatives of n-dodecane, e.g. dodecane-1,12-diacid and 12-aminododecanoic acid lactam.

Es wurde im weiteren Verlauf der Untersuchungen die überraschende Beobachtung gemacht, daß das 2,3-Dimethylbutadtien-(1,3) bei einer analogen B handlung mit den metallorganisehen Mischkatalysatoren kein ringförmiges Trimerisat liefert, daß vielmehr ein offenkettiges Trimerer in hohen Ausbeuten gebildet wird. It became the most surprising in the further course of the investigations Observation made that the 2,3-dimethylbutadtiene- (1,3) acted in an analogous manner with the organometallic mixed catalysts does not produce a ring-shaped trimer, that rather an open-chain trimer is formed in high yields.

Das Trimere entspricht der Summenformel Cls H30 und hat den Siedepunkt 1300 C bei 5 mm und den Brechungsindex »2Do = 1,4973. Bei der katalytischen Hydrierung unter Druck wird die Vierdoppelbindungen äquivalente Menge Wasserstoff aufgenommen, was die offenkettige Struktur beweist Die offenkettige Konstitution wird auch durch das IR-Spektrum bestätigt. Im Spektrum tritt bei 890 cm-' eine starke Bande auf, die der endständig verzweigten Doppelbindung zuzuordnen ist. The trimer corresponds to the molecular formula Cls H30 and has the boiling point 1300 C at 5 mm and the refractive index »2Do = 1.4973. In catalytic hydrogenation under pressure the four double bonds equivalent amount of hydrogen is absorbed, what the open-chain structure proves The open-chain constitution is also through the IR spectrum is confirmed. A strong band appears in the spectrum at 890 cm- ', which is to be assigned to the terminally branched double bond.

Es handelt sich bei dieser Trimerisation offenbar um einen völlig neuen Typ der Reaktionen von konugierten Diolefinen mit metallorganischen Mischkatalysatoren, denn es läßt sich zeigen, daß das trimere Dimethylbutadien nicht durch die übliche 1,2- bzw. 1,4-Addition von 3 Molekülen des Monomeren entstehen kann, da das Reaktionsprodukt neben zwei endständig verzweigten Doppelbindungen zwei mittelständige, und zwar konjugilerte Doppelbindungen aufweist. This trimerization is evidently a complete one new type of reactions of conjugated diolefins with organometallic mixed catalysts, because it can be shown that the trimeric dimethylbutadiene is not by the usual 1,2- or 1,4-addition of 3 molecules of the monomer can occur as the reaction product in addition to two terminally branched double bonds, two central ones, namely has conjugated double bonds.

Das Paar konjugierter Doppelbindungen läßt sich einmal im IR-Spektrum nachweisen, zum anderen gelingt es ohne Schwierigkeit, ein Molekül Maleinsäureanhydrid nach Diels-Alder zu addieren. Das Additionsprodukt entspricht der Summenformel C22 H32 03. The pair of conjugated double bonds can be seen once in the IR spectrum On the other hand, it is possible to detect a molecule of maleic anhydride without difficulty according to Diels-Alder to be added. The addition product corresponds to the empirical formula C22 H32 03.

Dem trimeren Dimethylbutadien kann folgende Konstitutionsformel zugrunde liegen: CHS CH3 CH3 CH3 CH3 CH3 1 1 H2C=C C-CH-C C=CH-C C=CH2 CH3 CH3 2,3,3,5,6,8,8,9-Octamethyldecatetraen- (1,4,6,9) oder CH3 CH3 CH3 CH3 CH3 CH3 H2C=C CH-CH2-CH=C C C = CHCH2CH C,,,CH2 2,3,6,7,10,1 1-Hexamethyldodecatetraen- (1,5,7,11) Als Katalysatoren zur Trimerisation des Dimethylbutadiens haben sich Mischungen von Halogeniden des Titans, vornehmlich Titantetrachlorid, und/oder Halogeniden bzw. Oxyhalogeniden des Chroms, vornehmlich Chromylchlorid, mit Aluminiumtrialkylen, Dialkyialuminiumhydriden oder/und Alkylaluminiumhalogeniden besonders bewährt. Dabei werden die Molverhältnisse von Ti : Al = 1: 3 bis 5 und Cr : Al = 1: 3 bis 5 bevorzugt.The trimeric dimethylbutadiene can be based on the following constitutional formula: CHS CH3 CH3 CH3 CH3 CH3 1 1 H2C = C C-CH-C C = CH-C C = CH2 CH3 CH3 2,3,3,5,6,8,8,9-octamethyldecatetraene (1,4,6,9) or CH3 CH3 CH3 CH3 CH3 CH3 H2C = C CH-CH2-CH = CCC = CHCH2CH C ,,, CH2 2,3,6,7,10,1 1-hexamethyldodecatetraene (1,5,7,11) Mixtures of halides of titanium, primarily titanium tetrachloride, and / or halides or oxyhalides of chromium, primarily chromyl chloride, with aluminum trialkyls, dialkyl aluminum hydrides and / or alkyl aluminum halides have proven particularly useful as catalysts for the trimerization of dimethylbutadiene. The molar ratios of Ti: Al = 1: 3 to 5 and Cr: Al = 1: 3 to 5 are preferred.

Man arbeitet mit Vorteil in einem indifferenten Lösungsmittel, wie einem aliphatischen bzw. aromatischen bzw. halogenierten Kohlenwasserstoff, bevorzugt aber in Benzol. It is advantageous to work in an inert solvent, such as an aliphatic or aromatic or halogenated hydrocarbon, preferably but in benzene.

Als Reaktionstemperatur kommen Temperaturen von 0 bis 1000 C in Frage, bevorzugt zwischen 20 und 500 C. Temperatures from 0 to 1000 C come into consideration as the reaction temperature, preferably between 20 and 500 C.

Die Ausbeuten an Trimeren betragen 70 bis 90§/o. The yields of trimers are 70 to 90%.

Das trimere Dimethylbutadien dient als wertvolles Ausgangsprodukt für organische Synthesen, besonders aber zur Darstellung stark methylverzweigter a,co-bifunktioneller Verbindungen, die für die Gewinnung von Kunststoffen, wie Polyester und Polyamide, Bedeutung besitzen. The trimeric dimethylbutadiene serves as a valuable starting product for organic syntheses, but especially for the preparation of highly methyl-branched ones a, co-bifunctional compounds used in the production of plastics such as polyester and polyamides, are important.

Beispiel In 1 1 abs. Benzol werden 4,8 cm3 (0,059 Mol) Chromylchlorid gelöst. Unter Rühren tropft man zu dieser Lösung langsam 33 cm3 (0,24 Mol) Aluminiumtriäthyl, wobei sich die Mischung erwärmt und ein Niederschlag ausfällt. Man rührt t/2 Stunde weiter, erwärmt auf 500 C und tropft dann 323 g Dimethylbutadien im Verlaufe einer Stunde ein. Die Mischung wird 24 Stunden bei 500 C kräftig gerührt. Danach zersetzt man den Ansatz mit der dem Aluminium äquivalenten Menge Methanol und verdünnter Schwefelsäure. Die organische Schicht wird mit Wasser gewaschen, mit Ca C12 getrocknet. Bei der Destillation erhält man 220g des Trimeren, das bei Kp.5 = 1300 C übergeht, n2,0 = 1,4973. Ausbeute 820/o, bezogen auf umgesetztes Dimethylbutadien. Der Destillationsrückstand besteht zum größten Teil aus einem Tetrameren des Dimethylbutadiens. Example In 1 1 abs. Benzene becomes 4.8 cc (0.059 mol) of chromyl chloride solved. 33 cm3 (0.24 mol) of aluminum triethyl are slowly added dropwise to this solution while stirring, the mixture heats up and a precipitate separates out. The mixture is stirred for t / 2 hour further, heated to 500 ° C. and then 323 g of dimethylbutadiene are added dropwise in the course of a Hour one. The mixture is stirred vigorously at 500 ° C. for 24 hours. After that it decomposes one the approach with the aluminum equivalent amount of methanol and diluted Sulfuric acid. The organic layer is washed with water, dried with Ca C12. In the Distillation gives 220g of the trimer, which passes over at bp 5 = 1300 C, n2.0 = 1.4973. Yield 820 / o, based on converted dimethylbutadiene. The still residue consists for the most part of a tetramer of dimethylbutadiene.

Claims (4)

PATENTANSPRUCHE 1. Verfahren zur Trimerisation von 2,3-Dimethylbutadien-(1,3) zu einem offenkettigen Trimeren, dadurch gekennzeichnet, daß 2,3-Dimethylbutadien-(1,3) in Gegenwart von indifferenten Lösungsmitteln der Einwirkung von Katalysatoren unterworfen wird, die in bekannter Weise aus Mischungen von Halogeniden des Titans und bzw. oder Halogeniden bzw. Oxyhalogeniden des Chroms mit Aluminiumtrialkylen, Dialkylaluminiumhydriden und/oder Alkylaluminiumhalogeniden erhalten werden. PATENT CLAIMS 1. Process for the trimerization of 2,3-dimethylbutadiene- (1,3) to an open-chain trimer, characterized in that 2,3-dimethylbutadiene- (1,3) subjected to the action of catalysts in the presence of inert solvents which is made in a known manner from mixtures of halides of titanium and or or halides or oxyhalides of chromium with aluminum trialkyls, dialkyl aluminum hydrides and / or alkyl aluminum halides. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Katalysatormischungen verwendet, in denen das Molverhältnis von Titan-bzw. Chromverbindungen zu Aluminiumverbindungen 1:3 bis 5 beträgt. 2. The method according to claim 1, characterized in that one catalyst mixtures used, in which the molar ratio of titanium or. Chromium compounds to aluminum compounds 1: 3 to 5. 3. Verfahren nach Ansprüchen 1 und 2, dadurch gekennzeichnet, daß man aliphatische, aromatische oder halogenierte Kohlenwasserstoffe, voszugsweise Benzol, als Lösungsmittel verwendet. 3. Process according to Claims 1 and 2, characterized in that one aliphatic, aromatic or halogenated hydrocarbons, preferably Benzene, used as a solvent. 4. Verfahren nach Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß man die Reaktion bei Temperaturen von 0 bis 1000 C, vorzugsweise von 20 bis 500 C, durchführt. 4. Process according to Claims 1 to 3, characterized in that the reaction is carried out at temperatures from 0 to 1000.degree. C., preferably from 20 to 500.degree C.
DEST14119A 1957-09-02 1958-08-12 Process for the trimerization of 2,3-dimethylbutadiene- (1,3) to an open-chain trimer Pending DE1078108B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1212064B (en) * 1961-06-07 1966-03-10 Basf Ag Process for the catalytic production of liquid, predominantly open-chain oligomers from 1,3-dienes
DE1216286B (en) * 1961-09-01 1966-05-12 Basf Ag Process for the catalytic production of liquid, predominantly open-chain oligomers from 1,3-dienes
US4668838A (en) * 1986-03-14 1987-05-26 Union Carbide Corporation Process for trimerization
US4853356A (en) * 1986-03-14 1989-08-01 Union Carbide Corporation Process for trimerization

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1212064B (en) * 1961-06-07 1966-03-10 Basf Ag Process for the catalytic production of liquid, predominantly open-chain oligomers from 1,3-dienes
DE1216286B (en) * 1961-09-01 1966-05-12 Basf Ag Process for the catalytic production of liquid, predominantly open-chain oligomers from 1,3-dienes
US4668838A (en) * 1986-03-14 1987-05-26 Union Carbide Corporation Process for trimerization
US4853356A (en) * 1986-03-14 1989-08-01 Union Carbide Corporation Process for trimerization

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