US3317620A - Cis, cis-cyclodecadiene-(1, 6) and its manufacture - Google Patents

Cis, cis-cyclodecadiene-(1, 6) and its manufacture Download PDF

Info

Publication number
US3317620A
US3317620A US358457A US35845764A US3317620A US 3317620 A US3317620 A US 3317620A US 358457 A US358457 A US 358457A US 35845764 A US35845764 A US 35845764A US 3317620 A US3317620 A US 3317620A
Authority
US
United States
Prior art keywords
cis
cyclodecadiene
grams
trans
process according
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.)
Expired - Lifetime
Application number
US358457A
Other languages
English (en)
Inventor
Wilke Gunther
Heimbach Paul
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
Application granted granted Critical
Publication of US3317620A publication Critical patent/US3317620A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
    • C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
    • C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/21—Alkatrienes; Alkatetraenes; Other alkapolyenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/271—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a nine- to ten- membered 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
    • C07C2/04—Preparation 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25—Migration of carbon-to-carbon double bonds
    • C07C5/2506—Catalytic processes
    • C07C5/2556—Catalytic processes with metals
    • 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
    • C07C2531/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

  • the present invention thus relates to cis, cis-cyclodecadime-(1,6) and to the manufacture of this hydrocarbon by isomerizing trans, cis-cyclodecadiene-(1,5) in the presence of catalytic quantities of active metals of Group VIII of the Periodic System.
  • Isomerization can conveniently be effected at temperatures of 0100 C. and as active catalysts there may be named by way of example Raney metals or noble metals separated under hydrogenation conditions, such as palladium which has previously been named or platinum.
  • the metals are obtained in active form by reducing the transition metal compounds with the aid of organo-metallic compounds of elements of Main Groups I to III of the Periodic System or of their hydrides or rather of their complex hydrides or even with these finely divided metals themselves.
  • a further possibility lies in decomposing the labile olefineor cis-cyclodecadiene-( 1,6) of acetylene vr-complexes of the transition metals either by heat or through reduction of ligands. In this manner for instance bis-cyclooctadiene-(1,5) nickel yields with hydrogen, cyclo-octane and highly active nickel and bis- 1r-allyl-palladium propane and palladium.
  • the process of the present invention can be carried out in presence of solvents, as for example, hexane, cyclohexane, benzol, ether or also alcohols when Raney metals are employed as catalysts.
  • solvents as for example, hexane, cyclohexane, benzol, ether or also alcohols when Raney metals are employed as catalysts.
  • the thermally unstable trans, cis-cyclodecadiene-(1,5) obtainable from butadiene and ethylene is converted to a stable isomer. It is recommended that the reaction product of the aforementioned process, containing cyclodecadiene-(1,5) is first caused to undergo isomerization, and thereafter the IO-ring component isolated in the form of the new stable isomer, for example by distillation. The cis, cis-cyclodecadiene-( 1,6) is then available for further reactions which call for higher temperatures.
  • FIG. 1 illustrates the LR spectra of cis-trans-cyclodecadiene-(1,5)
  • FIG. 2 illustrates the I-R spectra of cis, cis-cyclodecadiene-(1,6
  • Example 1 1 gram of nickel (II) -acetylacetonate is reacted with 1 gram of diethyl aluminum ethoxide.
  • the metallic nickel in highly active form thus obtained is' employed to isomerize 10 grams cis, trans-cyclodecadiene-(1,5). After working up there is obtained 3.9 grams (39%) divinylcyclohexane and 6.1 grams (61%) cis, cis-cyclodecadiene- (1,6).
  • Example 2 1 gram cobalt (lII)-acetylacetonate, 1.1 gram diethyl aluminum ethoxide and 10 grams of cis, trans-cyclodecadiene-(l,5) are used for the reaction. After working up there is obtained 1.6 grams (16%) divinylcyclohexane, 1.1 grams (11%) of an unidentified C -hydrocarbon, 6.6 grams (66%) cis,cis-cyclodecadiene-(1,6) and 0.7 grams (7%) of an unidentified C -hydrocarbon.
  • Example 3 1 gram iron (III) acetylacetonate, 1.1 gram diethylaluminum ethoxide and 10 grams cis, trans-cyclodecadicue-(1,5 are used for reaction. After working up there is obtained 3.7 grams (37%) divinylcyclohexane, 1.0 grams (10%) of an unidentified C -hydrocarbon, 4.8 grams (48%) cis, cis-cyclodecadiene-(1,6), and 0.5 grams (5%) of an unknown C -hydrocarbon.
  • Example 4 0.5 grams palladium (II) acetylacetonate, 0.4 grams diethylaluminum ethoxide and 10 grams cis, trans-cyclo- J decadiene-(1,5) are used for reaction. After working up there is obtained 1.0 grams divinylcyclohexane and 9.0 grams (90%) of cis, cis-cyclodecadiene-(1,6).
  • Example 5 2 grams Raney nickel are heated with grams cis, trans-cyclodecadiene-(1,5) for two days at 50 C. while stirring. Apart from 5.7 grams of unreacted cis, transproduct there can be isolated 9.3 grams (62%) cis, ciscyclodecadiene-( 1,6).
  • said metal catalyst is obtained by reducing a transition metal with the aid of an organo-met-allic compound of an element of main Group I and III, its hydride or its complex hydride.
  • Process according to claim 5 which comprises effecting said contacting in the presence of a solvent selected from the group consisting of ethers, aliphatic, cycloaliphatic, and aromatic hydrocarbon liquid in the reaction.
  • catalyst is metallic palladium obtained by reduction of palladium- (lI)-acetylacetonate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (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)
US358457A 1963-04-10 1964-04-09 Cis, cis-cyclodecadiene-(1, 6) and its manufacture Expired - Lifetime US3317620A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEST20502A DE1230023B (de) 1963-04-10 1963-04-10 Verfahren zur Herstellung von cis, cis-Cyclodecadien-(1, 6)

Publications (1)

Publication Number Publication Date
US3317620A true US3317620A (en) 1967-05-02

Family

ID=7458598

Family Applications (1)

Application Number Title Priority Date Filing Date
US358457A Expired - Lifetime US3317620A (en) 1963-04-10 1964-04-09 Cis, cis-cyclodecadiene-(1, 6) and its manufacture

Country Status (6)

Country Link
US (1) US3317620A (enExample)
BE (1) BE646244A (enExample)
CH (1) CH446312A (enExample)
DE (2) DE1230023B (enExample)
GB (1) GB1022875A (enExample)
NL (1) NL139294B (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3407238A (en) * 1965-09-13 1968-10-22 Montedison Spa Process for the preparation of cyclododecadienes
US5076460A (en) * 1991-02-13 1991-12-31 Hussell Donald E Three ball snap hinge box

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2391596B1 (de) 2009-01-28 2018-06-20 Basf Se Verfahren zur isolierung von dodecatrienal und seine verwendung als aromastoff
EP2391597B1 (de) 2009-01-28 2018-08-22 Basf Se Verfahren zur herstellung von reinem cyclododecanon
DE102014212602A1 (de) 2013-07-02 2015-01-08 Basf Se Verfahren zur Herstellung eines Ketons aus einem Olefin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3407238A (en) * 1965-09-13 1968-10-22 Montedison Spa Process for the preparation of cyclododecadienes
US5076460A (en) * 1991-02-13 1991-12-31 Hussell Donald E Three ball snap hinge box

Also Published As

Publication number Publication date
DE1230023B (de) 1966-12-08
BE646244A (enExample) 1900-01-01
NL6403826A (enExample) 1964-10-12
DE1288087B (de) 1969-01-30
CH446312A (de) 1967-11-15
NL139294B (nl) 1973-07-16
GB1022875A (en) 1966-03-16

Similar Documents

Publication Publication Date Title
Frey The gas phase pyrolyses of some small ring hydrocarbons
Sonogashira et al. The homogeneous hydrogenation of acetylenes by dicyclopentadienyltitaniumdicarbonyl
Yoshimoto et al. Palladium-catalyzed coupling reaction of aromatic compounds
US3022359A (en) Selective hydrogenation of cyclododecatriene to cyclododecene
Miller et al. Nickel-catalyzed skeletal rearrangements of 1, 4-dienes
US3317620A (en) Cis, cis-cyclodecadiene-(1, 6) and its manufacture
US2435403A (en) Cyclic alcohols and their preparation
Fusi et al. Homogeneous catalysis with transition metal complexes. Part VII: Heteronuclear platinum clusters as hydrogenation catalysts of carbon—carbon multiple bonds
US3258501A (en) Production of polycyclic compounds
US3360577A (en) Selective hydrogenation
US3655793A (en) Dimerization of conjugated dienes
US3391206A (en) Preparation of cyclic alkenes
US3265749A (en) Production of polycyclic compounds
Golden et al. Nickel-promoted skeletal rearrangements of 1, 4-dienes by a fragmentation process. Mechanistic relationship to an alkene-1, 3-diene addition reaction
US3369052A (en) Production of cyclic alkene
US3849510A (en) Hydrogen transfer process
GB2051119A (en) Preparation of 2 3-dimethylbutene-2
US3052737A (en) Synthesis of alkenyl substituted cycloalkanes
US3586727A (en) Process for the manufacture of substituted 8,10,and 12-member rings by the catalytic cooligomerization of unsaturated compounds
US3629347A (en) Cycloco-oligomerization to form multicyclic olefinic rings
US3309410A (en) Isomerization process
Misono et al. Reactions of 1, 3-Dienes with Acrylates by Means of Transition Metal Complex Catalysts
US3542896A (en) Olefin isomerization process
US3362984A (en) Cyclization of acetylenic compounds by co(co)3no
US5171907A (en) Preparation of hydrogenation catalyst and hydrogenation process therewith