DE1230023B - Process for the preparation of cis, cis-cyclodecadiene- (1, 6) - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Int. Cl .:

C07c

GERMAN

PATENT OFFICE

EDITORIAL

German AI .: 12 ο-25

Number: 1230023

File number: St 20502IV b / 12 ο Filing date: April 10, 1963 Opening day: December 8, 1966

The subject of an older proposal is a process for the mixed oligomerization of 1,3-diolefins with olefins or acetylenes, according to which, among other things, from butadiene and ethylene the trans, cis-cyclodecadiene- (l, 5) can be produced. This ring-shaped hydrocarbon has great technical properties Importance because it is used as a starting material for the production of α, ω-bifunctional derivatives of the n-decane can be used.

In the further development of said method it was found that the Cyclodecadien- (1.5) is a very thermally labile hydrocarbon which merges at temperatures between 80 and 150 ⁰ C in terms of a Cope rearrangement in 1,2-divinylcyclohexane.

This rearrangement has been found to be troublesome in that it can occur as soon as the hydrocarbon is isolated by distillation and can only be avoided if the distillation is carried out at greatly reduced pressure. Accordingly, the cyclodecadiene (1,5) can also only be subjected to those subsequent reactions which take place at a temperature of up to at most 100 ^° C. at which no rearrangement occurs.

It has now been found that these difficulties can be overcome if the trans, cis-cyclodecadiene- (1.5) is subjected to an isomerization which leads to a stable isomer. On the basis of known processes in which similar ring-shaped hydrocarbons are isomerized (cf. for example J. Am. Chem. Soc, Vol. 83 [1961], p. 2954), it was to be expected that in the course of such an isomerization a cyclodecadiene (1,3) would be formed, surprisingly it has now been found that the trans, cis-cyclodecadiene- (l, 5) during isomerization very smoothly into the previously unknown cis, cis-cyclodecadiene- (l, 6) with a melting point of 28 , 5 ⁰ C passes.

The constitution of this new hydrocarbon was made through hydrogenation, decomposition with ozone and IR and proton resonance spectrum proven (see Appendix). Of particular importance in terms of

Method of manufacture of cis, cis-cyclodecadiene- (l, 6)

Applicant:

Study Society Coal m. B. H.,

Mülheim / Ruhr, Kaiser- Wilhelm-Platz 1

Named as inventor: Dipl.-Chem. Dr. Günther Wilke,

Dipl.-Chem. Dr. Paul Heimbach, Mülheim / Ruhr

the commercial benefit is that this new isomer shows normal thermal stability.

According to the invention, the isomerization of trans, cis-cyclodecadiene (l, 5) is achieved by adding the starting compound in the presence of catalytic amounts of metals of Group VIII of the Periodic Table in active form or their chlorides, preferably palladium or palladium chloride Temperatures from 0 to 100 ⁰ C isomerized. As active catalyst metals, for. B. Raney metals can also be used or noble metals precipitated under hydrogenation conditions, such as the palladium or platinum already mentioned above. In general, the metals are obtained in active form if transition metal compounds of Group VIII of the Periodic Table are used with the aid of organometallic compounds of the elements of I to III. Main group or their hydrides or their complex hydrides or else reduced with the finely divided metals of these groups themselves. Finally, a further possibility consists in decomposing labile olefin or acetylene-II complex compounds of the transition metals of group VIII of the periodic table either thermally or by reducing the ligands. In this sense z. B. the bis-cyclooctadiene (l, 5) -nickel with hydrogen cyclooctane and highly active nickel and the bis-II-allylpalladium propane and palladium.

The process according to the invention can be carried out in the presence of solvents.

The process according to the invention can thus be used to prepare the butadiene and ethylene, thermally unstable trans, cis-cyclodecadiene- (l, 5) can be converted into a stable isomer. It It is recommended that a reaction product containing cyclodecadiene (1,5) be isomerized first subject and only then the 10-ring component

609 730/433

in the form of the new stable isomer, ζ. Β. by Distillation, isolate. The cts, cis-cyclodecadiene- (l, 6) Subsequent reactions that take place at higher temperatures are then also accessible.

The procedure of Examples 1 to 4 below was carried out as follows:

1 g of a transition metal acetylacetonate is dissolved or suspended in 10 ml of benzene and reduced with 1 mol of aluminum triethyl per equivalent of metal acetylacetonate. After adding 10 g of cis, trans-cyclodecadiene (1.5) in each case, the mixture is heated to 80 to 90 ^° C. for 24 hours with stirring. After the catalyst has been distilled off, the composition of the reaction product is determined by gas chromatography.

example 1

There are 1 g of nickel (Ilj-acetylacetonate, 1 g of Monoäthoxydiäthylaluminium and 10 g of cis ^ rans-cyclodecadiene (l, 5) used. After working up 2c 3.9 g = 39% divinylcyclohexane and 6.1 g = 61% cis, cis-cyclodecadiene- (1.6) are obtained.

Example2

There are 1 g of cobalt (III) acetylacetonate, 1.1 g of monoethoxydiethylaluminum and 10 g of cis, trans-cyclodecadiene (l, 5) used. After working up, 1.6 g = 16% divinylcyclohexane, 1.1 g, are obtained = 11% of an unknown Cio-hydrocarbon, 6.6 g = 66% cis, cis-cyclodecadiene- (1.6) and 0.7 g = 7% of an unknown Cio hydrocarbon.

Example 3

There are 1 g of iron (III) acetylacetonate, 1.1 g of monoethoxydiethylaluminum and 10 g of cis, trans-cyclodecadiene (l, 5) used. After working up, 3.7 g = 37% divinylcyclohexane, 1.0 g, are obtained = 10% of an unknown Cio-hydrocarbon, 4.8 g = 48% cis, cis-cyclodecadiene- (1.6) and 0.5 g = 5% of an unknown Cio hydrocarbon.

Example 4

There are 0.5 g of palladium (II) acetylacetonate, 0.4 g of monoethoxydiethylaluminum and 10 g of cis, trans-cyclodecadiene (l, 5) used. After working up, 1.0 g = 10% divinylcyclohexane and 9.0 g = 90% cis, cis-cyclodecadiene- (1.6) are obtained.

Example 5

2 g of Raney nickel are mixed with 15 g of ciSjtrans cyclodecadiene (l, 5) Heated to 50 ° C. for 2 days with stirring. In addition to 5.7 g of unreacted cis, trans-cyclodecadiene (l, 5) one can isolate 9.3 g = 62% cis, cis-cyclodecadiene- (l, 6).

Example 6

151 mg PtO ₂ are suspended in 10 ml benzene and _{reduced with 163 mg Al (C 2} Hs) 3. Then 4.5 g of cis, trans-cyclodecadiene (1.5) are added, and the mixture is heated to 40 ^° C. for 24 hours with stirring. After working up, 2.02 g of cis, trans-cyclodecadiene (1.5 ) (Conversion 55%) 2.21 g = 89% cis, cis-cyclodecadiene- (1.6) and 0.27 g = 11% of an unknown hydrocarbon.

Example 7

119 mg RhCU are suspended in 12 ml benzene and _{reduced with 388 mg Al (C 2} Hs) 3. Then 4.5 g of cis, trans-cyclodecadiene (1.5) are added and the mixture is heated to 40 ^° C. for 3.5 hours. After working up, 3.85 g of cis, trans-cyclodecadiene (1.5 ) (Conversion 14.5%) 0.59 g of cis ^ is-cyclodecadiene- (1.6) in addition to 0.06 g of two unknown hydrocarbons.

Example 8

129 mg RuCU are suspended in 10 ml benzene and _{reduced with 426 mg Al (C 2} Hs) 3. Then 4.5 g of cis, trans-cyclodecadiene (1.5) are added and the mixture is heated to 40 ^° C. for 3.5 hours. After working up, 4.05 g of cis, trans-cyclodecadiene (1.5 ) (Conversion 5%) 0.30 g = 66% cis, cis-cyclodecadiene- (l, 6) and 0.15 g = 33% of two unknown hydrocarbons.

Claims (3)

Patent claims: 1. A process for the preparation of cis ^ is-cyclodecadiene (l, 6), characterized in that one trans, cis-cyclodecadiene (l, 5) in the presence of catalytic amounts of metals of the VIII. Group of the Periodic Table in active form or their chlorides isomerized at temperatures of 0 to 100 ⁰ C. 2. The method according to claim 1, characterized in that one Raney metals, palladium, Platinum or palladium chloride used as catalysts. * 3. The method according to claim 1 and 2, characterized in that in the presence of Solvent works. 1 sheet of drawings 609 730/433 11.66 © Bundesdruckerei Berlin