DE1793716C3 - - Google Patents

Description

dium are at least partially soluble. io c) ethers, tertiary amines, alkyl or aryl

b) metal alkyls, metal aryls, Grignard compound phosphines or phosphites, compounds with fertilizers, metal hydrides or metal hydride carbon double bonds or carbon plcx compounds as organometallic compound triple bonds as electron donors,
fertilize and arise under normal or increased pressure and

c) ethers, tertiary amines, alkyl or aryl 15 at elevated temperatures, expediently in the presence phosphines or phosphites. Compounds of inert solvents dimerized.

with carbon double bonds or carbon It has now been found that with the help of

Triple fabric bonds as E / ekironendonato- Kobalfverbindungen to the skin of the Paleni J 468 706 ren, arise at normal or increased pressure called iron compounds 5-methyl-heptalriene and at elevated temperatures / usually in 2 ° (1,3,6) by catalytic dimerization of butadiene presence of inert solvents, after can be obtained in good yields.
Patenit I 468 706 marked accordingly, the invention relates to a

n e t that the dimerization in the presence of a change in the process / ur production of 5-methyleines Catalyst carries out, to the formation of which heptatriene (1,3,6) by catalytic dimerization of the iron compounds by cobalt compounds, butadiene in the presence of catalysts which from have been replaced. a) Iron compounds that have no carbonyl groups as

Contain ligands and are at least partially soluble in the reaction medium,

b) metal alkyls, metal aryls, Grignard compounds, metal hydrides or metal hydride complex

compounds as organometallic compounds and

c) ethers, tertiary amines, alkyl or aryl phosphines or phosphites, compounds with

In the German Auslegeschriften 1050 333.35 carbon double bonds or carbon-I 056 123 and I 085 523 are processes for the production of triple bonds as electron donors,

of cyclododecatrienes- (l, 5,9) among other ring- arise, at normal or increased pressure and at shaped hydrocarbons with at least 8 carbon elevated temperatures expediently in the presence fuel atoms and at least 2 double bonds of inert solvents, according to patent I 468 706 in the ring due to the action of titanium or chromium 4 < > This is characterized by the fact that the dimeric halides and organoaluminum compounds performs sation in the presence of a catalyst, too from isoprene, piperylene and preferably butadiene, the iron compounds are formed by cobalt temperatures Up to 150 C, compounds were expediently replaced in the presence.

of solvents, such as aliphatic, aromatic When 5-methylhepta-

or halogenated hydrocarbons. 45 trien- (1,3,6) it concerns a new connection,

It is also known that butadiene according to the properties thereof are given in the example, in the German patent specification 881 511 or in the process described in the invention, completely non-toxic US Pat Catalysts such as [R ₃ P] ₂ Ni (CO) ₂ or activation with acetylene under pressure and (ROP) ₂ Ni (CO) ₂ in mixtures of cyclooctadiene (1,5) 5 <> guarantee a fast reaction process. Vor / ugs- and 4-vinylcyclohexene can be converted. This way, organometallic compounds or catalysts are derived from the extremely toxic metal hydrides I to III. Group of the periodic Ni (CO) ₄ from and are also made from this. Systems used. The electron donors have the best results with the catalysts, the task obtained in the conversion of the transition of the type mentioned, if these are activated by a metal compounds with the organometallic pretreatment with acetylene under pressure or with the metal hydrides without addition, But even then, long reaction times of up to 100 hours, mostly in solid form, are necessary to keep the real or colloidal solution.
Generate sales. It is particularly advantageous in the presence of

Finally, it is known to have worked in the production of ^solution mills which are not attacked by the organometallic cyclododecatriene (1.5,9) compounds or metal hydrides made of aluminum alkyl halide and titanium by the action of catalytic compounds. As such, aliphatic, halide on butadiene compounds with semipolar aromatic or halide hydrocarbons double bond, such as sulfoxides, amine oxides or can be used.
Mitrone, add. 65 _Mj , connections of the

The main patent I 468 706 relates to a process related to cobalt for the production of catalysts, for the production of 5-methyl-heptatriene- (1,3.6) which are easily soluble in the solvents used, catalytic dimerization of butadiene, but it can also be difficult to remove in the solvents

i 793 716, 5

3 O 4

Soluble compounds catalysts are obtained, but in these cases the formation of Example I is required
Catalyst from its components considerably long- 15.5 g of Co (Ac ₂ ) are mixed with butadiene in 300 ml. For this reason, process-saturated benzene has reacted with 13.8 g of aluminum triethyl at OC according to compounds of cobalt especially 5 with intensive stirring. Then proven, in which the transition metal atoms are bonded to butadiene for 80 hours at 24 to 26 C in the organic residues, such as acetyl acetonate, solution introduced and then the catalyst washed out with acetic ester enolates, alcoholates, salts of weak 5 η HCl with admission of air. The organic acids or dimethylglyoxyl compound layer are washed again with saturated gens. The electron donors used are compounds such as sodium bicarbonate solution and water and dry, which are generally known as Lewis bases, then with sodium sulfate. At 10 ⁴ Torr can be drawn, since these compounds with free all volatile products up to a boiling point of pairs of electrons on other atomic groups distilled off 80 ° C. Residue = 83 g. That can be proportionate to the reaction. In this sense, the product (1827 g of distillate and 83 g of residue) has the following composition: ethers, especially cyclic ethers, 15:
tertiary amines, especially cyclic tertiary amines,

Alkylphosphines, arylphosphines, alkylphosphites, ^{aryl- 137} ° 8 _; ⁷¹ _ ⁸ % 5-methylheptatriene- (i, 3.6)

phosphites and especially triphenylphosphine for ¹⁰² S ~ 5.3% n-octatriene- (l, 3.6)

Use. The stabili- ² 8 0.1% vinylcyclohexane described above

The additives do not only have an effect of 20 ⁵ - ⁵ S ° - ³ % cyclooctadiene

through these compounds with lone pairs of electrons ³⁴⁷ < ⁵ 8 ¹⁸ · ² '; » open-chain C ₁₂ and C ₁₆ olefins

caused, but according to the invention can. * u ⁸³ S "-" 4.4% higher oligomers.
for this purpose also connections with CC or

C - C bonds, such as phenylacetylene, used The physical data of the n-octatriene- (l, trans-3,

will. There are also 25 cis-6) smd as electron donors:

Diolefins, especially the starting diolefins in question. Bp ₁₃₉ : 80.4 C, n ^{>> 20} : 1.4751. IR spectrum and

The task of the electron donors is to make the H'-NMR spectrum agree with that given in the conversion of the cobalt compounds with the structure,
organometallic compounds or with the metal hydrides without additives, mostly in solid form. Example 2
Catalysts in real or colloidal solution too
I ₁₃ IJe ₁₁ 20.6 g of CoAc ₃ are mixed in 250 ml with butadiene

The process is carried out at normal pressure or saturated benzene with 19.8 g of aluminum triethyl at OC

preferably at a slight overpressure of z. B. implemented with vigorous stirring. The solution is

1 to 20 atm. and at temperatures of 20 to 150 C 35 together with 3.2 kg of butadiene for 8 days at 10 C

executed. If left to stand in an autoclave as a particularly favorable temperature range, then that is not the case

Temperatures of 60 to 100 C have been found, since reacted butadiene is withdrawn and the mixture

On the one hand, the reaction worked up quickly as in Example 1 at these temperatures. The turnover is

runs enough, but on the other hand the purely thermal 51%. The reaction product (! 678 g) has the following

Dimerization or polymerization of the diolefin still 4 ° Composition:

barely noticeably begins. _A. , ". _ ". . .. ,,.,,, · ,,, _A >

The 5-methylheptatriene- (1,3,6) obtained can be converted into '«3 g - 84.9% of 5-methylheptatriene- 1 3,6)

p-xylene can be flavored. The importance of the " ⁷ S" JO% n-Oc atnen- (l rans-3, us-6)

Paraxylene is known for the manufacture of polyesters. ⁵ S 0, j / "vmyicycionexen

Furthermore, the 5-methylheptatricn- (1,3,6) is a 45 _n ⁵ _c ^g "Ao" Iu ,, r hi.r olefins

important starting material for the synthesis of fat- »« 5 g - 6.3% offcnketügen C ₁₂ - to C ₁₆ -Olef.ne

acid esters (through cooligomerization of methyl ²³ S "1,4 _{/ o} higher uligomers.
heptatriene (1,3,6) and acrylic acid esters !! to a tri-unsaturated C ,, - acid ester) or when used

for the production of so-called ester oils. 5 ° Example 3

Finally, the 5-methylheplatriene- (1,3,6) rj _he catalyst is as shown in Example 2

because of its 3 double bonds also in the production of ^, 13 g CoAc ₃ and 1.4 g aluminum triethyl) and with

Position of ter- or tetrapolymers used 12'oOg butadiene mixed. An 80 m reactor serves as the reactor

These polymers have double bonds too long copper capillaries with an inner width of 4 mm

lend, with the help of which a vulcanization or 55 _e j _nem free volume of 1 liter, which rolled up in

Networking is possible. . _{there is an oil bath} heated to go c. With help

Great industrial importance has the inventiveness _e j _ner injection pump, the reaction mixture modern method is also in that it does not neces- d _urcr, the capillary and is eingedig a 25 Atm, gedurchzuführen the process with hochgcrcinigtem butadiene 'notified expansion valve into a storage vessel Rather, a raw butadiene can be pumped in. Fs is worked up as in Example 1. The sets are how it z. B. immediately in the course of sales is 36%. The reaction mixture (428 g) butane Iv.w. Bulend hydration occurs. The dem has the following composition:
Butadiene admixed paraffins or olefins, z. B.
Butane, the n-butenes and isobutene do not react with 320, Og = 74.8% 5-methylheptatnen- (1, J, 6)
the catalyst and can also after 65 46.6 g - 10.9% n-octatnene- (l, trans-3, cis-b)
Reaction returned to the dehydrogenation stage 1.0 g-0.2% vinylcyclohexene
while the butadiene practically quantitatively 1.4 g 0.3% of an unknown C ₈ -UIcImS
is implemented. 2.9 g - 0.7% cyclooctadiene

50.0 g = Il, 7% ep- to C ₁₆ -Olefinc
5.6 g = 1.3% higher oligomers.

The methylheptatriene- (1,3,6) sicdel at 745 mm Hg at 115 to 115.5 C and shows the refractive index n / r ° = 1.4632. In the catalytic hydrogenation, the equivalent amount of hydrogen for 3 double bonds is taken up. The llydation product is identical to 3-methylhcptane. 5-Methylheptalriene adds 1 mole of maleic anhydride. The corresponding dicarboxylic acid is obtained from Snip by saponification. 173 to 175 C.

Claims (1)

1 2 jQ is marked. that one has butadiene in the presence Claim: of catalysts made from a) Fisen connections that do not have Carnony groups as Modification of the process / ur production of ligands and contained in the reaction medium 5-methyl-heptatriene- (1,3,6) are partially soluble by catalytic diminution, merization of butadiene in the presence of cata- b) metal alkyls, metallarys, Grignard compounds analyzers made from gene, metal hydrides or metal hydride complex a) Iron compounds that have no carbonyl group compounds as organometallic compounds contained as ligands and in the reaction and