DE3906434A1 - Process for an additionary reaction of a 1-olefin and a 1,3-diene - Google Patents

Abstract

The invention relates to a process for an additionary reaction of a 1-olefin and a 1,3-diene at -25 to +50@C in the presence of a ternary catalyst system composed essentially of (1) at least one salt of Fe, Ni, Pd or Cr, (2) a Grignard reagent, a lithium alkyl or magnesiumalkyl, and (3) a 1,4-diaza-1,3-diene of the formula <IMAGE> in which the radicals R<7> to R<10> have the following meanings: R<7> and R<10> can be C1-C8-alkyl or C6-C10-aryl, R<8> and R<9> can be H or C1-C8-alkyl or together with the atoms linking them form a carbocycle, or R<9> and R<10> together with the atoms linking them can form a heterocycle which contains nitrogen. The reaction product is a diunsaturated, optionally substituted hexane.

Description

The invention relates to a method for adding a 1-olefins of the general formula R¹-CH = CH₂, where R¹ = H, C₁-C₁₀ alkyl, C₃-C₁₀ omega alkenyl, C₁-C₁₀ alkoxy or Is C₆-C₁₀ aryl, to a 1,3-diene of the general formula

wherein the R² to R⁶ may be the same or different and H, C₁-C₄ alkyl, C₂-C₄ alkenyl or C₆-C₁₀ aryl mean. In this process, a substituted with R¹ to R⁵, obtained double unsaturated hexane derivative.

Such a method is already known from US-PS 39 27 137. A ternary catalyst system is used, which consists of 1) an iron salt or complex, 2) one Organoaluminum compound and 3) one of the group -N = C-C = N- containing connection exists. The ones mentioned under 3) Connections can change the structure

to have. The reaction temperature is 60 to 130 ° C specified.

It has now been found that temperatures from -25 to + 50 ° C, if instead of (to reduce the Organoaluminium compound required a Grignard reagent, a lithium alkyl or a  Magnesium alkyl used. Instead of an iron compound can one also a nickel, palladium or chromium compound use. An object of the invention is therefore a Process for the addition of a 1-olefin of the general Formula R¹-CH = CH₂, where R¹ = H, C₁-C₁₀ alkyl, Is C₃-C₁₀ omega alkenyl, C₁-C₁₀ alkoxy or C₆-C₁₀ aryl, to a 1,3-diene of the general formula

wherein the R² to R⁶ may be the same or different and Is H, C₁-C₄-alkyl, C₂-C₄-alkenyl or C₆-C₁₀-aryl, characterized in that the 1-olefin and 1,3-diene at -25 to + 50 ° C in the presence of a ternary Reacts catalyst system with each other, that essentially from (1) at least one salt of Fe, Ni, Pd or Cr, (2) a Grignard reagent, a lithium alkyl or one Magnesium alkyl, and (3) a 1,4-diaza-1,3-diene general formula

exists, the radicals R⁷ to R¹⁰ have the following meaning
R⁷, R¹⁰ can be C₁-C₈ alkyl or C₆-C₁₀ aryl
R⁸, R⁹ can be H or C₁-C₈-alkyl or form a carbocycle together with the atoms connecting them
R⁹ and R¹⁰ together with the atoms connecting them can form a nitrogen-containing heterocycle.

However, you can also separate the catalyst beforehand produce. Another object of the invention is hence a process for the addition of a 1-olefin general formula R¹-CH = CH₂, where R¹ = H, C₁-C₁₀ alkyl, C₃-C₁₀ omega alkenyl, C₁-C₁₀ alkoxy or C₆-C₁₀ aryl is to a 1,3-diene of the general formula

wherein the R² to R⁶ may be the same or different and Is H, C₁-C₄-alkyl, C₂-C₄-alkenyl or C₆-C₁₀-aryl, characterized in that the 1-olefin and 1,3-diene at -25 to + 50 ° C in the presence of a catalyst implemented with each other by adding a 1,4-diaza-1,3-diene of the general formula

to an Fe, Ni, Pd or Cr salt and subsequent reduction of the adduct with a Grignard reagent, a lithium alkyl or a magnesium alkyl has been prepared, the radicals R⁷ to R¹⁰ having the following meaning
R⁷, R¹⁰ can be C₁-C₈ alkyl or C₆-C₁₀ aryl
R⁸, R⁹ can be H or C₁-C₈-alkyl or form a carbocycle together with the atoms connecting them
R⁹ and R¹⁰ together with the atoms connecting them can form a nitrogen-containing heterocycle.

Preferably an iron salt or one is used Iron complex, for example a halide, sulfate,  Carboxylate or acetylacetonate. Is particularly preferred FeCl₂.

If the residues R⁹ and R¹⁰ together with them connecting atoms contain a nitrogen Form heterocycle, it is preferably around the pyridyl residue.

As 1-olefins such. B. 1-dodecene, 1-decene, 1-octene, 1-hexene, 1-pentene, 1-butene, propene, ethene, vinylcyclohexene, Styrene, but also double-terminal olefins such as 1,5-hexadiene or alkyl vinyl ether are suitable. Preferably 1-hexene, 1-pentene, 1-butene, Propene, ethene, vinylcyclohexene, styrene, methyl vinyl ether or ethyl vinyl ether, but especially propene, ethene, Styrene, methyl vinyl ether or ethyl vinyl ether.

For example, 1,3-octadiene, Piperylene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, trans, trans-2,4-hexadiene, 2,3-dimethylbutadiene, isoprene, 1,3-hexadiene or butadiene used. Preferably one uses isoprene, piperylene, 2,3-dimethylbutadiene, 1,3-hexadiene or butadiene.

Technical mixtures of dienes and terminal olefins, such as those used as C₄ or C₅ steps in "steam-cracking" occur without prior separation of the Alkyne or Allen components are implemented.

The 1,4-diaza-1,3-diene (hereinafter also referred to as "diazadiene" or "DAD"), the metal complexes of which Form a catalyst in the reaction according to the invention, are Schiff bases made from vicinal dicarbonyl compounds with aliphatic primary amines, aromatic primary Amines and chiral carbocyclic amines. As a vicinal Dicarbonyl compounds come e.g. B. glyoxyl, alkylglyoxals (such as methylglyoxal), diacetyl, 1,2-cyclohexanedione or Camphorquinone in question. The aliphatic primary amines can carry n-alkyl, sec.-alkyl or tert.-alkyl radicals; to be considered B. methylamine, ethylamine, n-propylamine,  n-butylamine, isopropylamine, cyclohexylamine, Diisopropylmethylamine, tert-butylamine. As aromatic primary amines come e.g. B. aniline and alkylanilines in question, as chiral carbocyclic amines e.g. B. methylamine and Bornylamine.

Preferred diazadiene (DAD) is diacetyldianil, glyoxal bis (2,6-dimethylanil), glyoxal bis (isopropylamine), glyoxal bis (diisopropylmethylimine) or biacetyl bis (2,6-dimethylanil).

Pyridylimines (PYM) are special DAD, namely Schiffsche Bases of pyridine-2-aldehyde or 2-acyl-pyridines with the called primary amines. Is preferred as PYM 2-benzoylpyridine (R) menthylimine.

The metal DAD catalysts used according to the invention are made by attaching DAD to an Fe, Ni, Pd or Cr salt or one of its complexes, preferably a Halide or sulfate, and subsequent reduction produced. For the reduction, Grignard reagents, Lithium alkyls, or magnesium alkyls, but especially Magnesium butadiene (x2THF) or magnesium isoprene be used. The reduction generally becomes Start of the addition in the reaction mixture. The addition reaction according to the invention is at temperatures from -25 to + 50 ° C, preferably at 0 to +50 ° C. As a reaction medium you can among the Reaction conditions of inert liquids such as benzene, Toluene, xylenes, hexane, cyclohexane, tetrahydrofuran use. But you can also use the reaction Use olefin itself as the reaction medium, if that Olefin is liquid under the reaction conditions. Preferably one works without an external solvent, i. H. either with the olefin as a solvent or entirely without Solvent.  

The catalyst becomes the mixture of (liquid) diene and added to a higher (liquid) olefin, or it will added to the (liquid) diene at low temperature and then a lower (gaseous) olefin under pressure initiated. The catalyst is at the end of the reaction still active or reusable.

The diene: olefin molar ratio can depend on olefin used within wide limits, for example between 10: 1 fluctuate to 1:10. Usually the olefin is in one Molar ratio of approx. 10: 1 to 1: 1 (olefin: diene) used. An olefin: diene ratio of is preferred 10: 1 to 5: 1.

The reaction leads to a di-unsaturated, possibly substituted hexane. Depending on the substitution pattern of the diene or the olefin can in the invention acyclic linkage different isomers arise. By suitable choice of the DAD ligand on the metal the proportions of different isomeric products in control wide limits. So when linking Isoprene linking with an olefin such as 1-butene 97.6 at position 1 of the isoprene (with DAD = biacetyl-bis (2,6-dimethylanil)) are redirected 97% at position 4 of the isoprene (with DAD = glyoxalbis (isopropylimine) Linking propene to various services can be done by 100% connection to C1 are redirected to up to 88% C2. On a given service, e.g. B. isoprene, can at Linkage with 1-butene of 93% connection to C1 (e.g. with Glyoxalbis (isopropylimine) are controlled 100% at C2 of butene (e.g. with biacetylbis (2,6-dimethylanil)). The extremely strong influence of steric and electronic Properties of the NN ligand can also be used for exploit enantioselective linkage by using chiral, optically pure DAD or PYM can be used.  

The following examples are intended to illustrate the invention explain. The percentages are always percentages by weight, if not stated otherwise. The abbreviations VCH and COD mean vinylcyclohexene and cyclooctadiene.

Scheme 1 shows the diazadienes used in the examples DAD1 to DAD9. Scheme 2 shows some more well-suited ones Diazadienes (DAD10 to DAD15).

The abbreviations DAD1 to DAD15 have the following meanings:
DAD1 = diacetyl-dianil
DAD2 = glyoxal bis (2,6-dimethylanil)
DAD3 = glyoxal bis (4-methylanil)
DAD4 = glyoxal-bis- (diisopropylmethylimine)
DAD5 = glyoxal-bis-cyclohexylimine
DAD6 = glyoxal-bis- (2,6-diisopropylanil)
DAD7 = glyoxal-bis-isopropylimine
DAD8 = diacetyl-bis- (2-methylanil)
DAD9 = diacetyl-bis- (2,6-dimethylanil)
DAD10 = camphorquinone-bis-anil
DAD11 = glyoxal-bis-methylimine
DAD12 = 2-acetylpyridine-menthylimine
DAD13 = pyridine-2-aldehyde-menthylimine
DAD14 = 2-benzoylpyridine-menthylimine
DAD15 = methylglyoxal bis-isopropylimine

Olefins with a boiling point above approx. 30 ° C were over Calcium hydride distilled. Butadiene, 1-butene and ethene were passed over 4 Å molecular sieve and thus dried. Propene was used without further cleaning.

The implementations were carried out as follows: (DAD) FeCl₂ and Mg-butadiene × 2 THF were in the Filled the reaction vessel and pipetted in the olefins or condensed. Solvents were usually used waived. Experiments with ethene or propene were carried out in Glass ampoules performed. The ampoules with Reaction mixture were liquid to the temperature Cooled nitrogen and melted under vacuum. Together with dry ice, these were placed in steel autoclaves (250-500 ml) included. The one with warming building back pressure was sufficient to the ampoules before To keep bursting.

The contents of the ampoule were shaken by the Laboratory autoclave was slowly rotated around a tilted axis (KPG stirrer). After the reaction, the autoclave Cooled to -78 ° C and the ampoule quickly in liquid Nitrogen cooled. Then the ampoule opened and their contents placed in diethyl ether. With verd. Sulfuric acid was washed, the organic phase with Magnesium sulfate dried and fractionally distilled.

I. Reactions with butadiene Example 1

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene = 2 THF
21. g (40 mmol) butadiene
7.8 g (280 mmol) ethene

were shaken at room temperature. Depends on the Response times were found at different levels (Z) -1,4-hexadiene = 1 and 2- (E) -4- (Z) -hexadiene = 2. Yours Identification was done by NMR spectroscopy.

Examples 2-4

0.28 mmol (DADX) FeCl₂, X = 1, 2, 3
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.1 g (40 mmol) butadiene
approx. (149 mmol) propene

After 18 h, DADX became dependent on the ligand used following distributions of 1,6-heptadiene = 3 and 2-methyl-1, (Z) -4-hexadiene = 4 found:

Example 5-8

0.28 mmol (DADX) FeCl₂, X = 1, 4, 5, 6
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.1 g (40 mmol) butadiene
4.2 g (75 mmol) 1-butene

and 1 ml of toluene as the internal standard were in for 16 h Glass flask stirred. In addition to VCH and COD, 5-methylidene (Z) -2-heptene = 7 and 1,6-octadiene = 8 as main products found. By-products with up to 10% share were precise analysis of a toluene-free catalyst mixture (by means of (DAD1) FeCl₂) as 2,6-octadiene = 5 and 3-methyl-1,6-heptadiene = 6 identified.

Samples were taken two hours after the start of the reactions and analyzed by gas chromatography. The ratio of Products did not differ from the one after 16 hours of stirring was determined. In example 7 that was The reaction is complete after this short time expired.

Example 5b

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
4.5 g C₄ cut

Volatile educts were no longer after 2 hours available. In addition to 43% VCH and 38% COD, 6% 7 and 8% 8 found.  

Example 9

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.8 g (52 mmol) butadiene and
52 g (620 mmol) 1-hexene

were stirred at room temperature for 24 h. After quenching was the witch phase of higher boiling components separated by distillation. In addition to 85% witches, it contained Isomerization products (E) -2-hexene (10%) and (Z) -2-hexene (GC / 13 C NMR). The homo- and co-dimers of the complete converted butadiene consisted of VCH (24%), COD (20%), 5-methylidene-2-nonene = 10 (8%), 5-ethenyl-1-octene (9%) = 9 and 1,5-decadiene = 11 (24%).

Example 10

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
1.4 g (26 mmol) butadiene and
3.5 g (42 mmol) 2-hexene ((E) / (Z) = 2: 1)

were worked up after 24 hours. In addition to the isodimers des Butadiene (VCH and COD), which were divided equally after 90 % conversion, no codimers were found. The isomer ratio of 2-hexene remained unchanged.

Example 11

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.8 g (52 mmol) butadiene
52 g (640 mmol) 1,5-hexadiene.

It was stopped after 12 hours. The excess 1,5-hexadiene was removed and could be used again. The residue consisted of 9% VCH and COD and two higher-boiling Codimer main components:
1, (E) -4,9-decatriene = 12 (46%), 5-methylidene-1,7-nonadiene = 13.

Example 12

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.8 g (52 mmol) butadiene and
49 g (700 mmol) 3-methyl-1-butene

were worked up after 6 hours. The mixture contained 44% VCH and 36% COD. Two codimers of 12% and 5% found. They were not clear identify because there is insufficient separation of VCH succeeded.

Example 13

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
1.4 g (26 mmol) butadiene and
7 g (120 mmol) methyl vinyl ether

Without stopping the catalysis, the organic ones Components recondensed. Excess vinyl ether became then expelled. In addition to 53% VCH and 42% COD 5% 1-methoxy-1, (Z) -4-hexadiene = 14a was found.

Example 14

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.8 g (52 mmol) butadiene and
28 g (333 mmol) ethyl vinyl ether

After 8 hours, all of the butadiene was converted. There were 33% VCH, 42% COD and 11% (analogous to example 13) 1-ethoxy-1, (Z) -4-hexadiene = 14b 1 H-NMR spectroscopy.

Example 15

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.1 g (39 mmol) butadiene and
14 g (142 mmol) diallyl ether

were stirred for 12 h. After hydrolytic workup with very heavily diluted sulfuric acid, about 1 g a mixture of at least 5 codimers (m / z = 150 = Molecular peak) isolated, with two main components with 44% or 30% real frequency.

Example 16

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.5 g (46 mmol) butadiene

were frozen (until homogeneous) after brief stirring and 36 g (348 mmol) of vinylbenzene were added. The initially the brown-red color of the solution turned violet. To complete butadiene conversion, the approach was dark brown colored.

1.73 g of butadiene isomers (15 mmol; VCH: COD 1.1) and 2.0 g (13 mmol) of codimers containing 90% 1-phenyl- (E) -1, (Z) -4-hexadiene = 15 contained.

Comparative example

The procedure was analogous to Example 16, but with FeCl₂, instead of (DAD1) FeCl₂. In addition to 50% codimers, 25% each Butadiene isotrimers found.

II. Reactions with isoprene Example 17

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
1.4 g (21 mmol) isoprene
6 g (214 mmol) ethene

After shaking for 24 hours at room temperature, 1.5 g (49% Th.) Codimers isolated, the 2-methyl-2, (E) -4-hexadiene = 16 (84%), 3-methyl- (Z) -2, (E) -4-hexadiene  = 17 (8%) and about 4% 2-methyl-1, (E) -4-hexadiene = 18; No isoprene isodimers were observed.

Example 18-19

100 mg (0.28 mmol) (DAD1) FeCl₂ or (DAD2) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
1.8 g (42 mmol) isoprene
6.7 g (160 mmol) propene

after 18 hours gave product mixtures containing 2-methyl-1, (E) 5-heptadiene = 19, 2,5-dimethyl-1,4-hexadiene = 20, 2-methyl-2, (E) 5-heptadiene = 21 and 2,4-dimethyl-1, (Z) -4-hexadiene = 22 contained.

Example 20-26

100 mg (0.28 mmol) (DADX) FeCl₂, X = 1, 2, 4, 7, 8, 9
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.1 g (31 mmol) isoprene
4.2 g (75 mmol) 1-butene

1 ml toluene as an internal standard. The distribution of the The following products were determined by gas chromatography.

23 = 3-methyl-5-methylidene (Z) -2-heptene
24 = 2,5-dimethyl-1,4-heptadiene
25 = 2-methyl-1, (E) -6-octadiene
26 = 2-methyl-2, (E) -6-octadiene.

Example 27

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
3.5 g (51 mmol) isoprene
60 g (600 mmol) 1,5-hexadiene

After stirring for 12 hours, 6.2 g (81% of theory) Codimers, 40% 8-methyl-5-methylidene-1,7-nonadiene = 27 and Contain 20% 2-methyl-2, (E) -8-decatriene = 28.

Example 28

100 mg (0.28 mmol) DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
3.5 g (51 mmol) isoprene
50 g (714 mmol) 3-methyl-1-butene

After 10 hours, 4.2 g (90% of theory) of reaction product isolated. About half consisted of 1,6-dimethylcyclooctadiene, otherwise 25% 2,6-dimethyl-5-methylidene-2-heptene = 29 in addition to 9% of one unknown codimers (m / z: 138 (M⁺, 5%), 69 (100%), 41 (90%), the rest below 15%.

Example 29

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.5 g (37 mmol) isoprene
17.5 g (168 mmol) vinylbenzene

After 2 hours with complete isoprene conversion Codimers are isolated, which are 70% off 5-methyl-1-phenyl- (E) -1,4-hexadiene = 30 passed.  

III. Reactions with piperylene (1,3-pentadiene) Example 30

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.1 g (41 mmol) piperylene
6.7 g (239 mmol) ethene

After 24 hours, 1.8 g (46% of theory) of 2-methyl-1, (Z) -4-hexadiene = 31 obtained, the purity of which is 96% exceeded.

Example 31

200 mg (0.56 mmol) (DAD1) FeCl₂
200 mg (0.88 mmol) Mg butadiene × 2 THF
1.75 g (26 mmol) piperylene
6.7 g (159 mmol) propene

gave 1.3 g after a reaction time of 10 hours (46% of theory) Codimers, the 72% 4-methyl-1,6-heptadiene = 32 and 18% contained 4-methyl-1, (E) -5-heptadiene = 33.

IV. Reactions with 2,3-dimethylbutadiene Example 32

100 mg (0.28 mmol) DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
1.44 g (18 mmol) 2,3-dimethylbutadiene
6.0 g (214 mmol) ethene

24 hours after the start of the reaction, 0.72 g (37% d. Th.) Codimers isolated. They consist of 60% 4,5-dimethyl-1,4-hexadiene = 34 and 25% 2,3-dimethyl-2, (E) -4-hexadiene = 35 together.  

Example 33

200 mg (0.56 mmol) (DAD1) FeCl₂
200 mg (0.88 mmol) Mg butadiene × 2 THF
1.75 g (18 mmol) 2,3-dimethylbutadiene
5.70 g (136 mmol) propene

1.7 g (70% of theory) were added within 10 hours. Codimers formed. A rotary column distillation delivered four fractions enriched in the products. The following isomers were then determined by NMR spectroscopy identified:

28% 2,3-dimethyl-1,6-heptadiene = 36
16% 5,6-dimethyl-1,5-heptadiene = 37
28% 2,4,5-trimethyl-1,4-hexadiene = 38
14% 2,3-dimethyl-2, (2) -5-heptadiene = 39

Example 34

180 mg (0.46 mmol) (DAD2) FeCl₂
170 mg (0.75 mmol) Mg-butadiene × 2 THF
2.1 g (26 mmol) 2,3-dimethylbutadiene
14 g (170 mmol 1,5-hexadiene

After 5 hours, the diene conversion was complete. There were only codimers isolated, namely 29% 7,8-dimethyl 5-methylidene-1,7-nonadiene = 40 and 67% 8.9 dimethyl-1,5-decatriene = 41, the preparative were cleaned by gas chromatography.

Example 35

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.1 g (26 mmol) 2,3-dimethylbutadiene
7.5 g (168 mmol) vinylbenzene

After 2 hours, 4.1 g (85% of theory) 1-phenyl-4,5-dimethyl- (E) -1,4-hexadiene = 42 (98% purity) isolated.  

V. Reactions with 2-methyl-1,3-pentadiene Example 36

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
2.8 g (34 mmol) of 2-methyl-1,3-pentadiene
9 g (321 mmol) ethene

After 24 hours, 1.7 g (31% of theory) of 3,5-dimethyl 1,4-hexadiene = 43 isolated.

Example 37

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
3.3 g (40 mmol) of 2-methyl-1,3-pentadiene
8.8 g (209 mmol) propene

8 hours after the start of the reaction, 1.9 g Isolated reaction products containing 75% 4,6-dimethyl-1,5- heptadiene = 44, 13% 2,3,5-trimethyl-1,5-hexadiene = 45, 8% 2,4,8-trimethyl-2,5,7-nonatriene = 46 (2-methyl-1,3-pentadiene isodimer) and 3% of a codimer from two methylpentadiene and one propene unit (MS: m / z = 206 (M⁺, 1%), 83 (100%), 53 (38%), 41 (25%), contained. The fractional distillation made it possible Enrichment of the individual substances.

VI. Reaction with 1, (E) -3-hexadiene Example 38

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
1.05 g (12.8 mmol) 1, (E) -3-hexadiene
4.2 g (150 mmol) ethene

After 12 hours at room temperature it became quantitative 3-ethyl-1, (Z) -4-hexadiene = 47 isolated.  

VII. Reaction with 3-methyl-1,3-pentadiene Example 39

100 mg (0.28 mmol) (DAD1) FeCl₂
100 mg (0.44 mmol) Mg-butadiene × 2 THF
0.7 g (8.5 mmol) 3-methyl-1,3-pentadiene
7.5 g (268 mmol) ethene

Within 6 hours, 0.65 g (70% of theory) Codimers formed that are 50% 3,4-dimethyl-1, (Z) -4-hexadiene = 48 and 35% 5-methyl-1,4-heptadiene = 49 contained.

Claims (9)

1. A process for adding a 1-olefin of the general formula R¹-CH = CH₂, where R¹ = H, C₁-C₁₀-alkyl, C₃-C₁₀-omega-alkenyl, C₁-C₁₀-alkoxy or C₆-C₁₀-aryl, to a 1,3-diene of the general formula wherein the R² to R⁶ may be the same or different and are H, C₁-C₄-alkyl, C₂-C₄-alkenyl or C₆-C₁₀-aryl, characterized in that the 1-olefin and the 1,3-diene in - 25 to + 50 ° C in the presence of a ternary catalyst system which essentially consists of (1) at least one salt of Fe, Ni, Pd or Cr, (2) a Grignard reagent, a lithium alkyl or a magnesium alkyl, and (3 ) a 1,4-diaza-1,3-diene of the general formula exists, the radicals R⁷ to R¹⁰ have the following meaning
R⁷, R¹⁰ can be C₁-C₈ alkyl or C₆-C₁₀ aryl
R⁸, R⁹ can be H or C₁-C₈-alkyl or form a carbocycle together with the atoms connecting them
R⁹ and R¹⁰ together with the atoms connecting them can form a nitrogen-containing heterocycle. 2. Process for adding a 1-olefin of the general formula R¹-CH = CH₂, where R¹ = H, C₁-C₁₀-alkyl, C₃-C₁₀-omega-alkenyl, C₁-C₁₀-alkoxy or C₆-C₁₀-aryl, to a 1,3-diene of the general formula wherein the R² to R⁶ may be the same or different and are H, C₁-C₄-alkyl, C₂-C₄-alkenyl or C₆-C₁₀-aryl, characterized in that the 1-olefin and the 1,3-diene in - 25 to + 50 ° C in the presence of a catalyst which reacts by the addition of a 1,4-diaza-1,3-diene of the general formula to an Fe, Ni, Pd or Cr salt and subsequent reduction of the adduct with a Grignard reagent, a lithium alkyl or a magnesium alkyl has been prepared, the radicals R⁷ to R¹⁰ having the following meaning
R⁷, R¹⁰ can be C₁-C₈ alkyl or C₆-C₁₀ aryl
R⁸, R⁹ can be H or C₁-C₈-alkyl or form a carbocycle together with the atoms connecting them
R⁹ and R¹⁰ together with the atoms connecting them can form a nitrogen-containing heterocycle. 3. The method according to claim 1 or 2, characterized characterized in that the 1,4-diaza-1,3-diene component of the catalyst diacetyldianil, glyoxal-bis (2,6-dimethyl-  anil), glyoxal bis (isopropylimine), glyoxal bis (diisopropyl) methylimine), biacetyl-bis (2,6-dimethylanil) or 2-benzoylpyridine- (R) -menthylimine used. 4. The method according to any one of claims 1 to 3, characterized characterized in that a catalyst is used which Contains iron. 5. The method according to any one of claims 1 to 4, characterized characterized in that to reduce the Catalyst metal uses a magnesium alkyl. 6. The method according to claim 5, characterized in that one as magnesium alkyl magnesium butadiene (× 2 THF) or Magnesium isoprene used. 7. The method according to any one of claims 1 to 6, characterized characterized in that the reaction at 0 to 50 ° C. carries out. 8. The method according to any one of claims 1 to 7, characterized characterized in that 1-olefin, 1-pentene, 1-butene, propene, ethene, vinylcyclohexene, styrene, Methyl vinyl ether or ethyl vinyl ether is used. 9. The method according to any one of claims 1 to 8, characterized characterized in that isoprene, piperylene, 2,3-dimethylbutadiene, 1,3-hexadiene or butadiene.