SU546598A1 - The method of obtaining aryl-substituted alkatrienes - Google Patents

Description

one

This invention relates to petrochemical synthesis, in particular, to a process for the preparation of aryl-substituted polyenes. These compounds, which are linear hydrocarbons, have an aryl substituent and three double bonds, are highly reactive compounds and can be used as monomers for modifying polyolefins and polydienes.

The oxygen-containing derivatives of these hydrocarbons (oxides, alcohols, ketones and others) can be used in the paint industry to produce fast-drying varnishes and paints.

The known methods for styrene co-oligomerization with butadiene are carried out in the presence of a three-component system consisting of a nickel compound, a phosphorus-containing modifier and an organoaluminum compound 1.

Common co-oligomerization conditions for preparing 1-phenyl - "- decatriene-1, 4.9 are from -10 to 200, preferably 30-100 ° C, the presence of a solvent, if the reaction is not carried out in an autoclave, the duration of the synthesis is 1 -24 hours

2

When preparing 1-phenyl-n-decatriene-1,4,9, styrene conversion is 35% with a selectivity of about 60% 2.

However, these catalytic systems turned out to be practically unsuitable) for carrying out the co-oligomerization of styrene with butadiene homologues. In particular, the reaction of isoprene with styrene does not work at all, and the reaction of styrene with pnierylene occurs in low yields.

The aim of the invention is to create a highly productive and technically convenient process for the preparation of aryl substituted alkathrynes.

This goal is achieved by the use of the method of obtaining arylmeasures, 1. alkenets with the co-oligomerization of vinyl aromatic hydrocarbons with 1,3-cie ovn and hydrocarbons at ~ 150 ° C in a solvent medium in the presence of a catalytic system consisting of divalent nickel, trialkyl aluminum and g / 7 -butylboard or compounds of general formula I or II

/ CHa-Os

IT BUT-SNG-C-SNG-O-B SNGO

The distinction of the proposed method is the use of a t-butylborate as a modifier or a compound I or P.

The method is carried out by the interaction of styrene with isoprene or piperylene (can be face- and tjuc-forms of dna, as well as their mixture) in the presence of a catalyst at O-150, reading 80-100 ° C, in a solvent. The reaction between styrene and isoprene leads to the generation of 1-phenyl-4,8-dimethyl-1,4,8-or 1,4,9-decatrieioB as the main products. 1,5-dpmethyl-1,5-cyclooctadiene, dipentene and trimethyl-1,5,9-cyclododecate are formed as ibolide admixtures. However, both due to their small total, and because of the easy separation of their formation, they prevent the production of pure linear cooligomers. The reaction proceeds according to the following scheme: the interaction of isoprene with null-nickel nickel in the presence of borate leads to the formation of a bis-allyl complex, which further coordinates with styrene. The latter serves as a matrix that determines the formation of feiyl dimethyldecatrienes. The reaction of styrene co-oligomerization with piperylemia and proceeds with the formation of predominantly 1-phenyl-6-methyl-1,4,9- and 1,4,10-didecatrieium. Cycloedimerpiperylene - 3,7 - dimethyl - 1,5cyclooctadiop and sodimer - 3-methyl-5-feiylcyclohexene are formed as mixtures. However, the yield of these impurities is low, so that they do not at all prevent the isolation and purification of linear cooligomers. The structure of linear cooligomers is proved by spectral and chemical data. Example 1. A solution of 2 g of Ni (AcAc) j, 3.6 g of A1 (C2H5) 3, 5 ml of isoprene in 20 ml of toluene is stirred at -5 ° C for 0.5 hour. Then, 1.22 g of boratetrap I (boric acid ester with tri-ethanolamine) is added and stirred for another 1 hour. The ratio of the catalyst components Ni:; AT ; A1: monomers 1.5: 0.97: 2.8: 114.5. A solution of a catalyst prepared as described above, 52 g of styrene, 68 g of isoprene, and heated at 100 ° C for 4 hours are introduced into a 300 ml steel autoclave in a stream of argon. The autoclave is cooled to 10 ° C, the content is discharged and distilled with steam. The distillate is separated, the aqueous layer is extracted with pentane and combined with the main amount of distillate, dried over MgSO4. After removal of the solvent, the residue is distilled in vacuo. 94.6 g of a mixture of oligomers, according to GLC, were obtained from 59% 1-phenyl-4,8 dimethyl-1, 4.8 (9) -decatrpenes, 23% dipentene, 7% 1,5-dimetpl-1,5- cyclooctadiene and trimet11L-1, 5,9-tsclclododekatriene. The products isolated by rectification on a column have the following constants: 1-Phenyl-4,8-dimethyl-1,4,8 (9) - decatrienes. 1.5453 UFT. kip 123 ° C / 1 mmHg 01: 262, e- 20,000. Spectrum () IR spectrum (V cm-1): 700, 750, 1500, 1600, ZOU (CP, aromatic), 820, 850 (CP, trisubstituted), 920, 1000 (C CH2, methylene), 970, 3030 (gran-SP-SP-SP), PMR spectrum (6 ppm): 0.95 (1.5 S, CH 3, J 4 Hz), 1.63 (7, 5H, C-CHg), 2 (4H, -SPg-), 2.75 (2H, C-SP2C), 4.7 (1H, C CH2), 6.1 (0.5 N, - CH C, multilett), 7 (, aromatic.), Gp / e 240. Hydrogenation on skeletal nickel gives 1-feiyl-4,8-dimethyldecane, m.p. 78 ° C / 06 mm Hg Art., “2 ° 1.4798. Trimethyl-1,5,9-cyclododecatriene, t. Kip. 155 ° C / 20 mmHg Art., "1.5041. The constants of dipeitene and 1,5-dimethyl-1,5-cyclooctadiae coincide with the literature data. Example 2. A solution of 2 g of Ni (AcAc) 2, 3.6 g of A1 (C2P5) s, 5 ml of iso-respiration in 20 ml of toluene is stirred at -5 ° C. within 0.5 hour Then, 1.02 g of bead II was added, which was obtained by boiling equimolar amounts of boric acid with pentaerythritol, and the mixture was not stirred at this temperature for another 1.5 hours. A solution of a catalyst prepared as described above, 52 g of styrene, 68 g of isoprene, and stirring the reaction mixture at 100 ° C for 4 hours are introduced into a steel autoclave with a capacity of 300 ml in a stream of argon. The autoclave is cooled, the catalpsate is distilled with steam. Oligomers were isolated as described in Example 1. 84 g of a mixture of oligomers was obtained, which according to GLC consisted of 50% Phagel-4, 8-dimethyl-1,4,8 (9) -decatrienes, 30% dipeithea, 15% 1, 5-dimethyl-1,5-cyclooctadiene and 5% trimethyl-1,5,9-cyclododecatriene. The constants of the hydrocarbons obtained coincide with the constants of the compounds obtained in Example 1. Example 3. Linear co-oligomerization of 52 g of styrene with 68 g of isoprene on a catalytic system consisting of 2 g of Ni (AcAc) 2, 3.6 g of A1 (C2H5) g, 5 ml of isoprene, 1.79 g of tributylborate (C4H90) zV at 100 ° C for 4 hours after the usual treatment (irimer 1) results in 51.6 g of a mixture of oligomers, which contains 53% 1-feiyl 4, according to GLC -dimethyl-1,4,8-decatriene, 33% dipentene and trimethyl-1,5,9-cyclododecatriene. 1,5-dimeyl-1, 5-cyclooctadiene is not formed. Example 4. To a solution of 3 g of Ni (AcAc) j, 4.4 g of A1 (C2H5) s, 8 ml of trans-piperylene in 20 ml of an oluol in a stream of argon at -5 ° C are added 1.83 g of boratrane 1 and the mixture move at this temperature for at least 1.5 hours. The catalyst solution is then transferred to a 300 ml steel autoclave, in which 52 g of styrene and 68 g of piperylene are added. Mons are heated with 100 ° C ture for 4 hours. the quench is cooled, catalyzed by steam distillation. The distillate is separated, the aqueous layer is leached with ientane and combined with the basic amount of distillate, dried over MgSO4.

After removal of the solvent, the residue is distilled in vacuo. 72 g of a mixture of oligomers, consisting, according to GLC, of 9% cyclodimers of piperylene, 23% cyclosodimer and 68% of 1-phenyl-6-megyl-1,4,9- and 1,4,10-udine carbonyl are obtained.

Hydrocarbons, isolated by distillation on a column, have the following constants.

1-Phenyl-6-methyl-1,4,8 (9) - undecatrienes, t. Bales. 1E5 ° C (1 mm Hg. Art., "20 1.5122. UV-spectrum (.f): 261, e 18000. IR-spectrum (v cm-1): 720, 750, 3010 (С-П- aromatic.), 920, 1000, 3080 (), 975, 3030 (trans-CH, CH-), h-NMR spectrum (b ppm): 1.25 (SP, SPZ, 1 6 Hz), 1.45 (4P, multiplet), 1.92 (RFP, C-SPZ-, multiplet), 2.72 (2P, C-SP2-C-, multiplet), 4.90 (2P, C SP2), 5.26 (4P, -SP SP-, multiplet).

Claims (2)

1. Pateit FRG 1201328, cl. 12 to 19/01, 1966. 2. US patent 3271468, cl. 260-668,1666.