RU2156767C2 - Method of preparing 1,2-bis(dialkylaluma)cis-1,2-diphenyl (alkyl)ethylenes - Google Patents

Abstract

FIELD: metallic and fine organic synthesis. SUBSTANCE: method comprises reacting dialkylaluminium chlorides of formula:

wherein R′ is Et, i-Bu with disubstituted acetylene of formula: R-≡-R wherein R is Ph, n-C₃H₇,n-C₄H₉ and metallic magnesium at

molar ratio of (25-35): 10: (10-14), respectively in the presence of titanocene d:chloride ((Cp₂TiCl₂)) in amount of 2-5 mole % respect to disubstituted acetylene in argon atmosphere under normal conditions in tetrahydrofuran and agitation for 6-10 hours. The new resulting compounds are useful as catalyst complex components in processes of polymerization and oligomerization of olefin and diene hydrocarbons. EFFECT: more efficient preparation method. 1 ex, 1 tbl

Description

Предлагаемые соединения могут найти применение в качестве компонентов каталитических комплексов в процессах полимеризации и олигомеризации олефиновых и диеновых углеводородов, а также в металлоорганическом и тонком органическом синтезе.The invention relates to a method for producing new organoaluminum compounds, specifically to 1,2-bis (dialkylalum) -cis-1,2-diphenyl (alkyl) ethylenes of the general formula (1):

The proposed compounds can be used as components of catalytic complexes in the polymerization and oligomerization of olefin and diene hydrocarbons, as well as in organometallic and fine organic synthesis.

или изопрена

с помощью диизобутилалюминийгидрида (i-Bu₂AlH) в автоклаве при температуре 80 - 85^oC за 13 часов по схеме:

Недостатки известного способа.The known method / Zakharkin L.I., Savina L.A. Izv. USSR Academy of Sciences. Ser. Chem. 1967. p. 78-84 / obtaining dialyuminium compounds, in particular 1,4-bis (diisobutylalum) butane and 1,4-bis- (diisobutylalum) -2-methylbutane by hydroalumination of butadiene

or isoprene

using diisobutylaluminum hydride (i-Bu ₂ AlH) in an autoclave at a temperature of 80 - 85 ^o C for 13 hours according to the scheme:

The disadvantages of this method.

 1. Hydroalumination of conjugated 1,3-dienes is accompanied by the formation of compaction products, in addition, the conversion of 1,3-dienes does not exceed 50%.

 2. The known method does not allow to obtain 1,2-bis (dialkylalum) -cis-1,2-diphenyl (alkyl) ethylenes.

Недостатки известного способа.A known method (G. Dozzi, S. Cucinella, A. Mazzei, J. Organomet. Chem., 164 (1979) p. 1-10) for the preparation of 1,4-bis (dialum) -2-methylbutane by hydroaluminating isoprene using amine aluminum hydride complex (AlH ₃ • N (CH ₃ ) ₃ ) in the presence of a titanocene dichloride catalyst (Cp ₂ TiCl ₂ ) at a temperature of 80 ^{° C.} for 1 hour. Hydrolysis of the resulting dialuminium compound leads to isopentane in 93% yield. The reaction proceeds according to the scheme:

The disadvantages of this method.

 1. The known method does not allow to obtain 1,2-bis- (dialkylalum) -cis-1,2-diphenyl (alkyl) ethylenes.

 Thus, in the literature there is absolutely no information on the regio- and stereoselective synthesis of 1,2-bis- (dialkylalum) -cis-1,2-diphenyl (alkyl) ethylenes.

 A new method for the regio- and stereoselective synthesis of 1,2-bis- (dialkylalum) -cis-1,2-diphenyl (alkyl) ethylenes is proposed.

= (25 - 35) : 10 : (10 - 14), предпочтительно 30 : 10 : 12, в присутствии катализатора титаноцендихлорида (Cp₂TiCl₂) в количестве 2-5 мол. % по отношению к дизамещенному ацетилену, предпочтительно 3 мол.%, в атмосфере аргона при комнатной температуре (22-24^o) и нормальном давлении в ТГФ при перемешивании в течение 6-10 часов. Получают 1,2-бис(диалкилалюма)-цис-1,2-дифенил(алкил)-этилены с выходами 72-94%. Реакция протекает по схеме:

Проведение указанной реакции в присутствии катализатора Cp₂TiCl₂ больше 5 мол. % не приводит к существенному увеличению выхода целевых продуктов. Использование катализатора Cp₂TiCl₂ менее 2 мол.% по отношению к дизамещенному ацетилену снижает выход диалюминиевых соединений (1), что связано с уменьшением реакционных центров. Опыты проводили при комнатной температуре (22-24^oC). При более высокой температуре (например, 50^o) увеличивается содержание продуктов уплотнения, при меньшей температуре (например, 0^o) снижается скорость реакции.The essence of the method consists in the interaction of dialkylaluminium chlorides (Et ₂ AlCl, i-Bu ₂ AlCl) with disubstituted acetylenes R-≡-R (diphenylacetylene, octin-4, depin-5) and metal magnesium, taken in a molar ratio

= (25 - 35): 10: (10 - 14), preferably 30: 10: 12, in the presence of a titanocene dichloride catalyst (Cp ₂ TiCl ₂ ) in an amount of 2-5 mol. % relative to disubstituted acetylene, preferably 3 mol.%, in an argon atmosphere at room temperature (22-24 ^o ) and normal pressure in THF with stirring for 6-10 hours. 1,2-bis (dialkylalum) -cis-1,2-diphenyl (alkyl) ethylenes are obtained in 72-94% yields. The reaction proceeds according to the scheme:

The specified reaction in the presence of a catalyst Cp ₂ TiCl ₂ more than 5 mol. % does not lead to a significant increase in the yield of target products. The use of the catalyst Cp ₂ TiCl ₂ less than 2 mol.% In relation to disubstituted acetylene reduces the yield of dialuminium compounds (1), which is associated with a decrease in reaction centers. The experiments were carried out at room temperature (22-24 ^o C). At a higher temperature (for example, 50 ^o ), the content of the seal products increases, at a lower temperature (for example, 0 ^o ) the reaction rate decreases.

Without the catalyst Cp ₂ TiCl _{2 the} reaction does not proceed. It is not possible to obtain dialyuminium compounds without Et ₂ AlCl and i-Bu ₂ AlCl, or replacing them with other organoaluminum compounds, for example AlEt ₃ , i-Bu ₃ Al, EtAlCl ₂ , i-Bu ₂ AlH.

в то время как в предлагаемом реакция протекает в присутствии металлического Mg, дизамещенных ацетиленов, а в качестве алюминийорганических соединений используют Et₂AlCl или i-Bu₂AlCl.Significant differences of the proposed method from the known:
1. In the known method, the amine complex of aluminum hydride (AlH ₃ • N (CH ₃ ) ₃ ) and isoprene are used

while in the proposed reaction proceeds in the presence of metallic Mg, disubstituted acetylenes, and Et ₂ AlCl or i-Bu ₂ AlCl is used as organoaluminum compounds.

 The advantages of the proposed method.

 1. The proposed method, unlike the known ones, allows one to obtain individual 1,2-bis (dialkylalum) -cis-1,2-diphenyl (alkyl) ethylenes, the synthesis of which is not described in the literature.

 The method is illustrated by examples.

Спектральные характеристики цис-стильбена (II): ИК-спектр (ν, см^-1): 3030, 1600, 1500, 1450, 1380, 1090, 980, 780, 710.Example 1. In a 50 ml glass reactor mounted on a magnetic stirrer, 30 mmol Et ₂ AlCl in 20 ml THF, 12 mmol magnesium (powder), 10 mmol tolane (Ph-≡-Ph) and 0.3 were placed under argon atmosphere. mmol Cp ₂ TiCl ₂ , stirred for 8 hours at room temperature (22-24 ^o ). Receive 1,2-bis (diethylalum) -cis-1,2-diphenylethylene with a yield of 87%, the yield was determined by the hydrolysis product. Hydrolysis of 1,2-bis- (diethylalum) -cis-1,2-diphenylethylene produces cis-stilbene (II), and during deuterolysis, respectively, 1,2-dideuterostilbene (III) according to the scheme:

Spectral characteristics of cis-stilbene (II): IR spectrum (ν, cm ^-1 ): 3030, 1600, 1500, 1450, 1380, 1090, 980, 780, 710.

1 H-NMR spectrum (δ, ppm): 6.57 s (2H, CH = CH), 7.12-7.57 m (10H, Ph). M ⁺ 180.

Spectral characteristics of 1,2-dideuterostilbene (III):
IR spectrum (ν, cm ^-1 ): 3080, 3030, 2240, 1950, 1600, 1500, 1440, 1180, 1150, 1070, 1020, 920, 750, 690, 540. PMR spectrum (δ, ppm ): 7.22 s (10H, Ph). ¹³ C NMR spectrum (δ, ppm): 130.75 t (CD, J = 23 Hz), 137.14 s (C ² ), 128.18 (C ³ ), 128.87 (C ⁴ ), 127.12 (C ⁵ ) M ⁺ 182.

 Other examples confirming this method are shown in the table.

All experiments were carried out at room temperature (22-24 ^o ) in THF. In other solvents (dioxane, ether, hexane, benzene, cyclohexane), the yield of the target product decreases sharply.

Claims (1)

The method of obtaining 1,2-bis (dialkylalum) -cis-1,2-diphenyl (alkyl) ethylenes of the general formula I

where R = Ph, n-C ₃ H ₇ , n-C ₄ H ₉ ;
R '= Et, i-Bu,
characterized in that the dialkylaluminium chloride R ' ₂ AlCl, where R' = Et, i-Bu, is reacted with a disubstituted acetylene of the formula R-≡-R, where R = Ph, n-C ₃ H ₇ , n-C ₄ H ₉ , and metal magnesium taken in a molar ratio

equal to (25 - 35): 10: (10 - 14), in the presence of a catalyst of titanocene dichloride (Cp ₂ TiCl ₂ ) in an amount of 2 - 5 mol% with respect to disubstituted acetylene in an argon atmosphere under normal conditions in tetrahydrofuran medium with stirring in for 6 to 10 hours

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