RU2043356C1 - Method of synthesis of 1,4-bis-(dialkylalumino)-trans-2,3-dialkylbutanes - Google Patents

Abstract

FIELD: organoaluminium compounds. SUBSTANCE: products: 1,4-bis-(dialkylalumino)-trans-2,3-dialkylbutanes were synthesized by interaction of α-olefins (1-hexene, 1-heptene, 1-octene) with diethylaluminium chloride or diisobutylaluminium chloride at metallic magnesium at the molar ratios (20-22):(20-22):10 in the presence of zirconium tetrachloride as catalyst at concentration 3-5 mole in argon atmosphere, at the room temperature, under normal pressure, in the medium of tetrahydrofurane, at stirring for 6-10 h. Yield is 74-90% EFFECT: improved method of synthesis. 1 tbl

Description

где R Et;
i Bu;
R' C₃H₇, C₄H₉, C₅H₁₁
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, в частности в регио- и стереоселективном синтезе транс-2,3-диалкилзамещенных 1,4-бутандиолов.The invention relates to new organoaluminum compounds, specifically to 1,4-bis (dialkylalum) -trans-2,3-dialkylbutanes of the general formula

where R Et;
i Bu;
R 'C ₃ H ₇ , C ₄ H ₉ , C ₅ H ₁₁
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, in particular in the regio- and stereoselective synthesis of trans-2,3-dialkyl-substituted 1,4-butanediols.

или изопрена

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

AlB

i-Bu₂AlH

i-Bu₂Al

AlB

Недостатки известного способа:
гидроалюминирование сопряженных 1,3-диенов сопровождается образованием продуктов уплотнения, кроме того конверсия 1,3-диенов не превышает 50%
известный способ не позволяет получать 1,4-бис(диалкилалюма)транс-2,3-диалкилбутаны.A known method for producing 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 ^{° C} for 13 hours according to the scheme:
i-bual

Alb

i-Bu ₂ AlH

i-Bu ₂ Al

Alb

The disadvantages of this method:
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%
the known method does not allow to obtain 1,4-bis (dialkylalum) trans-2,3-dialkylbutanes.

al

Недостатком известного способа является то, что он не позволяет получать 1,4-бис(диалкилалюма)-транс-2,3-диалкилбута- ны.A method is known as preparation of 1,4-bis (dialyuma) -2-methylbutane hydroalumination isoprene using an amine complex of aluminum hydride (AlH ^_3. N (CH _{3) 3} in the presence of a catalyst titanotsendihlorida (Cp ₂ TiCl ₂₎ for
. ⁸⁰ ° C for 1 h dialyuminievogo Hydrolysis of the resulting compound of isopentane leads to a yield of 93% The reaction proceeds according to the scheme:
AlH ₃ · N (CH _{3) 3} +

al

A disadvantage of the known method is that it does not allow to obtain 1,4-bis (dialkylalum) -trans-2,3-dialkylbutanes.

 Thus, in the literature there is no information on the regio- and stereoselective synthesis of 1,4-bis (dialkylalum) -trans-2,3-dialkylbutanes.

 The aim of the invention is the development of new types of higher diallyuminium compounds, namely 1,4-bis (dialkylalum) -trans-2,3-dialkyl-butanes.

10:(20-22):(20-22), преимуще- ственно 10:21:21, в присутствии катализатора тетрахлорида циркония (ZrCl₄) в количестве 3-5 мол. по отношению к металлическому магнию, предпочтительно 4 мол. в атмосфере аргона при комнатной температуре 23-25^оС и нормальном давлении в ТГФ при перемешивании в течение 6-10 ч. Получают 1,4-бис(диалкилалюма)-транс-2,3-диалкилбутаны с выходами 74-90% Реакция протекает по схеме
2R₂AlCl + Mg + 2R

R₂Al

lR₂
Проведение указанной реакции в присутствии катализатора ZrCl₄ больше 5 мол. не приводит к существенному увеличению выхода целевых продуктов. Использование катализатора ZrCl₄ менее 3 мол. по отношению к металлическому магнию снижает выход диалюминиевых соединений (I), что связано с уменьшением реакционных центров. Опыты проводили при комнатной температуре 23-25^оС. При более высокой температуре, например 50^оС увеличивается содержание продуктов уплотнения, при меньшей температуре, например 0^оС, снижается скорость реакции.This goal is achieved by the interaction of α-olefins (1-hexene, 1-heptene, 1-octene) with diethylaluminium chloride (Et ₂ AlCl) or diisobutylaluminium chloride (i-Bu ₂ AlCl) and magnesium metal, taken in a molar ratio of Mg R ₂ AlCl R

10: (20-22) :( 20-22), preferably 10:21:21, in the presence of a catalyst of zirconium tetrachloride (ZrCl ₄ ) in an amount of 3-5 mol. in relation to metallic magnesium, preferably 4 mol. in an atmosphere of argon at room temperature of 23-25 ^{° C} and normal pressure with stirring in THF for 6-10 h. The obtained 1,4-bis (dialkilalyuma) -trans-2,3-dialkilbutany in yields 74-90% reaction proceeds according to the scheme
2R ₂ AlCl + Mg + 2R

R ₂ Al

lR ₂
Carrying out the specified reaction in the presence of a catalyst ZrCl ₄ more than 5 mol. does not lead to a significant increase in the yield of target products. The use of catalyst ZrCl ₄ less than 3 mol. with respect to metallic magnesium reduces the yield of dialuminium compounds (I), which is associated with a decrease in reaction centers. Experiments were performed at room temperature 23-25 ° ^C. At higher temperatures, e.g. 50 ^{° C} increases the content of products of condensation at a lower temperature, eg ⁰ ° C, the reaction rate decreases.

Without the ZrCl ₄ catalyst, 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, α-олефинов, циркониевого катализатора (ZrCl₄), а в качестве алюминийорганических соединений используют Et₂AlCl или i-Bu₂AlCl₂.Essential difference of the proposed method is the use of known amine complex of aluminum hydride (AlH ^_3. N (CH _{3) 3),} titanium catalyst for (Cp ₂ TiCl ₂₎ and isoprene

, while in the proposed reaction proceeds in the presence of metallic Mg, α-olefins, a zirconium catalyst (ZrCl ₄ ), and Et ₂ AlCl or i-Bu ₂ AlCl _{2 is} used as organoaluminum compounds.

 The advantage of the proposed method is that, unlike the known ones, it allows the preparation of individual 1,4-bis (dialkylalum) -trans-2,3-dialkyl-butanes, the synthesis of which is not described in the literature.

_____→
Другие примеры, подтверждающие способ, приведены в таблице.PRI me R 1. In a glass reactor with a volume of 50 ml, mounted on a magnetic stirrer, in an argon atmosphere is placed 21 mmol of i-Bu ₂ AlCl in 20 ml of THF, 10 mmol of magnesium (powder), 21 mmol of 1-hexene and 0 , 4 mol of ZrCl ₄ , stirred for 8 hours at room temperature 23-25 ^about C. Receive 1,4-bis (diisobutylalum) -trans-2,3-dibutyl-butane with a yield of 84%
Spectral characteristics of 1,4-bis (diisobutylalum) -trans-2,3-dibutyl-butane ( ¹³ C NMR (δ, ppm):

_____ →
Other examples confirming the method are given in the table.

All experiments were performed at room temperature 23-25 ^{° C} in THF. In other solvents (dioxane, ether, hexane, benzene, cyclohexane), the yield of the target product sharply decreased.

Claims (1)

METHOD FOR PRODUCING 1,4-BIS (DIALKYLALUM) -TRANS-2,3-DIALKYLBUTANES of the general formula

where RC ₂ H ₅ or i C ₄ H ₉ ;
R ₁ C ₃ H ₇ , C ₄ H ₉ or C ₅ H _{1 1} ,
characterized in that the n-α-olefin containing C ₆ C ₈ is reacted with diethylaluminium chloride or diisobutylaluminium chloride and magnesium metal in a molar ratio of 10 (20 22) (20 22), respectively, in the presence of zirconium tetrachloride in an amount of 3 5 mol . with respect to magnesium, the process is carried out at room temperature in an argon atmosphere and normal pressure in tetrahydrofuran medium with constant stirring for 6 to 10 hours.

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