The way to obtain 1,4-bis[(dialkoxy)alyuma]-trans-2,3 - dialkylamino

 

(57) Abstract:

The invention relates to a method of obtaining new alyuminiiorganicheskikh compounds 1,4-bis-[(dialkoxy)alyuma] -TRANS-2,3-dialkylamino formula R=C2H5or C4H9R=C3H7C4H9or C5H11These compounds may find application as components of catalytic systems in the processes of polymerization and oligomerization of olefin and diene hydrocarbons. 1,4-bis-[(dialkoxy)alyuma] -TRANS-2,3-dialkylated obtained by interaction-olefins (1-hexene, 1-hepten, 1-octene) with dialkoxybenzene of the formula (RO)2AlCl where R=(C2H5-C4H9) and metallic magnesium in a molar ratio(20 22): (20 22) 10 in the presence of (C5H5)2ZrCl22 6 mol. in an argon atmosphere at room temperature, normal pressure in THF under stirring for 8 to 12 o'clock Exit 66 84% 1 table.

The invention relates to new alyuminiiorganicheskikh connections, specifically to 1,4-bis-[(dialkoxy)alyuma] TRANS-2,3-dialkylphenol, the General formula (I).

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The proposed compounds may find application as components of catalytic complexes of the om and fine organic synthesis, in particular in Regio - and stereoselective synthesis of TRANS-2,3-dialkylamides 1,4-butandiol.

The known method [1] obtain 1,4-bis-(Diisobutylene)butane and 1,4-bis-(Diisobutylene)-2-methylbutane hydroalumination butadiene (or isoprene ( ) using Diisobutylene-Nigeria (i-Bu2AlH) in an autoclave at a temperature of 80-85aboutWith over 13 h scheme:

i-Bu2AlAlB i-Bu2AlH (i-Bu2Al AlB

The disadvantages of this method: hydroalumination conjugated 1,3-dienes accompanied by the formation of seal products, in addition, the conversion of 1,3-dienes does not exceed 50% of the known method does not allow to obtain 1,4-bis-[(dialkoxy)alyuma]-TRANS - 2,3-dialkylated.

The known method [2] to obtain 1,4-bis-(dialume)-2-methylbutane hydroalumination of isoprene using an amine complex of aluminum hydride (AlH3N(CH3)3in the presence of catalyst titaniumdioxide (Cp2TiCl2) at a temperature of 80aboutWith over 1 h Hydrolysis obtained Deluminator connection leads to isopentane with the release of 93%, the Reaction proceeds according to the scheme:

AlH3N(CH3)3+ alal al al

The known method does not allow to obtain 1,4-bis-[(dialkoxy) alyuma]-TRANS-2,3-dialkylated.

The aim of the invention is the development of new types of higher dialuminium compounds, namely 1,4-bis-[(dialkoxy) alyuma]-TRANS-2,3-dialkylphenol with high Regio - and stereoselectivity.

This goal is achieved by the interaction of a-olefins (1-hexene, 1-hepten, 1-octene) with dialkoxybenzene of the formula (RO)2AlCl, where R Ft, n-Bu, and metal magnesium, taken in a molar with respect to Mg (RO)2AlCl R 10:(20-22):(20-22), mostly 10:21:21, in the presence of a catalyst of dicyclopentadienyltitanium (Cp2ZrCl2) in an amount of 2-6 mol. with respect to the metal magnesium, preferably 5 mol. in an argon atmosphere at room temperature (23-25aboutC) and normal pressure in THF under stirring for 8-12 hours Receive individual 1,4-bis-[(dialkoxy)alyuma] -TRANS - 2,3-dialkylated with outputs 66-84% the Reaction proceeds according to the scheme:

2(RO)2AlCl+Mg+2R (RO)(OR)2< / BR>
The obtained 1,4-bis-(dialkoxy)alyuma-TRANS-2,3-dialkylated contain two chiral center (C2and3and can be in the form of stereoisomeric pairs of CIS - and TRANS-configuration. An analysis of the received alyuminiiorganicheskikh compounds using NMR13From indicates the formation of iskette catalyst is greater than 6 mol. does not lead to a significant increase in the yield of the target products. The use of the catalyst Cp2ZrCl2less than 2 mol. with respect to the metal magnesium reduces the output dialuminium compounds (I), which is associated with a decrease in reaction centers. Experiments were performed at room temperature (23-25aboutC). At a higher temperature (for example, 50aboutC) increases the amount of seal products, at a lower temperature (for example, 0aboutC) decreases the reaction rate.

Without catalyst Cp2ZrCl2the reaction is not. Unable to get dialuminium connection without (EtO)2AlCl and (u-BuO)2AlCl, or replace them with other alyuminiiorganicheskikh connection, for example Alet3i-Bu3Al, EtAlCl2i-BuAlH.

Changing the ratio of initial reagents in the direction of increasing the content of dialkoxybenzene or-olefins relative to the Mg does not lead to a significant increase in the yield of the target product. Reduction of the initial reagents in relation to Mg reduces the yield of the target products.

In the known method are used amine complex of aluminum hydride (AlH3N(CH3)3), a titanium catalyst (Cf2TiCl2) and isoprene ( ), the ora (Cp2ZrCl2), and as the aluminum compounds used alkoxides (to)2AlCl or (n-BuO)2AlCl.

The proposed method, in contrast to the known, allows you to obtain an individual 1,4-bis-(dialkoxy)-TRANS-2,3-dialkylated, the synthesis of which are not described in literature.

P R I m e R 1. In a glass reactor with a volume of 50 ml, mounted on a magnetic stirrer, an argon atmosphere was placed 21 mol (n-BuO)2AlCl in 20 ml of THF, 10 mmol magnesium (powder), 21 mmol of 1-Hexene and 0.5 mmol Cp2ZrCl2, stirred for 10 h at room temperature (23-25aboutC). Receive 1,4-bis-[(di-n-butoxy)alyuma] TRANS-2,3-dibutylated exit 77% NMR Spectrum13With 1,4-bis-[(di-n-butoxy)alyuma]-TRANS-2,3-dibutylamine(M. D.):

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Other examples of the method shown in the table.

All experiments were performed at room temperature (23-25aboutC) in THF. In other solvents (dioxane, ether, hexane, benzene, cyclohexane) output target product was sharply decreased.

The WAY to OBTAIN 1,4-BIS[(DIALKOXY)ALYUMA] -TRANS-2,3-DIALKYLAMINO General formula

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where R is C2H5or C4H9;

R= C3H7C4H9or C5H11,

characterized in that ormula

(RO)2AlCl,

where R is ethyl or butyl,

and metallic magnesium in a molar ratio of 20 22 20 22 10 respectively in the presence of dicyclopentadienyltitanium 2 6 mol. in relation to magnesium and the process is conducted at room temperature in an argon atmosphere, normal pressure in the environment of tetrahydrofuran, with stirring for 8 to 12 hours

 

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The invention relates to a method of obtaining new alyuminiiorganicheskikh compounds 1,4-bis(dialkylamino)-TRANS-2,3-dialkylamino formulawhere R is C2H5or C4H9; R-C3H7C4H9C5H11

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(R2N)AlAl(NR2)

where R2N Et2NN

R1C3H7C4H9C5H11

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-Bui< / BR>
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