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

 

(57) Abstract:

Use in ORGANOMETALLIC chemistry, in particular in a method of producing 1,4-bis-[(N,N dialkylamino) alyuma]-TRANS-2,3-dialkylamino, for example 1,4-bis-[(N, N-diethylamino) alyuma]-TRANS - 2,3-tibetana. The inventive product is 1,4-bis-[(N, N-diethylamino)alyuma] -TRANS-2,3-Tibetan. Reagent 1: C6-C8olefin. Reagent 2: [(N,N-dialkylamino)aluminum chloride] (R2N)2AlCl, where R2N diethylamine or pyridine. Reagent 3: magnesium metal. Reaction conditions: molar ratio of reagents 1 2 3 (20 22): (20 22) 1, the process is conducted in the presence of a catalyst containing cyclopentadienylzirconium chloride and diisobutylaluminum hydride, taken in a molar ratio equal to 1 (2 4), in an argon atmosphere at room temperature in the environment of tetrahydrofuran for 8 to 12 hours 1 table.

The invention relates to new alyuminiiorganicheskikh connections, specifically to 1,4-bis-[(N, N-dialkylamino)-Aluma] TRANS-2,3-dealkylation, General formula I

(R2N)AlAl(NR2)

where R2N Et2N N

R1C3H7C4H9C5H11.

The proposed compounds may find application as components of catalytic completescan 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 85-85aboutWith over 13 h scheme:

i-Bu2AlH

The disadvantages of this method are: 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 way does not allow to obtain 1,4-bis-[(N,N-dialkylamino)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 (Cf2TiCl2)

temperature 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+ ala

However, this method does not allow to obtain 1,4-bis-[(N, N-dialkylamino)alyuma]-TRANS-2,3-dialkylated.

In lilalmotamok.

The aim of the invention is the development of new types of higher dialuminium compounds, namely 1,4-bis-[N,N-dialkylamino)- Aluma]-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 (N,N-dialkylamino)aluminofluoride formula (R2N)2AlCl, where R2N Et2N, N, and metal magnesium, taken in a molar ratio of

Mg: (Et2N)2AlCl: R 10:(20-22):(20- 22), mostly 10:21:21, in the presence of a catalyst dicyclopentadienyl - zirconiated (Cf2ZrCl2and diisobutylaluminium (i-Bu2AlH), taken in a molar ratio of 1:(2-4), mostly 1: 3. Cf2ZrCl2is taken in the amount of 2-6 mol. with respect to Mg, preferably 5 mol. in an argon atmosphere at room temperature (23-25aboutC) and normal pressure in THF. The reaction time is 8-12 hours Receive individual 1,4-bis-[N,N-dialkylamino)alyuma]-TRANS-2,3-di - alkylborane with outputs 78-95% the Reaction proceeds according to the scheme:

2(R2N)2AlCl+Mg+ 2R (R2N)2AlAl(NR2)2< / BR>
The obtained 1,4-bis-[(N,N-dialkylamino)alyuma]-TRANS-2,3-dialkylated contain two chiral center (C2and3and can nagoditi compounds using NMR 13From indicates the formation of exclusively single stereoisomer TRANS-configuration.

Without the complex catalyst (Cf2ZrCl2+ i-Bu2AlH) reaction is not. Unable to obtain the target products without (Et2N)2AlCl and NAlCl or replace them with other alyuminiiorganicheskikh connection, for example AlEt3i-Bu3Al, EtAlCl2i-Bu2AlCl.

The conduct of a specified reaction in the presence of a catalyst Cp2ZrCl2more than 6 mol. does not lead to a significant increase in the yield of the target products. The use of catalyst Cu2ZrCl2less 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, 0oC) decreases the reaction rate.

Changing the ratio of initial reagents in the direction of increasing the content of N,N-dialkylaminomethyl or-olefins relative to the Mg does not lead to a significant increase in the yield of target products. Reduction of the initial rumyniey complex of aluminum hydride (AlH3N(CH3)3), a titanium catalyst (Cf2TiCl2) and isoprene ( ), while in the proposed method, the reaction proceeds in the presence of metallic Mg-olefins, zirconium complex catalyst (Cf2ZrCl2+ i-Bu2AlH), and compounds of aluminum, use aluminum amides (Et2N)2AlCl or NAlCl

The proposed method, in contrast to the known, allows you to obtain an individual 1,4-bis-[(N, N-dialkylamino)alyuma] 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 mmol (Et2N)2AlCl in 20 ml of THF, 10 mmol magnesium (powder), 21 mmol of 1-hexene and a catalyst prepared by mixing 0.5 mmol Cf2ZrCl2with 1.5 mmol i-Bu2AlH in 3 ml of THF, stirred for 10 h at room temperature (23-25aboutC). Receive 1,4-bis-[N, N-diethylamino)alyuma]-TRANS-2,3-dibutylated exit 89%

An NMR spectrum13With 1,4-bis-[N,N-diethylamino)alyuma]-TRANS-2,3-dibutylamine (, memorial plaques) (C6D6, TMS):

< / BR>
Other examples of this method, shown in the table.

All experiments were performed at room temperature (23-ESCO decreased.

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

< / BR>
< / BR>
R1C3H7C4H9C5H11,

characterized in that the olefin containing C6C8, is subjected to the interaction with the (N, N-dialkylamino)aluminofluoride General formula

(R2N)2AlCl,

< / BR>
and metallic magnesium in a molar ratio of (20 22) (20 22) 10, respectively, in the presence of a catalyst containing dicyclopentadienyltitanium and diisobutylaluminium in a molar ratio of 1 2 4, and the process is conducted in an argon atmosphere at room temperature, normal pressure in the environment of tetrahydrofuran for 8 to 12 hours

 

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