The way to obtain 1,4-bis(dialkylamino) -trans-2,3 - dialkylamino

 

(57) Abstract:

The invention relates to a method of obtaining new alyuminiiorganicheskikh compounds 1,4-bis(dialkylamino)-TRANS-2,3-dialkylamino formula where R is C2H5or C4H9; R-C3H7C4H9C5H11. These compounds may be used as components of catalytic systems in the processes of polymerization and oligomerization of olefin and diene hydrocarbons. The inventive 1,4-bis (dialkylamino) -TRANS-2,3 - dialkylated get interaction-olefins (1-hexene, 1-hepten, 1-octene) with diethylaluminium or diisobutylaluminium and metallic magnesium in a molar ratio of (20-22) (20-22) 10 in the presence of a catalyst of zirconium tetrachloride in the amount of 3-5 mol. in an argon atmosphere at room temperature, normal pressure, in an environment of tetrahydrofuran under stirring for 6-10 hours Output 74-90 1 table.

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

where R Et;

i Bu;

R' C3H7C4H9C5H11< / BR>
The proposed connection can n and olefin and diene hydrocarbons, and in ORGANOMETALLIC and fine organic synthesis, in particular in Regio - and stereoselective synthesis of TRANS-2,3-dialkylamides 1,4-butandiol.

A method of obtaining 1,4-bis(Diisobutylene)butane and 1,4-bis(Diisobutylene)-2-methylbutane hydroalumination of butadiene or isoprene with diisobutylaluminium (i-Bu2AlH) in an autoclave at a temperature of 80-85aboutWith over 13 h scheme:

i-BuAl AlB i-Bu2AlH (i-Bu2Al AlB

The disadvantages of this method:

hydroalumination conjugated 1,3-dienes accompanied by the formation of seal products, additionally, the conversion of 1,3-dienes does not exceed 50%

the known method does not allow to obtain 1,4-bis(dialkylamino)TRANS-2,3-dialkylated.

The known method also obtain 1,4-bis(dialume)-2-methylbutane hydroalumination of isoprene using an amine complex of aluminum hydride (AlH3.N(CH3)3in the presence of a catalyst of titaniumdioxide (Cp2iCl2)

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+ al

The disadvantage JV the way in the literature there are no data on Regio - and stereoselective synthesis of 1,4-bis(dialkylamino)-TRANS-2,3-dialkylphenol.

The aim of the invention is the development of new types of higher dialuminium compounds, namely 1,4-bis(dialkylamino)-TRANS-2,3-dialkyl - butane.

This goal is achieved by the interaction of a-olefins (1-hexene, 1-hepten, 1-octene) with dietilaminsalicilat (Et2AlCl) or diisobutylaluminium (i-Bu2AlCl) and metallic magnesium, taken in a molar ratio of Mg R2AlCl R 10:(20-22):(20-22), advantage - ingly 10:21:21, in the presence of a catalyst of zirconium tetrachloride (ZrCl4) in the amount of 3-5 mol. with respect to the metal magnesium, preferably 4 mol. in an argon atmosphere at room temperature 23-25aboutC and normal pressure in THF with stirring for 6-10 hours Receive 1,4-bis(dialkylamino)-TRANS-2,3-dialkylated with outputs 74-90%, the Reaction proceeds according to the scheme

2R2AlCl + Mg + 2R R2AllR2< / BR>
The conduct of a specified reaction in the presence of a catalyst ZrCl4more than 5 mol. does not lead to a significant increase in the yield of the target products. The use of catalyst ZrCl4less than 3 mol. with respect to the metal magnesium reduces Noah temperature 23-25aboutC. At higher temperatures, for example 50aboutWith increasing content of products seals at a lower temperature, for example 0aboutWith reduced reaction rate.

Without catalyst ZrCl4the reaction is not. Unable to get dialuminium connection without Et2AlCl and i-Bu2AlCl, or replace them with other alyuminiiorganicheskikh connection, for example AlEt3i-Bu3Al, EtAlCl2i-Bu2AlH.

The major difference of the proposed method against known is the use of an amine complex of aluminum hydride (AlH3.N(CH3)3), titanium cat - lyst (Cf2TiCl2and isoprene , while in the proposed reaction proceeds in the presence of metallic Mg-olefins, zirconium catalyst (ZrCl4), and as alyuminiiorganicheskikh connections use Et2AlCl or i-Bu2AlCl2.

The advantage of the proposed method is that it in contrast to the known allows you to obtain an individual 1,4-bis(dialkylamino)-TRANS-2,3-dialkyl-butane, 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, in the atmosphere Eremeeva 8 h at room temperature 23-25aboutC. Obtain 1,4-bis(Diisobutylene)-TRANS-2,3-dibutil-butane with exit 84%

The spectral characteristics of 1,4-bis(Diisobutylene)-TRANS-2,3-dibutil-butane (NMR13With ( , m D.):

_____< / BR>
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(DIALKYLAMINO)-TRANS-2,3-DIALKYLAMINO General formula

< / BR>
where R is C2H5or i C4H9;

R1C3H7C4H9or C5H11,

characterized in that the n-olefin containing FROM6WITH8expose interaction with diethylaluminium or diisobutylaluminium and metallic magnesium in a molar ratio equal to 10 (20 22) (20 22), respectively, in the presence of zirconium tetrachloride in an amount of 3 to 5 mol. in relation to magnesium and the process is conducted at room temperature in an argon atmosphere and normal pressure in the environment of tetrahydrofuran under stirring for 6 to 10 hours

 

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< / BR>
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