The catalyst for producing 1,2-bis(dialkylamino)-1,2 - diphenylethylene

 

(57) Abstract:

The invention relates to catalysts, in particular to a catalyst for producing 1,2-bis(dialkylamino)-1,2-diphenylethylene. Describes a catalyst to obtain 1,2-bis(dialkylamino)-1,2-diphenylethylene obtained by the interaction douglasthe cobalt l2, adjuvants triphenylphosphine RH3R and dialkylaminoalkyl R2AlCl, where R= Et, n-Pr, as a reductant, in the following molar ratio of the components: l2: PH3R: R2AlCl= 1: (1,5-2,5): (2-6). The technical result - obtaining 1,2-bis(dialkylamino)-1,2-diphenylethylene with access 63-78%, the advantage of the catalyst is also available. table 1.

The invention relates to the field of catalysts, in particular catalysts for production of 1,2-bis(dialkylamino)-1,2-diphenylethylene (1), which can find application in organic and ORGANOMETALLIC synthesis.

Known two-component catalyst /g Dozzi, C. Cucinella, A. Mazzei. Hydrogenation Catalysts from Aluminum Hydride Derivatives and Transition Metal Compounds. J. Organometal. chem. , 164 (1979) 1-10/ for dialuminium compounds, namely 1,4-bis(dialume)-2-methylbutane consisting of titanzincoated Cp2TiCl2(Cp =2TiCl2), which in the country is produced and synthesized on the basis of pyrophoric Na, easily polymerizing Dicyclopentadiene C5H6and hygroscopic TiCl4in two stages:

a) C5H6+Na __ (5-C5H5)Na+H2< / BR>
b) TiCl4+(5-C5H5)Na __ (5-C5H5)2TiCl2+NaCl

In addition, a known catalyst is not possible to obtain 1,2-bis(dialkylamino)-1,2-diphenylethylene (1).

Known two-component catalyst /U. M. Dzhemilev, A. G. Ibragimov, M. N. Ergaliev, R. P. Muslumov. Synthesis and transformations of metallocycles. 16. Synthesis of a new class of acyclic alyuminiiorganicheskikh connections - threo-2,3-disubstituted 1,4-volumebutton using zirconium catalysts. WPI. An. The series of chem. , 1995, 8, 1561-1567/ for dialuminium compounds, namely 1,4-bis(ditylum)-TRANS-2,3-dialkylamino consisting of zirconatetitanate (Cp2ZrCl2and diethylaluminium Et2AlCl.

The disadvantage is the inaccessibility of one of the catalyst components (Cf2Zrl2), which in the country is not performed, in addition, a known catalyst is not possible to obtain 1,2-bis(dialkylamino)-1,2-Darrow (1).

The proposed catalyst is produced by interaction available douglasthe cobalt (CoCl2), an activator of triphenylphosphine (Ph3R) and dialkylaminoalkyl R2AlCl, where R= Et, n-Pr, taken in a molar ratio l2: PH3R: R2AlCl= 1: (1,5-2,5): (2-6). The role of R2AlCl is to restore CoCl2to cobalt in low-valence state (Witho), which stabilizes PH3R with the formation of the active complex.

In the presence of the specified catalyst formed 1,2-bis(dialkylamino)-1,2-diphenylethylene (1) outputs 63-78%. The reaction is carried out in an inert atmosphere by the interaction of diphenylacetylene (Ph--Ph) dialkylaminoalkyl and magnesium (powder), taken in a molar ratio Ph--Ph:R2AlCl:Mg = 10:20:10 at a temperature of 21-22oWith in tetrahydrofuran (THF) for 8 hours under the scheme:

< / BR>
[Co] = CoCl2-Ph3P-R2AlCl; R= Et, n-Pr

The amount of catalyst required for the reaction is 3-6 mol. % relative to the original diphenylacetylene.

Differences between the proposed catalyst from the known:

Components of the proposed catalyst are manufactured in the country duplissy cobalt (CoCl2) what is the examples.

Example 1. The preparation of the catalyst. In a glass reactor with a volume of ~ 50 ml installed on a magnetic stirrer, an argon atmosphere was placed 0.5 mmol l2, 1.0 mmol of RH3R, 5 ml of dry THF and at a temperature of -5oWith added dropwise 2.0 mmol E2tAlCl. Mix ~ 10 min to obtain an active catalyst.

Example 2. Carrying out the reaction of 1,2-dialuminium of diphenylacetylene. The resulting catalyst was added when -5oTo the reaction mass, consisting of 10 mmol of diphenylacetylene, 10 mmol magnesium powder and 20 mmol Et2AlCl in 10 ml of dry THF, stirred for 8 hours at a temperature of 21-22oC. Obtain 1,2-bis(ditylum)-1,2-diphenylethylene with the release of 72%. The yield of the target product (1) is determined using GC by analysis of the hydrolysis products. Products lateralize confirm receipt of the target product (1). When lateralize 1,2-bis(ditylum)-1,2-diphenylethylene (1) is formed CIS-1,2-dideuterio-1,2-diphenylethylene (2) according to the scheme:

< / BR>
An NMR spectrum13With (, memorial plaques , Me4Si, C6D6) CIS-1,2-dideuterio-1,2-diphenylethylene (2): 130.08 (1I , JC-D= 23.0 Hz), 137.09 (2), 128.13 (WITH3), 128.82 (WITH4), 127.82 (5).

Other examples confirming izopet is inromania of diphenylacetylene was carried out at room temperature (21-22o(C) within 8 hours.

The catalyst for producing 1,2-bis(dialkylamino)-1,2-diphenylethylene obtained by the interaction douglasthe cobalt l2, adjuvants triphenylphosphine RH3R and dialkylaminoalkyl R2lCl, where R= Et, n-Pr, as a reductant, in the following molar ratio of the components: l2: PH3R: R2AlCl= 1: (1,5-2,5): (2-6).

 

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