Catalyst to obtain 1-dialkylamino-2 - arylalkylamines

 

(57) Abstract:

The invention relates to the field of catalysts, in particular a catalyst to obtain 1-dialkylamino-2-arylalkylamines. Describes the catalyst obtained by the interaction douglasthe cobalt CoCl2, adjuvants triphenylphosphine Ph3P and dialkylaminomethyl as a reductant, taken in a molar ratio of 1:(0,51,5):(26) respectively. The advantage of the catalyst is its accessibility and selectivity. Technical result 1-dialkylamino-2-arylalkylamines with access 64-81%. table 1.

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

Known two-component catalyst /Ibragimov, A. G., Khafizova L. O., Satenaw, K., Khalilov L. M., Yakovlev, L. G., S. Rusakov Century, Dzhemilev, U. M. Izv. Ser. chem. , 1999, 8, 1594-1600/ to obtain substituted arylalkylamines, in particular 1-ethyl-2-arylalkylamines consisting of zirconatetitanate CpzZrCl2(Cp =5-C5H5and triethylaluminum Et3

Known two-component catalyst /Dzhemilev, U. M., A. G. Ibragimov, Khafizova L. O., S. V. Rusakov, L. M. Khalilov, Mendeleev Commun., 1997, 198-199/ to obtain substituted alumiiniumeramu, in particular 1-ethyl-2-arylalkylamines consisting of titanzincoated (Cp2TiCl2and EtAlCl2.

The disadvantage is the inaccessibility of one of the catalyst components (Cp2TiCl2), which in the country is produced and synthesized on the basis of pyrophoric Na, easily polymerizing cyclopentadiene5H6and hygroscopic TiCl4in two stages:

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

Thus, known in the literature catalysts allow to obtain from among substituted alumiiniumeramu only 1-ethyl-2-arylalkylamine; in addition, these catalysts are reaction or with insufficiently high selectivity, or inaccessible.

Pry the catalyst consists of available douglasthe cobalt (CoCl2), an activator of triphenylphosphine (Ph3P) and alkoxysilylated R2N-AlCl2where R=Et, n-Bu, n-Hex, taken in a molar ratio CoCl2: Ph3P: R2N-AlCl2=1:(0,5-1,5):(2-6). The role of R2N-AlCl2is to restore l2to cobalt in low-valence state, which complexesa with PH3R with the formation of the active catalyst.

In the presence of the specified catalyst formed 1-dialkylamino-2-arylalkylamine (1) outputs 64-81%. The reaction is carried out in an inert atmosphere by the interaction of arylolefins (styrene, para-methylstyrene) with dialkylaminomethyl R2N-AlCl2(R=Et, n-Bu, n-Neh) and magnesium, taken in a molar ratio at a temperature of 21-22oWith in tetrahydrofuran (THF) for 12 hours according to scheme 1, is given at the end of the description.

The amount of catalyst required for the reaction is 2-5 mol.% in relation to the original aillein.

Differences between the proposed catalyst from the known:

Components of the proposed catalyst are manufactured in the country duplissy cobalt (l2), available activator (Ph3P) and restorer (R22, 0.4 mmol Ph3P, 5 ml of dry THF and at a temperature of -5oWith added dropwise 1.6 mmol Et2N-AlCl2. Mix ~10 min to obtain an active catalyst.

EXAMPLE 2. Carrying out the reaction cycloalumination. The catalyst can also be added to ~ 5oTo the reaction mass, consisting of 10 mmol of fresh styrene 12 mmol of magnesium powder and 12 mmol Et2N-AlCl2in 10 ml of dry THF, stirred for 12 hours at a temperature of 21-22oC. Receive 1-diethylamino-2-phenylcyclopropane with the release of 73%. 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 the hydrolysis of 1-diethylamino-2-phenylaminopropyl (1) is formed ethylbenzene (2), and when lateralize respectively 1,2-dematerializer (3) of scheme 2, shown at the end of the description.

Spectral characteristics of ethylbenzene (2): So Kip. 136-137oS, nD221,4951. IR spectrum (cm-1): 690, 730, 1020, 1450, 1490, 1595, 2850, 3010, 3020. An NMR spectrum1N (, m D.): 1,19 (t, 3H, CH3, J=7,6 Hz), 7,05-7,20 (m, 5H, CH-arid (5), 127,90 d (6).

The spectral characteristics of the 1,2-dematerialise (3): So Kip. 135-136oS, nD201,4959. IR spectrum (cm-1): 690, 730, 1020, 1450, 1500, 1600, 2170 (CD),2850, 3020. An NMR spectrum1N (, m D.): 1,16 (d, 2H, CH2D, J=7,6 Hz), 7,02-of 7.24 (m, 5H, CH-arene.). An NMR spectrum13With (, m D.): 15,35 to (1I , JC-D= 22 Hz), 28,93 t (2I , JC-D=22 Hz), 144,33 C (3), 127,90 d (4), 128,37 d (5), 127,90 d (6).

Other examples of the invention, shown in the table.

The catalyst was prepared in THF at a temperature of -5oWith the response of cycloalumination was carried out at room temperature (21-22o(C) within 12 hours.

Catalyst to obtain 1-dialkylamino-2-arylalkylamines obtained by the interaction douglasthe cobalt l2, adjuvants triphenylphosphine Ph3P and dialkylaminomethyl R2N-AlCl2where R=Et, n-Bu, n-Hex, as reducing agent, in the following molar ratio of the components: l2:Ph3P:R2N-AlCl2=1:(0,51,5):(26).

 

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