RU2448113C2 - Method of producing 2,4,6,8-tetraphenylmagnesacycloundecane - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 2,4,6,8-tetraphenylmagnesacycloundecane of formula I:

The method involves reaction of styrene with magnesacyclopentane in the presence of a catalyst - zirconocene dichloride Cp₂ZrCl₂, in a dry argon atmosphere. Molar ratio styrene: magnesacyclopentane: Cp₂ZrCl₂ = 10:(10-14):(0.3-0.5). The method is carried out in tetrahydrofuran at room temperature (about 20°C) for 12-20 hours.

EFFECT: invention enables to obtain 2,4,6,8-tetraphenylmagnesacycloundecane, which can be used in synthesis of heterocyclic and bifunctional compounds, as well as components for catalyst systems in oligo- and polymerisation of unsaturated hydrocarbons.

1 tbl, 1 ex

Description

The present invention relates to methods for producing new organomagnesium compounds (MOS), specifically to a method for producing 2,4,6,8-tetraphenylmagnesacyclonedecane of the general formula (1):

The specified compound can find application in the synthesis of heterocyclic and bifunctional compounds, as well as as a component of catalytic systems in the processes of oligo- and polymerization of olefin, diene and acetylene hydrocarbons.

The known method [K.F. Fujita, Y. Onhnuma, H. Yasuda, H. Tani. Magnesium-butadiene Addition Compounds Isolation, Structural Analysis and Chemical Reactivity // J. Organomet. Chem., 201 (1976) 113] obtaining a unsaturated Mg-organic compound, namely magnesacyclonone-3,7-diene of the general formula (2) by reacting butadiene with metal magnesium in the presence of catalytic amounts of methyl iodide at a temperature of 40 ° C in tetrahydrofuran in 48 hours with a yield of 69% according to the scheme:

In a known manner, 2,4,6,8-tetraphenylmagnesacyclownes cannot be obtained (1).

A known method for the joint production of 2,4-diphenylmagnesacyclopentane (3) and 2-phenyl-4-alkylmagnesacyclopentanes (4) [U.M. Dzhemilev, PMSultanov, R.G. Gaimaldinov, PPMuslukhov, S.I. Lomakina, G.A. Tolstikov. Catalytic synthesis and conversion of magnesiumcycloalkanes. Communication 2. Synthesis of substituted magnesium cyclopentanes with the participation of zirconium complexes // Izv. USSR Academy of Sciences. Chemical Series 1992. No. 4. P.980-999] by the interaction of styrene and (R) ₂ Mg (where R = CH ₃ , C ₂ H ₅ ) in the presence of zirconacenedichloride Cp ₂ ZrCl ₂ taken in the molar ratio of styrene: MOC: Cp ₂ ZrCl ₂ = 100: 100 : (2-3). The reaction time is 7 hours, the yield of target products (3) and (4) is 98%. The reaction is carried out in a mixture of tetrahydrofuran-diethyl ether (1: 1) and proceeds according to the scheme:

This method does not lead to the formation of 2,4,6,8-tetraphenylmagnesacyclonedecane (1).

The known method [U.M. Dzhemilev, PMSultanov, R.G. Gaimaldinov, PPMuslukhov, G.A. Tolstikov. Catalytic synthesis and conversion of magnesiumcycloalkanes. I. New catalytic transformations in a series of magnesium cyclopentanes // Izv. USSR Academy of Sciences. Ser. Chem. 1991. No.6. S.1388-1393] the joint production of five-membered and seven-membered cyclic MOS, namely 2-phenylmagnesacyclopentane (5) and 2,4-diphenylmagnesacycloheptane (6) with yields of 70% and 5%, respectively, by the interaction of magnesacyclopentane (7) with styrene taken in a molar ratio of 1: 1, in the presence of 2-3 mol.% Cp ₂ ZrCl ₂ in tetrahydrofuran at 25 ° C (1.5 h) according to the scheme:

The known method does not allow to obtain MOS (1).

Thus, in the literature there is no information on the synthesis of 2,4,6,8-tetraphenylmagnesacycloundecane (I).

A new method is proposed for the synthesis of 2,4,6,8-tetraphenylmagnesacyclonedecane (1).

The essence of the method consists in the interaction of styrene with magnesacyclopentane (7) in the presence of a catalyst of zirconacene dichloride Cp ₂ ZrCl ₂ taken in the molar ratio of styrene: (7): Cp ₂ ZrCl ₂ = 10: (10-14) :( 0.3-0.5), preferably 10: 12: 0.4. The reaction is carried out in an argon atmosphere at room temperature (~ 20 ° C) and atmospheric pressure in an ether (tetrahydrofuran) solvent. The reaction time is 12-20 hours, the yield of the target product is 55-70%.

The reaction proceeds according to the scheme:

The reaction is accompanied by the release of an equimolar amount of ethylene. The target product (1) is formed only with the participation of starting reagents magnesacyclopentane (7), styrene and catalyst Cp ₂ ZrCl ₂ . In the presence of other olefins (e.g. oct-1-ene, 4-vinylcyclohex-1-ene, methylene alkanes, cycloolefins), other magnesium compounds (e.g. EtMgBr, EtMgCl, Et ₂ Mg, PhMgBr, PhMgCl, Ph ₂ Mg) or others transition metal complexes (for example, TiCl ₄ , Ti (OBu) ₄ , Zr (acac) ₄ , Cp ₂ TiCl ₂ , Ni (acac) ₂ , Fe (acac) ₃ ) the target product (1) is not formed.

The reaction in the presence of a catalyst Cp ₂ ZrCl ₂ more than 5 mol. % with respect to styrene does not lead to a significant increase in the yield of the target product (1). Use in the reaction of the catalyst Cp ₂ ZrCl ₂ less than 3 mol.% Reduces the yield of MOS (I). The experiments were carried out at room temperature (~ 20 ° C). At a higher temperature (for example, 50 ° C), the content of compaction products increases, at a lower temperature (for example, 0 ° C) the reaction rate decreases.

Changing the ratio of the starting reagents in the direction of increasing the content of magnesacyclopentane (7) with respect to styrene decreases the yield of the target product (1). A decrease in the amount of (7) with respect to styrene also reduces the yield of MOC (1).

Significant differences of the proposed method:

in the proposed method, the reaction time is 12-20 hours;

in the known method MOS (5) and (6) receive in 1.5 hours.

The proposed method has the following advantages:

The method allows to obtain with high regioselectivity and good yield 2,4,6,8-tetraphenylmagnesacyclonedecane of the general formula (1), the synthesis of which is not described in the literature.

The method is illustrated by the following examples.

EXAMPLE 1. In a 50 ml glass reactor mounted on a magnetic stirrer, 10 mmol of styrene, 10 mmol of magnesacyclopentane (0.5 M solution in THF) are placed in an argon atmosphere, at a temperature of 0 ° C 0.3 mmol of Cp ₂ ZrCl ₂ is stirred at room temperature 12 hours. Get individual 2,4,6,8-tetraphenylmagnesacyclone (1) with a yield of 55%. The yield of the target product was determined by the hydrolysis product. Hydrolysis of MOS (1) gives 1,3,5,7-tetraphenyldecane (8), and during deuterolysis, respectively, 1,10-dideutero-1,3,5,7-tetraphenyldecane (9):

Spectral characteristics of the hydrolysis product (8)

IR spectrum (ν _max , cm ^-1 ): 3080, 3060, 3030, 2920, 2850, 1520, 1485, 955, 780, 750. ¹ H NMR (400 MHz, CDCl ₃ , δ, ppm): 7.33-6.90 (m, 20H, arom.), 2.62-1.72 (m, 5H, CH-Ph), 1.08-1.59 (m, 10H, CH ₂ ), 0.74-0.77 (m, 3H, CH ₃ ). ¹³ C NMR (δ, ppm): 146.25, 145.97, 145.89, 145.80, 145.63, 145.41, 145.21, 144.92, 142.58, 142.48, 128.35, 128.26, 128.11, 127.98, 127.81, 127.68, 127.63, 127.57, 127.55, 126.05, 125.97, 125.93, 125.87, 125.76, 125.61, 125.55,45.37, 44.37, 44.01, 43.88, 43.82, 43.17, 42.89, 42.79, 41.63, 40.85, 40.85, 40.53, 40.29, 39.79, 39.09, 38.09, 37.38, 33.37, 33.42, 20.42, 20.35, 13.77. Mass spectrum, m / z: 446 [M] ⁺ .

Calculated for C ₃₄ H ₃₈ ,%: C 91.48; H 8.52. Found,%: C 91.39; H 8.54%.

Spectral characteristics of the deuterolysis product (9)

IR spectrum (ν _max , cm ^-1 ): 3080, 3060, 3030, 2920, 2850, 2275 (CD), 1620, 1520, 1495, 950, 780, 760.

¹ H NMR (400 MHz, CDCl ₃ , δ, ppm): 7.34-6.91 (m, 20H, arom.), 2.63-2.70 (m, 5H, CH-Ph); 1.06-1.58 (m 10H, CH ₂ ), 0.74 (m, 2H, CH ₂ D).

¹³ C NMR (CDCl ₃ , δ, ppm): 146.24, 145.39, 145.96, 145.87, 145.79, 145.62, 145.4, 145.19, 144.91, 142.57, 57, 142.47, 128.35, 128.52, 128.16, 128.10, 127.95, 127.80 , 127.67, 127.62, 127.56, 127.54, 126.15, 126.04, 125.95, 125.91, 125.86, 125.75, 125.59, 125.53, 125.53, 45.35, 44.35, 44.00, 43.89, 43.16, 42.89, 42.79, 41.61, 40.83, 40.51, 40.28, 39.78 , 39.08, 38.08, 37.77, 33.37 (t, J _CD = 19 Hz), 33.42 (t, J _CD = 19 Hz), 20.41, 20.33. 13.77 (t, J _CD = 19 Hz). Mass spectrum, m / z: 448 [M] ⁺ .

Calculated for C ₃₄ H ₃₆ D ₂ ,%: C 91.07; H, 8.03. Found,%: C 91.10; H + D 9.91%.

Other examples confirming the method are given in the table.

№№ The molar ratio of styrene: magnesacyclopentane: Cp ₂ ZrCl ₂ , mmol Reaction time, hour Yield (1),% one 10: 10: 0.3 12 55 2 10: 12: 0.4 twenty 69 3 10: 13: 0.5 twenty 70 four 10: 13: 0.5 fifteen 61 5 10: 11: 0.5 twenty 68 6 10: 12: 0.5 fifteen 60 7 10: 14: 0.5 twenty 65

All experiments were carried out at room temperature (~ 20 ° C) in THF.

Claims (1)

The method of obtaining 2,4,6,8-tetraphenylmagnesacyclonedecane of the formula (I)

characterized in that the interaction of styrene with magnesacyclopentane in the presence of a catalyst - zirconacene dichloride Cp ₂ ZrCl ₂ is carried out in an atmosphere of dry argon at a molar ratio of styrene: magnesacyclopentane: Cp ₂ ZrCl ₂ = 10: (10-14) :( 0.3-0, 5) in tetrahydrofuran at room temperature (~ 20 ° C) for 12-20 hours