RU2295529C1 - Method for preparing 10-chloro-1,7,8,9-tetraalkyl-4-methyl-4-aza-10-aluminatricyclo[5.2.1.02,6]dec-8-ene-3,5-diones - Google Patents

Abstract

FIELD: chemistry of organoaluminum compounds, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of compounds of the general formula (1):

wherein R means ethyl (Et), n-propyl (n-Pr), n-butyl (n-Bu). Method involves interaction of disubstituted acetylenes with aluminum trichloride in the presence of metallic Mg (powder) and catalyst (Cp₂ZnCl₂) in argon atmosphere under atmosphere pressure and at room temperature for 8 h followed by addition of N-methylmaleinimide and stirring the reaction mass for 6-8 h at room temperature. The yield of the end substance is 76-85%. Synthesized compounds can be used in fine organic and metalloorganic synthesis and as co=catalysts in processes of oligomerization and polymerization of olefins and couples dienes.

EFFECT: improved method of synthesis.

2 cl, 1 tbl, 1 ex

Description

The present invention relates to methods for producing new organoaluminum compounds (AOC), and specifically to a method for producing 10-chloro-1,7,8,9-tetraalkyl-4-methyl-4-aza-10-aluminate-tricyclo [5.2.1.0 ^2.6 ] dec-8-en-3,5-diones of the general formula (1):

where R = Et, n-Pr, n-Bu

The proposed compounds can be used in fine and organometallic synthesis, as well as as cocatalysts in the processes of oligo- and polymerization of olefins and conjugated dienes.

The known method [1, U. M. Dzhemilev, A. G. Ibrahimov, A. P. Zolotarev, PP Maslukhov, G. A. Tolstikov. Synthesis and transformation of metallocycles. Report 5. Regioselective synthesis of β-substituted aluminacyclopentanes by cyclomethylation of α-olefins with Et ₃ Al in the presence of Cp ₂ ZrCl ₂ // Izvestia AN SSSR. Ser. Chem. 1990. S. 2831-2841] obtaining unsaturated cyclic oxygen-containing organoaluminum compounds by the interaction of 2,7-octadiene-1-ol with triethylaluminium (AlEt ₃ ) in the presence of a catalyst of zirconocene dichloride (Cp ₂ ZrCl ₂ ) according to the scheme:

The known method does not allow to obtain 10-chloro-1,7,8,9-tetraalkyl-4-methyl-4-aza-10-aluminatricyclo [5.2.1.0 ^2,6 ] dec-8-en-3,5-diones ( one).

The known method [2, U. M. Dzhemilev, A. G. Ibrahimov, L. O. Khafizova, L. R. Yakupova, L. M. Khalilov. Cycloalumination of acetylenes and 1,4-enins with the participation of Zr-containing catalysts. Journal of Organic Chemistry, 2005, 41, 684] for the preparation of cyclic organoaluminum compounds (3) by the reaction of disubstituted acetylenes with ethyl aluminum dichloride (EtAlCl ₂ ) in the presence of a catalyst of zirconacene dichloride (Cp ₂ ZrCl ₂ ) followed by the addition of maleic anhydride and carrying out the reaction at a temperature of ~ 25 ° С according to the scheme:

In a known manner cannot be obtained 10-chloro-1,7,8,9-tetraalkyl-4-methyl-4-aza-10-aluminatricyclo [5.2.1.0 ^2,6 ] dec-8-en-3,5-dione (one).

Thus, in the literature there is no information on the selective preparation of 10-chloro-1,7,8,9-tetraalkyl-4-methyl-4-aza-10-aluminatricyclo [5.2.1.0 ^2,6 ] dec-8-en-3 5-diones (1).

A new method is proposed for producing 10-chloro-1,7,8,9-tetraalkyl-4-methyl-4-aza-10-aluminatricyclo [5.2.1.0 ^2,6 ] dec-8-en-3,5-diones (1 )

где R=Et, н-Pr, н-Bu с треххлористым алюминием (AlCl₃) в присутствии металлического Mg (порошок) и катализатора цирконацендихлорида (Cp₂ZrCl₂), взятыми в мольном соотношении

: AlCl₃: Mg : Cp₂ZrCl₂, равном 20:12:12:0.5, в атмосфере аргона при комнатной температуре (~20°С) и атмосферном давлении в тетрагидрофуране (ТГФ) в качестве растворителя в течение 8 часов с последующим добавлением N-метилмалеинимида в эквимольном по отношению к AlCl₃ количестве с перемешиванием реакционной массы 6-8 часов, предпочтительно 7 часов, при комнатной температуре (~20°С). Реакция протекает с образованием 10-хлоро-1,7,8,9-тетраалкил-4-метил-4-аза-10-алюминатрицикло[5.2.1.0^2,6]дец-8-ен-3,5-дионов (1) с выходом 76-85% по схеме:The essence of the method consists in the interaction of dialkyl substituted acetylenes of the General formula

where R = Et, n-Pr, n-Bu with aluminum trichloride (AlCl ₃ ) in the presence of metallic Mg (powder) and a catalyst of zirconacene dichloride (Cp ₂ ZrCl ₂ ), taken in molar ratio

: AlCl ₃ : Mg: Cp ₂ ZrCl ₂ equal to 20: 12: 12: 0.5, in an argon atmosphere at room temperature (~ 20 ° C) and atmospheric pressure in tetrahydrofuran (THF) as a solvent for 8 hours, followed by addition N-methylmaleinimide in an amount equimolar to AlCl ₃ with stirring of the reaction mass for 6-8 hours, preferably 7 hours, at room temperature (~ 20 ° C). The reaction proceeds with the formation of 10-chloro-1,7,8,9-tetraalkyl-4-methyl-4-aza-10-aluminatricyclo [5.2.1.0 ^2,6 ] dec-8-en-3,5-diones (1 ) with a yield of 76-85% according to the scheme:

10-Chloro-1,7,8,9-tetraalkyl-4-methyl-4-aza-10-aluminatricyclo- [5.2.1.0 ^2,6 ] dec-8-en-3,5-diones (1) only form only with the participation of AlCl ₃ , disubstituted acetylenes, metallic Mg, zirconium catalyst Cp ₂ ZrCl ₂ and N-methylmaleinimide. In the presence of other aluminum compounds (for example, AlEt ₃ , Bu ⁱ ₃ Al, Bu ⁱ ₂ AlH), other acetylenes (for example, terminal), other metals as an acceptor of halide ions (for example, Zn, Fe, Al), other catalysts (e.g. Zr (acac) ₄ , Cp ₂ TiCl ₂ , Pd (acac) ₂ , Ni (acac) ₂ , NiCl ₂ , Fe (acac) ₂ ), other diketones (e.g. o-benzoquinone or 9,10-anthraquinone ), target products (1) are not formed.

The reaction was carried out at room temperature (~ 20 ° C). At a higher temperature (for example, 40 ° C), there is no significant increase in the yield of the target products (1), and at a lower temperature (for example, 0 ° C), the reaction rate decreases.

не приводит к существенному повышению выхода целевых продуктов (1). Изменение соотношения исходных реагентов и катализатора в сторону их уменьшения по отношению к исходному дизамещенному ацетилену снижает выход целевых продуктов (1).Change in the ratio of the starting reagents (AlCl ₃ , Mg, N-methylmaleinimide) and the catalyst (Cp ₂ ZrCl ₂ ) in the direction of their increase relative to the starting disubstituted acetylene

does not lead to a significant increase in the yield of target products (1). A change in the ratio of the starting reagents and the catalyst in the direction of their decrease with respect to the starting disubstituted acetylene reduces the yield of the target products (1).

The reaction was carried out using THF as a solvent. In other solvents (for example, aliphatic or aromatic), the reaction does not proceed.

Significant differences of the proposed method.

In the proposed method for the preparation of cyclic oxygen-containing AOS, salt aluminum trichloride (AlCl ₃ ) and N-methylmaleiminimide are used as starting compounds, and in the known method, an organoaluminum compound ethylaluminium dichloride (EtAlCl ₂ ) and maleic anhydride.

The proposed method has the following advantages.

The method allows to obtain with high selectivity 10-chloro-1,7,8,9-tetraalkyl-4-methyl-4-aza-10-aluminatricyclo [5.2.1.0 ^2,6 ] dec-8-en-3,5-dione (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, in an argon atmosphere, 10 ml of THF, 20 mmoles of hex-1-in, 12 mg-at. Mg (powder) at a temperature of ~ 0 ° C 0.5 mmol of the catalyst Cp ₂ ZrCl ₂ and 12 mmol of AlCl ₃ , stirred for 8 hours at ~ 20 ° C, add 12 mmol of N-methylmaleiminimide, stirred for 7 hours at room temperature. Obtain 10-chloro-1,7,8,9-tetraethyl-4-methyl-4-aza-10-aluminatricyclo [5.2.1.0 ^2.6 ] dec-8-en-3,5-dione (1) with the yield 85% The yield of the target product and its structure are determined by the hydrolysis product (4).

Spectral characteristics of 4,5,6,7-tetraethyl-2-methyl-3a, 4,7,7a-tetrahydro-1-H-isoindole-1,3 (2H) -dione (4): ¹³ C NMR spectrum (δ , ppm): 12.26 (C ₈ ), 14.29 (C ₆ ), 19.92 (C ₅ ), 23.31 (C ₇ ), 24.06 (C ₉ ), 40.96 (C ₃ ), 41.35 (C ₂ ), 136.88 (C ₄ ), 178.08 (C ₁ ).

Other examples confirming the method are given in table 1.

Table 1 №№

The original disubstituted acetylene,

Molar ratio

: AlCl ₃ : Mg: Cp ₂ ZrCl ₂ : N-methylmaleinimide Total reaction time, hour Yield (1),% one 2 3 four 5 one.

hexin-3 20: 12: 12: 0.5: 12 fifteen 10-chloro-1,7,8,9-tetraethyl-4-methyl-4-aza-10-aluminatricyclo [5.2.1.0 ^2.6 ] dec-3-en-3,5-dione, 85 2.

octin 4 20: 12: 12: 0.5: 12 fifteen 10-chloro-1,7,8,9-tetrapropyl-4-methyl-4-aza-10-aluminatricyclo [5.2.1.0 ^2.6 ] dec-8-en-3,5-diones, 80 3.

decin-5 20: 12: 12: 0.5: 12 fifteen 10-chloro-1,7,8,9-tetrabutyl-4-methyl-4-aza-10-aluminatricyclo [5.2.1.0 ^2.6 ] dec-8-en-3,5-dione, 76

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

Claims (1)

The method of obtaining 10-chloro-1,7,8,9-tetraalkyl-4-methyl-4-aza-10-aluminatricyclo [5.2.1.0 ^2.6 ] dec-8-en-3,5-diones (1) total formulas

where R = Et, n-Pr, n-Bu, characterized in that the disubstituted acetylenes of the general formula

where R is Et, n-Pr, n-Bu, interact with aluminum trichloride AlCl ₃ in the presence of metallic Mg (powder) and a catalyst of zirconacene dichloride (Cp ₂ ZrCl ₂ ) in a molar ratio

AlCl ₃ : Mg: Cp ₂ ZrCl ₂ equal to 20: 12: 12: 0.5, in an argon atmosphere at atmospheric pressure and room temperature in tetrahydrofuran as a solvent for 8 hours, followed by the addition of N-methylmaleiminimide, taken in equimolar to AlCl ₃ amount, and stirring the reaction mass for 6-8 hours at room temperature (~ 20 ° C).