RU2541792C1 - METHOD OF OBTAINING Si-CONTAINING BIS-(ENDO-BICYCLO[4.2.1]NONA-2,4,7-TRIENES) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: claimed is method of obtaining Si-containing bis-(endo-bicyclo[4.2.1]nona-2,4,7-trienes) by interaction of Si-containing α,ω-diacetylenes with 1,3,5-cycloheptatriene in presence of catalytic system TiCl4-Et2AlCl at temperature 20-80°C, in benzene for 14-48 h. Method makes it possible to obtain individual Si-containing bis-(endo-bicyclo[4.2.1]nona-2,4,7-trienes), which can be components of high energy fuels for air-reactive rocket systems and products in synthesis of a number of medications.

EFFECT: increased output.

1 tbl, 10 ex

Description

The present invention relates to methods for producing new polycyclic compounds, specifically, to a method for producing Si-containing bis- (endobicyclo [4.2.1] nona-2,4,7-trienes) of general formula (I):

The specified compound belongs to the class of intense energy-intensive systems and can be used as components of high-energy fuels for air-rocket missile systems (GW Burdette, HR Lander, JR McCoy, J. Energy. 1978, 2, 289), intermediates in the synthesis of modern medicines exhibiting antitumor, antiviral and other types of activity (NA Petasis, MA Patane, Tetrahedron. 1992, 48, 5757).

The known method [JW. Kaagman, M. Rep, M. Horacek, P. Sedmera, J. Cejka, V. Varga, K. Mach. Titanium-catalyzed [4 + 2] and [6 + 2] cycloaddition of 1,4-bis (trimethylsilyl) buta-1,3-diyne // Collect. Czech Chem. Commun., 1996, V.61, 1722] for the preparation of a cycloduct (2) by reacting 1,3,5-cycloheptatriene (CHT) with trimethyl [4- (trimethylsilyl) -1,3-butadiinyl] silane in the presence of a TiCl ₄ - catalyst system Et ₂ AlCl at a temperature of 60 ° C in toluene for 8 hours with a yield of 91% according to the scheme:

In a known manner, Si-containing bis- (endobicyclo [4.2.1] nona-2,4,7-trienes) of general formula (1) cannot be obtained.

The known method [JH Rigby, CR Heap, NC Warshakoon. Studies on chromium (0) -mediated three component cycloaddition reactions // Tetrahedron, 2000, V.56, 2305] for the preparation of pentacyclic adducts (3) by the photocycloaddition reaction (η ⁶ -cycloheptatriene) of tricarbonylchrome and diines at room temperature for 1-2 hours scheme:

In a known manner, Si-containing bis- (endobicyclo [4.2.1] nona-2,4,7-trienes) of general formula (1) cannot be obtained.

Thus, in the literature there is no information on the selective synthesis of Si-containing bis- (endobicyclo [4.2.1] nona-2,4,7-trienes) (1).

There is no information in the literature on the synthesis of Si-containing bis- (endobicyclo [4.2.1] nona-2,4,7-trienes) of formula (1).

A method for the synthesis of Si-containing bis- (endobicyclo [4.2.1] nona-2,4,7-trienes) of the general formula (1) is proposed.

The essence of the method consists in the interaction of Si-containing α, ω-diacetylenes of the general formula (4) with CHT in the presence of the TiCl ₄ -Et ₂ AlCl catalyst system taken in a molar ratio Si-containing α, ω-diacetylene: CHT: TiCl ₄ : Et ₂ AlCl = (9-11): 20: (0.1-0.3): 4, preferably 10: 20: 0.2: 4. The reaction is carried out in an ampoule at a temperature of 20-80 ° C. The reaction time is 14-48 hours, the yield of the target product is 51-88%. As a solvent, benzene must be used.

The reaction proceeds according to the scheme:

The target products (1) are formed only with the participation of Si-containing α, ω-diacetylenes, TSHT and the TiCl ₄ -Et ₂ AlCl catalyst system. In the presence of other transition metal complexes (e.g., Cp ₂ ZrCl ₂ , Cp ₂ TiCl ₂ , Zr (acac) ₄ , Pd (acac) ₂ , Ni (acac) ₂ , Fe (acac) ₃ ), the target products (1) are not formed .

Carrying out the reaction in the presence of a TiCl ₄ catalyst is greater than 0.3 mmol per 10 mmol of Si-containing α, ω-diacetylene does not significantly increase the yield of the target products (1). The use of TiCl ₄ catalyst reaction less than 0.1 mmol per 10 mmol of Si-containing α, ω-diacetylene reduces the yield of adduct (1), which is associated with a decrease in catalytically active centers in the reaction mass. The experiments were carried out by heating 20-80 ° C. At a higher temperature (for example, 120 ° C), the yield of codimers decreases, probably due to side processes of decomposition and polymerization. At lower temperatures (for example, 20 ° C), the reaction rate decreases.

The proposed method has the following advantages:

1. The method allows to obtain in high yields individual Si-containing bis- (endobicyclo [4.2.1] nona-2,4,7-trienes) (1), the synthesis of which is not described in the literature.

The method is illustrated by the following examples:

Example 1. In a thermostated (~ 0 ° C) glass ampoule in an atmosphere of dry argon was charged 2 g (20 mmol) of 1,3,5-cycloheptatriene, 2.5 g (10 mmol) of trimethyl [8- (trimethylsilyl) -1,7- octadiinyl] silane, 0.022 ml (0.2 mmol) of TiCl ₄ in 1 ml of benzene and 3 ml of dry benzene. The ampoule was cooled to liquid nitrogen temperature, 0.6 ml (4 mmol, 90.2%) of Et ₂ AlCl was loaded into 1 ml of benzene and sealed. After heating at 80 ° C for 14 h, the ampoule was opened, the contents were treated with C ₂ H ₅ OH. Obtain 1,4-bis (8′-trimethylsilylbicyclo [4.2.1] nona-2 ′, 4 ′, 7′-trien-7′-yl) butane (1) in 86% yield.

Spectral characteristics of the adduct (1):

¹ H NMR spectrum (CDCl ₃ , δ, ppm) 1,4-bis (8′-trimethylsilylbicyclo [4.2.1] non-2 ′, 4 ′, 7′-trien-7′-yl) butane ( 1): 0.15 (s, 18H, 2SiMe ₃ ); 1.42-1.60 (m, 2H, C (9.9) H ₂ ); 2.11-2.20 (m, 2H, C (9.9) H ₂ ); 2.30-2.39 (m, 8H, C (10.10 ′, 11.11 ′) H ₂ ); 3.00 (3.15) (t, 2H, C (1.1 ′) H, J = 7 Hz); 3.09 (3.25) (t, 2H, C (6.6 ′) H, J = 7 Hz); 5.70-5.89 (m, 4H, C (3.3 ′, 4.4 ′) H); 6.06-6.24 (m, 4H, C (2.2 ′, 5.5 ′) H).

¹³ C NMR spectrum (CDCl ₃ , δ, ppm) 1,4-bis (8′-trimethylsilylbicyclo [4.2.1] non-2 ′, 4 ′, 7′-trien-7′-yl) butane ( 1): 0.68 (6C, 2SiMe ₃ ); 28.51 (C (11.11 ′)); 30.13 (C (10.10 ′)); 31.45 (31.51) (C (9.9)); 43.12 (46.11) (C (1,1 ′)); 48.28 (48.37) (C (6.6)); 123.06 (123.38) (C (3.3)); 124.34 (C (4.4)); 138.62 (C (7.7)); 139.08 (C (8.8)); 139.35 (C (5.5)); 139.95 (C (2.2)).

Other examples confirming the method are shown in table 1.

Table 1 No. p / p α, ω-diacetylene n The molar ratio of Si-containing α, ω-diacetylene: TST: TiCl ₄ : Et ₂ AlCl, mmol Temperature ° C Reaction time, hour Yield (1),% one trimethyl [8- (trimethylsilyl) -1,7-octadiinyl] silane 2 10: 20: 0.2: 4 80 fourteen 86 2 trimethyl [8- (trimethylsilyl) -1,7-octadiinyl] silane 2 10: 20: 0.2: 4 60 eighteen 84 3 trimethyl [8- (trimethylsilyl) -1,7-octadiinyl] silane 2 10: 20: 0.2: 4 40 twenty 83 four trimethyl [8- (trimethylsilyl) -1,7-octadiinyl] silane 2 10: 20: 0.2: 4 twenty 48 80 5 trimethyl [8- (trimethylsilyl) -1,7-octadiinyl] silane 2 11: 20: 0.2: 4 80 fourteen 85 6 trimethyl [8- (trimethylsilyl) -1,7-octadiinyl] silane 2 9: 20: 0.2: 4 80 fourteen 81 7 trimethyl [8- (trimethylsilyl) -1,7-octadiinyl] silane 2 10: 20: 0.3: 4 80 fourteen 88 8 trimethyl [8- (trimethylsilyl) -1,7-octadiinyl] silane 2 10: 20: 0.1: 4 80 fourteen 51 9 trimethyl [9- (trimethylsilyl) -1,8-nonadiinyl] silane 3 10: 20: 0.2: 4 80 fourteen 80 10 trimethyl [10- (trimethylsilyl) -1,9-decadiinyl] silane four 10: 20: 0.2: 4 80 fourteen 82

Claims (1)

The method of obtaining Si-containing bis- ( endo- bicyclo [4.2.1] nona-2,4,7-trienes) of the general formula (1):

characterized in that the Si-containing α, ω-diacetylenes of the general formula

interact with 1,3,5-cycloheptatriene (CGT) in the presence of the TiCl ₄ -Et ₂ AlCl catalyst system, with a molar ratio Si-containing α, ω-diacetylene: CGT: TiCl ₄ : Et ₂ AlCl = (9-11): 20: (0.1-0.3): 4, at a temperature of 20-80 ° C, in benzene, for 14-48 hours.