Levchenko et al.
2400
Russ. Chem. Bull., Int. Ed., Vol. 69, No. 12, December, 2020
Analysis of the reaction mixtures to confirm the purity of all
products was carried out using thin layer chromatography on
Merck Silicagel 60 F254 UV-254 plates.
References
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4-Bromocyclobutene (6). Benzocyclobutene (23.7 g, 22.8 mmol)
was emulsified in water (240 mL) and cooled in an ice bath.
Bromine (11.7 mL) was added to the resulting mixture in small
portions at a temperature of 0—5 C. The reaction mixture was
allowed to warm to 20 C and then stirred for 24 h. The reaction
was monitored by thin layer chromatography. Then n-hexane
(50 mL) and sodium sulfite were added to the mixture. The
mixture was stirred at 20 C for 30 min until complete discolor-
ation. The organic layer was separated, washed with water, and
dried over sodium sulfate. After distillation at 110—114 C and
reduced pressure, 30 g of a colorless liquid were obtained.
1H NMR (300 MHz, CDCl3) : 7.40 (d, 1 H, J = 7.8 Hz); 7.26
(s, 1 H, J = 7.0), 6.99 (d, 1 H, J = 7.8 Hz); 3.31—3.10 (m, 4 H).
Allyl-bis(benzocyclobuten-4-yl)methylsilane (9). 4-Bromo-
benzocyclobutene (6.1 g, 33.3 mmol) was added dropwise to
a mixture of magnesium (900 mg, 37.5 mmol) and allylmethyl-
dichlorosilane (2.62 g, 16.9 mmol) in THF (30 mL) at a tem-
perature of 30—40 C. Thereafter, the mixture was kept for 12 h,
and then water (10 mL) was added thereto and the product was
extracted with ethyl acetate. The product was purified by column
chromatography. Yield 2.4 g. 1H NMR (500 MHz, CDCl3) :
7.40 (d, 2 H, J = 7.2 Hz); 7.24 (s, 2 H); 7.09 (d, 2 H, J = 7.2 Hz);
5.91—5.71 (m, 1 H); 4.95 (d, 1 H, J = 17.0 Hz); 4.90 (d, 1 H,
J = 11.0 Hz); 3.22 (s, 8 H); 2.09 (d, 2 H, J = 8.0 Hz); 0.55
(s, 3 H). 13C NMR (75 MHz, CDCl3) : 147.33, 145.58, 134.99,
134.51, 132.90, 128.63, 122.25, 113.97, 29.96, 29.83, 22.61,
–4.32. Found: m/z 313.1373 [M + Na]. Calculated: 313.1383
[M + Na].
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14. J. Dechant, Ultrarotspektroskopische Untersuchungen an
Polymeren, Akademie-Verlag, Berlin, 1972, 516 pp.
The work was financially supported by the Ministry of
Research and Education of the Russian Federation (Agree-
ment on the provision of grants from the federal budget
in the form of subsidies dated November 22, 2019
No. 075-15-2019-1694; internal number of the Agreement
05.604.21.0227, unique identificator RFMEFI60419X0227).
Received August 28, 2020;
accepted September 30, 2020