4-(DIBROMOMETHYL)BENZALDEHYDE AND ITS REACTIONS
2211
Reaction of 4-(dibromomethyl)benzaldehyde 7
with isopropylamine 12а. A mixture of 0.5 g
(1.8 mmol) of 4-(dibromomethyl)benzaldehyde, 0.11 g
(1.8 mol) of isopropylamine and 0.2 g of molecular
sieves 3A in 10 mL of anhydrous benzene was kept for
24 h at room temperature and filtered. After removal of
solvent, 0.44 g (77%) of N-isopropyl-4-(dibromome-
thyl)benzenecarbimine 13а was obtained as a yellow
oily substance. 1Н NMR spectrum, δ, ppm: 1.25 d (6Н,
182 (4.7) [C8H7Br]+, 130 (6.1) [C6H12O2N]+, 103
(100.0) [C5H11O2]+, 75 (63.8) [C3H7O2]+. Found, %: С
42.53; Н 4.79; Br 40.51; N 3.44. C14H19Br2NO2.
Calculated, %: С 42.77; Н 4.88; Br 40.65; N 3.56.
N-(4,4-Diethoxybutyl)-4-(dibromomethyl)benzene-
carbimine (13d) was prepared similarly from 0.5 g
(1.8 mmol) of 4-(dibromomethyl)benzaldehyde and
0.32 g (1.8 mmol) of 4,4-diethoxybutanamine. Yield
1
0.72 g (92%), yellow oily compound. Н NMR spec-
3
СНMe2, JНН 6.3 Hz), 3.49 and 3.55 t (1Н, СНMe2,
3
trum, δ, ppm: 1.21 t (6Н, OCH2Me, JНН 7.0 Hz),
3JНН 6.3 Hz), 6.61 s (1Н, CHBr2), 7.55 and 7.72 d (4Н,
1.43–1.80 m (4Н, СН2СН2), 3.20–3.70 m (6Н, ОСН2,
3
С6Н4, JНН 8.5 Hz), 8.25 s (1Н, СН=N). 13С NMR
3
NCH2), 4.43 t (1Н, CHO2, JНН 5.0 Hz), 6.59 s (1Н,
spectrum, δС, ppm: 24.17 (Ме), 40.45 (СНBr2), 61.80
(NCH), 126.81 and 128.29 (СНarom); 126.81, 130.05,
137.86 and 143.63 (Сarom), 157.0 (CH=N). Mass-
spectrum, m/z (Irel, %): 317 (1.0) [М]+, 302 (16.2) [М –
CH3]+, 276 (0.32) [М – C3H5]+, 238 (100.0) [М – Br]+,
223 (38.5) [М – CH3Br]+, 182 (1.4) [С8Н7Br]+, 168
(9.4) [С7Н5Br]+, 144 (24.7) [М – CH3Br2]+, 117 (22.6)
[C8H7N]+, 103 (11.1) [С7Н5N]+, 89 (61.9) [С7Н5]+, 43
(55.3) [C3H7]+. Found, %: С 41.16; Н 4.03; Br 49.95.
C11H13Br2N. Calculated, %: С 41.41; Н 4.11; Br 50.09.
3
CHBr2), 7.52 d and 7.68 d (4Н, С6Н4, JНН 8.0 Hz),
8.20 s (1Н, СН=N). Found, %: С 46.71; Н 5.69; N
3.13. C17H25Br2NO2. Calculated, %: С 46.91; Н 5.80;
N 3.22.
1Н and 13С NMR spectra were recorded on Tesla
BS-567A (100 MHz) and Bruker AVANCE 400WB
(400.13 and 100.61 MHz) instruments in CDCl3.
Chromatomass-spectrometric analysis was performed
on a DFS instrument (Thermo Electron Corporation,
Germany) in the electron impact mode. Experimental
conditions: energy of ionizing electrons 70 eV, ion
source temperature 250°С; capillary column BPX5
SGE (32 mm × 50 m), carrier gas helium. For
compound 13c, the direct inlet system was used. The
temperature of ampule-evaporator was varied from 50
to 350°С. Mass-spectral data were treated by the use of
N-(4-Methoxyphenyl)-4-(dibromomethyl)benzene-
carbimine (13b) was prepared similarly from 0.25 g
(0.9 mmol) of 4-(dibromomethyl)benzaldehyde and
0.11 g (0.9 mmol) of 4-methoxybenzeneamine. Yield
1
0.35 g (100%), yellow crystals, mp 120–123°С. Н
NMR spectrum, δ, ppm: 3.82 s (3Н, ОMe), 6.64 s (1Н,
CHBr2), 6.87 and 7.18 d (4Н, С6Н4ОMe, 3JНН 9.1 Hz),
79
Xcalibur program. The peaks of ions with Br isotope
3
7.63 and 7.88 d (4Н, С6Н4СHBr2, JНН 7.8 Hz), 8.44 s
are given.
(1Н, СН=N). Found, %: С 46.79; Н 3.29; N 3.51.
C15H13Br2NO. Calculated, %: С 47.02; Н 3.43; N 3.65.
ACKNOWLEDGMENTS
N-(2,2-Diethoxyethyl)-4-(dibromomethyl)benzene-
carbimine (13c) was obtained from 0.5 g (1.8 mmol)
of 4-(dibromomethyl)benzaldehyde and 0.24 g (1.8 mmol)
of 2,2-diethoxyethaneamine. Yield 0.65 g (93%),
This work was performed with the financial support
from the Ministry of Education and Science of RF
within the framework of the basic part of State contract
no. 2014/56.
1
yellow crystals, mp 34–35°С. Н NMR spectrum, δ,
3
ppm: 1.15 t (6Н, OCH2Me, JНН 7.0 Hz), 3.56 quintet
and 3.71 quintet (4Н, ОСН2Me, 3JНН 7.0 Hz), 3.76 d (1Н,
REFERENCES
3
3
NCH2, JНН 5.2 Hz), 4.77 t (1Н, СНО2, JНН 5.2 Hz),
6.63 s (1Н, CHBr2), 7.59 d and 7.72 d (4Н, С6Н4, 3JНН
8.4 Hz), 8.26 s (1Н, СН=N). 13С NMR spectrum, δС,
ppm: 15.45 (OCH2Me), 40.08 (СНBr2), 62.45 (NCH2),
64.60 (OCH2Me), 101.89 (CHO2), 126.80 and 128.39
(СНarom), 137.48 and 143.91 (Сarom), 161.70 (CH=N).
Mass-spectrum, m/z (Irel, %): 346 (0.73) [M – C2H5O]+,
318 (0.29) [M – C4H9O]+, 302 (0.07) [M – C4H9O2]+,
288 (0.43) [M – C5H11O2]+, 268 (2.4) [M – C2H4OBr]+,
261 (0.4) [C8H7Br2]+, 238 (1.0) [M – C4H10OBr]+, 209
(2.2) [M – C5H11O2Br]+, 197 (1.8) [M – C6H11O2Br]+,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 9 2015