KOLCHINA et al.
860
1416, 1386, 1365, 1333, 1256, 1181, 1105, 1059, 976,
800. H NMR spectrum (CD3CN), δ, ppm: 1.14 d
[12H, CH(CH3)2, J = 6.9 Hz], 3.05 sept [2H, CH(CH3)2,
J = 6.9 Hz], 5.72 d.d (1H, =CH2, cis, J = 2.1, J =
10.2 Hz), 6.24 d.d (1H, =CH2, trans, J = 2.1, J =
2,6-Diisopropyl-N,N-dimethylaniline (Ia). Yield
4.0 g (98%). The boiling point and H NMR spectrum
were identical to those given in [3].
1
1
2,6-Diisopropyl-N,N-dimethyl-4-thiocyanato-
aniline (Ib). Yield 5.1 g (91%). The melting point and
1H NMR spectrum were identical to those given in [4].
17.1 Hz), 6.44 d.d (1H, CH=, Jcis = 10.2, Jtrans
=
17.1 Hz), 7.20–7.33 m (3H, Harom), 8.03 br.s (1H, NH).
Found, %: C 77.91; H 9.17; N 6.36. C15H21NO. Cal-
culated, %: C 77.88; H 9.15; N 6.05.
4-Bromo-2,6-diisopropyl-N,N-dimethylaniline
(Ic). Yield 4.2 g (75%), mp 64–65°C (from petroleum
ether, bp 40–70°C). IR spectrum (CHCl3), ν, cm–1:
3018, 2966, 2930, 2786, 1571, 1462, 1426, 1385,
1364, 1337, 1235, 1142, 1098, 1065, 939, 868, 810,
574. 1H NMR spectrum (CDCl3), δ, ppm: 1.18 d [12H,
CH(CH3)2, J = 6.8 Hz], 2.79 s (6H, CH3), 3.28 sept
[2H, CH(CH3)2, J = 6.8 Hz], 7.15 s (2H, Harom). Found,
%: C 59.87; H 7.80; Br 28.98; N 5.29. C14H22BrN.
Calculated, %: C 59.15; H 7.80; Br 28.12; N 4.93.
2,6-Diisopropyl-N-methylanilines Xa and Xb
(general procedure). A mixture of 23 ml (0.12 mol) of
aniline IIa or IIb and 9.5 ml (0.15 mol) of methyl
iodide was heated under reflux for 0.5 or 2.5 h, respec-
tively. The mixture was cooled to room temperature,
the resulting glassy material was ground with 200 ml
of water, and a 10% solution of sodium hydroxide was
added in portions (overall volume ~70 ml) to pH ~8–9.
The oily layer was separated, the aqueous phase was
extracted with diethyl ether, the extract was combined
with the organic phase, washed with water, and dried
over K2CO3, the solvent was distilled off, and the resi-
due was distilled under reduced pressure.
4-Dimethylamino-3,5-diisopropylbenzenethiol
(Id). Compound Ib, 1 g (3.3 mmol), was added in
portions at room temperature to a suspension of 0.21 g
(5.5 mmol) of LiAlH4 in 30 ml of THF, and the mix-
ture was heated for 2 h under reflux. The mixture was
cooled, unreacted LiAlH4 was filtered off, 200 ml of
water was added to the filtrate, sodium chloride was
then added, and the mixture was extracted with diethyl
ether. The extract was dried over K2CO3 and evaporat-
ed, and the residue was washed with a small amount of
alcohol. Yield 0.58 g (64%), mp 149–151°C (from
ethanol–hexane). IR spectrum (CHCl3), ν, cm–1: 3020,
2965, 2930, 2869, 2785, 1577, 1463, 1442, 1384,
1363, 1338, 1239, 1147, 1096, 1066, 939, 873, 831,
584. 1H NMR spectrum (CDCl3), δ, ppm: 1.03 d [12H,
CH(CH3)2, J = 6.9 Hz], 2.05 s (1H, SH), 2.68 s (6H,
CH3), 3.16 sept [2H, CH(CH3)2, J = 6.9 Hz], 7.11 s
(2H, Harom). Found, %: C 70.60; H 9.54; N 5.84;
S 13.48. C14H23NS. Calculated, %: C 70.84; H 9.77;
N 5.90; S 13.49.
2,6-Diisopropyl-N-methylaniline (Xa). Yield
17.0 g (75%), bp 79–81°C (1–2 mm). IR spectrum
(film), ν, cm–1: 3391, 3065, 2962, 2869, 2797, 1619,
1590, 1459, 1417, 1383, 1362, 1337, 1255, 1201,
1137, 1118, 1055, 933, 798, 759, 721, 660, 564, 528.
1H NMR spectrum (CDCl3), δ, ppm: 1.48 d [12H,
CH(CH3)2, J = 6.9 Hz], 2.95 s (3H, CH3), 3.07 s (1H,
NH), 3.52 sept [2H, CH(CH3)2, J = 6.9 Hz], 7.25–
7.39 m (3H, Harom). Found: m/z 191.1667 [M]+.
C13H21N. Calculated: M 191.1669.
2,6-Diisopropyl-N-methyl-4-thiocyanatoaniline
(Xb). Yield 63%, bp 189–191°C (25 mm). IR spectrum
(film), ν, cm–1: 3406, 3062, 2964, 2871, 2803, 2155,
1626, 1578, 1463, 1417, 1385, 1364, 1340, 1245,
1
1205, 1121, 1069, 910, 877, 734, 682, 596. H NMR
spectrum (CDCl3), δ, ppm: 1.33 d [12H, CH(CH3)2,
J = 6.8 Hz], 2.84 s (3H, CH3), 3.18 br.s (1H, NH),
3.30 sept [2H, CH(CH3)2, J = 6.8 Hz], 7.32 s (2H,
Harom). Found: m/z 248.1341 [M]+. C14H20N2S. Calcu-
lated: M 248.1342.
N-(2,6-Diisopropylphenyl)acrylamide (IX). Tri-
ethylamine, 4.2 ml (0.03 mol), was added under
stirring to a solution of 3.8 ml (0.02 mol) of compound
IIa in 20 ml of DMF, a solution of 3.5 ml (0.04 mol) of
acryloyl chloride in 10 ml of DMF was then added
over a period of 0.5 h at room temperature, and a white
solid separated. The mixture was stirred for 0.5 h
more, 100 ml of water was added, the precipitate dis-
solved, and a white solid precipitated again. The prod-
uct was filtered off, washed with water and hexane,
and dried in air. Yield 4.0 g (87%), mp 191–193°C
(from hexane). IR spectrum (CHCl3), ν, cm–1: 3292,
3080, 3003, 2967, 2871, 1667, 1628, 1588, 1487,
A solution of 1.91 g (0.010 mol) of compound Xa
and 1.52 g (0.025 mol) of ammonium thiocyanate in
15 ml of acetic acid was cooled to 10°C, a solution of
0.77 ml (0.015 mol) of bromine in 3 ml of acetic acid
was added dropwise at 12–15°C. The mixture was
stirred for 2 h at room temperature, poured into 200 ml
of water, neutralized by adding Na2CO3 in portions,
and extracted with diethyl ether. The extract was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 6 2011