KUKSENOK et al.
198
17b, 19a, and 19b and estimation of their ratio was
performed by GC-MS and HPLC methods applying
the addition of standard compounds. The following
retention times were established (min), GC: 12a 22.0,
12b 22.4, 13a 21.1, 13b 21.4, 14a 20.6, 14b 20.4, 15a
21.3, 15b 21.5, 16a 23.0, 16b 23.4, 17a 13.9, 17b 9.3,
18a 16.3, 19a 10.4, 19b 9.0; HPLC: 12a 7.5, 12b 7.2,
13a 8.3, 13b 8.0, 14a 7.7, 14b 8.3, 15a 7.8, 15b 7.5,
16a 23.0, 16b 23.4, 17a 4.9, 17b 6.1, 18a 6.4, 19a 7.5,
19b 7.2.
t (1H), 7.34–7.42 d (2H), 7.52–7.62 d (2H), 7.75–7.93
d (2H), 7.95–7.99 t (2H), 10.30 s (1H).
N-Phenyl-3-bromobenzamide (15b). Yield 62%,
1
mp 141–142°С. H NMR spectrum, δ, ppm: 7.10–
7.13 t (1H), 7.35–7.38 t (2H), 7.50–7.52 d (2H),
7.76–7.78 d (2H), 7.94–7.97 t (2H), 8.13 s (1H),
10.34 s (1H).
N-(4-Hydroxyphenyl)benzamide (16a). Yield 80%,
mp 209–211°С. 1H NMR spectrum, δ, ppm: 6.73–6.76
d (2H), 7.52–7.54 m (5H), 7.91–7.93 d (2H), 9.25 s
(1H). 13С NMR spectrum, δ, ppm: 114.93, 122.24,
127.46, 128.30, 130.65, 131.25, 135.14, 153.67,
164.83.
Amides 11–20. General procedure. A mixture of
10 mmol of ketone 1–10, 30 mmol of hydroxylamine
hydrochloride, 1 g of silica gel in 8 mL of formic acid
was heated at 80°С while stirring (TLC monitoring)
for the time indicated in the table. Silica gel was
filtered from the reaction mixture, the filtrate was
diluted with 150 mL of water and neutralized with
20% solution of NaOH. The separated precipitate of
amides 11, 12a, 12b–16a, 16b, and 18a was filtered
off, washed with water on the filter, and dried. Amides
17a, 17b, 19a, 19b, and 20 were extracted from the
water solution with toluene (3 × 20 mL), the extract
was dried with Na2SO4 and evaporated on a rotary
evaporator.
N-Phenylacetamide (17а). Mass spectrum: m/z
135 [M]+, 93, 66, 63, 43.
N-Methylbenzamide (17b). Mass spectrum: m/z
135 [M]+, 105, 77, 51.
N-(4-Nitrophenyl)acetamide (18а). Yield 90%,
1
mp 216–218°С. H NMR spectrum, δ, ppm: 3.37 s
(3H), 7.93–7.95 d (2H), 8.25–8.27 d (2H), 11.80 s
(1H).
N-Cyclohexylacetamide (19а). Mass spectrum: m/z
141 [M]+, 111, 97, 79, 69, 60, 54.
The prevailing amide isomer obtained from ketones
2–6 was isolated by recrystallization from 2-propanol.
Amides 17а, 17b and 19а, 19b were analyzed as
mixtures.
N-Methylcyclohexanecarboxamide (19b). Mass
spectrum: m/z 141 [M]+, 126, 112, 98, 84, 70, 56, 43,
28.
1
Benzanilide (11). Yield 98%, mp 162–163°С. H
Hexahydro-2H-azepin-2-one (20). Yield 79%, mp
NMR spectrum, δ, ppm: 7.08–7.13 t (1H), 7.33–7.39 t
(2H), 7.51–7.61 m (3H), 7.79–7.82 d (2H), 7.96–7.99
d (2H), 10.28 s (1H). 13С NMR spectrum, δ, ppm:
120.24, 123.54, 127.51, 128.27, 128.48, 131.43,
134.85, 139.02, 165.39.
1
68–70°С. H NMR spectrum, δ, ppm: 1.71–1.76 m
(6H), 2.40–2.45 m (2H), 3.14–3.24 m (2H), 6.49 br
(1H).
The study was carried out under the financial
support of the State contract “Nauka” (project no.
2387).
N-(2-Chlorophenyl)benzamide (12а). Yield 57%,
mp 103–104°С. 1H NMR spectrum, δ, ppm: 7.05–7.09
m (1Н), 7.31–7.33 t (1Н), 7.40–7.42 d (1Н), 7.49–7.52
m (2Н), 7.56–7.59 t (1Н), 7.89–7.92 d (2Н), 8.43 s
(1H), 8.56–8.58 d (1Н).
REFERENCES
1. Smith, M.B. and March, J., Advanced Organic
Chemistry, 5th Ed., New York: John Wiley & Sons,
2001.
N-Phenyl-3-chlorobenzamide (13b). Yield 85%,
mp 136–137°С. 1H NMR spectrum, δ, ppm: 7.09–7.14
t (1H), 7.34–7.39 t (2H), 7.54–7.59 t (1H), 7.65–7.68 d
(1H), 7.75–7.68 d (2H), 7.90–7.92 d (1H), 8.01 s (1H).
13С NMR spectrum, δ, ppm: 120.37, 123.79, 126.40,
127.35, 128.57, 130.34, 131.36, 133.18, 136.89,
138.79, 163.71.
2. Augustine, J.K., Kumar, R., Bombrun, A., and
Mandal, A.B., Tetrahedron Lett., 2011, vol. 52,
p. 1074.
3. Kaur, G., Rajput, J.K., Arora, P., and Devi, N.,
Tetrahedron Lett., 2014, vol. 55, p. 1136.
N-(4-Chlorophenyl)benzamide (14а). Yield 53%,
mp 187–189°С. 1H NMR spectrum, δ, ppm: 7.09–7.13
4. Maia, A., Albanese, D.C.M., and Landini, D.,
Tetrahedron, 2012, vol. 68, p. 1947.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 2 2016