Reactions of 4,5-dihydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexane] N-oxide with some nucleophilic reagents

Article abstract of DOI:10.1023/A:1017515318197

4,5-Dihydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexane] N-oxide reacted with cyanide ion and isopropyl magnesium bromide to give the corresponding 1-cyano- and 1-isopropyl-4,5-dihydro-5-methyl- 3H-spiro[benz-2-azepine-3-cyclohexane], but reaction with

Full text of DOI:10.1023/A:1017515318197

Chemistry of Heterocyclic Compounds, Vol. 37, No. 3, 2001
REACTIONS OF 4,5-DIHYDRO-
5-METHYL-3H-SPIRO[BENZ-
2-AZEPINE-3-CYCLOHEXANE]
N-OXIDE WITH SOME
NUCLEOPHILIC REAGENTS
A. V. Varlamov, D. G. Grudinin, A. I. Chernyshev, A. N. Levov,
N. I. Golovtsov, and R. S. Borisov
4,5-Dihydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexane] N-oxide reacted with cyanide ion and
isopropyl magnesium bromide to give the corresponding 1-cyano- and 1-isopropyl-4,5-dihydro-5-methyl-
3H-spiro[benz-2-azepine-3-cyclohexane], but reaction with phenyl magnesium bromide, benzyl magnesium
chloride, and nitromethane gave cyclic hydroxylamines: 1-substituted N-hydroxy-1,2,4,5-tetrahydro-5-
methyl-3H-spiro[benz-2-azepine-3-cyclohexanes] which were oxidized to the corresponding nitrones.
Keywords: benz-2-azepines, cyclic hydroxylamines, cyclic nitrones, nucleophilic additions, oxidation.
The [3+2] dipolar cycloadditions have been well studied for a series of nitrones in connection with the
wide synthetic possibilities of the isoxazolidines and isoxazolines formed in this way [2-5]. The reactions of
these nitrones (especially cyclic compounds) with nucleophilic reagents have been studied considerably less
[6,7]. The α-substituted hydroxylamines formed in this way can serve as starting materials for the synthesis of a
series of derivatives of acids and heterocyclic compounds [8-10].
In the present work, the reactions of 4,5-dihydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexane]
N-oxide (1) [11] with organo-magnesium compounds, nitromethane, potassium cyanide, and acetone
cyanohydrin have been studied for the first time.
The corresponding 1-substituted hydroxylamines of the spiro[benz-2-azepinecyclohexane] series 2 and 3
have been obtained in 42-62% yields from the reaction of the nitrone 1 with phenyl magnesium bromide and
benzyl magnesium chloride:
H3C
H3C
H3C
R
[O]
N
N
N
OH
R
R
O
2, 3, 5
4, 6
1, 7–10
1 R = H; 2, 7 R = Ph; 3, 10 R = CH2Ph; 4, 9 R = i-Pr; 5 R = CH2NO2; 6 R = CN; 8 R = PhCO
____________________________________________________________________________________________
Russian People's Friendship University, Moscow 117923. Russia; e-mail: avarlamov@sci.pfu.edu.ru.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, 376-382, March, 2001, Original article
submitted June 14, 1999.
346
0009-3122/01/3703-0346$25.00©2001 Plenum Publishing Corporation

Hydroxylamines 2 and 3 are crystalline compounds which are readily recrystallized from hexane
without marked decomposition. 1-Isopropyl-4,5-dihydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexane] (4)
was produced in 81% yield in place of the expected hydroxylamine when nitrone 1 reacted with isopropyl
magnesium bromide. The unpurified reaction mixture contained about 10% of N-hydroxy-1-isopropyl-1,2,4,5-
tetrahydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexane] according to the 1H NMR spectrum.
The reaction of nitrone 1 with nitromethane in the presence of base [8] gave the nitromethyl-substituted
hydroxylamine 5. Reaction of nitrone 1 with potassium cyanide in acid medium [12] occurred with vigorous
resinification of the reaction mixture from which no addition products were isolated. The reaction occurred
more readily in weakly basic media at 20°C and was accompanied by dehydration of the initially formed
addition product [6]. 1-Cyano-4,5-dihydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexane] (6) was obtained
in 29% yield. When acetone cyanhydrin was used as the source of cyanide ion in the presence of potassium
hydroxide and DMSO the yield of compound (6) increased to 84%.
Taking into account the synthetic possibilities of nitrones, we carried out oxidation of the synthesized
hydroxylamines 2 and 3 and the imine 4 into the N-oxides of 1-substituted 4,5-dihydro-5-methyl-3H-spiro[benz-
2-azepine-3-cyclohexanes] 7-10. The oxidation was carried out with 30% hydrogen peroxide in boiling acetone
in the presence of sodium tungstate. Under these conditions the benzyl group of compound 4 was oxidized to
benzoyl. When the oxidation was carried out in boiling ethanol the benzyl group was not affected. The
corresponding nitrone 9 was obtained in 67% yield.
The stretching frequency of the hydroxyl group appeared in the IR spectra of hydroxylamines 2, 3, 5 in
the 3226-3542 cm-1 region. The IR spectra of the nitrones 7-10 are characterized by the presence of C=N and
-1
→
N
O stretching frequencies in the 1493-1530 and 1227-1247 cm regions respectively. In the spectrum of the
cyanimine 4 the imine stretching band appears at 1655 cm-1. Stretching bands of the corresponding functional
groups appear in the IR spectra of the functionally substituted compounds 5, 6, and 8: 1560 and 1385 for NO2,
2230 for CN, and 1660 cm-1 for CO.
Only one set of signals is observed in the 1H NMR spectra of the hydroxylamines 2, 3, and 5 (Table 1)
which indicates the absence of geometric isomers with respect to the substituent R on carbon atom C(1). It may
be suggested that the bulky substituent occupies an equatorial position in compounds 2, 3, and 5. In the
spectrum of the mixture obtained from the reaction of compound 1 with isopropyl magnesium bromide, which
contains about 10% of the corresponding hydroxylamine and imine 4, only one doublet for proton 1-H was
observed at 3.98 ppm and a vicinal coupling J = 9.5 Hz. Because of the closeness of the values of the geminal
coupling of the protons of 1-R (CHAHB) and the vicinal coupling between 1-H and 1-R (CHAHB), it is difficult to
assign signals in the range 3.22-5.34 ppm in the spectra of compounds 3 and 5 to individual protons. The signals
with two maximal geminal and vicinal coupling constants (J = 10.3-13.4 Hz) are assigned to the 1-R proton
(CHAHB). Of the four doublet signals with coupling constants (J = 10.3-10.7 and 3.4-3.9 Hz), the closest values
of the chemical shifts, bearing in mind the distance of 1-H from nitro and phenyl substituents, should belong to
proton 1-H: 4.68 (J1,A = 10.3, J1,B = 3.9) in compound 3 and 4.79 (J1,A = 10.7, J1,B = 3.4) in hydroxylamine 5.
Because the signals of protons 4-Ha and 4-He are masked by the complex multiplets of the cyclohexane
fragment, it was not possible to measure their chemical shifts and coupling constants.
The presence of large axial-axial coupling constants between protons 5-H and 4-Ha (J = 11.0-14.0 Hz)
in the spectra of imine 6 and the nitrones 8-10 indicates that proton 5-H has an axial orientation and
consequently that the 5-CH3 methyl group has equatorial disposition which has been confirmed by X-ray
1
crystallography and H NMR spectroscopy on the example of 8-nitro-1,2,4,5-tetrahydro-1,5-dimethyl-3H-
spiro[benz-2-azepine-3-cyclohexane].*
_______
* To be published in a separate paper.
347

TABLE 1. 1H NMR Spectra of Compounds 2-10 in CDCl3 Solutions
Com-
Chemical shifts, δ, ppm (multiplicity), coupling constants , J, Hz
pound
1-Н
2-ОН
4-На
4-Не
5-Н
5-СН3
H-cyclohex.
6-Н-9-Н
1-R
5.68 (s)
4.12
1.3-2.0
1.2-1.9
3.59 (m)
1.24 (d)
3J = 7.3
1.2-2.0
6.6-7.8
6.6-7.8
2
3
(br. s)
(m)
4.68 (dd)
3J1,A = 10.3
3J1,В = 3.9
3.56
3.24 (m)
1.37 (d)
0.8-2.0
7.1-7.6
3.42 (А) (dd) 2J = 13.4
3J1,A = 10.3; 3.22 (В) (dd),
2J = 13.4 3J1,В = 3.9;
7.1-7.6 (Ph) (m)
(br. s)
3J = 7.0
(m)
—
—
4
1.80 (dd)
2J = 13.7
2.36 (dd)
2J = 13.7
3J4e,5 = 5.8
3.10 (m)
3J4a,5= 13.1,
3J4e,5 = 5.8
3J5,Mе = 7.0
1.29 (d)
3J = 7.0
1.1-2.0
7.1-7.45
1.08 (СН3) (d) 3J = 7.0;
1.40 (СН3) (d) 3J = 7.0;
3.77 (СН) (m) 3J = 7.0
(m)
3J4a,5 = 13.1
5.21 (А) (t) 2J = 3J1,A = 10.7;
5.34 (В) (dd),
5
6
4.79 (dd)
3J1,A = 10.7,
3J1,В= 3.4
3.99
1.2-1.9
3.26 (m)
1.40 (d)
3J = 7.0
1.2-1.9
7.1-7.4 (6Н...8Н) (m)
6.92 (9-Н) (d)
(br. s)
(m)
2J = 10.7 3J1,В = 3.4
—
—
—
—
—
—
—
—
—
—
1.85 (dd)
2J = 14.3
2.18 (dd)
2J = 14.3
3J4e,5 = 4.0
2.98 (m)
3J4a,5 = 11.0
3J4e,5 = 4.0
3J5,Mе = 7.0
3.39 (m)
3J4a,5 = 13.4,
3J4e,5 = 6.0
3J5,Mе = 6.7
3.45 (m)
3J4a,5 = 11.7,
3J4e,5 = 4.9
3J5,Mе = 7.0
3.10 (m)
3J4a,5 = 13.7,
3J4e,5 = 5.8
3J5,Mе = 6.7
1.33 (d)
3J = 7.0
1.1-2.0
7.29 (6-Н) (dd) 3J = 8.0
—
(m)
4J = 2.0; 7.35-7.42 (7-Н, 8-Н)
(td), 3J = 8.0, 4J = 2.0; 7.74
(9-Н) (dd) 3J = 8.0 4J = 2.0
3J4a,5 = 11.0
1.98 (t)
2.48 (dd)
2J = 13.4
3J4e,5 = 6.0
1.33 (d)
3J = 6.7
1.1-2.5
7.1-7.4 (6-Н, 8-Н) (m);
7.1-7.4 (m-, p-Ph) (m);
7.59 (о-Ph) (d)
7
2J = 3J4a,5 = 13.4
(m)
6.83 (9-Н) (d)
2.14 (dd)
2J = 14.0
2.51 (dd)
2J = 14.0
3J4e,5 = 4.9
1.45 (d)
3J = 7.0
1.2-2.4
7.0-7.7 (m)
7.1-7.4 (m)
7.1-7.4 (m)
7.0-7.7 (m-, p-Ph) (m);
7.97 (о-Ph) (m)
8
(m)
3J4a,5 = 11.7
1.80 (t)
2.36 (dd)
2J = 13.7
3J4e,5 = 5.8
1.29 (d)
3J = 6.7
0.8-2.5
(m)
1.08 (СН3) (d) 3J = 7.0;
1.40 (СН3) (d) 3J = 7.0;
3.78 (СН) (m) 3J = 7.0
9
2J = 3J4a,5 = 13.7
1.94 (t)
2.34 (dd)
2J = 14.0
3J4e,5 = 5.5
2.95 (m)
3J4a,5 = 14.0,
3J4e,5 = 5.5,
3J5,Mе = 6.7
1.21 (d)
3J = 6.7
1.0-2.5
4.32 (А) (d) 2J = 14.0;
4.17 (В) (d) 2J = 14.0
10
2J = 3J4a,5 = 13.7
(m)

Molecular ions corresponding to the molecular formula were observed in the mass spectra of
spiro[benz-2-azepine-3-cyclohexanes]. The decomposition of the molecular ions of the nitrones 1, 8, and 9
occur by three basic routes: hydroxyl elimination, splitting of the cyclohexane ring, and splitting of the
benzazepine ring (scheme, Table 2).
.
+
H3C
.
–(CH2CH2CH2)
+
[M – H]
A2
N
.
O
–H
A4
.
.
H3C
+
+
CH3
CH3
R
.
–2H
N
R
A5
R
O
A6
.
.
1, 7–9
–R , –H
+
M
CH3
.
–OH
A7
H3C
R
H3C
.
+
.
.
–CH3
or
N
N
N
+
R
A6
(R = H)
A3
The fragmentation of the M+ ions for compounds 8 and 9 is characterized by the elimination of the
benzoyl and isopropyl groups respectively from C1. The fragment ions with m/z 242 have intensities of 45 and
·
66% respectively. The ion [M-OH]+ 1) in the second stage of the decomposition eliminates CH3 to give
(Φ
fragment Φ
3. Decomposition of the benzazepine fragment of the molecule leads to the formation of the cation
TABLE 2. Intensities of Characteristic Ions in the Mass Spectra of Nitrones
1, 7-9 and the Cyano-substituted Benz-2-azepine 6
Com-
pound
Ions (intensities, %)
М+
Ф1
Ф2
Ф3
Ф4
Ф5
Ф6
243
226
—
211
201
132
130
1
7
8
9
6
(21)
(100)
(9)
(7)
(100)
(50)
319
302
319
287
277
208
206
(32)
(100)
(6)
(10)
(20)
(60)
(60)
347
330
—
315
305
236
234
(18)
(57)
(5)
(18)
(10)
(9)
285
268
284
(8)
253
243
174
172
(55)
(100)
(10)
(20)
(55)
(35)
252
—
251
—
210
157
155
(36)
(18)
(77)
(31)
(82)
349

radical of 3-substituted 1-methylindane Φ
5. Further fragmentation of this ion is characterized by consecutive
which leads to the indanes Φ6
elimination of either two hydrogen atoms or hydrogen and the substituent at C3
and Φ7
respectively. In distinction from 1,2,4,5-tetrahydro-5-methyl-3H-spiro[benz-2-azepine-3-cyclohexane]
[13] and the N-hydroxy derivatives 2, 3, and 5, where splitting of the cyclohexane ring in M+ ions is
accompanied by the elimination of a methyl, ethyl, or propyl group, a C3H6 group is eliminated in the
fragmentation of compounds 1, and 7-9
with the formation of a quite intense fragmentation ion Φ
4. Elimination
of the C3H6 particle is also characteristic of fragmentation of the M+ ion of the cyano substituted compound 6.
Fragmentation of the M+ of the N-hydroxy substituted benzazepines 2, 3, and 5 is characterized by
elimination of the hydroxyl and benzyl or nitromethyl radicals from C(1). Fragmentation of the benzazepine part
of the molecule in compounds 2, 3, and 5 also leads to the formation of the cation radical of 3R-1-methylindane,
which dissociates analogously to the process described above for the nitrones.
EXPERIMENTAL
IR spectra of KBr disks were recorded with a UR-20 spectrometer. Mass spectra were recorded with a
Varian MAT 112 with direct injection of the samples into the ion source with an ionizing voltage of 70 eV.
1H NMR spectra of about 2% solutions of the compounds synthesized in CDCl3 were recorded with a Bruker
WP-200 machine at 30°C. Chemical shifts were measured relative to TMS as internal standard. TLC was carried
out on Silufol UV-254 plates with 1:2 ethyl acetate–hexane as eluent, and development with iodine vapor. Silica
gel L 100/250 was used for column chromatography with 1:5 ethyl acetate–hexane as eluent. Melting points
were determined in glass capillaries and were not corrected.
N-Hydroxy-5-methyl-1-phenyl-1,2,4,5-tetrahydro-3H-spiro[benz-2-azepine-3-cyclohexane] (2).
Nitrone 1 (1.0 g, 4 mmol) was added in portions over 10 min to a solution of phenyl magnesium bromide
prepared from Mg (0.38 g, 16 mmol) and bromobenzene (1.29 g, 8 mmol) in absolute ether (25 ml). The mixture
was boiled for 1 h (monitored by TLC), poured onto ice, and treated with saturated ammonium chloride
solution. It was extracted with ether (3 × 30 ml), and dried over magnesium sulfate. The residue (1.13 g) after
evaporating the ether was recrystallized from hexane to give hydroxylamine 2 (0.55 g, 42%) as white crystals;
mp 105-106°C, Rf 0.60. IR spectrum: 3236 cm-1 (OH). Mass spectrum, m/z (Irel, %): 321 (17, M+), 304 (78),
207 (24), 130 (18), 114 (100), 103 (8), 91 (30), 77 (12). Found, %: C 82.0; H 8.1; N 4.7. C23H29NO. Calculated,
%: C 82.2; H 8.4; N 4.4.
1-Benzyl-N-hydroxy-5-methyl-1,2,4,5-tetrahydro-3H-spiro[benz-2-azepine-3-cyclohexane] (3).
Hydroxylamine 3 (3.44 g, 62%) was obtained as white crystals; mp 125-128°C, Rf 0.74, by the above method
from the interaction of nitrone 1 (4 g, 16 mmol) with benzyl magnesium chloride, synthesized from Mg (1.52 g,
66 mmol) and benzyl chloride (4.19 g, 33 mmol). IR spectrum: 3542 cm-1 (OH). Mass spectrum, m/z (Irel, %):
335 (15, M+), 318 (10), 244 (100), 211 (7), 131 (28), 130 (20), 114 (35), 103 (8), 91 (57), 77 (10). Found, %:
C 82.7; H 8.4; N 4.0. C22H27NO. Calculated, %: C 82.4; H 8.7; N 4.2.
1-Isopropyl-5-methyl-4,5-dihydro-3H-spiro(benz-2-azepine-3-cyclohexane] (4). Compound
4
(1.01 g, 87%) was obtained as a yellow viscous oil, Rf 0.91, after chromatography on silica gel, by an analogous
method from nitrone 1 (1 g, 4 mmol) and isopropyl magnesium bromide, synthesized from Mg (0.37 g,
16 mmol) and isopropyl bromide (0.98 g, 8 mmol). IR spectrum: 1637 (C=N), 1348, and 1387 cm-1 (i-Pr).
Found, %: C 84.4; H 10.2; N 5.0. M+ 269. C19H27N. Calculated, %: C 84.8; H 10.1; N 5.2. M 269.
N-Hydroxy-5-methyl-1-nitromethyl-1,2,4,5-tetrahydro-3H-spiro[benz-2-azepine-3-cyclohexane] (5).
Nitrone 1 (0.5 g, 2 mmol) followed by a mixture of DMSO (1.87 g, 24 mmol) and nitromethane (0.61 g,
10 mmol) in ethanol (10 ml) were added to a solution of sodium ethoxide (6 mmol) in ethanol (10 ml). The
mixture was kept at 20°C for 24 h and then at 50°C for 4 h. It was poured into water and extracted with
chloroform. The residue (0.54 g) was chromatographed on a silica gel column (30 × 2 cm). Hydroxylamine 5
(0.14 g, 23%) and the initial nitrone (0.06 g, 12%) were isolated. Compound 5, white crystals; mp 108-110°C
350

(hexane), Rf 0.71. IR spectrum: 3512 (OH), 1560 and 1385 cm-1 (NO2). Mass spectrum, m/z (Irel, %):
304 (2, M+), 286 (7), 244 (12), 190 (34), 130 (100), 115 (30), 103 (15), 91 (27), 77 (40). Found, %: C 67.4;
H 8.1; N 9.5. C17H24N2O3. Calculated, %: C 67.1; H 7.9; N 9.2.
1-Cyano-4,5-dihydro-5-methyl-3H-spiro(benz-2-azepine-3-cyclohexane] (6). A. A solution of
potassium cyanide (0.26 g, 4 mmol) in water (2 ml) was added gradually to a solution of nitrone 1 (0.5 g,
2 mmol) in THF (15 ml). The mixture was kept for a day at 20°C. After removal of the THF in vacuum, water
was added (50 ml) and the mixture was extracted with ether (4 × 20 ml). The extract was dried over magnesium
sulfate, the ether was evaporated, and the residue (0.43 g) was crystallized from hexane to give starting nitrone 1
(0.1 g, 20%). The mother liquor was chromatographed on silica gel to give compound 6 (0.15 g, 30%) as a
viscous light yellow oil, Rf 0.81. IR spectrum: 2230 (C=N), 1655 (C=N) cm-1. Mass spectrum, m/z (Irel, %):
252 (36, M+), 251 (18), 237 (30), 223 (23), 212 (14), 210 (27), 209 (21), 199 (22), 198 (51), 197 (36), 196 (14),
195 (20), 184 (19), 158 (14), 157 (31), 156 (100), 155 (82), 154 (33), 144 (36), 142 (36), 140 (62), 130 (30),
129 (83), 128 (71), 127 (41), 115 (79), 103 (29), 77 (41). Found, %: C 81.2; H 7.7; N 10.9. C17H20N2.
Calculated, %: C 81.0; H 7.9; N 11.1.
B. A solution of nitrone 1 (0.5 g, 2 mmol), potassium hydroxide (0.22 g, 4 mmol), DMSO (1.25 g,
16 mmol), and acetone cyanohydrin (0.51 g, 6 mmol) in ethanol (20 ml) was heated at 50°C for 1 h, then poured
into water (50 ml) and extracted with ether (3 × 20 ml). The residue (0.53 g) after evaporation of the ether was
chromatographed on a silica gel column (10 × 1 cm) to give compound 6 (0.42 g, 84%) identical in
chromatographic mobility and spectroscopic characteristics with a sample made by method A.
5-Methyl-1-phenyl-4,5-dihydro-3H-spiro[benz-2-azepine-3-cyclohexane] N-Oxide (7). A solution of
compound 2 (2.45 g, 7.6 mmol), sodium tungstate dihydrate (0.1 g, 0.3 mmol), and 30% hydrogen peroxide
(4.5 ml, 45.6 mmol) in acetone (10 ml) was boiled for 8 h (monitored by TLC). After evaporation of the
acetone, water (50 ml) was added to the residue and the mixture was extracted with chloroform. The extract was
washed with water and dried over magnesium sulfate. After removal of the chloroform, the residue was
crystallized from a mixture of hexane and ethyl acetate to give compound 7 (1.14 g, 55%) as white crystals;
mp 126-128°C, Rf 0.2. IR spectrum: 1493 (C=N), 1247 cm-1 (N O). Mass spectrum, m/z (Irel, %): 319 (32, M+),
→
318 (6), 302 (100), 287 (10), 277 (20), 260 (35), 224 (25), 208 (60), 207 (62), 206 (60), 199 (32), 191 (10),
190 (8), 178 (20), 165 (23), 131 (20), 130 (18), 129 (18), 128 (20), 115 (20), 103 (20), 91 (30), 77 (41).
Found, %: C 82.6; H 8.0; N 4.5. C22H25NO. Calculated, %: C 82.8; H 7.8; N 4.4.
1-Benzoyl-5-methyl-4,5-dihydro-3H-spiro[benz-2-azepine-3-cyclohexane] N-Oxide (8) was
obtained analogously to compound 7 from hydroxylamine 3 (0.5 g, 1.5 mmol). Compound 8 (0.41 g, 79%),
white crystals; mp 135-137°C, Rf 0.27. IR spectrum: 1666 (C=O), 1530 (C=N), 1247 cm-1 (N O). Mass
→
spectrum, m/z (Irel, %): 347 (18, M+), 330 (57), 315 (5), 305 (18), 288 (5), 276 (4), 242 (43), 236 (10), 235 (12),
234 (9), 226 (35), 225 (25), 224 (30), 131 (20), 130 (40), 129 (22), 116 (13), 115 (13), 105 (100), 95 (88),
78 (50), 77 (50). Found, %: C 79.4; H 7.2; N 4.1. C23H25NO2. Calculated, %: C 79.5; H 7.2; N 4.0.
1-Isopropyl-5-methyl-4,5-dihydro-3H-spiro[benz-2-azepine-3-cyclohexane] N-Oxide (9) was
obtained analogously to compound 8 from imine 4 (1.95 g, 6.8 mmol). Yield 1.14 g (59%), a viscous light
yellow which crystallized on prolonged standing; mp 68-70°C. IR spectrum: 1505 (C=N), 1230 cm-1 (N O).
→
Mass spectrum, m/z (Irel, %): 285 (55, M+), 284 (8), 268 (100), 253 (10), 252 (12), 243 (20), 242 (65), 226 (32),
199 (32), 190 (40), 174 (55), 173 (30), 172 (35), 161 (25), 160 (20), 158 (40), 157 (38), 146 (30), 144 (30),
143 (30), 131 (40), 130 (78), 129 (40), 128 (40), 115 (38), 103 (28), 91 (30), 77 (32), 43 (50). Found, %: C 79.6;
H 9.3; N 5.1. C19H27NO. Calculated, %: C 80.0; H 9.5; N 4.9.
1-Benzyl-5-methyl-4,5-dihydro-3H-spiro[benz-2-azepine-3-cyclohexane] N-Oxide (10). A solution
of hydroxylamine 3 (1.0 g, 3 mmol), 30% hydrogen peroxide (3 ml, 30 mmol), and sodium tungstate dihydrate
(40 mg, 0.12 mmol) in ethanol (15 ml) was boiled for 2 h. The ethanol was evaporated, water (50 ml) was
added, and the mixture was extracted with chloroform. The extract was dried over magnesium sulfate, the
chloroform was evaporated, and the residue was crystallized from a mixture of hexane and ethyl acetate to give
351

compound 10 (0.67 g, 67%) as white crystals; mp 143-145°C, Rf 0.25. IR spectrum: 1519 (C=N), 1227 cm-1
(N O). Mass spectrum, m/z (Irel, %): 333 (2), 317 (12), 275 (26), 226 (64), 220 (22), 130 (73), 115 (28),
→
103 (30), 91 (100), 77 (24). Found, %: C 82.6; H 8.3; N 4.5. M+ 333. C23H27NO. Calculated, %: C 82.9; H 8.1;
N 4.2. M 333.
This work was carried out with partial financial support from MNTP P. T. 402.95 MOPO RF "General
and technical chemistry" (grant 01.0203 F).
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