Mannich Bases from Bicyclo[2.2.1]hept-5-en-2-ylmethanol, Secondary Amines and Formaldehyde

Article abstract of DOI:10.1134/S1070363218100298

New Mannich bases were synthesized by reacting bicyclo[2.2.1]hept-5-en-2-ylmethanol with secondary amines and formaldehyde. Physicochemical characteristics, composition and structure of the synthesized compounds were determined by elemental analysis, IR,

Full text of DOI:10.1134/S1070363218100298

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 10, pp. 2204–2208. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © E.H. Mammadbayli, G.E. Hajiyeva, S.I. Ibrahimli, N.A. Jafarova, 2018, published in Zhurnal Obshchei Khimii, 2018, Vol. 88,
No. 10, pp. 1718–1722.
LETTERS
TO THE EDITOR
Mannich Bases from Bicyclo[2.2.1]hept-5-en-2-ylmethanol,
Secondary Amines and Formaldehyde
a
a
b
c
E. H. Mammadbayli *, G. E. Hajiyeva , S. I. Ibrahimli , and N. A. Jafarova
a
Institute of Petrochemical Processes of the National Academy of Sciences of Azerbaijan,
pr. Khojaly 30, Baku, 1025 Azerbaijan
*
e-mail: eldar_mamedbeyli@mail.ru
b
Ganja State University, Ganja, Azerbaijan
c
Azerbaijan State University of Oil and Industry, Baku, Azerbaijan
Received May 3, 2018
Abstract—New Mannich bases were synthesized by reacting bicyclo[2.2.1]hept-5-en-2-ylmethanol with
secondary amines and formaldehyde. Physicochemical characteristics, composition and structure of the syn-
1
13
thesized compounds were determined by elemental analysis, IR, H, C NMR spectroscopy and mass spectrometry.
Keywords: dicyclopentadiene, bicyclo[2.2.1]hept-5-en-2-ylmethanol, secondary amines, Mannich bases
DOI: 10.1134/S1070363218100298
Functionally substituted organic compounds including
heteroatoms (sulfur and nitrogen) are used as additives
to improve the quality of oils and fuels, as well as
effective biologically active substances, medicines,
pesticides, etc. [1, 2]. Depending on the structure and
nature of the heteroatom, the biological activity and
reactivity of these compounds vary.
One-pot Mannich reaction of bicyclo[2.2.1]hept-5-
en-2-ylmethanol 3 with secondary amines 5–12 and
formaldehyde 4 resulted in a series of aminomethoxy
derivatives of norbornene. The starting compound 3
was prepared from dicyclopentadiene 1 isolated from
the C side fraction of the liquid pyrolysis products.
5
Bicyclo[2.2.1]hept-5-en-2-ylmethanol 3 was obtained
by reacting cyclopentadiene 1 with allyl alcohol 2 in a
pressure reactor [12] at a ratio dicyclopentadiene : allyl
alcohol = 1 : 2.4 (170–180°С, 4–5 at) for 9 h (Scheme 1).
The target alcohol 3 was isolated with a yield of 74%.
Among the biologically active derivatives of
norbornene (bicyclo[2.2.1]hept-2-ene) amines are
especially valuable due to the presence in their
molecules of two pharmacophoric fragments: a
nitrogen-containing group [3] and a carbon scaffold
related to natural terpenes [4]. Antiviral activity is
characteristic of amines with norbornane structure [5].
The reaction of bicyclo[2.2.1]hept-5-en-2-yl-methanol
3 with formaldehyde 4 and secondary amines (diethyl-
amine 5, dipropylamine 6, dibutylamine 7, dipentyl-
amine 8, dihexylamine 9, piperidine 10, morpholine
Since biologically active compounds which combine
several pharmacophore fragments possess a more
effective action, it is important to synthesize new
compounds based on available raw materials by
effective methods [6–8] and to study their
physiological effect [9]. The Mannich reaction is one
of the convenient and effective methods for the
preparation of nitrogen-containing organic compounds
1
1, and azepane 12) led to the formation of amino-
methoxy derivatives of bicyclo[2.2.1]hept-5-en-2-yl-
methanol 13–20 in 43–71% yield (Scheme 2). The
reaction was carried out in benzene at 78–80°С for 4–
5
h at a molar ratio bicyclo[2.2.1]hept-5-en-2-yl-
methanol : formaldehyde : amine = 1 : 2 : 1.
Scheme 1.
[
10, 11]. In this regard, the synthesis and study of the
OH
OH
properties of new aminomethoxy derivatives of
norbornene prepared through the three-component
Mannich reaction is an important and urgent task.
+
1
2
3
2
204

MANNICH BASES FROM BICYCLO[2.2.1]HEPT-5-EN-2-YLMETHANOL
2205
Scheme 2.
4
8
10
5
9
O
OH
3
2
R
+
CH O + RH
7
2
−
H O
2
6
1
3
4
5−12
13−20
R = N(C
2
H
5
)
2
(5, 13), N(C
3
H
7
)
2
(6, 14), N(C
4
H
9
)
2
5 11 2 6 13 2
(7, 15), N(C H ) (8, 16), N(C H ) (9, 17), piperidine-1-yl (10, 18),
morpholine-4-yl (11, 19), azepane-1-yl (12, 20).
Compounds 13–20 are liquids with a characteristic
odor, insoluble in water, well soluble in organic
solvents (ethanol, acetone, benzene, CCl , CHCl ,
benzene was added dropwise to a dispersion of 0.2 mol
of paraformaldehyde in 20 mL of benzene with
stirring, then a solution of 0.1 mol of secondary amine
5–12 in 20 mL of benzene was added dropwise. The
resulting mixture was stirred for 4–5 h at 78–80°С.
After cooling, the mixture was treated with a 10%
ammonia solution, washed with distilled water until
4
3
etc.). The composition and the structure of compounds
1
1
3–20 were confirmed by elemental analysis, IR, H
1
3
and С NMR spectra.
In the IR spectrum of bicyclo[2.2.1]hept-5-en-2-
neutral, and dried with MgSO . After removal of
4
ylmethanol 3, there is a wide absorption band at
–
1
benzene., the residue was distilled in a vacuum.
3
500 cm , characteristic of the hydroxy group [13],
and in the IR spectra of aminomethoxy derivatives 13–
N-[(Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl]-
N-ethylethane-1-amine (13) was obtained from 12.4 g
(0.1 mol) of compound 3, 6 g (0.2 mol) of paraform
and 14.6 g (0.2 mol) of diethylamine. Yield 10.6 g
2
1
0 this band is missing. The absorption bands in 1288–
100 cm region are due to the stretching vibrations of
–
1
the C–N bond. In addition, the absorption bands at
–
1
20
20
4
2
952–2931 and 2857–2853 cm correspond to the
(51%), bp 102–104°С (4 mmHg), n 1.4672, d
D
3
–1
vibrations of the C–H bonds in the CH and CH
0.9395 g/cm . IR spectrum, ν, cm : 3057, 2961, 2858,
1629, 1460, 1359, 1215, 1057, 978, 932, 816, 715. Н
3
2
1
groups, respectively. The stretching vibrations of the
–
1
C–O bond appear in the range of 1100–1048 cm .
NMR spectrum, δ, ppm (J, Hz): 1.04 t (6H, CH , J =
3
6
7
7
.5), 1.26–1.37 m (2H, C H ), 1.78 d. d. d (2H, C H ,
2 2
J = 2.2, 2.1, 1.2 Hz), 2.68–2.92 m (3H, H ), 3.29–
.42 m (4H, СН N), 3.42 d (2H, C H O, J = 6.8), 4.17
s (2H, OC H N), 5.93–5.95 m (1H, =C H), 6.10–6.11
m (1H, =C H). С NMR spectrum, δ , ppm: 12.85
CH ), 12.86 (CH ), 29.0 (C ), 38.8 (C ), 42.0 (C ),
N), 49.04 (CH
71.0 (C ), 84.1 (C ), 132.3 (C ), 136.6 (C ). Mass
The starting allyl alcohol was dried with MgSO4
and distilled before use. Commercial diethylamine 5,
dipropylamine 6, dibutylamine 7, dipentylamine 8, di-
hexylamine 9, piperidine 10, morpholine 11, and
azepane 12 were distilled before use.
1,4,5
8
3
2 2
10
2
2
3
13
С
6
5
1
(
3 3
4
7
Bicyclo[2.2.1]hept-5-en-2-ylmethanol (3) was
obtained in a pressure reactor in 9 h at 170–180°C,
pressure of 4–5 at, and the ratio dicyclopentaene : allyl
alcohol = 1 : 2.4 [12]. Yield 74%, bp 82–83°С
43.8 (C ), 45.1 (C ), 49.03 (CH
2
2
N),
8
10
2
3
+
+
spectrum, m/z (Irel, %): 210 (5) [М + Н] , 209 (7) [М] ,
+
+
191 (13) [М – Н
О] , 176 (7), 167 (10) [М – С Н O] ,
2
2 2
2
0
20
3
(
10 mmHg), n 1.4970, d 1.027 g/cm . IR spectrum,
159 (10), 132 (13), 124 (10), 107 (8), 86 (100)
D 4
–
1
+
ν, cm : 3500 (O‒H), 2930–2895, 2880–2830 (СН ),
200–1100 (С‒N). Н NMR spectrum, δ, ppm (J, Hz):
.45 d. d (1Н, Н , J = 4.1, 13.4), 1.19 t (1Н, Н
J = 7.9), 1.44 t (1Н, Н
), 2.86 m (1Н, Н ), 3.29 m (1Н, Н ), 3.36–3.46 m
2Н, С Н ), 3.46 d. d. d (1Н, Н , J = 4.4, 4.6, 4.8), 3.92
br. s (1Н, ОН), 6.00–6.08 m (2Н, Н ). С NMR
spectrum, δ , ppm: 28.8 (С ), 41.8 (С ), 42.3 (С ), 43.6
[С H12N] , 79 (15), 58 (30), 44 (5). Found, %: С
5
2
1
1
0
74.56; Н 10.86; N 6.61. C13H23NO. Calculated, %: С
74.64; H 11.00; N 6.70.
6
exo
7anti
,
6
endo
, J = 4.1), 1.68–1.72 m (1Н,
N-[(Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl]-
N-propylpropane-1-amine (14) was obtained from 10 g
7
syn
5
4
Н
(
8
1
2
(
0.08 mol) of, compound 3, 5 g (0.16 mol) of para-
2
,3
13
formaldehyde and 8 g (0.08 mol) of dipropylamine.
6
5
1
С
20
Yield 8.0 g (43%), bp 119–122°С (4 mmHg), n
1
4
7
8
3
2
D
(
С ), 49.4 (С ), 65.8 (С ), 132.3 (С ), 137.8 (С ).
20
3
–1
.4670, d4 0.9228 g/cm . IR spectrum, ν, cm : 3059,
Aminomethoxy derivatives of bicyclo[2.2.1]hept-
-en-2-ylmethanol (13–20). A solution of 0.1 mol of
2957, 2933, 2868, 1685, 1463, 1364, 1343, 1202,
1091, 1068, 1048, 983, 962, 938, 903, 717. Н NMR
1
2
bicyclo[2.2.1]hept-5-en-2-ylmethanol 3 in 20 mL of
spectrum, δ, ppm (J, Hz): 0.90 t (6H, CH , J = 7.1),
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 10 2018

2
206
MAMMADBAYLI et al.
5
6
1,4,5
6
7
1
(
(
.26–1.46 m (7H, H , C H + 2CH CH ), 1.79–1.83 m
(5H, H
+ C H ), 1.79 d. d. d (2H, C H , J = 2.2, 2.1,
2 2
2
2
3
7
1
8
2H, C H ), 2.57 d. d (1H, H , J = 0.1, 1.2), 2.77 d. d
1H, H , J = 0.1, 1.2), 2.93–3.11 m (6H, 2СН N +
С Н О), 4.07 s (2H, OC H N), 5.94–6.11 m (2H,
C H + =C H). С NMR spectrum, δ , ppm: 11.30
1.2), 3.0–3.34 m (6H, 2СН N + С Н О), 4.08 s (1H,
OC H N), 4.09 s (1H, OC H N), 5.94–5.95 m (1H,
2 2
=C H), 6.11–6.12 m (1H, =C H). С NMR spectrum,
δ , ppm: 10.8 (CH ), 13.6 (CH ), 17.1 (CH CH ), 22.4
2
2 2
4
10
10
2
8
10
2
3
13
2
2
2
3
13
=
С
С
3
3
2
3
(
(
4
8
(
CH3), 11.31 (CH ), 21.15 (CH CH ), 21.16
(CH CH ), 27.2 (CH C H ), 27.7 (CH C H ), 33.1
3
2
3
2 3 2 2 5 2 2 5
6
5
1
4
6
5
CH CH ), 29.0 (C ), 38.8 (C ), 42.0 (C ), 43.8 (C ),
(CH C H ), 38.8 (CH C H ), 42.0 (C ), 43.8 (C ), 49.0
2 3 7 2 3 7
2
3
7
8
1
4
7
9.0 (C ), 53.73 (СН N), 53.74 (СН N), 71.1 (C ),
5.2 (C ), 132.3 (C ), 136.6 (C ). Mass spectrum, m/z
I , %): 238 (11) [М + Н] , 237 (9) [М] , 219 (7) [М –
(C ), 51.6 (C ), 52.2 (C ), 58.6 (СН N), 59.5 (СН N),
2
2
2 2
1
0
2
3
8
10
2
3
71.2 (C ), 85.5 (C ), 132.3 (C ), 136.6 (C ). Mass
spectrum, m/z (I , %): 294 (13) [М + Н] , 293 (11)
[М] , 276 (100) [М – ОН] , 275 (8) [М – Н O] , 262
(4) [М – ОН – СН ] , 209 (17) [M – С Н N] , 170
2 5 10
+
+
+
rel
rel
+
+
+
+
+
Н О] , 179 (15) [М – С Н O ] , 168 (5), 114 (100)
2
2
2
2
2
+
+
+
+
+
[С Н N] , 86 (41) [С Н O ] , 58 (21) [С Н O ] , 44
7
16
4
6
2
2
2
2
+
+
(
11). Found, %: С 75.82; Н 11.56; N 5.77. C H NO.
(50) [С Н N] , 114 (100), 58 (60), 43 (20) [С Н ] .
1
5
27
11 24 3 7
Calculated, %: С 75.95; H 11.39; N 5.91.
Found, %: С 77.66; Н 12.07; N 4.63. C19H35NO.
Calculated, %: С 77.82; H 11.95; N 4.78.
N-[(Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl]-
N-butylbutane-1-amine (15) was obtained from 12.4 g
N-[(Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl]-
N-hexylhexane-1-amine (17) was obtained from 12.4 g
(0.1 mol) of compound 3, 6 g (0.2 mol) of para-
(
0.1 mol) of compound 3, 6 g (0.2 mol) of para-
formaldehyde and 12.9 g (0.1 mol) of dibutylamine.
2
0
Yield 13 g (49%), bp 135°С (2 mmHg), n 1.4660,
formaldehyde and 15.7 g (0.1 mol) of dihexylamine.
D
20
3
–1
20
d4 0.9100 g/cm . IR spectrum, ν, cm : 3059, 2955,
Yield 20.4 g (64%), bp 192–194°С (6 mmHg), n
D
20
3
–1
2
1
931, 2862, 2803, 1685, 1459, 1364, 1343, 1272,
251, 1190, 1070, 1048, 984, 960, 933, 904, 717. Н
1.4645, d4 0.8854 g/cm . IR spectrum, ν, cm : 3058,
1
2927, 2857, 1635, 1459, 1361, 1221, 1172, 1063, 987,
1
NMR spectrum, δ, ppm (J, Hz): 0.92 t (6H, CH , J =
839, 717. Н NMR spectrum, δ, ppm (J, Hz): 0.91 t
3
5
6
7
(
1
.1), 1.34–1.50 m (7H, H , C H + 2CH CH ), 1.79 d. d. d
2H, C H , J = 2.3, 2.1, 1.2), 2.47 d. d (1H, H , J = 0.1,
.2), 2.63 d. d (1H, H , J = 0.1, 1.2), 2.77–2.93 m (4H,
CH C H ), 3.00–3.11 m (6H, 2СН N + С Н О), 4.07 s
1H, OC H N), 4.09 s (1H, OC H N), 5.93–5.94 m
1H, =C H), 6.10–6.11 m (1H, =C H). С NMR
(6H, 2CH , J = 7.1), 1.32–1.48 m [16H, (CH ) CH ],
2
2
3
3
2 4
3
7
1
7
1.79 d. d. d (2H, C H , J = 2.2, 2.1, 1.2), 2.47 d. d (1H,
2
2
4
1
4
H , J = 0.1, 1.2), 2.63 d. d (1H, H , J = 0.1, 1.2), 3.0–
8
8
10
3.12 m (6H, 2СН N + С Н О), 4.08 s (1H, OC H N),
2
2
5
2
10
2
2 2 2
1
0
10
2
(
(
4.09 s (1H, OC H N), 5.94–6.11 m (2H, =C H,
2
=C H). С NMR spectrum, δ , ppm: 13.57 (CH ),
2
2
2
3
13
3
13
С 3
spectrum, δ , ppm: 13.56 (CH ), 13.57 (CH ), 20.31
13.58 (CH ), 22.56 (CH CH ), 22.58 (CH CH ), 26.97
3 2 3 2 3
С
3
3
6
(
(
4
7
CH CH ), 20.33 (CH CH ), 29.0 (C ), 30.27
(CH C H ), 26.98 (CH C H ), 27.21 (CH C H ), 27.23
2
3
2
3
2 2 5 2 2 5 2 3 7
5
1
CH C H ), 30.28 (CH C H ), 38.8 (C ), 42.0 (C ),
(CH C H ), 28.03 (CH C H ), 28.04 (CH C H ), 31.7
2 3 7 2 4 9 2 4 9
2
2
5
2
2
5
4
7
6
5
1
4
7
3.8 (C ), 49.0 (C ), 51.41 (СН N), 51.42 (СН N),
1.1 (C ), 85.1 (C ), 132.3 (C ), 136.6 (C ). Mass spec-
(C ), 38.8 (C ), 42.0 (C ), 43.8 (C ), 49.0 (C ), 51.7
2
2
8
10
2
3
8
10
(СН N), 51.8 (СН N), 71.1 (C ), 85.1 (C ), 132.3
2 2
+
+
2
3
trum, m/z (I , %): 266 (8) [М + Н] , 265 (10) [М] ,
2
1
(C ), 136.6 (C ). Mass spectrum, m/z (I , %): 322 (18)
rel
rel
+
+
+
+
+
47 (8) [М – Н О] , 207 (15) [М – С Н O ] , 196 (5),
42 (100) [С Н NO] , 100 (70) [С Н N O] , 91 (7)
[М + Н] , 321 (20) [М] , 303 (9) [М – Н О] , 290 (13)
[М – OH – СН ] , 223 (6) [M – С Н N] , 198 (80)
2 6 12
2
2
2
2
2
+
+
+
+
8
16
4
8
2
+
+
[
С Н ] , 79 (13), 58 (60). Found, %: С 75.60; Н 10.84;
[С Н N] , 154 (30), 128 (100), 84 (15), 58 (60), 44
7
7
13 28
N 5.36. C H NO. Calculated, %: С 75.47; H 10.93; N
(12). Found, %: С 77.68; Н 12.31; N 4.24. C H NO.
17
31
21 39
5
.22.
N-[(Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl]-
N-pentylpentane-1-amine (16) was obtained from
2.4 g (0.1 mol) of compound 3, 6 g (0.2 mol) of para-
formaldehyde and 15.7 g (0.1 mol) of dipentylamine.
Calculated, %: С 78.50; H 12.15; N 4.36.
1-[(Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl]-
piperidine (18) was obtained from 12.4 g (0.1 mol) of
compound 3, 6 g (0.2 mol) of paraformaldehyde and
8.5 g (0.1 mol) of piperidine. Yield 9.92 g (45%), bp
1
20
20
20
3
Yield 21 g (71%), bp 185°С (13 mmHg), n 1.4680,
d4 0.9057 g/cm . IR spectrum, ν, cm : 3059, 2956,
138–141°С (8 mmHg), n 1.4958, d 0.9845 g/cm . IR
D
D 4
20
3
–1
–1
spectrum, ν, cm : 3058, 2931, 2857, 2780, 1629–
2
1
931, 2862, 1686, 1462, 1376, 1343, 1252, 1224,
192, 1069, 1050, 984, 962, 936, 903, 718. Н NMR
1570, 1446, 1411, 1367, 1343, 1313, 1228, 1184, 1127,
1
1
1048, 715, 662. Н NMR spectrum, δ, ppm (J, Hz):
6
7
spectrum, δ, ppm (J, Hz): 0.81–0.95 t (6H, CH , J =
1.26–1.54 m (4Н, С Н + С Н ), 1.55–1.75 m (4Н,
3
2 2
7
.3), 1.00–1.60 m [12H, (CH ) CH ], 1.33–1.52 m
NСН СН ), 2.01–2.08 m [2Н, N(СН ) СН ], 2.35–
2 2 2 2 2
2
3
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 10 2018

MANNICH BASES FROM BICYCLO[2.2.1]HEPT-5-EN-2-YLMETHANOL
2207
1
,4,5
3
13
2
.58 м (3Н, Н ), 2.99–3.02 m (6Н, 2СН N
+
2.1), 6.01 d. d (1Н, =С Н, J = 1.1, 2.1). С NMR
spectrum, δ , ppm: 27.20 [N(СН ) СН ], 27.21
2
cycle
8
10
С Н О), 3.94 d (1Н, ОС Н N, J = 16.1), 4.00 d. d
1Н, ОС Н N, J = 1.1, 16.1), 5.94 d. d (1Н, =С Н, J =
.6, 2.1), 6.10 d. d (1Н, =С Н, J = 0.6, 2.1). С NMR
spectrum, δ , ppm: 24.2 [N(СН ) СН ], 25.8
NСН СН ), 26.0 (NСН СН ), 29.0 (С ), 38.9 (С ),
2.2 (С ), 43.9 (С ), 49.3 (С ), 50.7 (СН N), 50.8
СН N), 72.5 (С ), 89.4 (С ), 132.5 (С ), 137.9 (С ).
Mass spectrum, m/z (I , %): 222 (8) [М + Н] , 221 (7)
2
2
С
2 2
2
1
0
2
(
0
[N(СН ) СН ], 28.58 (NСН СН ), 28.59 (NСН СН ),
2
2 2 2 2 2 2 2
3
13
6
7
1
4
5
29.2 (С ), 38.9 (С ), 42.1 (С ), 43.9 (С ), 49.3 (С ),
52.4 (СН N), 53.2 (СН N), 72.5 (С ), 89.6 (С ), 132.4
(С ), 136.9 (С ). Mass spectrum, m/z (I , %): 236 (10)
rel
[М + Н] , 235 (5) [М] , 166 (7), 142 (10), 128 (9), 112
8
10
С
2 2
2
2 2
6
7
3
2
(
4
(
2
2
2
2
1
4
5
+
+
2
8
10
3
2
+
+
(100) [С Н N + H] , 106 (5) [M – С Н NO] , 100
2
7 13 7 15
+
+
(25) [С Н N + H] , 79 (15), 58 (50), 44 (16). Found,
6 13
%: С 75.61; Н 10.80; N 5.39. C H NO. Calculated,
%: С 75.47; H 10.93; N 5.22.
rel
+
+
[
9
[
7
7
М] , 177 (12) [М – C Н О] , 124 (5), 114 (7), 107 (10),
2
4
15 25
+
8 (100) [С Н N] , 91 (15), 86 (10), 79 (5), 70 (15)
6
12
+
С Н N] , 68 (5), 66 (5), 56 (3), 42 (4). Found, %: С
5.98; Н 10.81; N 6.13. C H NO. Calculated, %: С
14 23
5.84; H 10.92; N 5.98.
4 8
IR spectra were obtained on a Spectrum BX and
Bruker Alpha II FTIR instruments (Germany) in the
–1
1
13
range of 4000–400 cm . H and C NMR spectra
were recorded on a Bruker AM-300 spectrometer at a
frequency of 300 MHz from С D solutions. Mass
4
-[(Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl]-
morpholine (19) was obtained from 12.4 g (0.1 mol) of
compound 3, 6 g (0.2 mol) of paraformaldehyde and
.7 g (0.1 mol) of morpholine. Yield 11.11 g (50%), bp
55–158°С (4 mmHg), n 1.4942, d 1.0389 g/cm . IR
spectrum, ν, cm : 3056, 2952, 2853, 1629, 1559,
452, 1356, 1257, 1109, 1067, 1053, 911, 859, 791,
17. Н NMR spectrum, δ, ppm (J, Hz): 0.37–0.41 m
2Н, С Н ), 1.11–1.67 m (2Н, С Н ), 2.56–2.74 m
3Н, Н ), 3.53–3.55 m (6Н, 2СН N
.78–3.79 m (4Н, СН Ocycle), 3.80 d. d (1Н, ОС Н N,
J = 1.2, 2.2), 3.84 d. d (1Н, ОС Н N, J = 1.2, 2.2),
.94 d. d (1Н, =С Н, J = 1.1, 2.1), 6.01 d. d (1Н,
С Н, J = 1.1, 2.1). С NMR spectrum, δ , ppm: 28.9
С ), 38.9 (С ), 42.2 (С ), 44.9 (С ), 49.2 (С ), 49.86
СН N), 49.87 (СН N), 66.72 (СН O), 66.73 (СН O),
2.1 (С ), 88.6 (С ), 132.5 (С ), 137.7 (С ). Mass spec-
trum, m/z (I , %): 224 (9) [М + Н] , 223 (20) [М] ,
6
6
spectra were taken on a VG-7070E mass spectrometer
(70 eV). Elemental analysis was performed on a Carlo
Еrba ЕА 1108 instrument. GLC analysis was per-
formed on an LHM-8 MD chromatograph, a steel
column (300 × 3 mm) with 5% polyethylene glycol
succinate on dinochrome II, carrier gas—helium
8
1
2
0
20
4
3
D
–
1
1
7
(
(
1
6
7
3
(40 cm /min), detector katharometer, column temperature
2
2
1
,4,5
8
+ С Н О),
150°C, the evaporator temperature 230°C. The
refractive index was measured on an Abbemat 350/500
refractometer. Density was determined on a DMA
4500 M instrument.
2
cycle
2
1
0
3
2
2
1
0
2
2
5
=
(
(
3
13
С
6
7
1
4
5
CONFLICT OF INTERESTS
No conflict of interests was declared by the authors.
REFERENCES
2
2
2
2
8
10
2
3
7
+
+
rel
+
+
2
1
[
5
9
1
05 (15) [М – Н О] , 179 (13) [М – С Н O] , 114 (5),
07 (7), 100 (100) [С Н NO] , 91 (20), 86 (12)
2 2 4
+
5
10
+
+
1. Kuliev, A.M., Khimiya i tekhnologiya prisadok k
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С Н NO] , 79 (22), 72 (5), 70 (25) [С Н N] , 66 (5),
4 8 4 8
+
6 (8) [С Н N] , 51 (5), 42 (10). Found, %: С 70.65; Н
3 6
.92; N 5.28. C H NO . Calculated, %: С 70.77; H
1
3
21
2
2
. Markova, I.V., Mikhailov, I.B., and Nezhentsev, M.V.,
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0.06; N 5.12.
1
-[(Bicyclo[2.2.1]hept-5-en-2-ylmethoxy)methyl]-
azepane (20) was obtained from 12.4 g (0.1 mol) of
compound 3, 6 g (0.2 mol) of paraformaldehyde and
3
. Kas’yan, L.I., Kas’yan, A.O., Okovityi, S.I., and
Tarabara, I.N., Aminy s karkasnymy fragmentami i ikh
proizvodnye (Amines with Cage Fragments and Their
Derivatives), Dnepropetrovsk: Dnepropetr. Univ., 2009.
9
1
.9 g (0.1 mol) of azepane. Yield 11.5 g (49%), bp
2
0
20
3
48°С (10 mmHg), n 1.5010, d4 0.9875 g/cm . IR
D
–
1
spectrum, ν, cm : 3058, 2923, 2856, 1643, 1449,
4. Mashkovskii, M.D., Lekarstvennye sredstva (Drugs),
1
9
364, 1340, 1234, 1188, 1141, 1069, 1045, 968, 930,
Moscow: Novaya Volna, 2002, vol. 1.
1
04, 829, 715. Н NMR spectrum, δ, ppm: 1.26–2.06
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10.1070/rcr4579
6
7
m (12Н, С Н + С Н + 4СН2cycle), 1.51–1.54 m (3Н,
Н
d (1Н, OС Н N, J = 1.2, 2.2), 4.08 d. d (1Н,
OС Н N, J = 1.2, 2.2), 5.94 d. d (1Н, =С Н, J = 1.1,
2
2
1
,4,5
8
), 2.26–3.87 m (6Н, С Н O + 2СН Ncycle), 4.04 d.
2 2
1
0
2
6. Tandura, S.N., Shumsky, A.N., Litvin, E.F., Kozlo-
va, L.M., Shuvalova, E.V., Sharf, V.Z., and Kolesni-
1
0
2
2
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 10 2018