CHUKHAJIAN et al.
354
Scheme 2.
O
C
O(CH2CH2)2O
Cu(OAc)2, FeCl3
+
+
RN
RNH
1a, 1b
2a, 2b
R = Me, Et.
films(PMBA)usedasbuildingblocksinthemanufacture
of photocatalytic cells [6].
bp 30°C (17–18 mmHg); nD20 1.4620]. According to 1H
NMR, the mixture contained 70% of methyl(prop-2-
ynyl)amine.
Allyl(methyl)amine (1a) and methyl(prop-2-
ynyl)amine (1b) (general procedure). Allyl chloride or
propargyl bromide in a 4 : 1 molar ratio, respectively,
was added in portions from a dropping funnel to a 40%
aqueous solution of methylamine at room temperature
under constant stirring. The solution was stirred at
room temperature for 3–4 h and then carefully acidified
with HCl. The mixture was then treated with ether to
extract unreacted halide. The amine hydrochloride
solution was concentrated under reduced pressure and
then transferred to a Favorsky flask equipped with a
Liebig condenser and a receiver cooled by ice. A highly
concentrated KOH solution was slowly added through
a dropping funnel to a heated reaction mixture. The
fractions boiling at 40–70°C (1a) and 45–92°C (1b)
were collected, dried over MgSO4, and placed into a
refrigerator. A day after, the amine layer was decanted,
dried over MgSO4, and distilled from a Favorsky flask.
Allyl(ethyl)amine (1b) and ethyl(prop-2-ynyl)-
amine (1d) (general procedure). The synthesis was
performed as described above, except that unreacted
ethylamine was collected in an absorption coil cooled
with ice. The fractions boiling at 64–78°C (1b) and 45–
92°C (1d) were collected and dried over MgSO4. A day
after, the amine layer was decanted, dried over MgSO4,
and distilled from a Favorsky flask.
Allyl(ethyl)amine (1b). Yield 20.6 g (62%), bp 74–
75°C, nD20 1.4196, mp 145–147°C (hydrochloride), does
1
not form picrate. H NMR spectrum (300.077 MHz,
DMSO-d6 + CCl4), δ, ppm: 1.05 t (3H, CH3, J 7.1 Hz),
2.17 br s (1H, NH), 2.56 q (2H, CH2CH3, J 7.1 Hz),
3.15 dt (2H, CH2CH=CH2, J 5.8, 1.5 Hz), 4.99 d.d.t
(1H, =CH2, J 10.2, 2.0, 1.5 Hz), 5.09 d.d.t (1H, =CH2,
J 17.2, 2.0, 1.5 Hz), 5.81 d.d.t (1H, =CH, J 17.2, 10.2,
5.8 Hz). 13C NMR spectrum (75.465 MHz, DMSO-d6 +
CCl4), δ, ppm: 14.8 (CH3), 42.8 (CH2CH3), 51.7
(CH2CH=CH2), 114.5 (=CH2), 137.1 (=CH). Found, %:
C 70.41; H 12.88; N 16.31. C5H11N. Calculated, %: C
70.53; H 13.02; N 16.45.
Allyl(methyl)amine (1a). Yield 6 g (65%), bp 64–
66°C(760mmHg), nD20 1.4110, mp(picrate)106–108°C;
the physicochemical constants are consistent with
published data [1, 4]. 1H NMR spectrum (300.077 MHz,
DMSO-d6 + CCl4), δ, ppm: 1.28 br.s (1H, NH), 2.32 s
(3H, CH3), 3.11 dt (2H, CH2, J 5.8, 1.5 Hz), 5.01 d.d.t
(1H, =CH2, J 10.2, 2.0, 1.5 Hz), 5.11 d.d.t (1H, =CH2,
J 17.2, 2.0, 1.5 Hz), 5.81 d.d.t (1H, =CH, J 17.2, 10.2,
5.8 Hz). 13C NMR spectrum (75.465 MHz, DMSO-d6 +
CCl4), δ, ppm: 35.2 (CH3), 53.7 (CH2), 114.6 (=CH2),
136.8 (=CH). Found, %: C 67.34; H 12.61; N 19.52.
C4H9N. Calculated, %: C 67.55; H 12.75; N 19.69.
1
A mixture comprising, according to H NMR, 70%
of allyl(ethyl)amine and 30% of dially(ethyl) amine
was also obtained (2 g; bp 75–78°C; nD20 1.4334).
Ethyl(prop-2-ynyl)amine (1d). Yield 6.8 g (48%),
bp80–83°C,nD201.4300,mp165–168°C(hydrochloride),
does not form picrate. 1H NMR spectrum (300.077 MHz,
DMSO-d6 + CCl4), δ, ppm: 1.04 t (3H, CH3, J 7.1 Hz),
2.36 t (1H, ≡CH, J 2.4 Hz), 2.63 q (2H, CH2CH3, J
7.1 Hz), 2.50 br.s (1H, NH), 3.29 d (2H, CH2C=CH, J
2.4 Hz). 13C NMR spectrum (75.465 MHz, DMSO-d6 +
CCl4), δ, ppm: 14.4 (CH3), 37.2 (CH2), 42.0 (CH2),
71.5 (≡CH), 82.3 (≡C). Found, %: C 72.11; H 10.77;
N 16.73. C5H9N. Calculated, %: C 72.24; H 10.91;
N 16.85.
Methyl(prop-2-ynyl)amine (1c). Yield 11.16 g
(55%), bp 82–85°C, nD20 1.4303, mp 141°C (oxalate);
the physicochemical constants are consistent with
1
published data [3]. H NMR spectrum (300.077 MHz,
DMSO-d6 + CCl4), δ, ppm: 2.36 s (3H, CH3), 2.39 t (1H,
≡CH, J 2.4 Hz), 2.47 br s (1H, NH), 3.26 d (2H, CH2, J
2.4 Hz). 13C (75.465 MHz, DMSO-d6 + CCl4), δ, ppm:
40.4 (CH3), 43.7 (CH2), 73.6 (≡CH), 78.2 (≡C). Found,
%: C 69.37; H 10.05; N 20.13. C4H7N. Calculated, %:
C 69.52; H 10.21; N 20.27.
A mixture comprising, according to 1H NMR, 60 %
of ethyl(prop-2-ynyl)amine and 40% of ethyldi(prop-
2-ynyl)amine was also obtained [1.5 g; 70–73°C
(60 mmHg); nD20 1.4836].
A mixture comprising methyl(prop-2-ynyl)amine
and an amine with a vinyl group was also obtained [3.7 g;
Attempted isolation of diallyl(ethyl)amine and
methyl- and ethyldi(prop-ynyl)amines failed.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 56 No. 2 2020