Synthesis of the unsaturated diamines by the Stevens rearrangement of 4-diethylaminobutyn-2-yl-containing ammonium salts

Article abstract of DOI:10.1134/S1070363212110096

Ammonium salts containing 4-diethylaminobutyn-2-yl and 2-alkenyl groups undergo the Stevens 3,2-rearrangement under the action of potassium hydroxide in anhydrous benzene to form the unsaturated diamines.

Full text of DOI:10.1134/S1070363212110096

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 11, pp. 1798–1800. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © M.O. Manukyan, K.S. Barseghyan, A.V. Babakhanyan, A.A. Shahkhatuni, A.Kh. Gyulnazaryan, 2012, published in Zhurnal
Obshchei Khimii, 2012, Vol. 82, No. 11, pp. 1807–1809.
Synthesis of the Unsaturated Diamines
by the Stevens Rearrangement
of 4-Diethylaminobutyn-2-yl-Containing Ammonium Salts
M. O. Manukyana,b, K. S. Barseghyana, A. V. Babakhanyanb,
A. A. Shahkhatunic, and A. Kh. Gyulnazaryana
a Institute of Organic Chemistry of Scientific Technological Center
of Organic and Pharmaceutical Chemistry, National Academy of Sciences of Armenia,
26 Azatutyan av., Yerevan, 0014 Armenia
e-mail: manukyanmeri@gmail.com
b Abovyan Armenian State Pedagogical University, Yerevan, Armenia
c Molecular Structure Research Center of the Scientific and Technological Center
of Organic and Pharmaceutical Chemistry, National Academy of Sciences of Armenia, Yerevan, Armenia
Received October 11, 2011
Abstract—Ammonium salts containing 4-diethylaminobutyn-2-yl and 2-alkenyl groups undergo the Stevens
3,2-rearrangement under the action of potassium hydroxide in anhydrous benzene to form the unsaturated
diamines.
DOI: 10.1134/S1070363212110096
Under the basic conditions the allyl- and propargyl-
containing ammonium salts undergo Stevens 2,3-
rearrangement to form the corresponding amines [1–
6]. In the case of 4-allyloxy(phenyloxy)butyn-2-yl-
containing salts the unsaturated aminoesters of
different structure have been obtained [7].
with a 2-alkenyl halides in a molar ratio of 3:1 in
anhydrous diethyl ether (Table 1).
The Stevens rearrangement of the obtained salts
IIa–IId was carried out under the action of powdered
potassium hydroxide in anhydrous benzene.
Under the reaction conditions the salts IIa–IId
were found to undergo the Stevens 2,3-rearrangement
to form the corresponding diamines IIIa–IIId (Table 2).
In order to obtain the unsaturated mixed diamines
we studied the Stevens rearrangement of ammonium salts
containing 4-diethylaminobutyn-2-yl and allyl groups.
The structure of the obtained compounds was
1
13
The initial ammonium salts IIa–IId were syn-
thesized by the reaction of 1-dimethylamino-4-diethyl-
aminobut-2-yne I obtained by the Mannich reaction [8]
confirmed by IR, H, and C NMR spectra (Table 3).
Their individuality was proved by the GLC and TLC
methods.
Table 1. Yields and elemental analysis data of ammonium salts IIa–IId
Found, %
Calculated, %
Comp. no.
Yiels, %
Rf
Formula
N
Hlg
N
9.69
10.83
9.24
7.67
Hlg
72
65
64
67
0.4
9.78
10.69
9.31
7.72
27.75
13.71
26.48
21.84
C13H25N2Br
C14H27N2Cl
C14H27N2Br
C19H29N2Br
27.68
13.73
26.40
21.92
IIa
IIb
IIc
0.43
0.45
0.38
IIdа
a mp of salt IId is 95–97°C.
1798

SYNTHESIS OF THE UNSATURATED DIAMINES BY THE STEVENS REARRANGEMENT
1799
(CH3)2NH, (CH2O)n
(C2H5)2NCH2C
CCH2N(CH3)2
H
(C2H5)2NCH2C CH
FeCl3, dioxane
I
R2
C
CR1=CH2
CH2CR1=CHR2
HlgCH2CR1=CHR2
Et2O
KOH
(CH3)2N
Hlg
(CH3)2N
C
H
C
CCH2N(C2H5)2
benzene
CH2C
CCH2N(C2H5)2
IIа_IId
IIIа_IIId
R1 = R2 = H (а), R1 = CH3, R2 = H (b); R1 = H, R2 = CH3 (c); R1 = H, R2 = C6H5 (d); Hlg = Br (a–c), Cl (b).
According to the 1H NMR spectra, compounds IIIc
and IIId exist as two diastereomers in a ratio of 25:75
and 10:90, respectively.
a Varian Mercury-300 spectrometer [300.075 MHz
(1H), 75.46 MHz (13C] in DMSO-d6–CCl4 (1:3) at
303 K relative to internal TMS.
EXPERIMENTAL
The GLC analysis was performed on a LKhM-80
instrument [ramp 50–220°C at a rate 16 deg min–1,
column 2000×3 mm, 10% Apiezon-L on Inerton-AW
(0.2–0.25 mm), the carrier gas helium, flow rate
The IR spectra were recorded on a Specord IR-75
instrument from the samples as a slurry in mineral oil
or as a thin layer. The NMR spectra were recorded on
Table 2. Yields, physicochemical characteristics, and elemental analysis data of compounds I, IIIa–IIId
Found, %
H
Calculated, %
H
Comp. Yield,
bp, °С
(mm Hg)
nD20
Formula
no.
%
C
N
C
N
60
41
55
45
51
86–87 (7)
1.4540
1.4670
1.4680
1.4730
1.5260
71.57
75.28
75.36
75.91
80.55
11.81
11.51
11.26
11.89
9.38
16.60
13.61
12.54
12.78
9.98
C10H20N2
C13H24N2
C14H26N2
C14H26N2
C19H28N2
71.43
75.00
75.67
75.67
80.28
11.90
11.54
11.71
11.71
9.86
16.67
13.46
12.62
12.62
9.86
I
130–131 (24)
128–129 (13)
130–132 (18)
142–144 (2)
IIIа
IIIb
IIIc
IIId
Table 3. IR, 1H, and 13C NMR spectral parameters of compounds I, IIIa–IIId
Comp.
no.
ν, cm–1
δ, ppm (J, Hz)
2240 (C≡C)
δН: 1.02 t (6H, CH2CH3, 3J 7.1), 2.19 s (6H, NCH3), 2.46 q (4H, NCH2CH3, 3J 7.1), 3.17 t (2H, CH2NMe2,
5J 2.0), 3.35 t (2H, CH2NEt2, 5J 2.0); δС: 12.2 (CH2CH3), 43.2 (C, NCH3), 46.4 (NCH2CH3), 39.9 (NCH2),
47.2 (NCH2), 78.7 and 78.9 (C≡C)
I
3
3
890, 920, 1650, δН: 1.01 t (6H, CH2CH3, J 7.2), 2.15 s (6H, NCH3), 2.27 m (2H, CH2), 2.46 q (4H, NCH2CH3, J 7.2),
IIIа
IIIb
IIIc
IIId
3
5
5
3
2
3015, 3085 (C=C); 3.29 d.d.t (1H, CH, J 8.0, 7.2, J 1.8), 3.37 d (2H, NCH2, J 1.8), 4.98 d.d.t (1Н, =CH2, J 10.2, J 2.0,
2250 (C≡C)
4J 1.2), 5.05 d.d.t (1H, =CH2, 3J 17.2, 2J 2.0, 4J 1.5), 5.80 d.d.t (1H, =CH, 3J 17.2, 10.2, 6.8)
915, 975, 1640, δН: 1.01 t (6H, CH2CH3, 3J 7.1), 1.74 t (3H, CH3, 4J 1.2), 2.16 s (6H, NCH3), 2.19–2.27 m (2H, CH2), 2.45
3015, 3085 (C=C); q (4H, NCH2CH3, 3J 7.1), 3.36 d (2H, NCH2, 5J 1.8), 3.43 d.d.t (1Н, CH, 3J 8.3, 7.0, 5J 1.8), 4.72 q (2Н,
2245 (C≡C)
=CH2, 4J 1.2)
3
3
920, 1640, 3015, δН: 1.03 t (6Н, CH2CH3, J 7.1), 1.06 d (3Н, CH3CH, J 6.7), 2.14 s (6Н, NCH3), 2.19–3.32 m (1H,
3090 (C=C); 2240 CHCH3), 2.48 q (4Н, NCH2CH3, 3J 7.1), 2.94 d.t (3Н, NCH, 3J 10.1, 5J 1.8), 3.37 d (2Н, CH2NEt2, 5J 1.8),
(C≡C)
4.87–5.05 m (2Н, CH2), 5.78 d.d.d (1Н, =CH, 3J 17.2, 10.4, 7.5)
920, 1640, 3025, 3085 δН: 1.02 t (6H, CH2CH3, 3J 7.1), 2.21 s (6H, NCH3), 2.50 q (4H, NCH2CH3, 3J 7.1), 3.19 d (2Н, CH2NEt2,
(C=C); 720, 765, 1500, 5J 2.0), 3.34 d.d.t (1H, CH, 3J 11.0, 7.6, 4J 1.0), 3.59 d.t (1H, NCH, 3J 11.0, 5J 2.0), 4.87 d.d.d (1H, =CH2,
1600, 3020, 3065 3J 18.0, J 1.8, J 1.0), 4.95 d.d.d (1H, =CH2, J 10.3, J 1.8, J 1.0), 6.08 d.d.d (1Н, =CH, J 18.0, 10.3,
2
4
3
2
4
3
(C6H5); 2235 (C≡C) 7.6), 7.11–7.34 m (5Н, C6H5)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 11 2012

1800
MANUKYAN et al.
60 ml min–1]. The TLC analysis was carried out on
Silufol UV-254 plates in an n-butanol–ethanol–water–
acetic acid system (10:7:6:4) detecting with iodine
vapor.
with ether. The combined extracts were dried with
magnesium sulfate. After the solvent removal the
residue was distilled in a vacuum.
ACKNOWLEDGMENTS
The starting 1-dimethylamino-4-diethylaminobut-2-
yne was obtained by the Mannich reaction [8].
This work was supported by the State Committee of
Science of Armenia.
Synthesis of ammonium salts IIa–IId. To a
solution of 0.045 mol of 1-dimethylamino-4-diethyl-
aminobut-2-yne in 10 ml of anhydrous ether was added
dropwise 0.015 mol of the corresponding 2-alkenyl
halide dissolved in 10 ml of anhydrous ether. The
reaction mixture was kept for 24 h at room tem-
perature. The resulting salt was washed several times
with anhydrous ether and dried in a desiccator over
CaCl2. The obtained compounds are waxy substances.
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