TABLE 3. 1H NMR Spectra of the Amines 4m–q and 5
Compound
Chemical shifts, δ, ppm (J, Hz)
3
4m
2.19 and 2.24 (3.6H, s and 2.4H, s, N(CH3)2); 3.95 and 4.03 (0.6H, d, J = 7.5 and
0.4H, d, 3J = 7.4, PhCH); 4.32–4.52 (2H, m, OCH2); 4.86 and 5.09 (0.6H, dt,
3J = 17.0, 2J = 1.5 and 0.4H, dt, 3J = 17.0, 2J = 1.5, =CH2); 4.91 and 5.28 (0.6H, td,
3J = 4.1, 4J = 1.5 and 0.4H, m, OCH); 5.03 and 5.13 (0.6H, dt, 3J = 10.1,
2J = 1.5 and 0.4H, dt, 3J = 10.1, 2J = 1.5, =CH2); 5.35 and 5.90 (0.4H, m and 0.6H,
3
3
3
m, ОCHCH=); 6.00 and 6.10 (0.4H, ddd, J = 17.0, J = 10.1, J = 7.4 and 0.6H,
ddd, 3J = 17.0, 3J = 10.1, 3J = 7.4, CH=CH2); 7.09–7.28 (5H, m, C6H5)
4n
4o
4p
0.92 and 1.02 (3.6H, t, 3J = 7.1 and 2.4H, t, 3J = 7.1, (CH3)2); 2.55 and 2.60 (2.4H,
3
3
3
q, J = 7.1 and 1.6H, q, J = 7.1, N(CH2)2); 3.93 and 4.02 (0.6H, d, J = 7.4 and
0.4H, d, 3J = 7.4, PhCH); 4.35–4.52 (2H, m, OCH2); 4.86 (0.6H, dt, 3J = 17.0,
2J = 1.5, =CH2); 5.01–5.14 (2H, m, =CH2 and OCH); 5.35 and 5.86 (0.4H, m and
0.6H, m, ОCHCH=); 5.47 (0.4H, td, 3J = 4.1, 4J = 1.6, OCH); 5.99 and 6.11 (0.4H,
3
3
3
3
3
3
ddd, J = 17.0, J = 10.1, J = 7.4 and 0.6H, ddd, J = 17.0, J = 10.1, J = 7.4,
CH=CH2); 7.08–7.28 (5H, m, C6H5)
0.83 and 0.89 (3.6H, t, 3J = 7.4 and 2.4H, t, 3J = 7.4, (CH3)2); 1.35 and 1.50 (2.4H,
m and 1.6H, m, (CH2CH3)2); 2.42 and 2.45 (2.4H, m and 1.6H, m, N(CH2)2); 3.99
and 4.05 (0.6H, d, 3J = 7.5 and 0.4H, d, 3J = 7.5, PhCH); 4.35–4.55 (2H, m, OCH2);
4.86 (0.6H, dt, 3J = 17.0, 2J = 1.5, =CH2); 5.00–5.16 (2H, m, =CH2 and OCH); 5.37
and 5.91 (0.4H, m and 0.6H, m, ОCHCH=); 5.48 (0.4H, td, 3J = 4.1, 4J = 1.6,
OCH); 6.00 and 6.13 (0.4H, ddd, 3J = 17.0, 3J = 10.1, 3J = 7.5 and 0.6H, ddd,
3J = 17.0, 3J = 10.1, 3J = 7.5, CH=CH2); 7.09–7.39 (5H, m, C6H5)
3
3
0.86 and 0.92 (3.6H, t, J = 7.0 and 2.4H, t, J = 7.0, (CH3)2); 1.15–1.50 (8H, m,
3
3
(CH2CH2)2); 2.45 and 2.50 (2.4H, t, J = 6.9 and 1.6H, t, J = 6.9, N(CH2)2); 3.96
and 4.02 (0.6H, d, 3J = 7.4 and 0.4H, d, 3J = 7.6, PhCH); 4.35–4.54 (2H, m, OCH2);
4.86 (0.6H, dt, 3J = 17.0, 2J = 1.5, =CH2); 5.00–5.15 (2H, m, =CH2 and OCH); 5.37
and 5.90 (0.4H, m and 0.6H, m, ОCHCH=); 5.46 (0.4H, td, 3J = 4.1, 4J = 1.5,
OCH); 6.00 and 6.11 (0.4H, ddd, 3J = 17.0, 3J = 10.1, 3J = 7.6 and 0.6H, ddd,
3J = 17.0, 3J = 10.1, 3J = 7.4, CH=CH2); 7.09–7.28 (5H, m, C6H5)
4q
2.38–2.52 and 2.57–2.67 (2.4H, m and 1.6H, m, N(CH2)2); 3.50–3.60 (4H, m,
O(CH2)2); 3.99 and 4.08 (0.6H, d, 3J = 7.4 and 0.4H, d, 3J = 7.4, PhCH); 4.37–4.57
3
(2H, m, OCH2); 4.90 (0.6H, td, J = 4.2, 4J = 1.5, OCH); 4.91 (0.6H, dt, 3J = 17.0,
2J = 1.5, =CH2); 5.05–5.17 (1.8H, m, =CH2 and OCH); 5.54 and 5.98 (0.4H, m and
3
3
3
0.6H, m, ОCHCH=); 6.09 and 6.17 (0.4H, ddd, J = 16.9, J = 10.1, J = 7.4 and
0.6H, ddd, 3J = 16.9, 3J = 10.1, 3J = 7.4, CH=CH2); 7.14–7.30 (5H, m, C6H5)
5
2.20 (6H, s, N(CH3)2); 3.01 (2H, dd, 3J = 6.5, 4J = 1.3, CH2); 6.19 (1H, dt, 3J = 15.9,
3
4
3J = 6.5, =CHCH2); 6.46 (1H, dt, J = 15.9, J = 1.3, =CHPh); 7.14–7.34 (5H, m,
C6H5)
EXPERIMENTAL
The IR spectra were recorded on a UR-20 spectrometer for films in chloroform (salts 3m–q) or in thin
1
layers (the remaining products). The H and 13C NMR spectra were obtained on a Varian Mercury 300 VX
spectrometer (300 and 75 MHz respectively) at 300 K in 1:3 DMSO-d6–CCl4 with the signals of the undeuterated
solvent as internal standard. The signals in the 1H NMR spectra were assigned by the DEPT and HMQC methods.
The known starting dialkyl(4-hydroxybutyn-2-yl)amines 1a–f were obtained as previously described
[3]; the melting points of their picrates agreed with the melting points of authentic samples.
(4-Hydroxy-2-butynyl)dimethylamine (1g). A mixture of propargyl alcohol (28 g, 500 mmol), para-
form (15 g, 500 mmol), dimethylamine (24 g, 530 mmol), ferric chloride (0.1 g), and CuCl (0.1 g) in dioxane
(150 ml) was kept at 90–95°C for 60 h. A 15% aqueous solution of HCl was added to the reaction mixture under
shaking until an acidic reaction was obtained. The dioxane was distilled off, the residue was made alkaline, and
the product was extracted with ether. The extract was dried with MgSO4 and evaporated [3]. Vacuum distillation
20
of the residue gave 15 g of the product 1g; bp 80–85°C (2 mmHg), nD = 1.4705, mp of picrate 78–79°C
1
(EtOH). IR spectrum, ν, cm−1: 1030, 1090, 3100–3400 (ОН), 2230 (disubstituted C≡C bond). H NMR
spectrum, δ, ppm (J, Hz): 2.21 (6Н, s, СН3); 3.18 (2Н, t, J = 1.9, NCH2); 4.07 (2Н, t, J = 1.9, ОСН2); 4.54 (1H,
br. s, ОН). Found, %: С 63.32; Н 9.96; N 12.23. C6H11NO. Calculated, %: С 63.71; Н 9.73; N 12.38.
422