TABLE 4. NMR Spectra of 3-(Aryloxy)thietanes 5a–e
Com-
pound
1H NMR spectrum, δ, ppm (
J, Hz)
13C NMR spectrum, δ, ppm
5a
3.33-3.43 (2H, m, CH2); 3.60-3.68 (2H, m, CH2);
5.31-5.42 (1H, m, CHO); 6.93 (1H, d, = 8.3, H-6);
7.06 (1H, t, = 7.7, H-4); 7.45-7.53 (1H, m, H-5);
35.2; 72.4; 115.3; 121.3;
125.7; 134.0; 140.1; 149.4
J
J
7.78-7.83 (1H, m, H-3)
5b
3.38-3.45 (2H, m, CH2); 3.53-3.60 (2H, m, CH2);
5.30-5.39 (1H, m, CHO);
35.0; 71.6; 109.3; 116.3;
121.7; 130.2; 149.0; 156.6
7.13 (1H, ddd,
7.42 (1H, t, = 8.3, H-5); 7.60 (1H, t,
7.81 (1H, ddd, = 0.8, = 2.5, = 8.3, H-4)
J
= 0.8,
J
= 2.5,
J
= 8.3, H-6);
J
J
= 2.5, H-2);
J
J
J
5c
3.36-3.45 (2H, m, CH2); 3.52-3.62 (2H, m, CH2);
5.31-5.42 (1H, m, CHO); 6.81-6.89 (2H, m, H-2,6);
8.10-8.18 (2H, m, H-3,5)
34.9; 71.5; 114.7; 125.9;
141.7; 161.0
5d
2.38 (3H, s, CH3); 3.35-3.41 (2H, m, CH2);
3.60-3.67 (2H, m, CH2); 5.30-5.39 (1H, m, CHO);
21.8; 35.3; 72.4; 115.9; 122.0;
125.9; 137.6; 145.7; 149.7
6.70 (1H, s, H-6); 6.84 (1H, d,
7.74 (1H, d, = 8.0, H-3)
J = 8.0, H-4);
J
5e
2.59 (3H, s, CH3); 3.38-3.49 (2H, m, CH2);
3.53-3.60 (2H, m, CH2); 5.30-5.40 (1H, m, CHO);
6.66-6.72 (2H, m, H-2,6); 8.01-8.06 (1H, m, H-5)
21.6; 35.0; 71.4; 112.5; 118.3;
127.6; 137.2; 142.5; 159.5
ionization, 70 eV) were obtained on an MKh-1321 instrument. High-resolution mass spectra (ESI or FAB) were
obtained on an IonSpec Fourier transform mass spectrometer. All melting points are uncorrected. Reactions
were monitored by thin-layer chromatography carried out on Macherey-Nagel ready-to-use plates AluGram
Alox N/UV254 using UV visualization or basic KMnO4 solution as a developing agent. Silica gel SiliCycle (60
mesh) was used for flash chromatography. All reagents and solvents were commercially available and were used
as supplied without additional purification.
The starting N-arylcyanamides 1a–k were synthesized according to literature methods (1a [11], 1b [26],
1c,f,g [17], 1d [23], 1e [12], 1h [27], 1i [28], 1j,k [20]).
Preparation of N-aryl-N-(thietan-3-yl)cyanamides 2a–k (General Method). The corresponding
N-arylcyanamide 1a–k (20 mmol) was added in one portion to a stirred solution of KOH (1.35 g, 24 mmol) in
water (80 ml). Then (chloromethyl)thiirane (2.40 g, 22 mmol) was added in one portion to the resulting solution,
and the reaction mixture was stirred at room temperature for 48 h. After that, CHCl3 (100 ml) was added, the
organic layer was separated, and the aqueous layer was extracted with CHCl3 (2×30 ml). The combined organic
phases were washed with 5% aqueous NaOH (2×50 ml), 100 ml water and 50 ml brine, and dried over MgSO4.
The solution was passed through a plug of silica gel (2 cm) eluting with CHCl3 (200 ml). The solvent was
removed on a rotary evaporator (bath temperature < 50°С) under reduced pressure, and the residue was
recrystallized from CHCl3–hexane (2c–k) or dried at 1 mm Hg (2a,b).
N-Phenyl-N-(thietan-3-yl)cyanamide (2a). Mass spectrum, m/z (Irel, %): 190 [M]+ (21), 144 (8), 104
(12), 91 (8), 77 (21), 73 (100), 65 (9), 51 (14), 45 (51), 39 (18).
N-(2,6-Dimethylphenyl)-N-(thietan-3-yl)cyanamide (2b). Found, m/z: 241.0770 [M+Na]+.
C12H14N2NaS. Calculated, m/z: 241.0775.
N-(4-Methoxyphenyl)-N-(thietan-3-yl)cyanamide (2c). Mass spectrum, m/z (Irel, %): 220 [M]+ (14),
174 (5), 147 (7), 73 (100), 45 (43), 39 (9). Found, %: C 60.09; H 5.65; N 12.65. C11H12N2OS. Calculated, %:
C 59.98; H 5.49; N 12.72.
N-(1-Naphthyl)-N-(thietan-3-yl)cyanamide (2d). Mass spectrum, m/z (Irel, %): 240 [M]+ (20), 115
(13), 73 (100), 45 (18). Found, %: C 70.06; H 5.06; N 11.78; C14H12N2S. Calculated, %: C 69.97; H 5.03;
N 11.66.
N-(2-Chlorophenyl)-N-(thietan-3-yl)cyanamide (2e). Found, m/z: 224.0174 [M]+. C10H9ClN2S.
Calculated, m/z: 224.0175.
1513