E. Łukowska, J. Plenkiewicz / Tetrahedron: Asymmetry 16 (2005) 2149–2156
2153
ppm: 20.67; 34.17; 66.57; 69.86; 111.55; 115.74; 126.59;
129.45; 156.31; 169.97. IR (Nujol, cmꢀ1) 2150 (CN);
1742 (CO). Anal. Calcd for C12H12NClSO3: C, 50.43;
H, 4.20; N, 4.90; S, 11.20. Found: C, 50.46; H, 4.10;
N, 4.75; S, 11.21.
3.2.8. ( )-2-((4-Chlorophenoxy)methyl)thiirane 3b. Oil.
1H NMR (CDCl3):
ppm: 2.31–2.61 (m, 2H
d
(CHCH2S)); 3.25 (m, 1H (OCH2CHCH2S)); 3.87–4.16
(m, 2H (OCH2CH)); 6.82–7.24 (m, 4H (Ph)). 13C
NMR (CDCl3): d ppm: 24.01; 31.40; 72.62; 114.92;
126.59; 129.50; 156.45. Anal Calcd for C9H9ClSO: C,
53.86; H, 4.48; Cl, 17.70; S, 15.9; Found: C, 53.36; H,
4.41; Cl, 17.38; S, 15.38.
3.2.3. ( )-3-Thiocyanato-1-(p-tolyloxy)propan-2-yl ace-
tate 7c. Colorless crystals; mp 27–28 ꢁC. 1H NMR
(CDCl3): d ppm: 2.16 (s, 1H (COCH3)); 2.29 (s, 3H
(CH3C6H5)); 3.32 (dd, 1H (CHCHaHbS); JHaCH
=
3.2.9. ( )-2-(p-Tolyloxymethyl)thiirane 3c. Oil. 1H
NMR (CDCl3): d ppm: 2.29 (s, 3H (CH3)); 2.32–2.61
(dd, 2H (CHCH2S)); 3.26 (m, 1H (CHaHbCHCH2));
3.86 (dd, 1H (OCHaHbCH); JHaHb = 10 Hz); 4.19 (dd,
1H (OCHaHbCH)); 6.80–7.10 (m, 4H (Ph)). 13C NMR
(CDCl3): d ppm: 20.46; 24.02; 31.45; 72.76; 114.57;
129.95; 130.51; 156.27. Anal. Calcd for C10H12SO: C,
66.66; H, 6.66; S, 17.77. Found: C, 66.01; H, 6.23; S,
17.55.
6.8 Hz; JHaHb = 14 Hz); 3.42 (dd, 1H (CHCHaHbS);
JHbCH = 4.4 Hz); 4.11 (dd, 1H (OCHcHdCH);
JHcCH = 4.4 Hz; JHcHd = 10 Hz); 4.17 (dd, 1H
(OCHcHdCH); JHdCH = 6 Hz); 5.41 (m, 1H (CH));
6.80–7.09 (m, 4H (Ph)). 13C NMR (CDCl3): d ppm:
20.61; 34.21; 66.36; 69.98; 111.67; 114.22; 129.92;
130.86; 155.58; 169.94. IR (Nujol, cmꢀ1) 2140 (CN);
1730 (CO). Anal. Calcd for C13H15NSO3: C, 58.86; H,
5.66; N, 5.28; S, 12.08. Found: C, 58.72; H, 5.71; N,
5.24; S, 12.43.
3.2.10.
idene)urea 4a. White crystals, mp 164.5–166 ꢁC. 1H
NMR (CD3COCD3): ppm: 3.37 (dd, 1H
( )-1-(5-(Phenoxymethyl)-1,3-oxathiolan-2-yl-
3.2.4. ( )-1-(2,4-Dichlorophenoxy)-3-thiocyanatopropan-
2-yl acetate 7d. Colorless crystals; mp 83–84 ꢁC. 1H
NMR (CDCl3): d ppm: 2.16 (s, 3H (CH3)); 3.38 (dd,
1H (CHCHaHbS); JHaCH = 6.4 Hz; JHaHb = 14.4 Hz);
3.47 (dd, 1H (CHCHaHbS); JHbCH = 4.8 Hz); 4.20 (dd,
1H (OCHcHdCH); JHcCH = 6 Hz; JHcHd = 10 Hz); 4.25
(dd, 1H (OCHcHdCH); JHdCH = 4.8 Hz); 5.44 (m, 1H
(CH)); 6.87–7.37 (m, 4H (Ph)). 13C NMR (CDCl3): d
ppm: 20.70; 34.04; 67.63; 69.82; 111.52; 114.61; 124.10;
127.10; 127.76; 140.19; 152.18; 170.01. IR (Nujol,
d
(CHCHaHbS); JHaCH = 8.4 Hz; JHaHb = 11.2 Hz); 3.52
(dd, 1H (CHCHaHbS); JHbCH = 7.2 Hz); 4.29 (dd, 1H
(OCHcHdCH); JHcCH = 5.6; JHcHd = 10.8 Hz); 4.37
(dd, 1H (OCHcHdCH); JHdCH = 3.6 Hz); 5.04 (m, 1H
(CH)); 6.10 (s, 1H (NH2)); 6.32 (s, 1H (NH2)); 6.98–
7.30 (m, 5H (Ph)).13C NMR (CD3COCD3): d ppm:
31.97; 68.14; 80.04; 115.40; 122.02; 130.35; 159.34;
163.59; 177.11. IR (Nujol, cmꢀ1) 3360, 3180 (NH2);
1693 (CO). Anal. Calcd for C11H12N2SO3: C, 52.38;
H, 4.76; N, 11.12; S, 12.69. Found: C, 51.99; H, 4.73;
11.05; S, 12.47.
cmꢀ1
) 2158 (CN); 1742 (CO). Anal. Calcd for
C12H11NCl2SO3: C, 45; H, 3.43; N, 4.37; Cl, 22.19; S,
10. Found: C, 45.11; H, 3.58; N, 4.33; Cl, 22.15; S, 9.84.
3.2.11. ( )-1-(5-((4-Chlorophenoxy)methyl)-1,3-oxathio-
lan-2-ylidene)urea 4b. White crystals, mp 179.5–
181.5 ꢁC. 1H NMR (CD3COCD3): d ppm: 3.35 (dd,
1H (CHCHaHbCH); JHaCH = 8.8 Hz; JHaHb = 10.8 Hz);
3.52 (dd, 1H (CHCHaHbS); JHbCH = 6.8 Hz); 4.30 (dd,
1H (OCHcHdCH); JHcCH = 5.6 Hz; JHcHd = 10.6 Hz);
4.36 (dd, 1H (OCHcHdCH); JHdCH = 3.6 Hz); 5.04 (m,
1H (CH)); 6.11 (s, 1H (NH2)); 6.33 (s, 1H (NH2));
7.01–7.32 (m, 4H (Ph)). 13C NMR (CD3COCD3): d
ppm: 31.90; 68.64; 79.91; 117.12; 126.45; 130.18;
158.18; 153.58; 177.10. IR (Nujol, cmꢀ1): 3360, 3180
(NH2)1692 (CO). Anal. Calcd for C11H11N2ClSO3:C,
46.07; H, 3.83; N; 9.77; Cl, 12.39; S, 11.16. Found: C,
46.53; H, 3.54; N, 9.27; Cl, 12.47; S, 11.02.
3.2.5. ( )-3-(4-Chlorophenoxy)-2-thiocyanatopropyl ace-
tate 8b. Oil. H NMR (CDCl3): d ppm: 2.28 (s, 3H
1
(CH3));
3.39
(dd,
1H
(C6H4OCHaHbCH);
JHaCH = 6.8 Hz; JHaHb = 14.4 Hz); 3.53 (dd, 1H
(C6H4OCHaHbCH); JHbCH = 6.4 Hz); 4.18 (m, 2H
(CHCH2OCOCH3)); 4.35 (m, 1H (CH)); 6.83–7.26 (m,
4H (Ph)).
3.2.6. ( )-2-Thiocyanato-3-(p-tolyloxy)propyl acetate
d
8c. Oil. 1H NMR (CDCl3):
ppm: 2.28 (s,
3H(CH3)); 3.39 (dd, 1H (CH3C4H4OCHaHbCH);
JHaCH = 6.8 Hz; JHaHb = 14 Hz); 3.56 (dd, 1H
(CH3C4H4OCHaHbCH); JHbCH = 6 Hz); 4.16 (dd, 1H
(CHCHcHdCH2OCO);
JHcCH = 5.6 Hz;
JHcHd =
10.4 Hz); 4.23 (dd, 1H (CHCHcHdCH2OCO);
JHdCH = 5.2 Hz); 4.34 (m, 1H (CH)); 6.80–7.09 (m, 4H
(Ph)).
3.2.12. ( )-1-(5-(p-Tolyloxymethyl)-1,3-oxathiolan-2-yl-
idene)urea 4c. White crystals, mp 176.5–179 ꢁC. 1H
NMR (CD3COCD3): d ppm: 2.24 (s, 3H (CH3)); 3.35
(dd, 1H (CHCHaHbS); JHaCH = 8.8 Hz; JHaHb
11.2 Hz); 3.51 (dd, 1H (CHCHaHbS); JHbCH = 6.8 Hz);
4.24 (dd, 1H (OCHcHdCH); JHcCH = 5.6 Hz;
=
3.2.7. ( )-2-(Phenoxymethyl)thiirane 3a. Oil. 1H NMR
(CDCl3): d ppm: 2.33–2.63 (m, 2H (CHCH2S)); 3.28 (m,
1H (CH)); 3.91 (dd, 1H (OCHaHbCH); JHaCH = 7.2 Hz;
JHcHd = 10.8 Hz); 4.32 (9dd, 1H (OCHcHdCH);
JHdCH = 4 Hz); 5.02 (m, 1H (CH)); 6.09 (s, 1H (NH2));
6.31 (s, 1H (NH2)); 6.87–7.11 (m, 4H (Ph)). 13C NMR
(CD3COCD3): d ppm: 20.42; 31.99; 68.33; 80.10;
115.32; 129.92; 130.74; 158.15; 163.40; 177.11. IR (Nu-
jol, cmꢀ1): 3360, 3180 (NH2); 1694 (CO). Anal. Calcd
for C12H14N2SO3: C, 54.13; H, 5.26; N, 10.52; S,
12.03. Found: C, 54.11; H, 5.13; N, 10.21; S, 11.91.
JHaHb = 10 Hz);
4.22
(dd,
1H
(OCHaHbCH);
JHbCH = 5.2 Hz); 6.91–7.32 (m, 5H (Ph)). 13C NMR
(CDCl3) ppm: 24.00; 31.37; 72.53; 114.62; 121.21;
129.53; 158.20. Anal. Calcd for C9H10SO: C, 65.06; H,
1
6.02; S, 19.27. Found: C, 64.98; H, 5.87; S, 19.01. H
NMR and 13C NMR spectra are identical with those
given in the literature.25