ꢂꢁꢁꢁ
F. Ye et al.: N-Dichloroacetyl-5-aryl-1,3-oxazolidinesꢀ
ꢀ203
δ 7.29 (m, 2H, ArH), 6.91 (m, 2H, ArH), 6.04 (s, 1H, Cl2CH), 5.18 (m, 2H,
NCH2), 3.80 (s, 3H, CH3), 3.49–3.56 (t, J = 9.9 Hz, 1H, OCH), 1.75 (s, 3H,
CH3), 1.68 (s, 3H, CH3); 13C NMR: δ 160.1, 159.6, 128.5, 127.9, 127.9, 114.2,
114.2, 96.7, 76.2, 67.0, 55.4, 52.9, 25.4, 23.3. Anal. Calcd for C14H17Cl2NO2:
C, 55.80; H, 5.69; N, 4.65. Found: C, 55.89; H, 5.73; N, 4.58.
Experimental
Infrared (IR) spectra were taken on a KJ-IN-27G infrared spectropho-
tometer using KBr pellets. H NMR spectra (300 MHz) and 13C NMR
1
spectra (75 MHz) were recorded on a Bruker Avance 300 MHz nuclear
magnetic resonance spectrometer in CDCl3 (unless stated otherwise).
Elemental analysis was performed on a Flash EA1112 elemental ana-
lyzer. X-Ray diffraction data were collected on a Bruker AXS II CCD
area-detector diffractometer, Mo Kα. Melting points were determined
on a Beijng Taike melting point apparatus (X-4) and are uncorrected.
All reagents were of analytical grade. Reactions and products were
routinely monitored by thin layer chromatography (TLC) on silica gel.
N-Dichloroacetyl-5-(p-methoxyphenyl)-2,2-dimethyl-1,3-oxazo-
lidine (4e)ꢀWhite crystals; yield 88%; mp 79–81°C; IR: ν 3022–3000
(C-H), 1672 (C=O), 1514 (Cl2HC-CO-), 1247 cm-1 (N-C-O); 1H NMR: δ 7. 2 7
(m, 4H, ArH), 6.06 (s, 1H, Cl2CH), 4.23 (m, 2H, NCH2), 3.52–3.58 (t, J =
9.9 Hz, 1H, OCH), 2.38 (s, 3H, CH3), 1.78 (s, 3H, CH3), 1.70 (s, 3H, CH3);
13C NMR: δ 159.6, 138.9, 133.6, 129.5, 129.5, 126.4, 126.4, 96.8, 76.4, 67.0,
52.9, 25.4, 23.3, 21.3. Anal. Calcd for C14H17Cl2NO3: C, 52.99; H, 5.40; N,
4.42. Found: C, 53.08; H, 5.46; N, 4.34.
Typical procedure for the synthesis N-
N-Dichloroacetyl-5-(2′-furyl)-2,2-dimethyl-1,3-oxazolidine
(4f)ꢀWhite crystals; yield 91%; mp 98–99°C. IR: ν 3250–3000 (C-H),
dichloroacetyl-5-aryl-1,3-oxazolidine 4a–l
1
1674 (C=O), 1423 (Cl2HC-CO-), 1139 cm-1 (N-C-O); H NMR: δ 7.44 (m,
1H, ArH), 6.46 (d, J = 3.3 Hz, 1H, ArH), 6.38 (m, 1H, ArH), 6.05 (s, 1H,
Cl2CH-), 5.18 (m, 2H, NCH2), 3.97 (m, 1H, OCH), 1.69 (s, 3H, CH3), 1.64
(s, 3H, CH3); 13C NMR: δ 159.6, 149.0, 143.6, 110.6, 110.0, 96.9, 69.9, 67.0,
48.9, 25.3, 23.5. Anal. Calcd for C11H13Cl2NO3: C, 47.65; H, 4.73; N, 5.05.
Found: C, 47.69; H, 4.71; N, 5.02.
Aryl substituted hydroxyalkylamine 1 (0.025 mol) and aldehyde or
ketone 2 (0.030 mol) were added to benzene (35 mL) and the mix-
ture was stirred briefly at 33–35°C followed by heating under reflux
with azeotropic removal of water with benzene. Then the mixture
was cooled to 0°C and treated with sodium hydroxide solution (33%,
0.03 mol). Aferwards, dichloroacetyl chloride (0.030 mol) was added
dropwise with stirring and cooling in an ice bath. Stirring was contin-
ued for 2 h. The organic phase was washed with water and dried over
anhydrous magnesium sulfate. The crude products were crystallized
from a mixture of ethyl acetate and light petroleum.
N-Dichloroacetyl-5-(2′-furyl)-2-methyl-2-n-propyl-1,3-
oxazolidine (4g)ꢀWhite crystals; yield 84%; mp 149–151°C; IR: ν
1
3083–2989 (C-H), 1681 (C=O), 1423 (Cl2HC-CO-), 1143 cm-1 (N-C-O); H
NMR: δ 7.47 (m, 1H, Ar-H), 6.49 (m, 1H, Ar-H), 6.40 (m, 1H, Ar-H), 6.08
(s, 1H, Cl2CH), 4.20 (m, 2H, N-CH2), 3.90 (t, J = 9.9 Hz, 1H, O-CH), 1.64
(s, 3H, CH3), 1.32 (m, 4H, CH2-CH2), 0.93 (m, 3H, CH3); 13C NMR: δ 159.5,
148.8, 143.7, 110.6, 110.1, 98.8, 69.8, 67.1, 49.9, 39.1, 22.9, 16.1, 13.9. Anal.
Calcd for C13H17Cl2NO3: C, 51.14; H, 5.62; N, 4.59. Found: C, 51.21; H,
5.56; N, 4.54.
N-Dichloroacetyl-5-(2′-thienyl)-2,2-dimethyl-1,3-oxazolidine
(4a)ꢀWhite crystals; yield 65%; mp 107–109°C; IR: ν 3250–2900
(C-H), 1681 (C=O), 1415 (Cl2HC-CO-), 1217 cm-1 (N-C-O); 1H NMR: δ 7.36–
7.38 (m, 1H, Ar-H), 7.15 (d, J = 3.5 Hz, 1H, ArH), 7.03 (m, 1H, ArH), 6.05
(s, 1H, Cl2CH), 5.40 (m, 2H, NCH2), 3.73 (t, J = 9.7 Hz, 1H, OCH), 1.75 (s,
3H, CH3), 1.70 (s, 3H, CH3); 13C NMR: δ 159.5, 139.5, 126.9, 126.4, 126.4,
97.0, 72.7, 67.0, 52.9, 25.4, 23.5. Anal. Calcd for C11H13Cl2NO2S: C, 45.05;
H, 4.47; N, 4.78; S, 10.91. Found: C, 45.12; H, 4.42; N, 4.71; S, 10.85.
N-Dichloroacetyl-5-(2′-furyl)-2,2-diethyl-1,3-oxazolidine
(4h)ꢀWhite crystals; yield 74%; mp 68–70°C; IR: ν 3050–2979 (C-H),
1
1660 (C=O), 1417 (Cl2HC-CO-), 1168 cm-1 (N-C-O); H NMR: δ 7.47 (m,
1H, Ar-H), 6.48 (m, 1H, Ar-H), 6.40 (m, 1H, Ar-H), 6.11 (s, 1H, Cl2CH),
4.26 (m, 2H, N-CH2), 3.97 (t, J = 9.9 Hz, 1H, O-CH), 1.82–2.36 (m, 4H,
2 × CH2), 0.88–0.99 (m, 6H, 2 × CH3); 13C NMR: δ 159.5, 149.4, 143.6,
110.6, 109.9, 102.1, 70.7, 67.1, 50.2, 29.3, 28.0, 8.3, 7.0. Anal. Calcd for
C13H17Cl2NO3: C, 51.14; H, 5.62; N, 4.59. Found: C, 51.18; H, 5.68; N, 4.48.
N-Dichloroacetyl-5-phenyl-2,2-dimethyl-1,3-oxazolidine
(4b)ꢀWhite crystals; yield 85%; mp 110–111°C; IR: ν 3250–2900
(C-H), 1610 (C=O), 1417 (Cl2HC-CO-), 1244 cm-1 (N-C-O); 1H NMR: δ 7.43
(m, 5H, ArH), 6.06 (s, 1H, Cl2CH), 5.18, 4.26 (m, 2H, NCH2), 3.54–3.60
(t, J = 9.7 Hz, 1H, OCH), 1.80 (s, 3H, CH3), 1.72 (s, 3H, CH3); 13C NMR:
δ 159.6, 136.7, 129.0, 128.8, 128.8, 126.4, 126.4, 96.9, 76.5, 67.0, 52.9, 25.4,
23.3. Anal. Calcd for C13H15Cl2NO2: C, 54.35; H, 5.27; N, 4.88. Found: C,
54.31; H, 5.24; N, 4.92.
N-Dichloroacetyl-5-(2′-furyl)-1,3-oxazolidine (4i)ꢀYellow oil;
yield 64%; IR: ν 3050–3000 (C-H), 1690 (C=O), 1450 (Cl2HC-CO-),
1
1200 cm-1 (N-C-O); H NMR: δ 7.47 (m, 1H, Ar-H), 6.43 (m, 2H, Ar-H),
6.08 (s, 1H, Cl2CH-), 5.11–5.41 (m, 3H, N-CH2-O and CH-O), 3.88–4.18
N-Dichloroacetyl-5-(p-chlorophenyl)-2,2-dimethyl-1,3-oxazolidine (m, 2H, N-CH2); 13C NMR: δ 160.4, 149.2, 143.6, 110.6, 109.7, 79.7, 74.1,
(4c)ꢀWhite crystals; yield 84%; mp 87–89°C; IR: ν 3022–3100 (C-H), 66.0, 47.4. Anal. Calcd for C9H9Cl2NO3: C, 43.37; H, 3.64; N, 5.62. Found:
1672 (C=O), 1515 (Cl2HC-CO-), 1218 cm-1 (N-C-O); 1H NMR: δ 7.38 (m, 4H, C, 43.29; H, 3.74; N, 5.74.
ArH), 6.04 (s, 1H, Cl2CH), 5.15, 4.26 (m, 2H, NCH2), 3.46 (t, J = 9.9 Hz, 1H,
OCH), 1.77 (s, 3H, CH3), 1.70 (s, 3H, CH3); 13C NMR: δ 159.6, 135.3, 134.7,
N-Dichloroacetyl-5-(2′-furyl)-2-phenyl-1,3-oxazolidineꢀ(4j)ꢀ
129.0, 129.0, 127.7, 127.7, 97.0, 75.8, 67.0, 52.7, 25.4, 23.3. Anal. Calcd for
C13H14Cl3NO2: C, 48.60; H, 4.40; N, 4.36. Found: C, 48.69; H, 4.49; N, 4.28.
White crystals; yield 61%; mp 78–79°C; IR: ν 3250–2900 (C-H), 1681
(C=O), 1421 (Cl2HC-CO-), 1168 cm-1 (N-C-O); 1H NMR: δ 7.45 (m, 8H, ArH),
6.53 (s, 1H, Cl2CH), 6.13 (s, 1H, H-C), 5.39 (t, J = 6.04 Hz, 1H, O-CH), 4.38,
4.21 (m, 2H, N-CH2); 13C NMR: δ 160.9, 149.9, 143.5, 137.1, 129.5, 129.3,
129.3, 126.5, 126.5, 110.6, 109.5, 90.1, 72.3, 66.3, 48.5. Anal. Calcd for
C15H13Cl2NO3: C, 55.38; H, 4.03; N, 4.31. Found: C, 55.42; H, 4.01; N, 4.35.
N-Dichloroacetyl-5-(p-methylphenyl)-2,2-dimethyl-1,3-oxazoli-
dine (4d)ꢀWhite crystals; yield 86%; mp 96–98°C; IR: ν 3018–2958
(C-H), 1670 (C=O), 1545 (Cl2HC-CO-), 1215 cm-1 (N-C-O). 1H NMR (CDCl3):