Reaction of (N-isocyanimino)triphenylphosphorane with an α-Haloketone 371
added dropwise a solution of 4-chlorobenzoic acid
225 (100), 197 (14), 183 (55), 155 (29), 102 (33), 75
(32), and 43 (71).
(1 mmol) in CH2Cl2 (5 mL) at room temperature
over 15 min. The mixture was stirred for 4 h. The
solvent was removed under reduced pressure, and
the viscous residue was purified by flash column
chromatography (silica gel; petroleum ether–ethyl
acetate (2:1)). The solvent was removed under
reduced pressure and the products were obtained.
The characterization data of the compounds are
given below:
2-[5-(4-Chlorophenyl)-1,3,4-oxadiazol-2-yl]-1,1,
1-trifluoro-2-propanol (4a): White crystals; mp:
145.5–147.1◦C; Yield: 85%. IR (KBr) (νmax, cm−1):
3281, 1607, 1488, 1159, 1095, 716. 1H NMR
1,1,1-Trifluoro-2-[5-(3-fluorophenyl)-1,3,4-oxadia-
zol-2-yl]-2-propanol (4d): Yellow crystals; mp: 95.1–
97.0◦C; Yield: 85%. IR (KBr) (νmax, cm−1): 3280,
1
1605, 1165, 1087, 776. H NMR (CDCl3, 250 MHz):
δH 1.93 (s, 3H, CH3), 4.34 (s, 1H, OH, exchanged
by D2O addition), 7.23–7.88 (m, 4H, arom). 13C
NMR (CDCl3, 62.5 MHz): δC 20.48 (CH3), 72.33 (q,
2
2 JCF = 32.1 Hz, C CF3), 114.60 (d, JCF = 24.5 Hz,
2
CH, arom), 119.93 (d, JCF = 20.8 Hz, CH, arom),
4
123.33 (d, JCF = 3.8 Hz, CH, arom), 123.90 (q,
3
1 JCF = 285.6 Hz, CF3), 125.11 (d, JCF = 8.2 Hz, C,
arom), 131.44 (d, 3 JCF = 8.2 Hz, CH, arom), 163.14 (d,
1 JCF = 248.5 Hz, C, arom), 164.47 and 165.85 (2C N).
Anal. Calcd for C11H8F4N2O2 (276.2): C, 47.84; H,
2.92; N, 10.14%. Found: C, 47.90; H, 2.95; N,
10.11. MS: m/z (%) (EI) 276 (M+, 7), 207 (9), 165
(22), 123 (100), 95 (63), 75 (30), 69 (18), and 42
(68).
(CDCl3,250 MHz): δH 1.93 (s, 3H, CH3), 4.51 (s, 1H,
3
OH, exchanged by D2O addition), 7.50 (d, JHH
=
3
8.5 Hz, 2H, arom), 7.99 (d, JHH = 8.5 Hz, 2H,
arom).13C NMR (CDCl3, 62.5 MHz): δC 20.46 (CH3),
72.32 (q, 2 JCF = 32.2 Hz, C CF3), 121.76 and 139.22
1
(2C, arom), 123.90 (q, JCF = 286.1 Hz, CF3),128.80
and 129.96 (4CH, arom), 164.19 and 166.03 (2C N).
Anal. Calcd for C11H8ClF3N2O2 (292.6): C, 45.15; H,
2.76; N, 9.57%. Found: C, 45.22; H, 2.71; N, 9.50. MS:
m/z (%) (EI) 294 ([M+ + 2], 24), 292 (M+, 54), 225
(27), 223 (63), 183 (33), 181 (100), 139 (62), 111 (51),
74 (51), 62 (26), and 43 (84).
1,1,1-Trifluoro-2-(5-phenyl-1,3,4-oxadiazol-2-yl)-
2-propanol (4e): White crystals; mp: 120.0–121.4◦C;
Yield: 85%. IR (KBr) (νmax, cm−1): 3320, 1560, 1156,
1084, 708. 1H NMR (CDCl3, 250 MHz): δH 1.94
(s, 3H, CH3), 5.08–5.35 (br. s, 1H, OH; exchanged
by D2O addition), 7.41–7.68 (m, 3H, arom), 8.04
3
2-[5-(3-Chlorophenyl)-1,3,4-oxadiazol-2-yl]-1,1,
1-trifluoro-2-propanol (4b): Yellow crystals; mp:
87.0–88.8◦C; Yield: 83%. IR (KBr) (νmax, cm−1): 3477,
1561, 1478, 1159, 1105, 720. 1H NMR (CDCl3,
250 MHz): δH 1.93 (s, 3H, CH3), 4.29 (s, 1H, OH, ex-
changed by D2O addition), 7.35–8.12 (m, 4H, arom).
13C NMR (CDCl3, 62.5 MHz): δC 20.52 (CH3), 72.34 (q,
(d, JHH = 7.0 Hz, 2H, arom). 13C NMR (CDCl3,
2
62.5 MHz): δC 21.22 (CH3), 72.92 (q, JCF = 32.1 Hz,
C CF3), 123.81 (C, arom), 124.65 (q, 1 JCF = 286.2 Hz,
CF3), 128.17, 130.15 and 133.46 (5CH, arom), 165.04
and 167.35 (2C N). Anal. Calcd for C11H9F3N2O2
(258.2): C, 51.17; H, 3.51; N,10.85%. Found: C, 51.15;
H, 3.55; N, 10.81. MS: m/z (%) (EI) 258 (M+, 9), 189
(16), 147 (25), 105 (81), 90 (9), 77 (100), 63 (14), and
43 (53).
1
2 JCF = 32.1 Hz, C CF3), 123.91 (q, JCF = 285.6 Hz,
CF3), 124.87 and 135.71 (2C, arom), 125.64, 127.48,
130.92 and 132.87 (4CH, arom), 164.53 and 165.62
(2C N). Anal. Calcd for C11H8ClF3N2O2 (292.6): C,
45.15; H, 2.76; N, 9.57%. Found: C, 45.09; H, 2.80;
N, 9.50. MS: m/z (%) (EI) 292 (M+, 4), 223 (5), 138
(33), 113 (19), 110 (32), 91 (19), 74 (55), 69 (48), and
42 (100).
1, 1, 1-Trifluoro-2-[5-(4-methylphenyl)-1, 3, 4-
oxadiazol-2-yl]-2-propanol (4f): Yellow crystals;
mp: 111.7–113.6◦C; Yield: 87%. IR (KBr) (νmax
,
cm−1): 3238, 1502, 1160, 1109, 725. 1H NMR
(CDCl3,250 MHz): δH 1.92 and 2.42 (2s, 6H, 2CH3),
5.08–5.35 (br. s, 1H, OH; exchanged by D2O addi-
3
2-[5-(4-Bromophenyl)-1,3,4-oxadiazol-2-yl]-1,1,
1-trifluoro-2-propanol (4c): White crystals; mp:
153.6–155.5◦C; Yield: 84%. IR (KBr) (νmax, cm−1):
tion), 7.30 (d, JHH = 7.9 Hz, 2H, arom), 7.92 (d,
3 JHH = 7.9 Hz, 2H, arom). 13C NMR (CDCl3,
62.5 MHz): δC 20.55 and 22.02 (2CH3), 72.26 (q,
2 JCF = 32.1 Hz, C CF3), 120.40 and 143.53 (2C,
1
3237, 1602, 1484, 1158, 1078, 727. H NMR (CDCl3,
1
250 MHz): δH 1.93 (s, 3H, CH3), 4.16 (s, 1H, OH; ex-
arom), 124.02 (q, JCF = 285.6 Hz, CF3), 127.49
changed by D2O addition), 7.68 (d, 3 JHH = 8.0 Hz, 2H,
and 130.20 (4CH, arom), 164.08 and 166.88 (2C N).
Anal. Calcd for C12H11F3N2O2 (272.2): C, 52.94; H,
4.07; N, 10.29%. Found: C, 52.87; H, 4.09; N, 10.35.
MS: m/z (%) (EI) 272 (M+, 100), 203 (84), 161 (79),
160 (76), 136 (19), 119 (66), 91 (84), 77 (14), 65 (21),
and 43 (31).
3
arom), 7.93 (d, JHH = 8.0 Hz, 2H, arom). 13C NMR
2
(CDCl3, 62.5 MHz): δC 20.44 (CH3), 72.32 (q, JCF
=
32.1 Hz, C CF3), 122.21 and 127.67 (2C, arom),
1
123.88 (q, JCF = 286.2 Hz, CF3), 128.90 and 132.93
(4CH, arom), 164.19 and 166.14 (2C N). Anal. Calcd
for C11H8BrF3N2O2 (337.1): C, 39.19; H, 2.39; N,
8.31%. Found: C, 39.13; H, 2.43; N, 8.24. MS: m/z
(%) (EI) 338 ([M+ + 2], 65), 336 (M+, 64), 269 (64),
1,1,1-Trifluoro-2-[5-(3-methoxyphenyl)-1,3,4-oxa-
diazol-2-yl]-2-propanol (4g): Yellow crystals; mp:
80.0–81.5◦C; Yield: 88%. IR (KBr) (νmax, cm−1):
Heteroatom Chemistry DOI 10.1002/hc