Â
I. Gomez et al. / Tetrahedron 56 (2000) 4043±4052
4047
columnchromatography(see, footnotes inTables1±4) afford-
ing the pure title compounds. Yields are included in
Tables 1±4. Physical, spectroscopic and analytical data, as
well as the literature reference for the known compounds,
follow:
158.45; m/z 338 (M111, ,1%), 337 (M1, ,1), 322 (43),
279 (13), 236 (12), 220 (16), 207 (30), 204 (18), 178 (10),
164 (10), 162 (17), 150 (27), 149 (100), 148 (15), 132 (11),
131 (18), 122 (16), 121 (74), 120 (28), 106 (24), 104 (13),
101 (20), 100 (29), 93 (53), 92 (12), 85 (21), 80 (11), 79
(57), 78 (55), 65 (10), 59 (44), 52 (17), 51 (12), 43 (68), 42
(19), 41 (22).
2,2-Dimethyl-1-(pyrid-2-yl)propan-1-ol (2a).22 Colour-
less oil, tr 9.6; Rf 0.52 (hexane/ethyl acetate: 1:1); n (®lm)
3386 (OH), 3088, 3064, 1595 (HCvC), 1063 cm21 (CO);
dH (CDCl3) 0.90 (9H, s, 3£CH3), 4.35 (1H, s, CHOH), 4.46
(1H, s, OH), 7.15±7.65, 8.48 (3 and 1H, respectively, m, and
d, respectively, J4.9 Hz, ArH); dC (CDCl3) 25.6 (3C),
35.75, 80.15, 121.9, 122.45, 135.25, 147.3, 160.2; m/z 166
(M111, ,1%), 150 (M12CH3, 1), 109 (100), 79 (21), 78
(17), 53 (11), 52 (11), 41 (16).
(1S,2R,4S)-N-Isobutyl-2-hydroxy-7,7-dimethyl-2-(pyrid-
2-yl)bicyclo[2.2.1]hept-1-ylmethanesulfonamide (2f).26
Pale yellow oil, tr 14.3; Rf 0.4 (hexane/ethyl acetate: 7:3);
[a]2D5180.3 (c 0.1, CH2Cl2); n (®lm) 3404 (OH,NH), 1593
(HCvC), 1139 (CO), 1076 cm21 (SO); dH (CDCl3)
0.95[6H, d, J6.7 Hz, (CH3)2CH], 1.05 (3H, s, CH3C),
1.30 (3H, s,CH3), 1.45±2.00 [8H, m, CH2CH2CHCH2,
CH(CH3)2], 2.75±2.95 (2H, m, CH2NH), 2.97, 3.70 (1 and
1H, respectively, 2d, J15.3 Hz, CH2S), 4.80 (1H, m, NH),
6.01 (1H, s, OH), 7.25±7.75, 8.50±8.55 (3 and 1H, respec-
tively, 2m, ArH); dC (CDCl3) 19.95 (2C), 21.55 (2C), 26.45,
27.2, 28.85, 44.75, 47.6, 50.25, 50.7, 53.2, 55.1, 82.05,
111.55, 122.15, 122.6, 136.65, 146.6; m/z 331 (M1235,
,1%), 201 (11), 160 (17), 146 (25), 122 (37), 121 (29),
108 (31), 107 (10), 106 (21), 93 (95), 91 (11), 80 (14), 79
(75), 78 (100), 67 (20), 55 (14), 53 (20), 52 (18), 51 (27), 44
(18), 43 (17), 41 (60).
1-Phenyl-1-(pyrid-2-yl)methanol (2b).23 Pale yellow oil, tr
13.4; Rf 0.70 (ethyl acetate); n (®lm) 3350 (OH), 3060,
3028, 1593 (HCvC), 1051, 1026 cm21 (CO); dH (CDCl3)
5.49 (1H. s, OH), 5.73 (1H, s, CHOH), 7.10±7.60, 8.46 (8
and 1H, respectively, m, and d, respectively, J4.3 Hz,
ArH); dC (CDCl3) 75.0, 121.1, 122.2 (2C), 126.8, 127.5,
128.35 (2C), 136.7, 143.05, 147.7, 161.1; m/z 186
(M111, 4%), 185 (M1, 34), 184 (20), 108 (34), 105 (11),
80 (31), 79 (100), 78 (43), 77 (40), 53 (13), 52 (33), 51 (41),
50 (14), 44 (12).
(E)-4-Phenyl-2-(pyrid-2-yl)-3-buten-2-ol (2g).25,27 White
solid, mp 106±1088C (ethyl acetate/hexane); tr 15.5; Rf
0.49 (hexane/ethyl acetate: 1:1); n (®lm) 3256 (OH),
3084, 3055, 1590 (HCvC), 1180 cm21 (CO); dH (CDCl3)
1.72 (3H, s, CH3), 5.55 (1H, s, OH), 6.46 (1H, d, J15.9 Hz,
CHCO), 6.73 (1H, d, J15.9 Hz, CHCHCO), 7.15±7.70,
8.50±8.55 (8 and 1H, respectively, 2m, ArH); dC
(CD3COCD3) 29.7, 75.1, 120.45, 122.75 (2C), 127.2 (2C),
127.5, 128.0, 129.3 (2C), 137.65, 137.80, 148.6, 165.9;
m/z 226 (M111, ,1%), 225 (M1, 3), 209 (17), 208
(100), 207 (19), 206 (26), 182 (25), 122 (13), 106 (17),
104 (36), 102 (11), 79 (23), 78 (44), 77 (17), 52 (14), 51
(21), 43 (33).
3-(Pyrid-2-yl)pentan-3-ol (2c). tr 8.7; Rf 0.20 (hexane/ethyl
acetate: 1:1); n (®lm) 3327 (OH), 3033, 1605 (HCvC),
1150 cm21 (CO); dH (CDCl3) 0.68 (6H, t, J7.4 Hz,
2£CH3), 1.65±2.05 (4H, m, 2£CH2), 5.28 (1H, s, OH),
7.15±7.30, 7.65±7.75, 8.50±8.55 (1, 2 and 1H, respectively,
3m, ArH); dC (CDCl3) 7.7 (2C), 34.65 (2C), 76.4, 119.6,
121.55, 136.75, 147.05, 163.35; m/z 150 (M12CH3, 2%),
137 (17),136 (100), 118 (25), 117 (22), 80 (21), 79 (24), 78
(16), 53 (13), 52 (23), 51 (17); HRMS: M12CH3, found
150.0917. C9H12NO requires 150.0919.
1-Phenyl-1-(pyrid-2-yl)ethanol (2d).24 Pale yellow oil, tr
13.2; Rf 0.59 (hexane/ethyl acetate: 1:1); n (®lm) 3385
(OH), 3087, 3059, 1591 (HCvC), 1062 cm-1 (CO); dH
(CDCl3) 1.91 (3H, s, CH3), 5.85 (1H, s, OH), 7.10-7.65,
8.47 (8, and 1H, respectively, m and d, respectively,
J4.8 Hz, ArH); dC (CDCl3) 29.05, 74.95, 120.15,
121.85, 125.75, 126.8 (2C), 128.05 (2C), 136.85, 147.0,
147.25, 164.6; m/z 200 (M111, 9%), 199 (M1, 66), 184
(47), 180 (23), 156 (15), 122 (47), 121 (11), 106 (30), 105
(22), 104 (14), 91 (16), 80 (34), 79 (85), 78 (74), 77 (40), 52
(30), 51 (40), 50 (12), 43 (100).
N-Phenyl-N-[1-phenyl-1-(pyrid-2-yl)]methylamine (2h).28
Yellow oil, tr 17.8; Rf 0.49 (hexane/ethyl acetate: 4:1); n
(®lm) 3392 (NH), 3052, 3024, 1601 cm21 (HCvC); dH
(CDCl3) 5.50 (1H, s, NH), 5.55 (1H, s, CHNH), 6.60±
6.65, 7.05±7.40, 8.50±8.55 (3, 10 and 1H, respectively,
5m, ArH); dC (CDCl3) 63.0, 113.4 (3C), 117.2, 121.65,
121.95, 127.15 (2C), 128.6 (2C), 128.9 (2C), 136.6, 142.3,
146.8, 148.9, 160.6; m/z 261 (M111, 9%), 260 (M1, 46),
183 (29), 182 (100), 169 (13), 168 (91), 167 (60), 166 (10),
104 (13), 78 (10), 77 (37), 51 (21).
1,2:5,6-Di-O-isopropyliden-3-(pyrid-2-yl)-a-d-allofura-
nose (2e).5c,25 White solid, mp 129±1318C (ethyl acetate/
hexane); tr 16.3; Rf 0.70 (hexane/ethyl acetate: 1:1);
[a]2D5161.4 (c 1.9, CH3COCH3); n (melted) 3472 (OH),
3059, 1591 (HCvC), 1071 cm21 (CO); dH (CDCl3) 1.18
(3H, s, CH3), 1.38 (3H, s, CH3), 1.40 (3H, s, CH3), 1.65
(3H, s, CH3), 3.20±3.25 (1H, m, CHCH2), 3.55±3.60 (2H,
m, CH2), 3.79 (1H, s, OH), 4.23 (1H d, J5.5 Hz,
CHCHCH2), 4.66 (1H, d, J3.7 Hz, CHCHO2), 6.15 (1H,
d, J3.7 Hz, OCHO), 7.20±7.25, 7.65±7.75, 8.52 (1, 2 and
1H, respectively, 2m and d, respectively, J4.9 Hz, ArH);
dC (CDCl3) 25.0, 26.2, 26.3, 26.7, 65.35, 73.55, 81.5, 83.15,
83.65, 105.5, 108.45, 112.2 (2C), 121.1, 122.5, 136.0, 147.9,
4-Hydroxy-1-(pyrid-2-yl)-1-butanone (2i). Pale yellow
oil, tr 8.8; Rf 0.49 (ethyl acetate); n (®lm) 3372 (OH),
1584 (HCvC), 1696 (CvO), 1044 cm21 (CO); dH
(CDCl3) 2.00±2.10 (2H, m, CH2CH2CH2), 2.49 (1H, m,
OH), 3.33 (2H, t, J6.7 Hz, CH2CvO), 3.70±3.75 (2H,
m, CH2O), 7.45±8.05, 8.65±8.70 (3 and 1H, respectively,
2m, ArH); dC (CDCl3) 27.65, 34.25, 62.0, 121.85, 127.25,
137.1, 148.85, 153.4, 202.45; m/z 166 (M111, ,1%), 165
(M1, 2), 134 (48), 122(16), 121 (13), 118 (11), 107 (16), 106
(30), 93 (24), 80 (20), 79 (100), 78 (99), 55 (11), 53 (11), 52
(50), 51 (58), 50 (17), 43 (13), 41 (22); HRMS: M1, found
165.0790. C9H11NO2 requires 165.0789.