5496 J . Org. Chem., Vol. 63, No. 16, 1998
Novak et al.
DMSO-d6) δ 148.0 (C), 143.8 (C), 129.6 (C), 128.1 (CH), 127.6
(CH), 127.3 (CH), 126.6 (CH), 113.4 (CH), 77.3 (CH), 77.1 (CH).
th r eo- a n d er yth r o-1,2-Dih yd r oxy-1-p h en yl-2-(4-a cet-
a m id op h en yl)eth a n e (5 a n d 6). The appropriate amino diol
(88 mg, 0.39 mmol) was dissolved in 20 mL of dry THF followed
by the addition of 54 µL of Et3N. This mixture was stirred as
30 µL of acetyl chloride in 1 mL of THF was added slowly.
After being stirred at room temperature for 20 min, the
mixture was heated on a steam bath for another 20 min. After
cooling, 25 mL of brine was added, and the layers were
separated. The aqueous layer was extracted (5 × 25 mL) with
more THF. The combined THF extracts were evaporated, and
the crude product was dried under vacuum. The product was
purified by TLC on silica gel with 9/1 EtOAc/CH2Cl2 eluent.
1H NMR (300 MHz, CDCl3) δ 7.46 (3H, m), 7.30 (3H, m), 7.20-
7.10 (4H, m), 4.59 (2H, s), 2.13 (3H, s); 13C NMR (75.5 MHz,
CDCl3) δ 168.3 (C), 138.4 (C), 135.7 (C), 131.2 (C), 129.0 (CH),
128.7 (CH), 128.7 (CH), 127.9 (CH), 119.6 (CH), 69.6 (CH), 69.2
(CH), 24.7 (CH3); high-resolution MS C16H16N7O (M + 1)
requires m/e 322.1416, found 322.1418 (0.1); C9H9N4O requires
m/e 189.0777, found 189.0770 (2.4); C9H9N2O requires m/e
161.0715, found 161.0711 (76); C7H6N3 requires m/e 132.0562,
found 132.0591 (1.3); C7H7N2 requires m/e 119.0609, found
119.0605 (69); C7H6N requires m/e 104.0501, found 104.0483
(37).
t h r eo-1-Azid o-2-h yd r oxy-1-p h e n yl-2-(4-a ce t a m id o-
p h en yl)eth a n e (10): 1H NMR (300 MHz, CDCl3) δ 7.35-
7.30 (1H, m) 7.32 (2H, d, J ) 8.4 Hz), 7.24-7.18 (3H, m), 7.08-
7.04 (2H, m), 7.01 (2H, d, J ) 8.5 Hz), 4.70 (1H, d, J ) 8.1
Hz), 4.57 (1H, d, J ) 8.0 Hz), 2.11 (3H, s); 13C NMR (75.5 MHz,
CD2Cl2) δ 167.8 (C), 137.6 (C), 135.8 (C), 134.8 (C), 128.1 (CH),
128.0 (CH), 127.5 (CH), 127.2 (CH), 118.7 (CH), 77.1 (CH), 72.4
(CH), 24.0 (CH3); high-resolution MS (mixture of 10 and 11)
C16H17N4O2 (M + 1) requires m/e 297.1351, found 297.1327
(0.2); C9H10NO2 requires m/e 164.0712, found 164.0694 (80);
C7H8NO requires m/e 122.0606, found 122.0581 (71); C7H6N
requires m/e 104.0501, found 104.0495 (29).
er yth r o-1-Azid o-2-h yd r oxy-1-p h en yl-2-(4-a cet a m id o-
p h en yl)eth a n e (11) (by subtraction, some peaks are obscured
by those of the major isomer): 1H NMR (300 MHz, CDCl3) δ
7.43 (2H, d, J ) 8.6 Hz) 7.19 (2H, d, J ) 8.3 Hz) 4.78 (1H, d,
J ) 6.6 Hz) 4.65 (1H, d, J ) 6.6 Hz), 2.14 (3H, s); 13C NMR
(75.5 MHz, CD2Cl2) 137.8 (C), 135.3 (C), 128.3 (CH), 128.2
(CH), 127.7 (CH), 127.3 (CH), 118.8 (CH), 76.1 (CH), 70.8 (CH).
2-Azid o-1-h yd r oxy-1-p h en yl-2-(4-a cet a m id op h en yl)-
eth a n e (12 or 13): 1H NMR (300 MHz, CDCl3) δ 7.39 (2H, d,
J ) 8.5 Hz), 7.20-7.18 (3H, m), 7.09-7.06 (3H, m), 7.03 (2H,
d, J ) 8.5 Hz), 4.71 (1H, d, J ) 8.1 Hz), 4.59 (1H, d, J ) 8.1
Hz), 2.14 (3H, s); 13C NMR (75.5 MHz, CDCl3) δ 168.1 (C),
139.1 (C), 138.0 (C), 131.7 (C), 128.6 (CH), 128.2 (CH), 128.2
(CH), 126.9 (CH), 119.4 (CH), 77.9 (CH), 72.4 (CH), 24.7 (CH3);
high-resolution MS C16H17N4O2 (M + 1) requires m/e 297.1351,
found 297.1360 (0.7); C16H16N4O2 requires m/e 296.1273, found
296.1295 (0.1); C9H9N4O requires m/e 189.0777, found 189.0810
(2.1); C9H9N2O requires m/e 161.0715, found 161.0724 (44);
C7H7N2 requires m/e 119.0609, found 119.0612 (93); C7H7O
requires m/e 107.0497, found 107.0481 (77).
1
5: H NMR (300 MHz, DMSO-d6) δ 9.86 (1H, s), 7.35 (2H,
d, J ) 8.5 Hz), 7.13 (3H, m), 7.05 (2H, m), 6.96 (2H, d, J ) 8.5
Hz), 5.36 (2H, s(br)), 4.53 (1H, d, J ) 6.5 Hz), 4.50 (1H, d, J )
6.5 Hz), 1.99 (3H, s); 13C NMR (75.5 MHz, DMSO-d6) δ 168.4
(C), 142.7 (C), 138.2 (C), 137.2 (C), 127.8 (CH), 127.6 (CH),
127.5 (CH), 127.0 (CH), 118.2 (CH), 78.1 (CH), 77.8 (CH), 24.3
(CH3); high-resolution MS C16H17NO3 requires m/e 271.1209,
found 271.1186 (0.2); C9H10NO2 requires m/e 164.0712, found
164.0744 (100); C7H8NO requires m/e 122.0606, found 122.0626
(84); C7H7O requires m/e 107.0497, found 107.0488 (12).
6 (by subtraction): 1H NMR (300 MHz, DMSO-d6) δ 9.90
(1H, s), 7.41 (2H, d, J ) 8.5 Hz), 7.18 (3H, m), 7.10-7.02 (4H,
m), 5.47 (2H, s(br)), 4.53 (1H, d, J ) 5.0 Hz), 4.49 (1H, d, J )
5.0 Hz), 2.00 (3H, s); 13C (75.5 MHz, DMSO-d6) δ 168.4 (C),
143.6 (C), 131.4 (C), 131.0 (C), 127.9 (CH), 127.7 (CH), 127.6
(CH), 127.0 (CH), 118.5 (CH), 77.3 (CH), 77.0 (CH), 25.1 (CH3);
high-resolution MS: C16H17NO3 requires m/e 271.1209, found
271.1233 (0.2); C9H10NO2 requires m/e 164.0712, found 164.0732
(100); C7H8NO requires m/e 122.0606, found 122.0656 (64);
C7H7O requires m/e 107.0497, found 107.0500 (3.7).
Azid e Ad d u cts. These were isolated as described above
and purified by chromatographic methods (also described
above) to yield the compounds 7-9, the mixture of 10 and 11,
and 12 or 13.
3-Azid o-N-a cetyl-4-a m in ostilben e (7): IR (KBr) 2120,
1660, 1600, 1530, 1300 cm-1 1H NMR (300 MHz, CDCl3) δ
;
8.28 (1H, d, J ) 8.4 Hz), 7.45 (3H, m) 7.35-7.15 (5H, m), 6.98
(2H, s), 2.15 (3H, s); 13C NMR (75.5 MHz, CDCl3) δ 167.9 (C),
144.8 (C), 136.9 (C), 133.7 (C), 131.6 (C), 128.9 (CH), 128.7
(CH), 127.8 (CH), 127.1 (CH), 126.5 (CH), 124.0 (CH), 120.7
(CH), 115.0 (CH), 24.8 (CH3); high-resolution MS C16H14N4O
requires m/e 278.1176, found 278.1155 (9.5%).
Ack n ow led gm en t. This work was supported by a
grant from the American Cancer Society (CN-23K).
NMR spectra were obtained on equipment made avail-
able from an NSF grant (CHE-9012532). Electron
ionization high-resolution mass spectra were obtained
at the Ohio State University Chemical Instrumentation
Center.
t h r eo-1,2-Dia zid o-1-p h e n yl-2-(4-a ce t a m id op h e n yl)-
eth a n e (8): IR (KBr) 2105, 1665, 1600, 1535, 1255, 825 cm-1
;
1H NMR (300 MHz, CDCl3) δ 7.35-7.25 (3H, m), 7.17 (3H,
m), 7.05-6.90 (4H, m), 4.54 (2H, s), 2.07 (3H, s); 13C NMR (75.5
MHz, CDCl3) δ 168.3 (C), 138.2 (C), 135.6 (C), 131.4 (C), 128.7
(CH), 128.6 (CH), 128.3 (CH), 127.6 (CH), 119.4 (CH), 70.6
(CH), 70.1 (CH), 24.6 (CH3); high-resolution MS C16H16N7O (M
+ 1) requires m/e 322.1416, found 322.1442 (0.1); C9H9N4O
requires m/e 189.0777, found 189.0808 (3.4); C9H9N2O requires
m/e 161.0715, found 161.0679 (93); C7H6N3 requires m/e
132.0562 found 132.0540 (1.5); C7H7N2 requires m/e 119.0609,
found 119.0635 (81); C7H6N requires m/e 104.0501, found
104.0494 (39).
Su p p or tin g In for m a tion Ava ila ble: Table of hydrolysis
rate constants for 1a in the presence and absence of N3-, and
13C NMR spectra for 1a , 4-11, and 12 or 13 (11 pages). This
material is contained in libraries on microfiche, immediately
follows this article in the microfilm version of the journal, and
can be ordered from the ACS; see any current masthead page
for ordering information.
er yth r o-1,2-Dia zid o-1-p h en yl-2-(4-a cet a m id op h en yl)-
eth a n e (9): IR (KBr) 2100, 1665, 1600, 1535, 1255, 840 cm-1
;
J O980500Z