6
A.Yu. Barkov et al. / Tetrahedron xxx (2016) 1e8
1.5 Hz, 1H, H-40), 7.62 (dd, J¼8.0, 1.5 Hz, 1H, H-60), 7.78 (dd, J¼8.5,
2.2 Hz, 1H, H-4), 7.80 (d, J¼2.2 Hz, 1H, H-6), 11.92 (s, 1H, OH); 13C
132.8, 133.4, 133.5, 136.6, 137.1, 153.8, 160.9, 197.2, 199.2. Anal. Calcd
for C25H23NO4: S, 74.80; O, 5.77; N, 3.49. Found: S, 74.51; O, 5.51;
N, 3.47.
NMR (126 MHz, CDCl3)
d 23.9, 25.8, 28.4, 53.7, 117.6, 118.3, 118.7,
119.2, 129.7, 131.7, 132.6, 133.1, 133.4, 135.9, 155.0, 162.9, 199.3,
202.9. Anal. Calcd for C20H21NO3: S, 74.28; O, 6.55; N, 4.33. Found:
S, 74.15; O, 6.42; N, 4.28.
4.2.11. (3-Benzoyl-4-morpholinophenyl) (5-chloro-2-hydroxyphenyl)
methanone (8k). Yield 0.22 g (52%), mp 142e143 ꢁC, yellow
powder. IR (ATR): 1655, 1624, 1580, 1550, 1494, 1462, 1450,
4.2.6. 1-[5-(2-Hydroxy-5-methylbenzoyl)-2-piperidinophenyl]ethan-
1-one (8f). Yield 0.16 g (47%), mp 62e63 ꢁC, yellowish powder. IR
(ATR): 1682, 1630, 1587, 1483, 1451, 1402, 1381, 1338 cmꢀ1; 1H NMR
1327 cmꢀ1 1H NMR (400 MHz, CDCl3)
; d 3.06e3.14 (m, 4H,
N(CH2)2), 3.35e3.43 (m, 4H, O(CH2)2), 7.02 (d, J¼8.9 Hz, 1H, H-30),
7.11 (d, J¼8.5 Hz, 1H, H-3), 7.44 (dd, J¼8.9, 2.4 Hz, 1H, H-40), 7.49 (t,
J¼7.7 Hz, 2H, Hm), 7.58e7.64 (m, 2H, H-60, Hp), 7.79e7.88 (m, 4H,
(500 MHz, CDCl3)
d 1.59e1.82 (m, 6H, 3CH2), 2.28 (s, 3H, Me), 2.64
(s, 3H, Me), 3.09e3.17 (m, 4H, N(CH2)2), 6.97 (d, J¼8.4 Hz, 1H, H-30),
7.10 (d, J¼8.5 Hz, 1H, H-3), 7.31 (dd, J¼8.4, 1.9 Hz, 1H, H-40), 7.38 (d,
J¼1.9 Hz, 1H, H-60), 7.75 (dd, J¼8.5, 2.2 Hz, 1H, H-4), 7.80 (d,
J¼2.2 Hz, 1H, H-6), 11.71 (s, 1H, OH). Anal. Calcd for
H-4, H-6, Ho), 11.75 (s, 1H, OH); 13C NMR (126 MHz, CDCl3)
d 51.6,
66.1, 117.2, 119.9, 120.1, 123.4, 128.5, 129.4, 130.0, 130.3, 131.9,
133.0, 133.5, 133.6, 135.9, 136.4, 154.2, 161.4, 196.8, 198.1. Anal.
Calcd for C24H20ClNO4: S, 68.33; O, 4.78; N, 3.32. Found: S, 68.41;
O, 4.74; N, 3.34.
C
21H23NO3$0.5H2O: S, 72.81; O, 6.98; N, 4.04. Found: S, 72.45; O,
6.62; N, 3.71.
4.2.12. Ethyl
(8l). Yield 0.21 g (62%), light yellow oil. IR (ATR): 1716, 1622, 1585,
1508, 1482, 1445, 1421 cmꢀ1 1H NMR (500 MHz, CDCl3)
1.19 (t,
2-(diethylamino)-5-(2-hydroxybenzoyl)benzoate
4.2.7. 1-[5-(2-Hydroxybenzoyl)-2-morpholinophenyl]ethan-1-one
(8g). Yield 0.15 g (46%), mp 119e120 ꢁC, yellow powder. IR (ATR):
1681, 1622, 1580, 1554, 1482, 1448, 1437 cmꢀ1; 1H NMR (500 MHz,
;
d
J¼7.1 Hz, 6H, 2Me), 1.37 (t, J¼7.1 Hz, 3H, Me), 3.35 (q, J¼7.1 Hz, 4H,
2NCH2), 4.35 (q, J¼7.1 Hz, 2H, OCH2), 6.90 (ddd, J¼8.0, 7.4, 1.0 Hz,
1H, H-50), 6.99 (d, J¼8.8 Hz, 1H, H-3), 7.06 (dd, J¼8.3, 1.0 Hz, 1H, H-
30), 7.48 (ddd, J¼8.3, 7.4, 1.6 Hz, 1H, H-40), 7.66 (dd, J¼8.0, 1.6 Hz,
1H, H-60), 7.73 (dd, J¼8.8, 2.3 Hz, 1H, H-4), 8.01 (d, J¼2.3 Hz, 1H, H-
CDCl3) d 2.66 (s, 3H, Me), 3.11e3.17 (m, 4H, N(CH2)2), 3.85e3.92 (m,
4H, O(CH2)2), 6.90 (ddd, J¼8.0, 7.3, 0.8 Hz, 1H, H-50), 7.07 (dd, J¼8.6,
0.8 Hz, 1H, H-30), 7.11 (d, J¼8.4 Hz, 1H, H-3), 7.51 (ddd, J¼8.6, 7.3,
1.6 Hz, 1H, H-40), 7.60 (dd, J¼8.0, 1.6 Hz, 1H, H-60), 7.80 (dd, J¼8.4,
2.2 Hz, 1H, H-4), 7.82 (d, J¼2.2 Hz, 1H, H-6), 11.88 (br s, 1H, OH).
Anal. Calcd for C19H19NO4: S, 70.14; O, 5.89; N, 4.31. Found: S,
69.83; O, 5.90; N, 4.26.
6), 11.93 (s, 1H, OH); 13C NMR (126 MHz, CDCl3)
d 12.4, 14.2, 46.0,
61.2, 117.3, 118.3, 118.5, 119.5, 120.9, 126.5, 133.0, 133.4, 134.2,
135.5, 152.9, 162.7, 168.3, 198.6. Anal. Calcd for
20H23NO4$0.25H2O: S, 69.45; O, 6.85; N, 4.05. Found: S, 69.71;
O, 6.83; N, 3.92.
C
4.2.8. 1-[5-(2-Hydroxy-5-methylbenzoyl)-2-morpholinophenyl]
ethan-1-one (8h). Yield 0.16 g (47%), mp 150e151 ꢁC, yellowish
powder. IR (ATR): 1681, 1631, 1583, 1478, 1453, 1370, 1339 cmꢀ1; 1H
4.2.13. Ethyl 2-(diethylamino)-5-(2-hydroxy-5-methylbenzoyl)ben-
NMR (400 MHz, CDCl3)
d
2.28 (s, 3H, Me), 2.67 (s, 3H, Me), 3.11e3.18
zoate (8m). Yield 0.20 g (55%), light yellow oil. IR (ATR): 1718, 1629,
(m, 4H, N(CH2)2), 3.85e3.92 (m, 4H, O(CH2)2), 6.98 (d, J¼8.4 Hz, 1H,
H-30), 7.11 (d, J¼8.4 Hz, 1H, H-3), 7.33 (d, J¼8.4 Hz, 1H, H-40), 7.36 (s,
1H, H-60), 7.78 (dd, J¼8.4, 2.0 Hz, 1H, H-4), 7.82 (d, J¼2.0 Hz, 1H, H-
1585, 1507, 1482 cmꢀ1; 1H NMR (500 MHz, CDCl3)
d
1.19 (t, J¼7.1 Hz,
6H, 2Me), 1.37 (t, J¼7.1 Hz, 3H, Me), 2.29 (s, 3H, Me), 3.36 (q,
J¼7.1 Hz, 4H, 2NCH2), 4.34 (q, J¼7.1 Hz, 2H, OCH2), 6.96 (d, J¼8.4 Hz,
1H, H-30), 6.99 (d, J¼8.8 Hz, 1H, H-3), 7.29 (dd, J¼8.4, 1.8 Hz, 1H, H-
40), 7.44 (d, J¼1.8 Hz, 1H, H-60), 7.72 (dd, J¼8.8, 2.2 Hz, 1H, H-4), 8.02
(d, J¼2.2 Hz, 1H, H-6), 11.72 (s, 1H, OH); 13C NMR (126 MHz, CDCl3)
6), 11.68 (s, 1H, OH); 13C NMR (126 MHz, CDCl3)
d 20.6, 29.0, 52.7,
66.7, 117.5, 118.2, 118.8, 127.9, 131.3, 131.5, 132.7, 133.2, 133.4, 137.2,
153.7, 160.9, 199.3, 202.5. Anal. Calcd for C20H21NO4: S, 70.78; O,
6.24; N, 4.13. Found: S, 70.42; O, 6.25; N, 4.14.
d
12.4, 14.2, 20.5, 46.0, 61.1, 117.3, 118.0, 119.2, 120.9, 126.7, 127.6,
132.7, 133.3, 134.3, 136.5, 152.8, 160.6, 168.3, 198.5. Anal. Calcd for
C21H25NO4$0.25H2O: S, 70.08; O, 7.14; N, 3.89. Found: S, 70.15; O,
7.37; N, 3.99.
4.2.9. (3-Benzoyl-4-morpholinophenyl)
anone (8i). Yield 0.22 g (57%), mp 137e138 ꢁC, light yellow pow-
der. IR (ATR): 1654, 1620, 1587, 1480, 1447 cmꢀ1 1H NMR
(500 MHz, CDCl3) 3.02e3.10 (m, 4H, N(CH2)2), 3.31e3.38 (m, 4H,
(2-hydroxyphenyl)meth-
;
d
4.2.14. Ethyl
5-(2-hydroxybenzoyl)-2-(pyrrolidin-1-yl)benzoate
O(CH2)2), 6.90 (ddd, J¼8.0, 7.3, 1.0 Hz, 1H, H-50), 7.06 (dd, J¼8.4,
1.0 Hz, 1H, H-30), 7.10 (d, J¼8.5 Hz, 1H, H-3), 7.46 (t, J¼7.8 Hz, 2H,
Hm), 7.50 (ddd, J¼8.4, 7.3, 1.4 Hz, 1H, H-40), 7.60 (tt, J¼7.4, 1.3 Hz,
1H, Hp), 7.65 (dd, J¼8.0, 1.4 Hz, 1H, H-60), 7.80 (dd, J¼8.2, 1.3 Hz, 2H,
Ho), 7.82 (d, J¼2.1 Hz, 1H, H-6), 7.87 (dd, J¼8.5, 2.1 Hz, 1H, H-4),
(8n). Yield 0.20 g (59%), mp 84e85 ꢁC, yellowish powder. IR (ATR):
1699, 1619, 1582, 1538, 1511, 1478, 1444, 1416 cmꢀ1
(400 MHz, CDCl3)
;
1H NMR
1.38 (t, J¼7.1 Hz, 3H, Me), 1.92e2.08 (m, 4H,
d
2CH2), 3.27e3.44 (m, 4H, N(CH2)2), 4.35 (q, J¼7.1 Hz, 2H, OCH2),
6.80 (d, J¼8.9 Hz, 1H, H-3), 6.89 (ddd, J¼8.0, 7.4, 1.0 Hz, 1H, H-50),
7.06 (dd, J¼8.3, 1.0 Hz, 1H, H-30), 7.47 (ddd, J¼8.3, 7.4, 1.6 Hz, 1H, H-
40), 7.66 (dd, J¼7.9, 1.6 Hz, 1H, H-60), 7.75 (dd, J¼8.9, 2.2 Hz, 1H, H-4),
8.07 (d, J¼2.2 Hz, 1H, H-6), 11.93 (s, 1H, OH); 13C NMR (126 MHz,
11.89 (s, 1H, OH); 13C NMR (126 MHz, CDCl3)
d 51.6, 66.1, 117.2,
118.4, 118.7, 119.2, 128.4, 130.0, 130.57, 130.60, 132.8, 133.1, 133.44,
133.46, 136.1, 136.4, 153.9, 163.0, 197.2, 199.2. Anal. Calcd for
C
24H21NO4: S, 74.40; O, 5.46; N, 3.62. Found: S, 74.23; O, 5.14; N,
CDCl3) d 14.3, 25.9, 51.0, 61.2, 113.3, 116.4, 118.2, 118.4, 119.7, 124.2,
3.59.
132.8, 133.6, 134.5, 135.2, 150.1, 162.6, 168.1, 198.2. Anal. Calcd for
20H21NO4$0.25H2O: S, 69.85; O, 6.30; N, 4.07. Found: S, 69.84; O,
C
4.2.10. (3-Benzoyl-4-morpholinophenyl) (2-hydroxy-5-
methylphenyl)methanone (8j). Yield 0.20 g (50%), mp 152e153 ꢁC,
light yellow powder. IR (ATR): 1656, 1630, 1581, 1552, 1494, 1479,
6.32; N, 4.30.
4.2.15. Ethyl
5-(2-hydroxy-5-methylbenzoyl)-2-(pyrrolidin-1-yl)
1451, 1371, 1330 cmꢀ1; 1H NMR (400 MHz, CDCl3)
d
2.28 (s, 3H, Me),
benzoate (8o). Yield 0.20 g (57%), mp 109e110 ꢁC, yellowish pow-
3.04e3.11 (m, 4H, N(CH2)2), 3.33e3.41 (m, 4H, O(CH2)2), 6.97 (d,
J¼8.4 Hz,1H, H-30), 7.10 (d, J¼8.5 Hz,1H, H-3), 7.31 (dd, J¼8.4,1.6 Hz,
1H, H-40), 7.42 (d, J¼1.6 Hz, 1H, H-60), 7.47 (t, J¼7.7 Hz, 2H, Hm), 7.60
(t, J¼7.4 Hz, 1H, Hp), 7.79e7.83 (m, 3H, H-6, Ho), 7.85 (dd, J¼8.5,
der. IR (ATR): 1694,1623,1590,1517,1478,1425,1395 cmꢀ1; 1H NMR
(500 MHz, CDCl3)
d
1.38 (t, J¼7.1 Hz, 3H, Me), 1.96e2.05 (m, 4H,
2CH2), 2.29 (s, 3H, Me), 3.33e3.39 (m, 4H, N(CH2)2), 4.35 (q,
J¼7.1 Hz, 2H, OCH2), 6.80 (d, J¼8.9 Hz, 1H, H-3), 6.96 (d, J¼8.4 Hz,
1H, H-30), 7.28 (dd, J¼8.4, 2.1 Hz, 1H, H-40), 7.45 (d, J¼2.1 Hz, 1H, H-
60), 7.75 (dd, J¼8.9, 2.2 Hz,1H, H-4), 8.08 (d, J¼2.2 Hz,1H, H-6),11.72
2.1 Hz, 1H, H-4), 11.70 (s, 1H, OH); 13C NMR (126 MHz, CDCl3)
d 20.6,
51.7, 66.2, 117.2, 118.2, 118.9, 127.8, 128.4, 130.0, 130.5, 130.7, 132.7,