K. M. Khan et al. / Bioorg. Med. Chem. 14 (2006) 344–351
349
1
1515, 1343, 1453, 843; H NMR (400 MHz, CD3OD): d
55 (100%); Anal. Calcd for C23H28O5: C, 71.85; H,
7.34. Found: C, 71.81; H, 7.33.
7.55 (d, J = 7.8 Hz, 1H, H-4), 7.33 (td, J = 7.8 Hz,
J = 1.7 Hz, 1H, H-5), 7.21 (td, J = 7.8 Hz, J = 1.7 Hz,
1H, H-4), 6.98 (d, J = 7.8 Hz, 1H, H-6), 4.17 (m, 1H,
H-7), 2.33–2.60 (m, 2H, H-2/H-20), 2.09–2.32 (m, 8H,
H-6/H-4/H-60/H-40), 1.97–2.0 (m, 4H, H-5/H-50); EIMS:
m/z 393 (11), 391 (12), 310 (5), 227 (4), 199 (100), 129 (6),
101 (14), 84 (17), 55 (35); Anal. Calcd for C19H19BrO4:
C, 58.33; H, 4.89. Found: C, 58.30; H, 4.86.
3.2.17. 3-Methoxy-4-hydroxyphenyl-2,20-methylenebis-
(5,5-dimethylcyclohexane-1,3-dione) 17. Yield: 89%;
mp: 176–178 ꢂC; Rf: 0.51 (CH2Cl2/EtOAc, 8:2); UV
(CHCl3): kmax 278 (loge = 3.48) nm; IR (KBr): mmax
3123, 1611, 1603, 1511, 1465, 1338, 846 cmꢀ1 1H
;
NMR (400 MHz, CDCl3): d 6.85 (d, J = 1.8 Hz, 1H,
H-200), 6.61 (d, J = 8.1 Hz, 1H, H-500), 6.57 (dd,
J = 8.1 Hz, J = 1.8 Hz, 1H, H-600), 4.95–5.05 (m, 1H,
H-7), 3.85 (s, 3H, OCH3), 3.74–3.80 (m, 2H, H-2/H-
20), 2.13–2.59 (m, 8H, H-4/H-6/H-40/H-60), 1.09 (s, 6H,
2· CH3), 0.99 (s, 6H, 2· CH3); EIMS: m/z 414 (14),
396 (41), 349 (4), 257 (6), 217 (37), 160 (39), 133 (20),
83 (42), 55 (38%); Anal. Calcd for C24H30O6: C, 69.54;
H, 7.30. Found: C, 69.55; H, 7.29.
3.2.13. 2-Chlorophenyl-2,20-methylenebis-(cyclohexane-
1,3-dione) 13. Yield: 4.87 g, 99.65%; mp: 199–200 ꢂC;
Rf: 0.62 (CH2Cl2/EtOAc, 8:2); UV (CHCl3): kmax 261.3
(loge = 4.11) nm; IR (KBr): mmax 3145, 2951, 1719,
1
1515, 1343, 1453, 843; H NMR (400 MHz, CDCl3): d
7.26 (d, J = 7.4 Hz, 1H, H-4), 7.18 (td, J = 7.4 Hz,
J = 1.2 Hz, 1H, H-5), 7.12 (td, J = 7.4 Hz, J = 1.2 Hz,
1H, H-4), 6.98 (d, J = 7.8 Hz, 1H, H-6), 4.17 (m, 1H,
H-7), 2.33–2.60 (m, 2H, H-2/H-20), 2.09–2.32 (m, 8H,
H-6/H-4/H-60/H-40), 1.97–2.0 (m, 4H, H-5/H-50); EIMS:
m/z 348 (5), 346 (6), 311 (3), 246 (4), 227 (3), 199 (100),
136 (10), 112 (9), 84 (16), 55 (26); Anal. Calcd
for C19H19ClO4: C, 58.33; H, 4.89. Found: C, 58.30; H,
4.88.
3.2.18.
3-Ethoxy-4-hydroxyphenyl-2,20-methylenebis-
(5,5-dimethylcyclohexane-1,3-dione) 18. Yield: 90%; mp:
182–184 ꢂC; Rf: 0.52 (CH2Cl2/EtOAc, 8:2); UV (CHCl3):
kmax 266 (loge = 3.39) nm; IR (KBr): mmax 3123, 1615,
1
1601, 1520, 1470, 1341, 841 cmꢀ1; H NMR (400 MHz,
CDCl3): d 6.66 (d, J = 2.0 Hz, 1H, H-200), 6.60 (d,
J = 8.3 Hz, 1H, H-500), 6.48 (dd, J = 8.3 Hz, J = 2.0 Hz,
1H, H-600), 4.98–5.09 (m, 1H, H-7), 3.95 (dd,
J = 13.4 Hz, J = 6.4 Hz, 2H, OCH2CH3), 3.74–3.80 (m,
2H, H-2/H-20), 2.05–2.50 (m, 8H, H-4/H-6/H-40/H-60),
1.34 (t, J = 6.4 Hz, 3H, OCH2CH3), 1.14 (s, 6H, 2·
CH3), 1.04 (s, 6H, 2· CH3); EIMS: m/z 428 (11), 414 (3)
384 (6), 364 (7), 292 (12), 257 (16), 217 (33), 160
(39), 133 (20), 83 (42), 55 (38%); Anal. Calcd
for C25H32O6: C, 70.07; H, 7.53. Found: C, 70.01; H,
7.53.
3.2.14. 3-Chlorophenyl-2,20-methylenebis-(cyclohexane-
1,3-dione) 14. Yield: 4.87 g, 99.65%; mp: 199–200 ꢂC;
Rf: 0.62 (CH2Cl2/EtOAc, 8:2); UV (CHCl3): kmax 261.3
(loge = 4.11) nm; IR (KBr): mmax 3145, 2951, 1719, 1515,
1343, 1453, 843; 1H NMR (400 MHz, CDCl3): d 7.26 (d,
J = 7.4 Hz, 1H, H-4), 7.18 (td, J = 7.4 Hz, J = 1.2 Hz,
1H, H-5), 7.12 (td, J = 7.4 Hz, J = 1.2 Hz, 1H, H-4),
6.98 (d, J = 7.8 Hz, 1H, H-6), 4.17 (m, 1H, H-7), 2.33–
2.60 (m, 2H, H-2/H-20), 2.09–2.32 (m, 8H, H-6/H-4/H-
60/H-40), 1.97–2.0 (m, 4H, H-5/H-50); EIMS: m/z 348 (5),
346 (6), 311 (3), 246 (4), 227 (3), 199 (100), 136 (10), 112
(9), 84 (16), 55 (26); Anal. Calcd for C19H19ClO4: C,
58.33; H, 4.89. Found: C, 58.35; H, 4.89.
3.2.19. 4-Methoxyphenyl-2,20-methylenebis-(5,5-dimeth-
ylcyclohexane-1,3-dione) 19. Yield: 96%; mp: 185–
186 ꢂC; Rf: 0.56 (CH2Cl2/EtOAc, 8:2); UV (CHCl3):
kmax 301 (loge = 3.45) nm; IR (KBr): mmax 3123, 1614,
3.2.15. Phenyl-2,20-methylenebis-(5,5-dimethylcyclohex-
ane-1,3-dione) 15. Yield: 98%; mp: 194–195 ꢂC; Rf:
0.61 (CH2Cl2/EtOAc, 8:2); UV (CHCl3): kmax 261
(loge = 3.37) nm; IR (KBr): mmax 3123, 2958, 1610,
1605, 1512, 1470, 1343, 839 cmꢀ1
;
1H NMR
(400 MHz, CDCl3): d 6.97 (d, J = 8.4 Hz, 2H, H-200/H-
600), 6.79 (d, J = 8.4 Hz, 2H, H-300/H-500), 5.22–5.40 (m,
1H, H-7), 3.77 (s, 3H, OCH3), 3.70–3.75 (m, 2H, H-2/
H-20), 2.26–2.45 (m, 8H, H-4/H-6/H-40/H-60), 1.20 (s,
6H, 2· CH3), 1.07 (s, 6H, 2· CH3); EIMS: m/z 398
(13), 349 (4), 273 (7), 257 (78), 227 (66), 146 (24), 117
(19), 83 (100), 55 (92%); Anal. Calcd for C24H30O5: C,
72.34; H, 7.59. Found: C, 72.31; H, 7.60.
1601, 1512, 1461, 1334, 849 cmꢀ1
;
1H NMR
(400 MHz, CDCl3): d 7.06–7.26 (m, 5H, Ar-H), 5.52–
5.54 (m, 1H, H-7), 3.69–3.80 (m, 2H, H-2/H-20), 2.23–
2.46 (m, 8H, H-4/H-6/H-40/H-60), 1.21 (s, 6H, 2·
CH3), 1.08 (s, 6H, 2· CH3); EIMS: m/z 368 (31), 253
(4), 227 (100), 171 (28), 140 (23), 102 (27), 82 (3), 55
(62%); Anal. Calcd for C23H28O4: C, 74.97; H, 7.66.
Found: C, 74.95; H, 7.65.
3.2.20. 3-Methoxyphenyl-2,20-methylenebis-(5,5-dimeth-
ylcyclohexane-1,3-dione) 20. Yield: 94%; mp: 199–
201 ꢂC; Rf: 0.53 (CH2Cl2/EtOAc, 8:2); UV (CHCl3):
kmax 277 (loge = 3.66) nm; IR (KBr): mmax 3123, 1612,
3.2.16. 4-Hydroxyphenyl-2,20-methylenebis-(5,5-dimeth-
ylcyclohexane-1,3-dione) 16. Yield: 93%; mp: 190–
192 ꢂC; Rf: 0.52 (CH2Cl2/EtOAc, 8:2); UV (CHCl3):
kmax 289 (loge = 3.95) nm; IR (KBr): mmax 3100, 1606,
1601, 1509, 1465, 1347, 844 cmꢀ1
;
1H NMR
(400 MHz, CDCl3): d 7.15 (td, J = 8.0 Hz, J = 2.0 Hz,
1H, H-500), 6.63–6.70 (m, 3H, H-200/H-400/H-600), 5.31–
5.49 (m, 1H, H-7), 3.70 (s, 3H, OCH3), 3.77 (s, 3H,
OCH3), 3.68–3.75 (m, 2H, H-2/H-20), 2.28–2.45 (m,
8H, H-4/H-6/H-40/H-60), 1.21 (s, 6H, 2· CH3), 1.07 (s,
6H, 2· CH3); EIMS: m/z 398 (38), 349 (11), 271 (100),
259 (83), 227 (90), 203 (39), 171 (29), 141 (22), 83 (30),
55 (8%); Anal. Calcd for C24H30O5: C, 72.34; H, 7.59.
Found: C, 72.35; H, 7.60.
1600, 1512, 1465, 1344, 848 cmꢀ1
;
1H NMR
(400 MHz, CDCl3): d 7.32 (d, J = 8.4 Hz, 2H, H-200/H-
600), 6.72 (d, J = 8.4 Hz, 2H, H-300/H-500), 5.06–5.10 (m,
1H, H-7), 3.68–3.80 (m, 2H, H-2/H-20), 2.15–2.27 (m,
8H, H-4/H-6/H-40/H-60), 1.04 (s, 6H, 2· CH3), 0.99 (s,
6H, 2· CH3); EIMS: m/z 384 (22), 367 (12), 292 (4),
253 (11), 227 (45), 171 (7), 140 (19), 102 (17), 82 (3),