Y.B. Kiran et al. / European Journal of Medicinal Chemistry 43 (2008) 885e892
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1
Anal. Calcd for (C17H26O6P2) (%): C, 52.55; H, 6.75. Found:
C, 52.61; H, 6.78.
(Pe*Caliphatic); 31P NMR (CDCl3) d 23.81, ꢀ5.68; H NMR
(acetone-d6) d 8.05e7.53 (m, 4H, ArH), 4.35, 4.10 [(d,
J ¼ 10.5, 14.7 Hz), 1H, He*Ce], 3.47e3.28 (m, 8H, 4 ꢁ e
CH2e), 2.59e1.53 (m, 10H, Ne(C2H5)2), 1.43, 0.98 (2s,
6H, 2 ꢁ CH3) and 1.42, 0.96 (2s, 6H, 2 ꢁ CH3); 13C NMR (ac-
etone-d6) d 79.24 and 78.17 (2JCP(4) ¼ 5.7 and 6.9 Hz, C-4 and
C-40), 46.15 (C-5 and C-50), 78.93 and 77.68 (2JCP(6) ¼ 8.1 and
7.5 Hz, C-6 and C-60), 23.63, 22.45, 22.33 and 22.20
(4 ꢁ CH3), 34.46, 34.19 (*C), 136.31 (C-100), 128.17 (C-200
and C-600), 115.73 (C-0000 and C-500), 153.97 (C-400), 46.22
(Ne(CH2e)2), 13.81 (2 ꢁ -CH3). Anal. Calcd for
(C21H35NO6P2) (%): C, 54.90; H, 7.68. Found: C, 54.97; H,
7.69.
4.1.1.2. Bis-(5,5-dimethyl-2-oxo-2l5-[1,3,2]-dioxaphosphinan-
2-yl)-4-chlorophenylmethane (7b). Yield: 78%; mp 215e
217 ꢂC; IR (KBr) nmax 1227 (P]O), 763 cmꢀ1 (Pe
*Caliphatic); 31P NMR (CDCl3) d 14.66, ꢀ5.26; 1H NMR
(acetone-d6) d 8.05e7.53 (m, 4H, ArH), 4.35, 4.10 [(d,
JPH ¼ 10.5, 14.7 Hz), 1H, He*Ce], 3.47e3.28 (m, 8H,
4 ꢁ eCH2e), 1.43, 0.98 (2s, 6H, 2 ꢁ CH3) and 1.42, 0.96
(2s, 6H, 2 ꢁ CH3); 13C NMR (acetone-d6) d 78.41 and 78.17
2
(d, JCP(4) ¼ 6.7 and 6.8 Hz, C-4 and C-40), 46.15 (C-5 and
2
C-50), 77.93 and 76.67 (d, JCP(6) ¼ 7.1 and 6.5 Hz, C-6 and
C-60), 21.24, 21.17, 20.79 and 20.28 (4 ꢁ CH3), 32.41, 31.92
(*C), 129.65 (C-100), 128.83 (C-200 and C-600), 131.52 (C-300
and C-500), 138.83 (C-400); FABMS m/z (%): 422 (13)
4.1.1.6. Bis-(5,5-dimethyl-2-oxo-2l5-[1,3,2]-dioxaphosphinan-
2-yl)-pyridylmethane (7f). Yield: 72%; mp 165e166 ꢂC; IR
(KBr) nmax 1243 (P]O), 712 cmꢀ1 (Pe*Caliphatic); 31P
NMR (CDCl3) d 15.62, ꢀ8.14; 1H NMR (acetone-d6)
d 8.49e7.16 (m, 4H, ArH), 4.61, 4.23 [(d, JPH ¼ 16.8,
17.5 Hz), 1H, He*Ce], 3.69e3.08 (m, 8H, 4 ꢁ eCH2e),
0.77, 0.68 (2s, 6H, 2 ꢁ CH3) and 0.69, 0.67 (2s, 6H,
ꢃ
[M þ 2], 420 (34) [Mþ ], 392 (32), 350 (59), 322 (35), 273
(54), 232 (40), 167 (27), 149 (29), 102 (100). Anal. Calcd
for (C17H25ClO6P2) (%): C, 48.27; H, 5.96. Found: C, 48.35;
H, 6.01.
4.1.1.3. Bis-(5,5-dimethyl-2-oxo-2l5-[1,3,2]-dioxaphosphinan-
2-yl)-4-methylphenylmethane (7c). Yield: 85%; mp 152e
154 ꢂC; IR (KBr) nmax 1237 (P]O), 765 cmꢀ1 (Pe*Caliphatic);
31P NMR (CDCl3) d 20.14, 15.52; 1H NMR (acetone-d6)
d 7.51e7.12 (m, 4H, ArH), 4.71, 4.60 [(d, JPH ¼ 9.7, 11.4)
1H, He*C], 4.43e4.37 (m, 4H, 2 ꢁ eCH2e) and 4.18e3.98
(m, 4H, 2 ꢁ eCH2e), 2.94 (m, 3H, Ar-CH3), 1.35, 0.99 (2s,
6H, 2 ꢁ CH3) and 1.3, 0.98 (2s, 6H, 2 ꢁ CH3); 13C NMR (ac-
etone-d6) d 79.32 and 78.29 (2JCP(4) ¼ 8.9 and 7.7 Hz, C-4 and
C-40), 45.75 (C-5 and C-50), 75.89 and 76.24 (2JCP(6) ¼ 8.1 and
7.6 Hz, C-6 and C-60), 21.07, 20.23, 20.17 and 20.07
(4 ꢁ CH3), 34.36, 33.17 (*C), 143.27 (C-100), 129.40 (C-200
and C-600), 131.15 (C-300 and C-500), 139.15 (C-400), 21.8 (Ar-
CH3). Anal. Calcd for (C18H28O6P2) (%): C, 53.70; H, 7.02.
Found: C, 53.75; H, 7.07.
2 ꢁ CH3); 13C NMR (CDCl3):
d
79.24 and 78.17
(2JCP(4) ¼ 5.7 and 6.9 Hz, C-4 and C-40), 46.15 (C-5 and C-
50), 78.93 and 77.68 (2JCP(6) ¼ 8.1 and 7.5 Hz, C-6 and C-
60), 23.08, 22.85, 22.38 and 22.07 (4 ꢁ CH3), 34.46, 34.19
(*C), 137.32 (C-100), 128.47 (C-200 and C-00), 149.53 (C-300
and C-500). Anal. Calcd for (C17H25NO8P2) (%): C, 49.36; H,
6.47. Found: C, 49.43; H, 6.51.
4.1.1.7. Bis-(5,5-dimethyl-2-oxo-2l5-[1,3,2]-dioxaphosphinan-
2-yl)-styrylmethane (7g). Yield: 73%; mp 167e168 ꢂC; IR
(KBr) nmax 1237 (P]O), 742 cmꢀ1 (Pe*Caliphatic); 31P
NMR (CDCl3) d 12.65, ꢀ4.27; 1H NMR (acetone-d6)
d 7.82e6.03 (m, 5H, AreH), 4.20, 3.80 [(d, JPH ¼ 5.7,
6.1 Hz) 1H, He*Ce], 3.47e3.25 (m, 8H, 4 ꢁ eCH2e),
1.02, 0.94 (2s, 6H, 2 ꢁ CH3) and 1.00, 0.91 (2s, 6H,
2 ꢁ CH3). The signals for the vinyl unit CH]bCHe are not
a
4.1.1.4. Bis-(5,5-dimethyl-2-oxo-2l5-[1,3,2]-dioxaphosphinan-
2-yl)-3-nitrophenylmethane (7d). Yield: 77%; mp 178e
179 ꢂC; IR (KBr) nmax 1251 (P]O), 753 cmꢀ1 (Pe*Caliphatic);
31P NMR (CDCl3) d 18.50, ꢀ5.55; 1H NMR (acetone-d6)
d 8.35e7.47 (m, 4H, ArH), 5.25, 4.94 [(d, JPH ¼ 18.7,
11.8 Hz), 1H, He*Ce], 4.08e3.07 (m, 8H, 4 ꢁ eCH2e),
1.29, 0.98 (2 s, 6H, 2 ꢁ CH3) and 1.17, 0.86 (2 s, 6H,
2 ꢁ CH3); 13C NMR (acetone-d6) d 80.02 and 79.29 (d,
2JCP(4) ¼ 9.9 and 8.5 Hz, C-4 and C-40); 46.67 (C-5 and C-50),
76.89 and 75.94 (2JCP(6) ¼ 7.8 and 9.3 Hz, C-6 and C-60),
22.17, 21.12, 21.04 and 21.01 (4 ꢁ CH3), 35.36, 33.29 (*C),
148.45 (C-100), 123.02 (C-200); 118.45 (C-300), 123.31 (C-400),
129.38 (C-500), 139.95 (C-600); FABMS m/z (%): 437 (16)
[Mþ þ 4Hþ], 433 (9) [Mþ], 391 (18), 302 (89), 289 (18), 284
(8), 154 (100), 136 (59). Anal. Calcd for (C16H25NO6P2) (%):
C, 47.09; H, 5.81. Found: C, 47.14; H, 5.92.
distinguishable due to their merging with aromatic hydrogen
signals; 13C NMR (CDCl3) d 81.79 and 79.27 (2JCP(4) ¼ 9.7
and 8.9 Hz, C-4 and C-40), 47.25 (C-5 and C-50), 78.93 and
77.68 (2JCP(6) ¼ 8.1 and 7.5 Hz, C-6 and C-60), 22.15, 21.97,
21.92 and 21.86 (4 ꢁ CH3), 35.54 and 35.19 (J ¼ 7.9 and
6.3 Hz, C), 129.17 (aC), 151.87 (bC), 139.12 (C-100), 127.92
*
(C-200 and C-600), 131.24 (C-300 and C-500), 130.31 (C-400).
Anal. Calcd for (C19H28O6P2) (%): C, 55.05; H, 6.81. Found:
C, 55.13; H, 6.87.
4.1.1.8. Bis-(5,5-dimethyl-2-oxo-2l5-[1,3,2]-dioxaphosphinan-
2-yl)-1-propenylmethane (7h). Yield: 68%; mp 161e163 ꢂC;
IR (KBr) nmax 1239 (P]O), 757 cmꢀ1 (Pe*Caliphatic). 31P
1
NMR (CDCl3) d 22.44, 13.43; H NMR (acetone-d6) d 6.99
(1H, ebCH ), 5.82 (1H, aCHe), 4.21, 3.80 [(d, JPH ¼ 5.9,
6.4 Hz) 1H, He*Ce], 3.47e3.25 (m, 8H, 4 ꢁ eCH2e), 1.78
c
(3H, CH3e), 1.09, 0.98 (2s, 6H, 2 ꢁ CH3) and 1.08, 0.89
4.1.1.5. Bis-(5,5-dimethyl-2-oxo-2l5-[1,3,2]-dioxaphosphinan-
2-yl)-4-N,N-dimethyl phenylmethane (7e). Yield: 77%; mp
178e179 ꢂC; IR (KBr) nmax 1261 (P]O), 753 cmꢀ1
(2s, 6H, 2 ꢁ CH3); 13C NMR (acetone-d6) d 79.24 and 78.17
(2JCP(4) ¼ 5.7 and 6.9 Hz, C-4 and C-40), 46.15 (C-5 and
C-50), 78.93 and 77.68 (2JCP(6) ¼ 8.1 and 7.5 Hz, C-6 and