Kumar et al.
(E)-15. Yield 0.51 g (80%); mp 165-167 °C; IR (KBr, cm-1
JOCArticle
(E)-12. Yield (E þ Z) 0.63 g (84%); mp 192-194 °C; IR (KBr,
cm-1) 3108, 2965, 2886, 1781, 1632, 1566, 1476, 1426, 1285,
1221, 1049, 995; 1H NMR (400 MHz, CDCl3) δ 0.63 and 0.92 (2
s, 6H), 3.55-3.61 and 4.09-4.14 (2 m, 4H), 6.61 (d, 3J = 8.7 Hz,
1H), 6.84 (d, 3J = 10.1 Hz, 1H), 7.25-7.40 (m, 7H), 7.96 (d, 3J
= 10.1 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 21.2, 21.6, 32.3
(d, 3J=6.0 Hz), 75.2, 75.3, 101.9 (d, 1J(P-C)=201.0 Hz), 115.9,
117.5, 121.0, 121.1, 122.1, 127.3, 128.1, 128.9, 129.3, 130.9,
)
3077, 2961, 2882, 1634, 1597, 1557, 1476, 1447, 1383, 1289, 1221,
1051, 997; 1H NMR (400 MHz, CDCl3) δ 0.66 and 0.94 (2 s, 6H),
2.29 (s, 3H), 3.60 (dd, 3J=16.0 Hz, 2J ∼ 11.1 Hz, 2H), 4.08-4.13
(ddft, 3J=2J ∼ 11.1 Hz, 2H), 6.75 -7.39 (m, 9H), 7.77 (s, 1H);
13C NMR (100 MHz, CDCl3) δ 18.5, 21.2, 21.7, 32.3 (d, 3J = 5.9
Hz), 75.1, 75.2, 98.1 (d, 1J(P-C) = 202.7 Hz), 115.9, 117.8, 117.83,
121.6, 123.4, 123.7,126.9, 128.0,131.27,131.32 134.4, 134.5, 138.3,
152.6, 159.9 (d, 2J=34.5 Hz); 31P NMR (160 MHz, CDCl3) δ 16.4;
LC-MS m/z 383 [Mþ1]þ. Anal. Calcd for C22H23O4P: C, 69.10; H,
6.06. Found: C, 69.18; H, 6.10.The other isomer [δ(P) 13.0] was
present in the reaction mixture, but we did not succeed in isolating
it in a pure state.
131.0, 132.8, 133.96, 134.0, 151.8, 159.0 (d, J=35.0 Hz); 31P
2
NMR (160 MHz, CDCl3): δ 12.5; LC-MS m/z 447 [M]þ, 449 [M
þ2]þ. Anal. Calcd for C21H20O4PBr: C, 56.39; H, 4.51. Found:
C, 56.33; H, 4.52. X-ray structure was determined for this
compound.
(Z)-12. Mp 182-185 °C; IR (KBr, cm-1) 2967, 2924, 1883,
(E)-16. Yield (EþZ) 0.44 g (59%); mp 201-203 °C; IR (KBr,
cm-1) 3077, 2963, 1626, 1595, 1572, 1555, 1445, 1370, 1285,
1221, 1055, 1005; 1H NMR (400 MHz, CDCl3) δ 0.66 and 0.92 (2
s, 6H), 3.57-3.63 and 4.06-4.11 (2 m, 4H), 6.82-7.46 (m, 14H),
7.89 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 21.2, 21.6, 32.3 (d, 3J
1
1748, 1628, 1570, 1476, 1422, 1254, 1213, 1057, 1005; H NMR
(400 MHz, CDCl3) δ 0.79, 1.18 (2 s, 6H), 3.68-3.92 (m, 4H), 6.31
(d, 3J = 10.0 Hz, 1H), 6.65 (dd, 3J = 10.0 Hz, 5J = 3.1 Hz, 1H),
7.07-7.41 (m, 8H); 13C NMR (100 MHz, CDCl3) δ 21.0, 22.0,
32.3 (d, 3J=6.0 Hz), 75.87, 75.94, 101.9 (d, 1J(P-C)=180.7 Hz),
115.8, 117.9, 119.8, 119.9, 121.8, 127.72, 127.74, 128.8, 129.1,
129.3, 130.98, 131.0, 133.5, 133.97, 134.0, 151.9, 158.1; 31P
NMR (160 MHz, CDCl3) δ 9.2;. LC-MS m/z 447 [M]þ, 449
[M þ 2]þ. Anal. Calcd for C21H20O4PBr: C, 56.39; H, 4.51.
Found: C, 56.44; H, 4.52. X-ray structure was determined for this
compound.
(E)-13 (Isomer Purity ∼95%). Yield (E þ Z) 0.50 g (60%); mp
172-174 °C; IR (KBr, cm-1) 3104, 2959, 2884, 1773, 1632, 1563,
1474, 1422, 1285, 1221, 1049, 995; 1H NMR (400 MHz, CDCl3)
δ 0.63 and 0.92 (2 s, 6H), 3.55-4.14 (m, 4H), 6.50 (d, 3J=8.7 Hz,
1H), 6.82 (d, 3J ≈ 10.2 Hz, 1H), 7.26-7.49 (m, 7H), 7.94 (d, 3J ≈
10.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 21.2, 21.6, 32.2 (d,
3J=6.0 Hz), 75.15, 75.21, 101.8 (d, 1J(P-C)=201.0 Hz), 117.8,
120.8, 122.6, 127.2, 128.1, 128.7, 130.9, 133.9, 135.2, 138.7,152.6,
159.0 (d, 2J = 34.0 Hz); 31P NMR (160 MHz, CDCl3) δ 14.8; LC-
MS m/z 495 [Mþ1]þ. Anal. Calcd for C21H20O4PI: C, 51.03; H,
4.08. Found: C, 51.43; H, 4.10.
1
= 5.0 Hz), 75.1, 75.2, 100.4 (d, J(P-C) = 202.0 Hz), 116.2,
118.8, 120.4, 123.3, 125.9, 127.0, 128.0, 128.5, 128.6, 128.7,
128.8, 131.0, 134.3, 136.6, 142.5, 153.1, 159.6 (d, 2J=35.0 Hz);
31P NMR (160 MHz, CDCl3) δ 15.9; LC-MS m/z 445 [M þ 1]þ.
Anal. Calcd for C27H25O4P: C, 72.96; H, 5.67. Found: C, 72.87;
H, 5.68.
(Z)-16. Mp 167-169 °C; IR (KBr, cm-1) 3057, 2975, 2878,
1620, 1595, 1566, 1441, 1364, 1265, 1057, 1005, 988, 945; 1H NMR
(400 MHz, CDCl3) δ 0.80 and 1.21 (2 s, 6H), 3.73-3.91 (m, 4H),
6.26 (s, 1H), 6.99-7.42 (m, 14H); 13C NMR (100 MHz, CDCl3) δ
21.1, 22.1, 32.4 (d, 3J ∼ 6.0 Hz), 75.95, 76.01, 100.7 (d, 1J(P-C) =
181.1 Hz), 116.6, 117.4, 117.5, 120.3, 123.3, 126.0, 127.5, 128.5,
128.7, 128.8, 131.0, 131.1, 131.2, 134.4, 134.5, 136.4, 142.8, 153.3,
158.7; 31P NMR (160 MHz, CDCl3) δ 12.5; LC-MS m/z 445 [Mþ
1]þ. Anal. Calcd for C27H25O4P: C, 72.96; H, 5.67. Found: C,
72.87; H, 5.69.
(Z)-17. The procedure was similar to that for 10, but here we
used 20 mol % of PPh3 as a catalyst. Yield 0.10 g (15%); mp 201 -
203 °C; IR (KBr, cm-1) 3351, 3059, 2949, 1642, 1607, 1485,
1352, 1225, 1059, 1005, 945; 1H NMR (400 MHz, CDCl3) δ 0.77
and 1.19 (2 s, 6H), 2.57 (br d, 2J=14.8 Hz, 3J<2.0 Hz, 1H), 2.84
(dd, 2J = 14.8 Hz, 3J=5.6 Hz, 1H), 3.70-3.84 (m, 5H), 4.70 (br,
1H), 6.99-7.35 (m, 9H); 13C NMR (100 MHz, CDCl3) δ 21.0,
22.1, 32.3 (d, 3J=6.0 Hz), 33.2 (d, 3J = 10.0 Hz), 63.3, 76.1, and
(Z)-13 (Isomeric Purity ∼95%). Mp 177-179 °C; IR (KBr,
cm-1) 3057, 2967, 1624, 1593, 1566, 1476, 1420, 1244, 1211, 1057,
1
1005; H NMR (400 MHz, CDCl3) δ 0.80 and 1.19 (2 s, 6H),
3.69-3.93 (m, 4H), 6.30 (d, 3J=8.0 Hz, 1H), 6.65 (dd, 3J = 8.0 Hz,
5J = 4.0 Hz, 1H), 6.95-7.60 (m, 8H); 13C NMR (100 MHz,
CDCl3) δ 21.1, 21.6, 32.3 (d, 3J = 6.0 Hz), 75.8, 75.9, 102.3 (d, 1J
(P-C) = 180.0 Hz), 118.2, 119.6, 122.3, 126.4, 128.9, 129.3, 131.0,
134.0, 135.3, 139.4, 152.7, 158.0; 31P NMR (160 MHz, CDCl3) δ
11.4; LC-MS m/z 495 [M þ 1]þ. Anal. Calcd for C21H20O4PI: C,
51.03; H, 4.08. Found: C, 51.08; H, 4.01.
2
1
76.2 (2 d, J ∼ 7.0 Hz), 108.8 (d, J(P-C)=172.0 Hz), 116.9,
123.1, 124.9, 127.7, 128.1, 128.7, 130.1, 130.8, 130.9, 133.9,
134.0, 151.3, 160.5; 31P NMR (160 MHz, CDCl3) δ 11.1; LC-
MS m/z 387 [Mþ1]þ. Anal. Calcd for C21H23O5P: C, 65.28; H,
6.00. Found: C, 65.30; H, 5.99.
(E)-14. Yield (E þ Z) 0.47 g (70%); mp 132-134 °C; IR (KBr,
cm-1) 3042, 2961, 1632, 1578, 1553, 1474, 1412, 1260, 1231, 1096,
1061, 1003; 1H NMR (400 MHz, CDCl3) δ 0.65 and 0.94 (2 s, 6H),
3.48 (s, 3H), 3.58-3.64 and 4.08-4.13 (2 m, 4H), 6.81 (d, 3J=7.6
Hz, 1H), 6.92 (m, 3J ∼ 10.0 Hz, 1H), 7.26-7.45 (m, 7H), 7.88 (d,
3J = 9.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 21.2, 21.7, 32.3
(d, 3J=6.0 Hz), 57.4, 75.2, 75.3, 100.4 (d, 1J(P-C)=202.0 Hz),
116.2, 119.6, 119.8, 119.9, 121.2, 123.4, 127.1, 128.1, 130.6, 131.06,
131.12, 134.3, 143.3, 147.1, 159.5 (d, 2J=35.0 Hz); 31P NMR (160
MHz, CDCl3) δ 15.5; LC-MS m/z 399 [M þ 1]þ. Anal. Calcd for
C22H23O5P: C, 66.33; H, 5.82. Found: C, 66.39; H, 5.82.
(E)-18. Thiscompound isolated along with13 fromthereaction
of allene 9a with 5-iodo salicylaldehyde. Yield 0.07 g (8%); mp
214-216 °C; IR (KBr, cm-1) 3279, 3059, 2920, 1640, 1595, 1472,
1406, 1225, 1053, 1003; 1H NMR (400 MHz, CDCl3) δ 0.62 and
0.96 (2 s, 6H), 2.85 (br, 1H), 3.29-3.33 (m, 1H), 3.56-3.66 (m,
2H), 3.78-3.83 (m, 1H), 4.05 (m, 2H), 4.90-4.93 (m, 1H), 6.48-
7.69 (m, 8H); 13C NMR (100 MHz, CDCl3) δ 21.1, 21.8, 32.5 (d,
3J=6.3 Hz), 33.5, 62.9, 75.6, 75.7, 118.9, 127.4, 128.0, 128.1, 130.7,
2
130.8, 133.5, 133.9, 134.0, 151.3, 160.1 (d, J = 33.8 Hz). The
spectrum was very noisy, probably because of dehydration during
recording. Hence the position of P-C carbon was not identified.
31P NMR (160 MHz, CDCl3) δ 14.2; LC-MS: m/z 512 [M]þ. Anal.
CalcdforC21H22O5PI:C, 49.24;H, 4.33. Found:C,49.21; H, 4.25.
2. Reaction of Allene 9b with Salicylaldehydes and 2-Hydro-
xyacetophenone. Synthesis of Phosphono-chromenols (19, 20, 23,
24) and Phosphono-chromenes (21, 22). General Procedure. To a
solution of allene 9b (0.420 g, 2.08 mmol) and salicylaldehyde
(3.12 mmol) in DMSO (4 mL) was added a 10% solution of
DBU in DMSO (0.6 mL, corresponds to 0.06 g of DBU, 0.42
mmol), and the mixture was heated at 80 °C for 10-12 h. The
contents were washed with water (2 ꢀ 10 mL) and extracted with
(Z)-14. Mp 151-154 °C; IR (KBr, cm-1) 3067, 2961, 1630,
1580, 1476, 1441, 1402, 1248, 1092, 1059, 1009, 986; 1H NMR
(400 MHz, CDCl3) δ 0.78 and 1.21 (2 s, 6H), 3.79-3.94 (m, 4H),
3
3.95 (s, 3H), 6.26 (d, J = 9.6 Hz, 1H), 6.70-6.77 (m, 2H),
6.93-7.39 (m, 7H); 13C NMR (100 MHz, CDCl3) δ 21.0, 22.2,
32.2 (d, 3J=6.0 Hz), 57.4, 75.9, 76.0, 100.8 (d, 1J(P-C)=181.0
Hz), 115.6, 118.9, 119.1, 119.4, 120.9, 123.3, 127.5, 128.0,
128.8, 130.5, 131.16, 131.21, 134.55, 134.61, 143.0, 147.6, 158.1;
31P NMR (160 MHz, CDCl3) δ 12.0; LC-MS m/z 399 [Mþ1]þ.
Anal. Calcd for C22H23O5P: C, 66.33; H, 5.82. Found: C, 66.42;
H, 5.75.
5402 J. Org. Chem. Vol. 74, No. 15, 2009