SPECIAL FEATURES OF REACTION OF 2-(5-METHYL-2-PHENYL-2H-1,2,3-...
307
expansion of the six-membered ring to a seven-membered
with a high regioselectivity (only 1,3,2-dioxaphosphepine
was obtained).
washed with a mixture of hexane and dichloromethane
and dried in a vacuum. Yield 89%. IR spectrum, ν, cm–1:
3412, 3119, 3058, 2985, 2940, 2874, 2696, 1752, 1690,
1603, 1562, 1545, 1494, 1477, 1452, 1388, 1370, 1268,
1239, 1207, 1156, 1113, 1076, 1056, 1021, 925, 851, 831,
2-(5-Methyl-2-phenyl-2H-1,2,3-diazaphosphol-
4-yl)-4H-benzo[d]-1,3,2-dioxaphosphorin-4-
one (I). To 2.82 g (0.010 mol) of trimethylsilyl
2-trimethylsiloxybenzoate [5] under an inert at-
mosphere was slowly added 2.77 g (0.010 mol) of
4-(dichlorophosphino)-5-methyl-2-phenyl-2H-1,2,3-
diazaphosphol. Trimethylchlorosilane was removed in
a vacuum (165–200 mm Hg) in an argon flow. The residue
was dried in a vacuum (0.1 mm Hg) and was further used
without additional purification. Yield 73%, mp 97–98°С.
IR spectrum, ν, cm–1: 3440, 3100, 3066, 3027, 3012,
2958, 2914, 1734, 1664, 1606, 1579, 1492, 1475, 1457,
1424, 1383, 1346, 1286, 1227, 1206, 1153, 1129, 1070,
1043, 1014, 960, 930, 904, 880, 869, 787, 767, 754,
1
781, 738, 703, 628, 584, 557, 512. Н NMR spectrum, δ,
ppm (J, Hz): 8.06 d. d (Н6, 1Н, 3JНCCH 7.9, 4JНCСCH 1.7),
7.68 d (Н7b, 1Н, 3JНCCH 8.2), 7.59 d.d.d (Н8, 1Н, 3JНCCH 7.4,
3JНСCH 8.0, 4JНCСCH 0.8), 7.38 d.d (Н8b, 1Н, 3JНCCH 8.1,
3JНСCH 7.3), 7.27–7.32 m (Н9b, Н7b, 2Н), 7.10 d (Н9, 1Н,
3
3JНCCH 8.2), 4.41 q (part В of АВ system, JНАHВ 7.1),
4.27 q (part А of АВ system, 3JНАHВ 7.1), 2.71 s (Н10b, 1Н),
1.33 t (Н12, 3Н, 3JНCCH 7.1), 1.18 t (Н15, 3Н, 3JНCCH 7.1).
13С NMR spectrum (the appearance of the signal in the
spectrum 13С-{1Н} is given in parentheses), δ, ppm (J, Hz):
88.62 d (d) (C4, 2JРОС 8.3); 185.34 d (s) (C5, 3JНССС 3.3);
125.88 m (d) (C5а, 3JРОСС 1.8); 131.81 br. d.d.d (d) (C6,
3
5
1
1JНС 166.3, JНССС 8.4, JРОСССС 1.4); 126.63 d.d.d (d)
748, 686, 656, 632, 586, 543, 527, 496, 473. Н NMR
(C7, 1JНС 164.4, 3JНССС 8.2, 5JРОСССС 1.0); 137.00 d.d.d.d
spectrum, δ, ppm (J, Hz): 8.05 d. d (Н5, 1Н, 3JНCCH 8.0,
4JНCСCH 1.9), 7.30 d.d (Н6, 1Н, 3JНCCH 7.6, 3JНСCH 6.6),
7.59 d.d.d (Н7, 1Н, 3JНCCH 7.6, 3JНСCH 8.3, 4JНCСCH 1.6),
7.10 d (Н8, 1Н, 3JНCCH 8.2), 7.66 d.d (Н7b, 1Н, 3JНCCH 8.5,
4JPNСCH 1.6), 7.38 d.d (Н8b, 1Н, 3JНCCH 8.6, 3JНСCH 6.7),
(s) (C8, JНС 164.1, JНССС 8.9, JНСС 2.0, JНСС 1.2);
122.25 d.d.d.d (d) (C9, 1JНС 159.8, 3JРОСС 5.7, 2JНСС 2.3,
2JНСС 1.0); 149.20 d.d.d.d (s) (C9а, 2JРОС 8.4, 3JНССС 7.0,
1
3
2
2
2
3
3JНССС 5.2, JНСС 2.3); 163.00 d.t (d) (C10, JРОСС 7.4,
3JНССС 3.4); 162.04 d.t (d) (C13, 3JРОСС 8.3, 3JНССС 3.4);
7.20 t.d (Н9b, 1Н, 3JНCCH 7.6, 4JНССCH 2.0), 2.69 с (Н10b
,
63.73 t.q (s) (C11, JНС 149.5, JНСС 4.4); 63.52 t.q (s)
1
2
1Н). 13С NMR spectrum (the appearance of the signal
in the spectrum 13С-{1Н} is given in parentheses), δ,
ppm (J, Hz): 162.28 d.d (br.s) (C4, 2JРОС 8.5, 3JНCCС 8.4);
116.10 d.d (m) (C4a, 3JРОСС 11.7, 5JРСРОСС 3.3); 124.58 d.d
(s) (C5, 1JНС 164.7, 3JНССС 7.7); 131.53 d.d.d (br.s) (C6,
1JНС 166.4, 3JНССС 8.4, 2JНСС 2.1); 120.27 d.d.d (s) (C7,
1JНС 159.0, 3JНССС 7.7, 2JНСС 1.4); 136.87 d.d.d (s) (C8,
(C14, 1JНС 149.5, 2JНСС 4.4); 13.80 q.t (с) (C12, 1JНС 127.4,
2JНСС 2.6); 13.71 q.t (с) (C15, JНС 127.7, JНСС 2.6);
132.13 d.d.q (d.d) (C4b, 1JРС 199.2, 1JРС 50.3, 3JНССС 2.8,
3JНССС 2.8); 158.90 d.d.q (d.d) (C5b, 2JРСС 11.0, 2JРСС 5.0,
1
2
2JНСС 6.6); 142.60 t.d (d) (C6b, JРNС 9.0, JНСС 2.8);
120.57 d.d.d.d (d) (C7b, 1JНС 162.2, 3JPNCС 9.7, 3JНССС 7.9,
2JНСС 1.4); 129.54 d.d.d (s) (C8b, 1JНС 162.3, 3JНССС 8.1,
2JНСС 1.1); 128.13 d.t (s) (C9b, 1JНС 161,4, 3JНССС 7.5);
2
2
3
2
1JНС 161.8, JНССС 9.1, JНСС 1.9); 157.68 m (d) (C8а,
2JРОС 8.0); 148.48 d.d.q (d.d) (C4b, 1JРС 63.5, 1JРС 56.1,
3JНССС 2.5); 158.38 d.d.q (d.d) (C5b, 2JРСС 23.8, 2JРСС 5.5,
15.63 q (s) (C10b, JНС 129.6). 31Р-{1H} NMR spec-
1
trum, δ, ppm (J, Hz): 251.30 br.d (2JРСР 76.3), 14.9 d
(2JРСР 76.3). Mass spectrum, m/z: 516 [M]+·, 487 [M –
С2Н4], 470 [M – OEt + H], 424 [M – 2 C2H4], 398
[M –C(C(O)OEt)2], 313 [M – C(C(O)OEt)2 – C(O)], 121
[C6H4OHC(O)], 92 [C6H4O], 77 [C6H5].
2
2JНСС 6.4); 155.43 m (d) (C6b, JРNС 7.3); 120.55 d.d.d
(d) (C7b, 1JНС 161.8, 3JPNCС 9.5, 3JНССС 7.3); 129.55 d.d
1
3
(s) (C8b, JНС 161.0, JНССС 8.0); 127.78 d.t (s) (C9b,
1JНС 162.5, 3JНССС 7.3); 15.41 q.d (d) (C10b, 1JНС 128.8,
3JРССС 8.4). 31Р-{1H} NMR spectrum, δ, ppm (J, Hz):
238.5 br.d (2JРСР 16.6), 156.3 d (2JРСР 16.6). Mass
spectrum, m/z: 342 [M]+·.
NMR spectra were registered on spectrometers Bruker
MSL-400 (31Р, 162.0 MHz), Bruker Avance-600 (1Н,
600 MHz; 13С, 13С-{1Н}, DEPT, 150.9 MHz) in CDCl3.
As internal reference served HMDS (1Н) or solvent (13С);
Н3РО4 was used as external reference (31Р). IR spectra
were recorded on a spectrophotometer Bruker Vector-22
from mulls of the samples in mineral oil. Mass spectra
were measured on an instrument DFS Thermo Electron
Corporation (ionizing electrons energy 70 eV, ion source
2-(5-Methyl-2-phenyl-2H-1,2,3-diazaphosphol-
4-yl)-2,5-dioxo-4,4-bis(diethyldicarbonyl)benzo[2,3-
f]-1,3,2-dioxaphosphepine (II). To 1.71 g (0.005 mol)
of compound I in 10 ml of dichloromethane under an
inert atmosphere at cooling to –10°С was added 0.87 g
(0.005 mol) of diethyl mesoxalate. On removing the sol-
vent light-yellow oily substance was obtained that was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 48 No. 2 2012