268 Shi et al.
TABLE 2 1H and 31P Chemical Shifts of 6a–f (TMS, CDCl3) and Coupling Constants J (Hz)
6aꢀ
6a
6bꢀ
6b
6cꢀ
6c
6d
6e
6f
0.78 (s, 3H, CH3), 0.90 (s, 3H, CH3), 3.30 (sb, 1H, OH), 3.91 (dd, 1H, 2 J P H = 20.6, 3 J H H = 11.2, CH P),
4.12–4.58 (m, 2H,CH2), 5.76 (d, 1H, 3 J P H = 10.6, CH Ar), 5.76–5.98 (m, 1H, CH C P), 6.20–6.57 (m, 3H,
CH CH CH Ar), 7.17–7.25 (m, 9H , Ar H)
0.69 (s, 3H, CH3), 1.05 (s, 3H, CH3), 3.34 (sb, 1H, OH), 3.90 (dd, 1H, 2 J P H = 19.8, 3 J H H = 10.8, CH P),
4.16–4.42 (m, 2H, CH2), 5.66 (d, 1H, 3 J P H = 10.2, CH Ar), 5.72–6.00 (m, 1H, CH C P), 6.29–6.66 (m, 3H,
CH CH CH Ar), 7.20–7.30 (m, 9H , Ar H)
2
0.75 (s, 3H, CH3), 0.89 (s, 3H, CH3), 3.25 (sb, 1H, OH), 3.91 (dd, 1H, J P H = 20.2, 3 J H H = 9.4, CH P),
4.20–4.62 (m, 2H, CH2), 5.80 (d, 1H,3 J P H = 9.9, CH Ar), 5.76–5.98 (m, 1H, CH C P), 6.20–6.57 (m, 3H,
CH CH CH Ar), 7.06–7.26 (m, 9H, Ar H). δ 31P: 14.83
0.70 (s, 3H, CH3), 1.08 (s, 3H, CH3), 3.10 (sb, 1H, OH), 3.92 (dd, 1H, 2 J P H = 18.6, 3 J H H = 10.0, CH P),
4.26–4.70 (m, 2H, CH2), 5.65 (d, 1H, 3 J P H = 10.4, CH Ar), 5.72–6.00 (m, 1H, CH C P), 6.29–6.66 (m, 3H,
CH CH CH Ar), 7.08–7.39 (m, 9H , Ar H). δ 31P: 13.26
0.76 (s, 3H, CH3), 0.92 (s, 3H, CH3), 2.90 (sb, 1H, OH), 3.89 (dd, 1H, 2 J P H = 23.4, 3 J H H = 10.8, CH P),
4.28–4.46 (m, 2H, CH2), 5.72 (d, 1H, 3 J P H = 10.4, CH Ar), 5.78–5.98 (m, 1H, CH C P), 6.20–6.57 (m, 3H,
CH CH CH Ar), 7.00–7.36 (m, 9H , Ar H)
0.72 (s, 3H, CH3), 1.05 (s, 3H, CH3), 3.28 (sb, 1H, OH), 3.99 (dd, 1H, 2 J P H = 19.8, 3 J H H = 10.8, CH P),
4.20–4.52 (m, 2H, CH2), 5.64 (d, 1H, 3 J P H = 10.3, CH Ar), 5.72–6.12 (m, 1H, CH C P), 6.24–6.76 (m, 3H,
CH CH CH Ar), 7.08–7.40 (m, 9H , Ar H)
0.76 (s, 3H, CH3), 1.10 (s, 3H, CH3), 3.08 (sb, 1H, OH), 3.89 (dd, 1H, 2 J P H = 19.2, 3 J H H = 11.7, CH P),
4.18–4.56 (m, 2H, CH2), 5.80 (d, 1H, 3 J P H = 10.4, CH Ar), 5.89–6.02 (m, 1H, CH C P), 6.40–6.78 (m, 3H,
CH CH CH Ar), 7.15–7.27 (m, 9H , Ar H)
0.75 (s, 3H, CH3), 1.08 (s, 3H, CH3), 3.22 (sb, 1H, OH), 3.82 (dd, 1H, 2 J P H = 18.6, 3 J H H = 11.0, CH P),
4.21–4.67 (m, 2H, CH2), 5.55 (d, 1H, 3 J P H = 11.0, CH Ar), 5.82–5.92 (m, 1H, CH C P), 6.58–6.90 (m, 3H,
CH CH CH Ar), 7.10–7.45 (m, 9H , Ar H)
0.72 (s, 3H, CH3), 1.04 (s, 3H, CH3), 3.38 (sb, 1H, OH), 3.86 (dd, 1H, 2 J P H = 19.4, 3 J H H = 10.6, CH P),
4.14–4.42 (m, 2H, CH2), 5.60 (d, 1H, 3 J P H = 10.4, CH Ar), 5.78–5.96 (m, 1H, CH C P), 6.50–6.71 (m, 3H,
CH CH CH Ar), 7.11–7.36 (m, 9H , Ar H)
isomers were received first and then the cis isomers
(Tables 1 and 2).
General Procedure for the Synthesis of
4-Aryl-5,5-dimethyl-1,3,2-dioxaphosphinane
2-Oxides (5)
IR and MS of 6a. IR (KBr, cm−1): 3336 (sb, OH),
2947, 1677 (s), 1489 (s), 1261 (s, P O), 1104, 1050,
949 (s, P O C) EI-MS (m/e): 418 (22.3%), 420 (M+,
3:1), 401 (69.8%), 403 (23.3%), 273 (49.1%), 275,
256, 245 (82.4%), 227, 193 (84.3%), 171 (94.7%), 145
(96.3%), 125 (100%), 107, 91, 77, 63, 56.
Compound 4 (0.1 mol) and 1,2-dichloroethane
(30 ml) were added into a 100-ml reaction flask, the
solution of 0.1 mol of PCl3 in 20 ml of 1,2-dichl-
oroethane was added dropwise with cooling in ice.
The mixture was then stirred at 5–10◦C for 2 h,
0.1 mol of anhydrous ethanol in 10 ml of 1,2-dichl-
oroethane was added dropwise at room temperature,
and the mixture was refluxed for 1–1.5 h and evap-
orated at reduced pressure. The residual solid was
recrystallized from toluene to afford the pure prod-
uct as white crystal. 5a: Ar: Ph, yield: 83%, m.p. 182–
183◦C. 5b: Ar: 4-ClPh, yield: 91%, m.p. 179–180◦C.
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ethyl acetate (1:2–4, v/v) as the eluent. First, the trans
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