L.C. Baldwin, M.J. Fink / Journal of Organometallic Chemistry 646 (2002) 230–238
−1
233
−
1
d=1.113 g ml , 0.012 mol) followed by 10 ml of THF
was then introduced into the addition funnel. The flask
was placed into an ice bath and the reaction mixture
allowed to cool with magnetic stirring for 15 min. The
ethylene glycol solution was added dropwise over a
period of 10 min and the reaction mixture was allowed
to stir for an additional one h at 0 °C. The bath was
removed and the solution was stirred for an additional
IR (benzene, cm ): 2964.3 (s), 2938.6 (m), 2899.9 (m),
2876.1 (s), 1462.7 (w), 1452.2 (w), 1415.2 (w), 1385.6
(w), 1367.9 (w), 1261.2 (w), 1188.1 (m), 1157.3 (w),
926.88 (w), 882.77 (s), 740.48 (s); MS (EI, 70 eV) m/z:
+
+
i
294.2 [M , 8.82%]; 251.2 [M − Pr, 100%]; 209.1
+
i
(95.66%); 161.1 [M −OP Pr , 97.15]; HRMS:
2
C H O P , Calc.: 294.1878. Found: 294.1891.
14
32
2 2
24 h. At this point no reaction had occurred. The
2.1.8. Ph P(O)CH CH (O)PPh (2c)
2
2
2
2
solution was further heated to 70 °C for 5 h and still
there was no reaction. Finally, the flask was heated at
Ph POCH CH OPPh was heated overnight, with
2 2 2 2
stirring, in a 100-ml Schlenk flask at 250 °C under
nitrogen. The resulting oily solid was dissolved in
CH Cl . Addition of pentane precipitated 0.5 g of a
1
30 °C for 9–12 h (the NEt and THF had boiled off).
3
A tan oil with a solid precipitate resulted. The sample
was put under vacuum to remove any remaining
volatiles. A white waxy oil resulted. Hexane was added
and the solid was filtered. The solid was washed with
hexane and dried on the frit. We assigned this solid as
2
2
1
white fluffy solid. Yield: 9.1%; m.p.: 263–264 °C; H-
NMR (l, CDCl ): 7.71 (m, 8H, C–Haromatic), 7.51 (t,
3
4H, C–Haromatic), 7.43 (t, 8H, C–Haromatic), 2.53 (d, 4H,
3
1
1
–CH CH –);
P{ H}-NMR (l, CDCl ): 33.5 (s);
2
2
3
t
31
1
13
1
Bu P(O)H on the basis of P-NMR, H-NMR, and
C{ H}-NMR (l, CDCl ): 132.0 (s, phenyl), 130.8 (m,
2
3
1
mass spectral analysis. Yield: 1.4 g (31%) H-NMR (l,
CDCl ): 1.25 (d, J =15.2 Hz, 2 Bu), 6.05 (d, JPH=
4
phenyl), 128.8 (m, phenyl), 22.4–21.2 (m, –CH CH –);
2 2
3
t
1
MS (EI, 70 eV) m/z: 429.1(2.38), 354.1(40.43),
353.1(100.00), 337.1(25.85), 229.1(72.78), 201.1(34.61);
HRMS: C H O P , Calc.: 430.1252. Found: 430.1252.
3
PH
3
1
28 Hz); P-NMR (l, CDCl ): 67.4 (s); MS (EI, 70 eV)
3
+
+
t
m/z 162 [M ], 106 [M −butylene], 57 ( Bu, 100%).
.1.6. Cy P(O)CH CH (O)PCy (2a)
26
24
2 2
2
2.1.9. Cy PCH CH PCy (3a)
2
2
2
2
2
2
2
2
Cy POCH CH OPCy (4.89 g, 0.011 mol) was placed
Cy P(O)CH CH (O)PCy (6.13 g, 0.013 mol) was
2
2
2
2
2 2 2 2
into a 100-ml Schlenk flask under N and, with stirring,
was heated at 250 °C for 14 h. Upon cooling, a white
solid had formed. The solid was washed and sonicated
placed into a 500-ml Schlenk flask equipped with a
reflux condenser. Xylene (250 ml) was syringed into the
2
−
1
flask, followed by HSiCl (13.6 ml, d=1.3417 g ml
,
3
with wet benzene and deionized H O, and then filtered
on a medium frit in the atmosphere. Drying at 45 °C/
0.13 mol). The mixture was heated at 155 °C for 18 h.
The xylene was removed via distillation and the flask
was heated at 120 °C for 10–20 min in vacuo. Approx-
imately 90 ml of benzene was syringed into the flask.
The mixture was cooled in a NaCl/ice bath and stirred
for 15 min. A degassed 20% NaOH solution (50 ml)
was then introduced via syringe. The bath was removed
and the mixture was stirred for an additional 6 h at r.t.
Two layers had formed. The benzene layer was cannu-
2
0
.06 mm for 10 h gave 4.56 g of the white solid
1
product. Yield: 93.3%; m.p.: 194–195 °C; H-NMR (l,
d -benzene): 2.20–0.85 (broad multiplet), 2.02 (s, –
6
3
1
1
CH CH –);
P{ H}-NMR (l, CDCl3): 51.9 (s);
2
2
1
3
1
C{ H}-NMR (l, CDCl ): 37.2–36.2 (m, P–CH ),
3
2
26.5 (t, cyclohexyl), 26.9 (d, cyclohexyl), 25.6 (s, cyclo-
hexyl), 16.0–15.0 (m, P–C–Hcyclohexyl); IR (benzene,
−
1
cm ): 2936.3 (s), 2858.7 (s), 1447.6 (w), 1265.2 (m),
153.0 (w), 854.86 (m), 824.85 (w), 735.88 (s), 705.22
lated into a dry Schlenk flask containing MgSO . The
4
1
mixture was stirred at r.t. for 6–12 h. The solution was
then filtered and the solvent removed in vacuo yielding
5.12 g of a crude white solid. Sublimation at 135 °C/
0.06 mm gave 4.61 g of a pure white product. Yield:
+
(
s); MS (EI, 70 eV) m/z: 454.3 [M , 9.62%], 371.2
+
[
[
M −Cy, 87.98%], 290.1(39.8), 289.1(100.00%), 241.2
M −OPCy , 81.71%], 207.1 (16.21%); HRMS:
+
2
1
C H O P , Calc.: 454.3130. Found: 454.3117.
81%; m.p.: 96–97 °C lit. [16a] 96–97 °C; H-NMR (l,
2
6
48
2 2
31
1
d6-benzene) 2.0–1.0 (broad m); P{ H}-NMR (l, d -
6
i
i
2
.1.7. Pr P(O)CH CH (O)P Pr (2b)
benzene) 1.84 (s).
2
2
2
2
i
i
Pr POCH CH OP Pr (1.27 g, 0.0043 mol) was
2
2
2
2
i
i
placed into a 25-ml Schlenk flask with a magnetic
stirring bar under nitrogen. The product was heated
with stirring at 245 °C overnight. The resulting oily
solid was crystallized from benzene/pentane to yield 1.1
2.1.10. Pr PCH CH P Pr (3b)
2
2
2
2
A 250-ml Schlenk flask, with a coiled reflux con-
denser attached, was charged with 1.0 g (0.0034 mol) of
i
i
Pr (O)PCH CH (O)P Pr in a nitrogen-filled dry box.
2
2
2
2
g of a white fluffy solid. Yield: 87%; m.p.: 105.5–
A magnetic stirring bar was placed into the flask. The
setup was then connected to a Schlenk line under
1
1
06.2 °C; H-NMR (l, d -benzene): 1.84 (d, 4H, –
6
CH CH –), 1.60– 1.45 (br m, 4H, –CH(CH ) ),
nitrogen. Toluene (50 ml) was then syringed into the
2
2
3 2
31
1
−1
1
.0–0.8 (two multiplets, 12H, –CH ); P{ H}-NMR
flask followed by HSiCl (5.0 ml, d=1.3417 g ml
,
3
3
13
1
(
l, d –benzene): 53.3 (d); C{ H}-NMR (l, d -ben-
0.050 mol). The solution was stirred 34 h at 130 °C in
an oil bath. The reaction flask was then cooled in an ice
6
6
i
zene): 26.5–25.4 (m, –CH CH –), 16.0–14.5 (m, Pr);
2
2