SYNTHESIS OF NEW PHOSPHINES AND P-HETEROCYCLES
1759
P 6.49. C29H38N2OP. Calculated, %: C 75.00; H 8.24;
N 6.00; P 6.72.
1,5-Di-p-tolyl-3,7-di(5 -allyl-2 -ethoxybenzyl)-3,7-
5
5
dithioxo-1,5,3 ,7 -diazadiphosphacyclooctane XI.
Sulfur, 0.039 g, and 5 ml of benzene were added to
0.41 g of IX. The mixture was heated until the re-
actants dissolved. The precipitate that formed after
cooling of the reaction mixture was filtered off,
washed with acetonitrile, and dried. Yield 0.2 g (44%),
1,5-Di-p-tolyl-3,7-di(5 -allyl-2 -ethoxybenzyl)-
1,5,3,7-diazadiphosphacyclooctane IX. Paraform,
1.23 g, was added to 4.27 g of V, and the mixture was
heated on a water bath until it became homogeneous.
The resulting compound VI was dissolved in 25 ml
of ethanol, and a solution of 2.23 g of p-toluidine in
20 ml of ethanol was added. The mixture was refluxed
on a water bath for 3 h. The white precipitate was
filtered off, washed with ethanol, and crystallized
from acetonitrile. Yield of IX 2.6 g (37%), mp 198
1
mp 115 C. IR spectrum (mull in mineral oil), , cm :
792 (C Har), 1616 (C=Car), 1640 (C=C), 3080
1
(C Har). H NMR spectrum (C6D6), , ppm (J, Hz):
3
0.99 t (6H, OCH2CH3, JHH 7), 2.11 s (6H, CH3
3
C6H4), 3.24 d (4H, CH2CH=CH2, JHH 6.5), 3.36 d
2
(4H, PCH2Ar, JPH 11.75), 3.54 q (4H, OCH2CH3,
1
200 C. IR spectrum (mull in mineral oil), , cm :
2
3JHH 7), 4.04 d (4H, PCHaN, JHH 16.1), 4.21 d (4H,
1
790 (C Har), 1614 (C=Car), 1638 (C=C). H NMR
2
PCHbN, JHH 16.1), 5.00 5.10 m (4H, CH2=CH),
spectrum (DMSO-d6), , ppm (J, Hz): 1.36 t (6H,
3
5.86 6.02 m (2H, CH2=CH), 6.50 d (2H, C3Har, JHH
3
OCH2CH3, JHH 6.9), 2.06 s (6H, CH3C6H4), 2.76 s
3
8), 6.90 7.05 m (C4Har), 6.94 d (o-C6H4, JHH 8.2),
3
3
(4H, PCH2Ar), 3.31 d (4H, CH2CH=CH2, JHH 6.3),
6.67 d (m-C6H4, JHH 8.2) (total integral intensity
2
2
10H), 7.40 s (2H, C6Har). 31P NMR spectrum (DMF),
P, ppm: 45.71. Found, %: C 70.41; H 7.56; N 3.63;
P 8.57; S 9.22. C42H52N2O4P2S. Calculated, %: C
70.99; H 7.32; N 3.94; P 8.73; S 9.01.
3.76 d.d (4H, PCHaN, JHH 15.25, JPH 3.75), 3.93
4.10 m (8H, OCH2CH3, PCHeN), 4.98 5.10 m (4H,
CH2=CH), 5.85 6.00 m (2H, CH2=CH), 6.04 d (4H,
3
3
o-C6H4, JHH 8.3), 6.67 d (4H, m-C6H4, JHH 8.3),
6.91 7.19 m (6H, C6H3). 31P NMR spectrum (DMF),
P, ppm: 48.97. Found, %: C 74.93; H 7.34; N 4.67;
P 8.75. C42H52N2O2P2. Calculated, %: C 74.34; H
7.67; N 4.12; P 9.14.
REFERENCES
1. Miedaner, A., Curtis, C.J., Barkley, R.M., and
Dubois, D.L., Inorg. Chem., 1994, vol. 33, no. 24,
p. 5482.
1,5-Di-p-tolyl-3,7-di(5 -allyl-2 -ethoxybenzyl)-3,7-
5
5
dioxo-1,5,3 ,7 -diazadiphosphacyclooctane X. To
a suspension of 0.2 g of IX in 3 ml of acetone, we
added a solution of 0.1 g of 33% H2O2 in 3 ml of
acetone. The mixture was stirred at room temperature
for 3 days. The precipitate was filtered off, washed
with acetone, and crystallized from DMF. Yield of X
1.99 g (95%), mp 245 250 C. IR spectrum (mull in
2. Musina, E.I., Kuznetsov, R.M., Nikonov, G.N., Balue-
va, A.S., and Gubanov, E.F., Zh. Obshch. Khim., 1999,
vol. 69, no. 6, p. 928.
3. Arbuzov, B.A., Erastov, O.A., Nikonov, G.N., Arshi-
nova, R.P., Romanova, I.P., and Kadyrov, R.A., Izv.
Akad. Nauk SSSR, Ser. Khim., 1983, no. 8, p. 1846.
1
4. Arbuzov, B.A. and Nikonov, G.N., Adv. Heterocyclic
Chem., 1994, vol. 61, no. 1, p. 59.
5. Arbuzov, B.A., Erastov, O.A., and Nikonov, G.N., Izv.
Akad. Nauk SSSR, Ser. Khim., 1979, no. 12, p. 2771.
mineral oil), , cm : 792 (C Har), 1184 (P=O), 1614
1
(C=Car), 1638 (C=C), 3072 (C Har). H NMR spec-
trum (DMSO-d6), , ppm (J, Hz): 1.30 t (6H, OCH2
3
CH3, JHH 7), 2.16 s (6H, CH3C6H4), 3.11 d (4H,
2
2
PCH2Ar, JPH 11.3), 3.78 d (4H, PCHaN, JHH 15),
3.99 q (4H, OCH2CH3, 3JHH 7), 4.14 d.d (4H, PCHeN,
6. Arbuzov, B.A., Erastov, O.A., Nikonov, G.N., Zyabli-
kova, T.A., Arshinova, R.P., and Kadyrov, R.A., Izv.
Akad. Nauk SSSR, Ser. Khim., 1986, no. 7, p. 1571.
2
2JHH 15, JPH 5.2), 4.98 5.11 m (4H, CH2=CH),
5.86 6.02 m (2H, CH2=CH), 6.76 7.12 m (14H,
7. Arbuzov, B.A., Erastov, O.A., Nikonov, G.N., Arshino-
va, R.P., and Kadyrov, R.A., Izv. Akad. Nauk SSSR,
Ser. Khim., 1980, no. 3, p. 721.
C6H4, C6H3). 31P NMR spectrum (in pyridine),
,
P
ppm: 39.73. Found, %: C 71.89; H 7.65; N 3.71; P
8.73. C42H52N2O4P2. Calculated, %: C 71.05; H 7.32;
N 3.94; P 8.72.
8. JPN Patent 56-6406, 1981, Ref. Zh. Khim., 1982,
5N105P.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 11 2002