CONDENSATION OF RESORCINOL WITH PHOSPHORYLATED ACETALS
415
and 8.4 g of acetal IIb. Yield 7.31 g (81%), mp >
of water, 50 ml of ethanol, 7.75 ml of conc. HCl,
1
and 9.56 g of acetal IId. Yield 6.81 g (67%), mp >
250 C. IR spectrum (KBr), , cm : 1160 (P=O),
1
1
3100 3580 (OH). H NMR spectrum (methanol-d4):
250 C. IR spectrum (KBr), , cm : 1165 (P=O),
1.42 d (24H, CH3), 1.81 m (8H, CH2P), 4.01 m (4H,
OCH), 5.10 br.m (4H, CH), 6.23 s (4H, o-CHarom),
7.30 s (4H, m-CHarom). 31P NMR spectrum (CD3OD):
3100 3580 (OH). 31P NMR spectrum (CD3OD),
P
32.90 ppm. Found, %: C 51.60; H 6.15; P 11.04.
C48H68O20P4. Calculated, %: C 52.94; H 6.25;
P 11.40.
33.3 ppm. Found, %: C 50.45; H 5.53; P 10.07.
P
C44H60O20P4. Calculated, %: C 51.16; H 5.81;
P 12.02.
4,6,10,12,16,22,24-Octahydroxy-2,8,14,20-tetra
[[(butoxy)ethylphosphinoyl]methyl]pentacyclo-
[19.3.1.13,7.19,13.115,19]-octacosa-1(25),3,5,7(28),9,11,
13(27),15,17,19(26),21,23-dodecaene (VI). A mixture
of 2.15 g of resorcinol, 20 ml of water, 15 ml of
ethanol, and 5.2 ml of conc. HCl was treated dropwise
with stirring and cooling with a solution of 5.2 g of
acetal V in 5 ml of ethanol. The reaction mixture was
stirred for 1 h at 50 C and for 5 days at 20 C. The
oily layer was decanted, triturated with acetonitrile,
and dried in a vacuum (5 h, 90 C, 0.04 mm Hg) to
give 4.3 g (77%) of compound VI as a white amor-
phous powder darkening on heating above 250 C
4,6,10,12,16,18,22,24-Octahydroxy-2,8,14,20-
tetra[[hydroxy(isopropoxy)phosphinoyl]methyl]-
pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,
7(28),9,11,13(27),15,17,19(26)21,23-dodecaene
(IVc) was obtained analogously from 0.83 g of re-
sorcinol, 10 ml of water, 10 ml of ethanol, 10 ml of
conc. HCl, and 2.1 ml of acetal IIc. Yield 1.94 g
(86%), mp 235 C (decomp.). IR spectrum (KBr), ,
1
1
cm : 1162 (P=O), 3100 3580 (OH). H NMR spec-
3
trum (methanol-d4), , ppm: 1.46 t (12H, CH3, JHH
7.0 Hz), 1.4 1.6 br.m (8H, CH2), 1.83 m (8H, CH2P),
3.85 m (8H, OCH2), 5.17 br.m (4H, CH), 6.26 s (4H,
o-CHarom), 7.28 s (4H, m-CHarom). 31P NMR spectrum
1
(decomp.). IR spectrum, , cm : 1160 (P=O); 3100
1
3580 (OH). H NMR spectrum (methanol-d4), , ppm
(J, Hz): 0.83 m (24H, CH3), 1.24 m (32H, CH2),
3.72 m (8H, CH2), 4.59 m (4H, CH), 6.26 br.s (4H,
o-Harom), 7.17 br.s (4H, m-Harom), 9.0 br.s (8H, OH).
13C NMR spectrum (methanol-d4), C, ppm (J, Hz):
(CD3OD):
30.82 ppm. Found, %: C 50.97; H 5.56;
P 11.57. C4P4H60O20P4. Calculated, %: C 51.16; H
5.81; P 12.02.
1
2
1
4.27 q [C8, JCH 124.7, JCC 6.28), 12.49 q (C12, JCH
4,6,10,12,16,18,44,24-Octahydroxy-2,8,14,20-tet-
ra[[(butoxy)hydroxyphosphinoyl]methyl]penta-
124.7), 17.28 t (C11, JCH 123.74), 19.52 d.t (C7, JPC
1
1
cyclo[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),
9,11,13(27),15,17,19(26),21,23-dodecaene (IVd) was
prepared analogously by addition of a solution of
1.75 g of acetal IId in 4 ml of ethanol to a mixture of
0.62 g of resorcinol, 8 ml of water, 8 ml of ethanol,
and 1.4 ml of conc. HCl. Yield 1.2 g (78%), mp 165
166 C. 1H NMR spectrum (methanol-d4), , ppm
1
1
90.6, JCH 119.8), 31.21 t (C10, JCH 120.3), 61.82 t
(C9, JCH 125.6, JPC 8.97), 101.81 d (C4, JCH
1
2
1
121.73), 120.64 s (C3), 128.22 d (C1, JCH 145.39),
1
152.65 s (C2). 31P NMR spectrum (DMSO):
P
59.7 ppm. M 1159. Found, %: C 58.64; H 8.22.
C56H84O16P4. Calculated, %: C 59.15; H 7.39.
3
(J, Hz): 1.10 t (12H, CH3, JHH 7.0), 1.4 1.70 br.m
O,O-Diethyl S-(2,2-diethoxyethyl) phosphoro-
dithioate (VII). A mixture of 4.16 g of S-sodium
O,O-diethyl phosphorodithioate and 9.85 g of bromo-
acetal I was heated for 1 h at 100 C, cooled to 20 C,
and treated with 10 ml of water and 15 ml of diethyl
ether. The ether layer was removed and dried over
magnesium sulfate. The ether and excess bromoacetal
were removed in a water-jet-pump vacuum to obtain
1.7 g (28%) of compound VII as a light yellow oil.
1H NMR spectrum (DMSO-d6), , ppm (J, Hz):
1.12 m (12H, CH3), 2.71 d.d (2H, SCH2, 3JHH 7.0 Hz,
3JPH 10.2 Hz), 3.48 m (4H, POCH2), 4.07 q (4H,
(16H, CH2), 1.89 m (8H, CH2P), 4.20 m (8H, OCH2),
5.17 m (4H, CH), 6.48 s (4H, o-CHarom), 7.32 s (4H,
m-CHarom). 13C NMR spectrum (methanol-d4),
,
ppm (J, Hz): 13.99 q (CH3, JCH 124.4), 19.64Ct
1
1
1
[(CH2)2, JCH 122.06], 33.48 t (CH2P, JCH 125.60),
1
1
66.71 t (CH2O, JCH 142.60), 69.65 d.d (CH, JCH
2
1
150.90, JCP 7.04), 104.05 d (Cm, JCH 155.90),
1
122.53 s (CaromCH), 129.96 d (o-CaromCH, JCH
154.60), 154.26 s (CaromOH). 31P NMR spectrum
(CD3OD): P 31.14 ppm. M 1114. Found, %: C 52.55;
H 6.43; P 11.85. C48H68O20P4. Calculated, %: C
52.94; H 4.25; P 11.40.
3
3
OCH2, JHH 7.0 Hz), 4.51 t (1H, CH, JHH 7.0 Hz).
31P NMR spectrum (DMSO): P 93.6 ppm. Found, %:
P 9.98. C10H23O4PS2. Calculated, %: P 10.26.
4,6,10,12.16,18,22,24-Octahydroxy-2,8,14,20-
tetra[[hydroxy(isobutoxy)phosphinoyl]pentacyclo-
[19.3.1.13,7.19.13.115,19]octacosa-1(25),3,5,7(28),9,11,
13(27),15,17,19(26).21.23-dodecaene (IVe) was
prepared analogously from 3.41 g of resorcinol, 50 ml
4,6,10,12,16,18,22,24-Octahydroxy-2,8,14,20-tet-
rakis[(diethoxyphosphinothioyl)sulfanylmethyl]-
pentacyclo[19.3.1.13,7.19.13.115,19]octacosa-1(25),3,5,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 3 2006