SYNTHESIS OF DI(ADAMANTYLALKYL) TOSYLOXYMETHYLPHOSPHONATES
837
(CH3, p-Tol), 28.60 s (CH, Ad), 31.84 s (C, Ad), 37.01
s (CH2, Ad), 42.54 s (CH2, Ad), 44.28 d (AdCH2·
CH2O, 3JCP 6.03 Hz), 61.20 d (CH2O, 1 JCP 167.5 Hz),
Tol), 145.24 s (p-C, p-ol); 31P NMR spectrum, δP
18.16 ppm. Mass spectrum, m/z: 623 [M]+. Found, %:
C 61.70; H 7.62. C32H47O8PS. Calculated, %: C 61.72;
H 7.61.
2
63.97 d (AdCH2CH2O, JCP 6.8 Hz), 128.32 s (m-CH,
p-Tol), 130.08 s (o-CH, p-Tol), 131.97 s (i-C, p-Tol),
145.52 s (p-C, p-Tol); 31P NMR spectrum, δP 18.01 ppm.
Mass spectrum, m/z: 591 [M]+. Found, %: C 65.05; H
8.00. C32H47O6PS. Calculated, %: C 65.06; H 8.02.
Di[4-(1-Adamantyloxy)butyl] tosyloxymethylphos-
phonate (Vf). Yield: 38.7%. H NMR spectrum, δ,
1
ppm: 1.55–2.18 m (30H, Ad, 8H, 4CH2), 2.45 s (3H,
CH3, p-Tol), 3.38 t [4H, AdOCH2(CH2)3O, 2JHH 7.00 Hz],
Di[1-(1-adamantyl)ethyl] tosyloxymethylphosphonate 4.10 m [4H, AdO(CH2)3CH2O], 4.18 d (2H, CH2O,
1
(Vc). Yield 35.0%, mp 165ºC. H NMR spectrum, δ,
ppm: 1.20 d (6H, CH3, 2JHH 7.0 Hz), 1.40–5.2 m (30H,
Ad), 2.45 s (CH3, p-Tol), 4.12 m ( 4H, CH2O, 2CHO),
7.35 d, 7.80 d (4H, p-Tol); 13C NMR spectrum, δC,
ppm: 15.46 d (CH3, 3JPC 1.5 Hz), 21.73 s (CH3, p-Tol),
28.16 s (CH2, Ad), 36.68 s (C, Ad), 37.01 s (CH2, Ad),
2JHP 8.20 Hz), 7.38 d, 7.80 d (4H, p-Tol, AB-system);
13C NMR spectrum, δC, ppm: 21.78 s (CH3, p-Tol),
26.53 s (AdOCH2CH2CH2CH2O), 27.59 d (AdOCH2CH2·
3
CH2CH2O, JPC 6.0 Hz), 30.57 s (CH2, Ad), 36.58 s
(CH2, Ad), 41.67 s (CH, Ad), 58.92 s [AdOCH2(CH2)3O],
61.26 d ( CH2O, 1JCP = 169.1 Hz), 67.36 d [AdO(CH2)3·
1
2
37.70 s (CH, Ad), 62.54 d (CH2O, JPC 169.8 Hz),
CH2O, JPC = 6.8 Hz], 71.94 s (CO, Ad), 128.32 s (m-
83.12 d ( CHO, 2JPC 7.54 Hz), 128.27 s (m-CH, p-Tol),
129.98 s (o-CH, p-Tol), 131.97 s (i-C, p-Tol), 145.38 s
(p-C, p-Tol); 31P NMR spectrum, δP 14.16 ppm (first
diastereomer), 14.63 ppm (second diastereomer). Mass
spectrum, m/z: 591 [M]+. Found, %: C 65.05; H 8.00.
C32H47O6PS. Calculated, %: C 65.06; H 8.02.
CH, p-Tol), 130.10 s (o-CH, p-Tol), 131.84 s (i-C, p-
Tol), 145.54 s (p-C, p-Tol); 31P NMR spectrum, δP
16.10 ppm. Mass spectrum, m/z: 679 [M]+. Found, %:
C 63.70; H 8.18. C36H55O8PS. Calculated, %: C 63.69;
H 8.17.
Di{2-[2-(1-adamantyloxy)ethyloxy]ethyl} tosyl-
1
Di[3-(1-adamantyl)propyl] tosyloxymethylphospho- oxymethylphosphonate (Vg). Yield 36.4%. H NMR
1
nate (Vd). Yield 35.4%. H NMR spectrum, δ, ppm:
1.05 m (4H, AdCH2CH2CH2O), 1.45 t (4H, AdCH2·
CH2CH2O), 1.49–1.65 m (24H, CH2, Ad ), 1.95 s (6H,
CH, Ad), 2.45 s (3H, CH3, p-Tol), 4.00 m (4H, CH2O),
4.20 d (2H, CH2O, 2JHP 8.2 Hz) , 7.35 d, 7.80 d (4H, p-
Tol, AB-system); 13C NMR spectrum, δC, ppm: 21.77 s
(CH3, p-Tol), 28.60 s (CH2, Ad), 31.84 s (C, Ad),
37.01 s (CH2, Ad), 42.54 s (CH, Ad), 44.28 d
spectrum, δ, ppm: 1.45–2.20 m (30H, Ad), 2.45 s (3H,
CH3, p-Tol), 3.55 m (8H, 4CH2O), 3.70 m (4H,
2CH2O), 4.20 m (4H, 2CH2O), 4.28 d (2H, CH2O, 2JHP
8.2 Hz), 7.35 d, 7.80 d (4H, p-Tol, AB-system); 13C
NMR spectrum, δC, ppm: 21.77 s (CH3, p-Tol), 30.62 s
(CH2, Ad), 35.94 s (CH2, Ad), 36.15 s (CH2, Ad),
40.98 s (CH2, Ad), 41.05 s (CH2, Ad), 45.90 s (CH,
1
Ad), 59.52 d (OCH2CH2O), 61.63 d (CH2O, JPC
3
1
(AdCH2CH2CH2O, JPC 6.0 Hz), 61.20 d (CH2O, JPC
171.3 Hz), 66.30 d (OCH2CH2OP, 2JPC 6.79 Hz), 70.14
2
3
167.5 Hz), 63.97 d (AdCH2CH2 CH2O, JPC 6.8 Hz),
d (OCH2CH2OP, JPC 5.3 Hz), 71.28 s (OCH2CH2O),
128.32 s (m-CH, p-Tol), 130.08 s (o-CH, p-Tol),
131.97 s (i-C, p-Tol ), 145.52 s (p-C, p-Tol); 31P NMR
spectrum, δP 15.95 ppm. Mass spectrum, m/z: 619 [M]+.
Found, %: C 65.97; H 8.32. C34H51O6PS. Calculated,
%: C 65.99; H 8.31.
72.71 s (CO, Ad), 128.33 s (m-CH, p-Tol), 130.04 s
(o-CH, p-Tol), 132.03 s (i-C, p-Tol), 145.40 s (p-C, p-
Tol); 31P NMR spectrum, δP 17.25 ppm. Mass spec-
trum, m/z: 711 [M]+. Found, %: C 60.82; H 7.82.
C36H55O10PS. Calculated, %: C 60.83; H 7.80.
Di[2-(1-Adamantyloxy)ethyl] tosyloxymethylphos-
phonate (Ve). Yield 38.7%, mp 53–55ºC. H NMR
Di(3-ethyl-1-adamantylmethyl)
tosyloxymethyl-
1
1
phosphonate (Vh). Yield 39.2%. H NMR spectrum,
2
spectrum, δ, ppm: 1.52 q (12 H, Ad), 1.70 s (12H, Ad),
2.12 s (6H, Ad), 2.45 s (3H, CH3, p-Tol), 3.58 m (4H,
AdOCH2CH2O), 4.15 m (4H, AdOCH2CH2O), 4.30 d
δ, ppm: 0.76 t (6H, CH3CH2Ad, JHH 7.0 Hz), 1.08 q
2
(4H, CH3CH2Ad, JHH 7.00 Hz), 1.50 s ( 12H, CH2,
Ad), 1.65 q (12H, CH2, Ad), 2.08 s (4H, CH, Ad), 2.45
2
(2H, CH2O, JHP 8.20 Hz), 7.35 d, 7.80 d (4H, p-Tol,
s (3H, CH3, p-Tol), 3.60 m (4H, AdCH2O), 4.20 d (2H,
AB-system); 13C NMR spectrum, δC, ppm: 21.66 s
(CH3, p-Tol), 30.47 s (CH2, Ad), 36.36 s (CH2, Ad),
41.39 s (CH, Ad), 59.11 d (AdOCH2CH2O, 3JPC 5.0 Hz),
CH2O, JHP 7.00 Hz) 7.35 d, 7.80 d (4H, p-Tol, AB-
2
system); 13C NMR spectrum, δC, ppm: 7.18 s
(CH3CH2Ad), 21.7 s (CH3, p-Tol), 27.98 s (CH2, Ad),
1
3
61.74 d (CH2O, JPC 169.8 Hz), 67.02 d (AdOCH2·
33.93 d (C, Ad, JPC = 6.0 Hz), 35.85 s (CH3CH2Ad),
2
CH2O, JPC 7.5 Hz), 72.62 s (CO, Ad), 128.26 s (m-
36.91 s (CH2, Ad), 38.77 s (CH, Ad), 60.99 d (CH2O,
2
CH, p-Tol), 129.92 s (o-CH, p-Tol), 132.01 s (i-C, p-
1JPC 169.80 Hz), 63.97 d (AdCH2O, JPC 32.50 Hz),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 5 2012