SYNTHESIS, STRUCTURE, AND REACTIVITY OF GERMANIUM-CONTAINING
213
13C NMR (CDCl3, δ, ppm) (for XII): 18.18, 56.68,
13C NMR (CDCl3, δ, ppm): 50.06, 56.81, 57.58
60.95 (NCH2); 63.27 (OCH2); 116.05, 119.90, 128.24, (OCH2, NCH2); 127.87, 128.25, 131.24, 134.12 (aro-
149.32 (aromatic carbons).
matic carbons).
erythro-4,12-Dimethyl-2,3,10,11-tetraphenyl-
1,7,9,15-tetraoxa-4,12-diaza-8-germaspiro[7,7]pen-
tadecane (IX). A mixture of dialkanolamine IV (2.6 g,
9.7 mmol), Ge(OÖt)4 (1.23 g, 4.9 mmol), and benzene
(25 mL) was refluxed for 50 h. The volatile compounds
were removed in vacuo, and the residue was recrystal-
lized from toluene to give 2.28 g (76%) of compound
For C11H17GeNO4 anal. calcd. (wt %): C, 44.06; H,
5.71; N, 4.67.
Found (wt %): C, 43.80; H, 5.58; N, 4.36.
2,2-Dihydroxy-6-methyl-1,3,6,2-dioxazagermocane
(XV). Water (3 mL) was added to a solution of ger-
maspiro-bis-ocane X (2 g, 6.5 mmol) in toluene
(25 mL). The reaction mixture was stirred for 72 h. The
volatile compounds were removed in vacuo, and the
residue was recrystallized from a methanol/acetone
mixture (1 : 3) to give 1.3 g (89%) of compound XV as
colorless crystals.
1H NMR (CDCl3, δ, ppm): 2.58 (s, 3H, NCH3);
2.65–2.71 (m, 4H, NCH2); 3.75–3.79, 3.85–3.90 (both m,
4H, OCH2).
13C NMR (CDCl3, δ, ppm): 44.59 (NCH3); 55.82
(NCH2); 58.10 (OCH2).
According to 1H and 13C NMR data, the filtrate con-
tained dialkanolamine I.
1
IX as a white powder. The H and 13C NMR spectra
exhibited signals for three diastereomers, which were
not unambiguously assigned.
1H NMR (CDCl3, δ): 2.15, 2.28, 2.33 (all s, 6H,
CH3N); 2.44–2.51, 3.33–3.48, 3.96–3.98, 4.18–4.33
(all m, 8H, CH2); 3.46, 3.72 (both d, 2H, NCH2), 5.23
(d), 5.54 (br.s), 6.03 (br.s, 2H, OCH); 6.90–7.09, 7.26–
7.34 (both m, 20H, aromatic protons).
13C NMR (CDCl3, δ, ppm): 43.31, 43.79, 45.21
(NCH3); 56.44, 57.88, 58.78 (NCH2); 60.87, 61.28
(NCH) (signal for one diastereomer was not observed);
72.53, 74.36, 75.55, 73.64, 75.36, 74.74 (OCH);
125.84, 126.06, 126.19, 126.38, 126.88, 126.95,
127.06, 127.18, 127.28, 127.36, 127.42, 127.84,
127.92, 128.09, 129.29, 130.54, 130.80, 130.91,
141.59, 141.83, 142.51 (aromatic carbons).
Cyclotrigermanoxane (XVI). A toluene solution
of germaspiro-bis-ocane X (0.1 mL) was allowed to
stand in air at room temperature for several days. This
gave crystals suitable for X-ray diffraction.
For C34H38GeN2O4 anal. calcd. (wt %): C, 66.46; H,
6.10; N, 4.52.
6-Methyl-1,3,6,2-dioxazagermocane-2,2-diyl bis(tri-
fluoroacetate) (XVIII). A solution of (CF3CO)2O
(0.54 g, 0.24 mmol) in dioxane (10 mL) was slowly
Found (wt %): C, 66.96; H, 6.00; N, 4.21.
threo-4,12-Dimethyl-2,3,10,11-tetraphenyl-1,7,9,15- added to a solution of 2,2-dichloro-6-methyl-1,3,6,2-
tetraoxa-4,12-diaza-8-germaspiro[7,7]pentadecane dioxazagermocane XVIII (0.21 g, 0.8 mmol) in diox-
(XIII) was prepared as described for X by refluxing dial- ane (10 mL). The trifluoroacetyl chloride evolved was
kanolamine V (0.4 g, 1.5 mmol), Ge(OÖt)4 (0.19 g, collected in a trap cooled to –78°ë. For complete
removal of the chloride, the reaction mixture was vig-
orously stirred for 2 h at 40°ë. The resulting solid resi-
due was washed with ether to give 0.31 g (92%) of
compound XVIII as a white powder.
1H NMR (CDCl3, δ, ppm): 3.01 (s, 3H, NCH3); 3.61
(t, 4H, CH2); 4.81 (t, 4H, CH2).
0.7 mmol), and benzene (10 mL) for 50 h. Recrystalli-
zation from toluene gave 0.38 g (89%) of compound
XIII as a white powder.
1H NMR (CDCl3, δ): 2.29 (s, 6H, CH3N); 2.41–2.51
(m, 4H, NCH2); 3.61 (d, 2H, NCH), 3.67–3.77 (m, 4H,
OCH2); 5.04 (d, 2H, OCH); 7.07–7.13, 7.19–7.26, 7.34
(all m, 20H, aromatic protons).
13C NMR (CDCl3, δ, ppm): 41.69 (CH3); 54.78,
61.67 (CH2).
For C34H38GeN2O4 anal. calcd. (wt %): C, 66.46; H,
6.10; N, 4.52.
19F NMR (CDCl3, δ, ppm): –77.39 (s, CF3).
Found (wt %): C, 66.80; H, 6.27; N, 4.58.
erythro-6-Methyl-4,5-diphenyl-2,2-difluoro-1,3,6,2-
dioxazagermocane (XIX). A solution of BF3 · Et2O
(0.05 g, 0.33 mmol) in CH3CN (7 mL) was added drop-
wise to a solution of 2,2-diethoxygermocane VIII
(0.21 g, 0.50 mmol) in CH3CN (3 mL) heated to 50°ë.
The mixture was stirred at 50°C for 8 h and the volatile
compounds were removed in vacuo. Ether (5 mL) was
added to the residue and the mixture was stirred for 2 h.
The precipitate was collected on a filter and dried in
vacuo to give compound XIX (0.14 g, 72%) as a white
6-Benzyl-2,2-dihydroxy-1,3,6,2-dioxazagermocane
(XIV). GeO2 (1.1 g, 11 mmol) was added in one portion
to a mixture of diethanolamine II (2.1 g, 11 mmol) and
water (10 mL). The mixture was refluxed for 4 h, water
was removed at a reduced pressure, and the residue was
recrystallized from a methanol/acetone mixture (1 : 3) to
give 1.7 g (56%) of compound XIV as a white powder.
1H NMR (CDCl3, δ, ppm): 2.44–2.50, 2.92–2.98
(both m, 4H, NCH2); 3.75–3.79, 3.98–4.03 (both m,
4H, OCH2); 4.13 (s, 2H, CH2Ph); 7.19–7.22, 7.29–7.31
(both m, 5H, aromatic protons).
1
solid. The H and 13C NMR spectra exhibited signals
for two diastereomers in 3 : 1 ratio.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 54 No. 2 2009