STERICALLY ORIENTED SYNTHESIS AND STRUCTURE OF NEW
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233–235°С (decomp.). Н NMR spectrum (200 MHz,
(CD3)2SO, 30oС) δ, ppm 5.11 s (2Н, Н3h), 6.28 s (2Н,
(С8), 22.47 s (С8), 31.69 s (С7), 32.68 s (С7), 39.69 s
(C1), 68.11 s (С6), 68.94 s (С6), 69.14 s (С6), 69.73 s
Н3v), 6.34 s (4Н, Н1), 6.38 d (4Н, Н2′, JНН 6.8 Hz),
(С6), 106.32 t (C5, JPC 18.3 Hz), 108.46 t (C5, JPC
15.7 Hz), 123.03 s (C8′), 124.16 s (C3′), 124.87 s (C6′),
125.29 s (C7′), 126.03 s (C2′), 126.60 s (C4′), 127.18 s
(C2), 127.58 s (C5′), 128.09 s (C2), 130.64 s (C9′),
132.32 s (C10′, С3), 133.06 s (С3), 137.75 s (C1′),
149.01 s (С4), 149.81 s (С4). Found, %:С 63.30, Н
5.95, Р 12.11. C108H120O24P8 Calculated С 63.28, Н
5.90, Р 12.09.
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6.84 d.d (4Н, Н7′, 3JНН 8.0 Hz), 6.92 d.d (4Н, Н3′, 3JНН
7.3 Hz), 7.08 d.d (4Н, Н6′, JНН 7.0 Hz), 7.27 d (4Н,
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Н8′, 3JНН 7.8 Hz), 7.33 d (Н4′, 3JНН 8.1 Hz), 7.46 d (Н5′,
3JНН 8.3 Hz), 8.1-8.3 br.s (8Н, ОН). Mass spectrum,
m/z: 1308 (100%) [M+]. Found, %: С 62.47, Н 3.43.
С68Н44Br4О8. Calculated, %: С 62.41, Н 3.39.
Resorcinarene Id. To a solution of 5 g (0.0403
mol) of 2-methylresorccinol and 14.3 g (0.04 mol) of
benzaldehyde in 38 ml of 95% ethyl alcohol was added
dropwise 9.4 ml of concentrated hydrochloric acid.
The reaction mixture was stirred for 35 h. Precipitate
separated was filtered off, suspended in 20 ml of ethyl
alcohol and after shaking for 20 min it was filtered
off. The operation was repeated twice. The precipitate
was filtered off and dried for 20 h at 130–140°C
Phosphoresorcinarene IIb was prepared similarly
to compound IIа by reaction of 0.99 g (0.945 mmol) of
Ib with 1.94 g (9.45 mmol) of phosphorous neo-
pentyleneamide for 50 h. Yield 79 %, mp above 360°
С. 31Р NMR spectrum (80 MHz, СDС13, 30°C), δ,
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ppm: 118.37, 120.21. H NMR spectrum (200 MHz,
СDС13, 30°C), δ, ppm: –0.41 s (12Н, Н8), 0.49 s (12Н,
Н8), 0.83 s (12Н, Н8), 1.22 s (12Н, Н8), 2.14 m (4H,
H6e), 2.18 s (6H, Н9), 2.38 s (6H, Н9), 3.02 d.d (4Н,
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(1 mm Hg). Yield 80 %, mp 293–294°С. Н NMR
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spectrum [200 MHz, (CD3)2SO, 30°С], δ, ppm: 1.93 s
(6Н, СН3), 2.11 s (6Н, СН3), 5.37 s (2Н, Н3h), 5.62 s
(4Н, Н1), 6.20 s (2Н, Н3v), 6.67 m (8Н, НРh), 6.87 m
(12Н, НРh), 7.02 s (4Н, ОН), 7.48 s (4Н, ОН). Found,
%:С 78.80, Н 5.11. C52H40O8 Calculated, %: С 78.77,
Н 5.09.
Н6e, JHH 10.4 Hz, JРH 11.9 Hz), 3.19 d.d (4Н, Н6e,
2JHH 10.4 Hz, JРH 11.6 Hz), 3.44 d.d (4Н, Н6e, JHH
10.4 Hz, 3JРH 11.0 Hz), 3.78 d.d (8Н, Н6a, 2JHH 11.00 Hz,
3JPH 2.2 Hz), 3.92 d.d (4Н, Н6a, 2JHH 10.4 Hz, 3JPH 2.2 Hz),
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4.30 d.d (4Н, Н6a, JHH 10.4 Hz, JPH 2.2 Hz), 5.07 s
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(2Н, Н3h), 6.10 s (2Н, Н3v), 6.21 s (4Н, Н1), 6.54 d
(4Н, H2′, 3JHH 7.3 Hz), 6.84 d.d (4Н, H7′, JHH 7.6 Hz),
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6.88 d.d (4Н, H3′, 3JHH 7.7 Hz), 7.04 d.d (4Н, H6′, 3JHH
7.3 Hz), 7.28 d (4Н, H8′, 3JHH 8.4 Hz), 7.34 d (4Н, H4′,
Phosphoresorcinarene IIа. A mixture of 0.1 g
(0.105 mmol) of resorcinarene Iа and 0.215 g (1.05 mmol)
of phosphorous neopentyleneamide in 1 ml of dioxane
was heated for 65 h at 90–95°С. The precipitate
formed was filtered off and washed with di-oxane.
The product was dried for 10 h at 75–80°С (1 mm
Hg). Yield 67 %, mp above 360°С. 31Р NMR spectrum
3JHH 8.4 Hz), 7.41 d (4Н, H5′, JHH 8.0 Hz). 13С NMR
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spectrum (50 MHz, СDС13, 30°C), δ, ppm: 12.18 s
(С8), 13.09 s (C9), 22.20 s (С8), 22.40 s (С8), 22.61 s
(С8), 32.18 s (С7), 32.69 s (С7), 42.57 s (C1), 68.59 s
(С6), 69.23 s (С6), 123.65 s (C8′), 123.89 s (C3′), 124.93 s
(C6′,7′), 126.32 s (C2,2′), 126.79 s (C2,4′), 128.06 s (C5′),
129.53 s (C5), 130.24 s (C5), 131.29 s (С3,9′), 131.61 s
(C10′), 133.06 s (С3), 138.21 s (C1′), 148.98 s (С4).
Mass spectrum, m/z: 2106 (100%) [M+]. Found, %: С
63.90, Н 6.15, Р 11.80. C112H128O24P8 Calculated С
63.87, Н 6.13, Р 11.77.
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(80 MHz, СDС13, 30°C), δ, ppm: 114.30, 115.40. H
NMR spectrum (200 MHz, СDС13, 30°C), δ, ppm:
–0.40 s (12Н, Н8), 0.54 s (12Н, Н8), 0.85 s (12Н, Н8),
1.22 s (12Н, Н8), 2.38 d.d (4Н, Н6e, 2JHH 10.7 Hz, 3JРH
11.0 Hz), 2.65 d.d (4Н, Н6a, 2JHH 10.7 Hz, 3JPH 2.4 Hz),
2.78 d.d (4Н, Н6e, 2JHH 10.4 Hz, 3JРH 11.3 Hz), 3.17 d.d
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(4Н, Н6e, JHH 10.4 Hz, JРH 10.7 Hz), 3.31 d.d (4Н,
Н6a, 2JHH 10.4 Hz, 3JPH 2.4 Hz), 3.37 d.d (4Н, Н6e 2JHH
Phosphoresorcinarene IIc was prepared similarly
to compound IIа by reaction of 0.07 g (0.05 mmol) of
Ic with 0.11 g (0.5 mmol) of phosphorous neopentyl-
eneamide for 18 h. Yield 75 %, mp above 360°С
(decomp.). 31Р NMR spectrum (80 MHz, СDС13, 30°C):
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11.0 Hz, JРH 11.4 Hz), 3.75 d.d (4Н, Н6a, JHH 11.0
Hz, 3JРH 11.4 Hz), 4.27 d.d (4Н, Н6a, 2JHH 10.4 Hz, 3JPH
2.7 Hz), 5.24 s (2Н, Н3h), 6.38 s (4Н, Н1), 6.45 s (2Н,
Н3v), 6.55 d (4Н, H2′, JHH 7.0 Hz), 6.88 d.d (4Н, H7′,
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3JHH 7.7 Hz), 6.93 d.d (4Н, H3′, JHH 7.6 Hz), 7.01 t
δ, ppm 118.37, 120.21. H NMR spectrum (200 MHz,
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(2Н, Н5, JPH 2.7 Hz), 7.04 d.d (4Н, H6′, JHH 7.6 Hz),
7.20 t (2Н, Н5, 4JPH 2.1 Hz), 7.30 d (8Н, H4,8, 3JHH 8.4 Hz),
7.40 d (4Н, H5′ 3JHH 8.4 Hz). 13С NMR spectrum (50 MHz,
СDС13, 30°C): δ, ppm 21.06 s (С8), 22.03 s (С8), 22.30 s
СDС13, 30°C): δ, ppm 0.41 s (12Н, Н8), 0.52 s (12Н,
Н8), 0.82 s (12Н, Н8), 1.22 s (12Н, Н8), 2.02 d.d (4H,
H6e, 2JHH 11.2 Hz, 3JРH 9.5 Hz), 3.08 d.d (4Н, Н6e, 2JHH
10.4 Hz, 3JРH 10.6 Hz), 3.31 d.d (4Н, Н6e, 2JHH 11.0 Hz,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 3 2008