General Papers
ARKIVOC 2014 (iv) 24-37
Data for 5. Mp: 264 °C, Rf: 0.35 (cyclohexane/ether 1/1.5), IR ν cm-1: 3456 (OH), 2229 (CN),
1H NMR (400 MHz, CDCl3): δ 1.42, 1.44 (2 s, 6H, 2 CH3), 2.59 (d, 1H, OH, J = 3 Hz), 3.37,
3.41 (2 s, 6H, 2 OCH3), 3.80-3.90 (m, 1H), 3.88 (t, 1H, J = 8 Hz), 3.98 (d, 1H, J = 5.5 Hz), 4.05
(t, 1H, J = 8 Hz), 4.17 (dd, 1H, J = 8Hz, J = 10.5 Hz), 4.27 (d, 1H, J = 8 Hz), 4.28 (d, 1H, J =
10.5 Hz), 4.39 (t, 1H, J = 8 Hz), 7.30-7.40 (m, 5 H, C6H5). 13C NMR (75 MHz, CDCl3): δ 18.9
(2 CH3), 48.4 (OCH3), 48.5 (OCH3), 50.0, 62.7, 70.0, 72.5, 72.8, 74.9, 90.6, 101.8, 102.1 (Civ),
113.7 (CN), 127.8, 129.1, 129.2 (CArH), 135.9 (CAr). MS (IC, NH3): m/z [M + H]+ 391. HRMS
(IC, NH3) m/z: calcd. for C20H26N2O6Na [M+Na]+: 413.1689; found 413.1692
Data for 6. Rf: 0.25 (cyclohexane/ether 1/1.5), IR ν cm-1: 3450 (OH), 2229 (CN). 1H NMR (400
MHz, CDCl3): δ 1.41, 1.44 (2 s, 6H, 2 CH3), 2.57 (d, 1H, OH, J = 2.5 Hz), 3.41, 3.45 (2s, 6H, 2
OCH3), 3.69 (t, 1H, J = 9 Hz), 3.84 (dd, 1H, J = 9 Hz, J = 5 Hz), 4.0-4.10 (m, 1H), 4.27 (d, 1H, J
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= 7.5 Hz), 4.33 (dd, 1H, J = 11 Hz, J = 5Hz), 4.30-4.40 (m, 2H), 7.30-7.40 (m, 5H, C6H5). C
NMR (75 MHz, CDCl3): δ 18.7, 18.8 (2 CH3), 47.8 (OCH3), 48.3 (OCH3), 48.9, 62.7, 69.8,
72.9, 73.5, 74.3, 91.6, 101.7, 102.0 (Civ), 113.9 (CN), 127.8, 129.0, 129.1 (CArH), 135.7 (CAr).
MS (IC, NH3): m/z [M + H]+ 391.
Crystallographic data for 6a. C20 H26 N2 O6, orthorhombic, P21 21 21, colorless, a =
6.9853(5) Å, b= 10.5499(6) Å, c = 26.538(2) Å, V= 1955.7(2) Å3, T = 293(2)K, Z = 4, Final R
(I > 2 σ(I)): R1 = 0.0463, wR2 = 0.0986, GOF = 1.070. Structural information for 6a has been
deposited with CCDC as 845878.
Crystallographic data for 6b. C20 H26 N2 O6, orthorhombic, P21 21 21, colorless, a =
6.6354(1) Å, b= 12.4162(2)(6) Å, c = 24.790(2)Å, V = 2042.4(2) Å3, T = 293(2)K, Z = 4, Final
R (I > 2 σ(I)): R1 = 0.0441, wR2 = 0.0834, GOF = 1.154. Structural information for 6b has been
deposited with CCDC as 845879.
General procedure for the synthesis of 6,7-dimethoxy-9-methoxymethoxy-6,7-dimethyl-3-
phenyl-octahydro-1,5,8-trioxa-3a-aza-cyclopenta[a]naphthalene-4-carbonitrile (7) and
7,8-dimethoxy-5-methoxymethoxy-7,8-dimethyl-3-phenyl-octahydro-1,6,9-trioxa-3a-aza-
cyclopenta[a]naphthalene-4-carbonitrile (8). To a solution of 5 (50 mg, 0.13 mmol) or of 6
(65 mg, 0.15 mmol) in dry CHCl3 (1 mL), was added at 0 °C methoxymethyl chloride (26 µL,
2.5 eq., 0.32 mmol) and N-N-diisopropylamine (68 µL, 3 eq., 0.4 mmol). The resulting mixture
was refluxed for 3 h, then let to cool down to rt. The solution was quenched with water and
extracted with dichloromethane (5 x 30 mL). The combined organic layers were dried over
anhydrous Na2SO4, filtered and evaporated to dryness. After purification by chromatography on
silica gel using as eluent a mixture of cyclohexane/ether 1/0.5) the compound 7 was recovered as
a colorless oil (7.5 mg, 77%).
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Data for 7. Rf : 0.60 (cyclohexane/ether 1/1.5), H NMR (400 MHz, CDCl3): δ 1.34, 1.40 (2 s,
6H, 2 CH3), 3.40, 3.42, 3.52 (3s, 9H, 3 OCH3), 3.77 (t, 1H, J = 8 Hz), 3.83 (t, 1H, J = 8 Hz), 3.96
(d, 1H, J = 5.5 Hz), 3.99 (t, 1H, J = 8 Hz), 4.28 (d, 1H, J = 8 Hz), 4.30-4.40 (m, 2H, H-8), 4.46
(t, 1H, J = 10 Hz), 4.85-5.00 (2d, 2H, OCH2O, J = 6.5 Hz), 7.20-7.50 (m, 5H, C6H5). 13C NMR
(75 MHz, CDCl3): δ 18.7, 19.0 (2 CH3), 48.2, 48.8, 55.4 (3XOCH3), 62.5, 70.1, 72.3, 74.3, 75.4,
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