K. Drandarov – W. Kantlehner · Orthoamides and Iminium Salts
709
(1R)-1-[(1S,3S,5R,6R,8R)-3,8-Bis(4-methoxyphenyl)-
490 mg (72%), slightly pink fine needles; m. p. 196–198 ◦C.
2,4,7,9-tetraoxabicyclo[4.4.0]decan-5-yl]-1-prop-2-yne-1-yl – Rf = 0.58 (CHCl3-THF, 10 : 0.2). – FT-IR (ATR): ν = 3271
4-nitrobenzoate (18)
(C≡CH), 2933, 2841 (OCH3), 1739 (C=O), 1608 and 1586
(Ar), 1531 and 1516 (Ar and NO2), 1346, 1245 (NO2),
1225 (C=C-O), 1092, 1027, 1010, 827, 778, 719 cm−1. –
1H NMR (500 MHz, [D6]DMSO): δ = 8.37 [d, J = 8.8 Hz,
2H, 4-NO2-Ph, m-H], 8.23 [d, J = 8.8 Hz, 2H, 4-NO2-Ph,
o-H], 7.40 and 7.27 [2d, J = 8.8 Hz, 4H, C(2II)H, C(6II)H,
and C(2III)H, C(6III)H], 6.94 and 6.91 [2d, J = 8.8 Hz, 4H,
C(3II)H, C(5II)H, and C(3III)H, C(5III)H], 5.74 [s, 1H, C(3)],
5.51 [s, 1H, C(8)], 5.47–5.42 [m, 1H, C(1I)H], 4.42 and
4.41 [dd, J = 8.8, 1.7 Hz, C(5)H], 4.16 [s, 1H, C(6)H], 4.14
[bs, 2H, C(10)H2], 4.02 [bs, 1H, C(1)H], 3.76 and 3.75 [2s,
6H, 2 ArOCH3], 2.90 [t, J = 2.5 Hz, 1H, C≡CH], 2.83
[dt, J = 17.0, 2.7 Hz, 1H, C(2I)Ha], 2.74 and 2.73 [2dd,
J = 17.0, 2.7 Hz, 1H, C(2I)Hb]. – 13C NMR (125.76 MHz,
[D6]DMSO): δ = 163.08 (C=O), 159.47 and 159.23 [C(4II)
and C(4III)], 150.36 [4-NO2-Ph, C(4)], 134.61 [4-NO2-Ph,
C(1)], 130.71 [4-NO2-Ph, C(2) and C(6)], 130.56 and 130.20
[C(1II) and C(1III)], 127.38 and 126.94 [C(2II), C(6II),
C(2III), C(6III)], 123.92 (4-NO2-Ph, C(3) and C(5)], 113.30
and 113.18 [C(3II), C(5II), C(3III), C(5III)], 99.30 [C(3)],
98.81 [C(8)], 79.30 [C(3I)], 76.37 [C(5)], 73.26 [C(4I)],
69.30 [C(1I)], 69.05 [C(1)], 68.88 [C(10)], 68.04 [C(6)],
55.04 and 54.99 (2 ArOCH3), 20.29 [C(2I)]. – C31H29NO10
(575.56): calcd. C 64.69, H(5.08), N 2.43; found C 62.61, H
5.20, N 2.37.
4-Nitrobenzoyl chloride (400 mg, 2.16 mmol) was added
to a mixture of the alkynol 15 (800 mg, 1.94 mmol), tri-
ethylamine (3 mL), and acetonitrile (20 mL), and the mix-
ture was stirred at r. t. overnight. A 10% aqueous solution
of NH4Cl (20 mL) was added, the mixture was extracted
with CHCl3, the organic extract was washed with water and
concentrated under reduced pressure. The crystalline residue
was dissolved in boiling ethanol (ca. 250 mL). After cooling
to r. t. the crystallized product was collected by filtration to
yield compound 18, which was recrystallized from toluene.
Yield 800 mg (73%), yellowish fine needles; m. p. 206–
208 ◦C. – Rf = 0.43 (CHCl3-THF, 10 : 0.2). – FT-IR (ATR):
ν = 3294 (C≡CH), 2890, 2834 (OCH3), 1727 (C=O), 1613
and 1586 (Ar), 1530 and 1518 (Ar and NO2), 1272 and
1244 (C=C-O and NO2),, 1172, 1100, 1033, 997, 832, 778,
713 cm−1. – 1H NMR (500 MHz, [D6]DMSO): δ = 8.34 [d,
J = 8.8 Hz, 2H, 4-NO2-Ph, m-H], 8.24 [d, J = 8.8 Hz, 2H, 4-
NO2-Ph, o-H], 7.40 and 7.22 [2d, J = 8.8 Hz, 4H, C(2II)H,
C(6II)H, and C(2III)H, C(6III)H], 6.95 and 6.90 [2d, J =
8.8 Hz, 4H, C(3II)H, C(5II)H, and C(3III)H, C(5III)H], 5.80
[s, 1H, (C(3)H], 5.75 and 5.74 [dd, J = 8.8, 2.0 Hz, C(1I)H],
5.50 [s, 1H, C(8)H], 4.55 and 4.54 (dd, J = 8.8, 2.0 Hz,
C(5)H], 4.23 [bs, 1H, C(6)H], 4.15 [bs, 2H, C(10)H2], 4.02
[s, C(1)H], 3.76 and 3.75 (2s, 6H, 2 ArOCH3), 3.69 [d, J =
2.0 Hz, C≡CH)]. – 13C NMR (125.76 MHz, [D6]DMSO):
δ = 162.75 (C=O), 159.55 and 159.28 [C(4II) and C(4III)],
150.52 [4-NO2-Ph, C(4)], 133.89 [4-NO2-Ph, C(1)], 130.88
(4-NO2-Ph, C(2)H and C(6)H], 130.46 and 130.11 [C(1II)
and C(1III)], 127.47 and 126.94 [C(2II), C(6II), C(2III),
C(6III)], 123.93 [4-NO2-Ph, C(3)H and C(5)H], 113.34 and
113.22 [C(3II), C(5II), C(3III), C(5III)], 99.33 [C(3)], 98.87
[C(8)], 78.89 [C(2I)], 77.97 [C(5)], 76.89 [C(3I)], 69.14
[C(1)], 68.88 [C(10)], 67.65 [C(6)], 61.76 [C(1I)], 55.05 and
54.99 (2 ArOCH3). – C30H27NO10 (561.53): calcd. C 64.17,
H 4.85, N 2.49; found C 64.86, H 4.98, N 2.36.
(1R)-1-[(1S,3S,5R,6R,8R)-3,8-Bis(4-methoxyphenyl)-
2,4,7,9-tetraoxabicyclo[4.4.0]decan-5-yl]-1-methoxy-prop-
2-yne (20)
NaH (60% paraffin suspension, 1.85 g, 1.11 g NaH,
46 mmol) was added in small portions at r. t. under N2 to
a stirred mixture of compound 15 (15.9 g, 38.6 mmol) and
MeI (10.5 g, 74 mmol) in anhydrous DMF (75 mL). The mix-
ture was stirred for additional 3 h at r. t., then poured into
cold water (150 mL). The precipitate was collected by filtra-
tion, washed with water, and air-dried. The obtained yellow-
ish solid was suspended in methanol (400 mL) and the sus-
pension refluxed for 1 h. After cooling to r. t., the crystalline
material was collected by filtration, washed with methanol
and diethyl ether and dried to yield compound 8. Yield 15 g
(91%), colorless crystals; m. p. 176–178 ◦C. – Rf = 0.65
(CHCl3-THF, 10 : 0.2). – 1H NMR (500 MHz, [D6]DMSO):
(1R)-1-[(1S,3S,5R,6R,8R)-3,8-Bis(4-methoxyphenyl)-
2,4,7,9-tetraoxabicyclo[4.4.0]decan-5-yl]-1-but-3-yne-1-yl
4-nitrobenzoate (19)
4-Nitrobenzoyl chloride (250 mg, 1.35 mmol) was added δ = 7.38 and 7.36 [2d, J = 8.6 Hz, 4H, C(2II)H, C(6II)H,
to a mixture of homoalkynol 16 (500 mg, 1.17 mmol), tri- C(2III)H, C(6III)H], 6.94 and 6.93 [2d, J = 8.9 Hz, 4H,
ethylamine (3 mL), and acetonitrile (20 mL), and the mix- C(3II)H, C(5II)H, C(3III)H, C(5III)H], 5.69 [s, 1H, C(3)H],
ture was stirred at r. t. overnight. The solvent was removed 5.62 [s, 1H, C(8)H], 4.20 and 4.19 [dd, J = 9.5, 2.0 Hz, 1H,
at reduced pressure. The solid residue was suspended in C(1I)H], 4.13 [bt, 2H, J = 15 Hz, C(10)H2], 4.07–4.02 [m,
methanol. The crystalline material was collected by fil- 2H, C(5)H and C(6)H], 3.92 [bs, 1H, C(1)H], 3.75 (s, 6H,
tration, washed with methanol and dried to yield com- 2 ArOCH3), 3.42 (d, J = 2.0 Hz, 1H, C≡CH), 3.35 [s, 3H,
pound 19, which was recrystallized from acetonitrile. Yield C(1I)OCH3]. – 13C NMR (125.76 MHz, [D6]DMSO): δ =