PAPER
Synthesis and Properties of 1,6-Difunctionalized Cyclodeca-3,8-diynes
435
chromatography on silica gel (hexane–Et2O, 1:1) to yield 0.404 g
factors) have been deposited at the Cambridge Crystallographic
(65%) of 15 as a colorless solid.
Data Centre CCDC No. 200224.
Mp 84–85 °C.
X-ray Structural Analysis of 14(a,a)19
IR (KBr): 2917, 2849, 1727, 1716, 1627, 1428, 894 cm–1.
1H NMR (300 MHz, CDCl3): δ = 9.68–9.66 (d, 2 H, J = 4.42 Hz),
2.67–2.43 (m, 10 H).
13C NMR (75 MHz, CDCl3): δ = 201.50 (d), 81.49 (s), 46.80 (d),
Molecular formula C14H14N2, Mr = 210.27, crystal size
0.36 × 0.34 × 0.32 mm3, space group P21/n, a = 6.7497(2),
b = 8.7005 (3), c = 10.0577(3) Å, β = 102.062(1)°, V = 577.61(3)
Å3, Z = 2, ρcalcd = 1.209 Mg/m3, t T = 200 K, limiting indices –8h8,
–11k11, –13l13, scan range [°] 3.13<θ<27.47, λ = 0.71073 Å, re-
46.76 (d), 19.70 (t), 19.65 (t).
flections
R(int) = 0.0217, R1 = 0.034, wR2 = 0.090, S(GooF) = 1.10,
max = 0.21 [eÅ–3], ( min = 0.16 [eÅ–3]. Crystallographic data
collected/unique/observed
5740/1321/1164,
Anal. Calcd for C12H12O2: C, 76.57; H, 6.43. Found: C, 76.31; H,
6.39.
(
)
)
(excluding structure factors) have been deposited at the Cambridge
Crystallographic Data Centre CCDC No. 200225.
4,9-Bis(2-methoxyvinyl)-cyclodeca-1,6-diyne (16)
To a stirred suspension of (methoxymethyl)triphenylphosphonium
chloride (1.92 g, 5.60 mmol) in anhyd THF (20 mL) under argon at-
mosphere was added dropwise a solution of n-BuLi (3.55 mL, 1.6
M in hexane). The deep red reaction mixture was allowed to stir for
1.5 h. A solution of dialdehyde 15 (0.207 g, 1.10 mmol) in anhyd
THF (5 mL) was added and allowed to stir at r.t. overnight. The re-
action was quenched by adding H2O (10 mL) and the aqueous layer
was extracted with Et2O (25 mL). The combined organic layers
were washed with brine (15 mL), dried (MgSO4) and evaporated to
remove the solvent. The crude product was purified by chromatog-
raphy on silica gel (hexane–Et2O, 9:1) to yield the isomeric mixture
(4 isomers) of enol ether 16 (164 mg, 61%) as a colorless solid.
Acknowledgment
We are grateful to the Deutsche Forschungsgemeinschaft, the Fonds
der Chemischen Industrie and the BASF Aktiengesellschaft, Lud-
wigshafen, for financial support. S. K. C. thanks the A. v. Humboldt
Foundation for a fellowship.
References
(1) (a) Ziegler, K. In Methoden der Organischen Chemie,
Houben-Weyl, Vol. IV/2; Müller, E., Ed.; Georg Thieme
Verlag: Stuttgart, 1955, 729–822. (b) Illuminati, G.;
Mandolini, L. Acc. Chem. Res. 1981, 14, 95.
(2) (a) Dale, J. Angew. Chem., Int. Ed. Engl. 1966, 5, 1000;
Angew. Chem. 1966, 78, 1070. (b) Dietrich, B.; Viout, P.;
Lehn, J.-M. In Macrocyclic Chemistry; VCH: Weinheim,
1993.
(3) (a) Gleiter, R.; Merger, R. In Modern Acetylene Chemistry;
Stang, P. J.; Diederich, F., Eds.; VCH: Weinheim, 1995,
285–319. (b) Gleiter, R. Angew. Chem., Int. Ed. Engl. 1992,
31, 27; Angew. Chem. 1992, 104, 29.
Mp 115–117 °C.
IR (KBr): 2917, 1656, 1469, 1262 cm–1.
1H NMR (500 MHz, CDCl3): δ = 6.38–6.34 (m, 6 H), 5.87–5.85 (m,
2 H), 4.88–4.83 (m, 6 H), 4.60–4.55 (m, 2 H), 3.56–3.55 (m, 6 H),
3.49 (s, 18 H), 2.90–2.88 (m, 2 H), 2.41–2.35 (m, 24 H), 2.22–2.17
(m, 14 H).
13C NMR (125 MHz, CDCl3): δ = 147.36, 147.31, 147.25, 147.24,
146.14, 146.13, 108.73, 105.98, 82.18, 81.82, 65.10, 59.74, 56.04,
56.02, 55.88, 35.00, 27.50, 27.45, 27.40, 27.35, 25.96, 25.91, 25.84.
HRMS–FAB: m/z calcd for [C16H21O2]+, 245.1463; found,
245.1493.
(4) Gleiter, R.; Merger, R.; Nuber, B. J. Am. Chem. Soc. 1992,
114, 8921.
(5) Etournaud, A.; Wyler, H. Helv. Chim. Acta 1973, 56, 625.
(6) Brillon, D.; Deslongchams, P. Tetrahedron Lett. 1986, 27,
1131.
(7) Ramming, M. unpublished results.
(8) Ramming, M. Diplomarbeit; Universität Heidelberg:
Germany, 1992.
(9) (a) Cregge, R. J.; Herrmann, J.-L.; Lee, C. S.; Richman, J. E.;
Schlessinger, R. H. Tetrahedron Lett. 1973, 15, 2425.
(b) Petragnani, N.; Yonashiro, M. Synthesis 1982, 521.
(10) Chandrasekaran, S.; Kluge, A. F.; Edwards, J. A. J. Org.
Chem. 1977, 42, 3972.
Preparation of the Bisaldehyde 17
A diastereomeric mixture of enol ether 16 (0.195 g, 0.800 mmol),
p-toluenesulfonic acid (76.0 mg, 0.400 mmol), H2O (2 mL) and di-
oxane (8 mL) was heated under reflux for 2 h. The cooled mixture
was diluted with H2O (5 mL), extracted with Et2O (20 mL), and the
combined extracts were washed with brine (10 mL), dried (MgSO4)
and concentrated to yield 0.116 g (67%) of bisaldehyde 17 (dia-
stereomeric ratio 4:3) as a colorless solid.
Mp 104 °C.
IR (KBr): 2926, 1719, 1637,1435, 1261, 1098 cm–1.
1H NMR (500 MHz, CDCl3): δ = 9.79 (s, 2 H), 2.74–2.70 (m, 4 H),
(11) Hassner, A.; Alexanian, V. Tetrahedron Lett. 1978, 20,
4475.
2.42–2.34 (m, 8 H), 2.25–2.19 (m, 2 H).
13C NMR (125 MHz, CDCl3): δ = 201.19 (d), 200.96 (d), 81.63 (s),
81.53 (s), 47.60 (t), 47.08 (t), 28.22 (d), 28.07 (d), 25.02 (t), 24.94
(t).
HRMS (EI+): m/z calcd for [C14H16O2]+, 216.1150; found,
(12) Noller, C. R.; Adams, R. J. Am. Chem. Soc. 1926, 48, 1080.
(13) Hayashi, H.; Nakanishi, K.; Brandon, C.; Marmur, J. J. Am.
Chem. Soc. 1973, 95, 8749.
(14) Roedig, A. In Methoden der Organischen Chemie, Houben-
Weyl, Vol. V/4; Müller, E., Ed.; Georg Thieme Verlag:
Stuttgart, 1960, 595–605.
(15) (a) Omura, K.; Swern, D. Tetrahedron 1978, 34, 1651.
(b) Manusco, A. J.; Swern, D. Synthesis 1981, 165.
(16) Gleiter, R.; Karcher, M.; Jahn, R.; Irngartinger, H. Chem.
Ber. 1988, 121, 735.
(17) Kessler, H. Angew. Chem., Int. Ed. Engl. 1970, 9, 219;
Angew. Chem. 1970, 82, 237.
216.1148.
X-ray Structural Analysis of 13(a,e)19
Molecular formula C12H14Br2, Mr
= 318.05, crystal size
0.37 × 0.35 × 0.35 mm3, space group P21/n, a = 11.951(4),
b = 9.501(2), c = 11.668(3) Å, β = 118.58(2)°, V = 1163.4(5) Å3,
Z = 4, ρcalcd = 1.82 Mg/m3, T = 193 K, limiting indices 0h15, 0k12,
–15l13, scan range [°] 2.9<θ<28.0, λ = 0.71073 Å, reflections
(18) Ritter, J.; Gleiter, R.; Irngartinger, H.; Oeser, T. J. Am.
Chem. Soc. 1997, 119, 10599.
(19) Data sets were collected on a Enraf-Nonius CAD4 [13(a,e)]
and a Bruker Smart CCD diffractometer.
collected/unique/observed
2923/2796/2064,
R(int) = 0.034,
R1 = 0.041, wR2 = 0.075, S(GooF) = 1.06, (
)
max = 0.61 [eÅ–3],
(
)
min = –0.65[eÅ–3]. Crystallographic data (excluding structure
Synthesis 2003, No. 3, 431–435 ISSN 0039-7881 © Thieme Stuttgart · New York