1486
Scheme 7.
1. Experimental
AlCl3-Catalysed reaction of cyclododecene with propylene oxide:AlCl3 (180 g:1.35 mol) was suspen-
ded in CH2Cl2 (1 litre), and cooled to −30°C. A mixture of cyclododecene (200 g:1.2 mol) and propylene
oxide (100 g:1.72 mol) was added dropwise with stirring under N2, maintaining this temperature with
external cooling. After complete addition (1 h), the reaction mixture was immediately quenched by
addition to a stirred mixture of ice (2 litres) and Et2O (2 litres). The organic layer was separated,
washed, and dried over MgSO4. The solvent was removed in vacuo, and the residue chromatographed
(silica:hexane) to give recovered cyclododecene (19.6 g). Further elution, using (hexane 90%:Et2O 10%)
as eluent gave a colourless oil (61.3 g:25.2%), identified as 2-cyclododecylpropan-1-al (7), which could
be reduced by various procedures (NaBH4 or H2, 5% Pd/C) to give material (2), spectroscopic properties
identical to an authentic sample. Continued elution gave a colourless oil (44.6 g:18.3%), identified as
2-methyltetradecahydrocyclododeca[b]furan (3), whose spectroscopic characteristics were identical to a
commercial sample of (3) (Lignoxan®, ex Wacker).
The solvent polarity was increased (hexane 50%:Et2O 50%). Following elution of two poorly-defined
multicomponent mixtures [(2.3 g)+(8.7 g)], a further discrete major product was isolated as a colourless
oil (64.8 g:26.6%). This material was identified as 1-(2-cyclododecenyl)propan-2-ol (8). 13C NMR
(CDCl3): δ 135.7 (CH_CH), 132.2 (CH_CH), 67.7 (CH(CH3)OH), 46.0 (CH2CH(CH3)OH), 41.9
(CHCH2CH(CH3)OH), 34.0 (CH2), 32.4 (CH2), 26.5 (CH2), 26.1 (CH2), 26.1 (CH2), 25.7(CH2), 24.7
(CH2), 23.6 (CH2), 23.4 (CH2), 22.8 (CH3).
References
1. Hafner,W.; Gebauer, H.; Markel, E.; Regiert, M. US Patent 4,948,780 (August, 1990).
2. Consortium fur Elektrochemische Industrie GmbH, US Patent 4,496,748 (January, 1985).
3. Vukicevic, R.; Konstantinovic, S.; Joksovic, L.; Ponticelli, G.; Mihailovic, M. Lj. Chem.Lett. 1995, 275.
4. Munro, D.; Sell, C. S. World Patent WO 9921847 (May, 1999).
5. Newman, C. P.; Rossiter, K. European Patent EP 276,998 (January, 1987).
6. Munro, D.; Sell, C. S.; World Patent WO 9921817 (May, 1999).
7. Ebel, K.; Pinkos, R. World Patent WO 9857914 (December, 1998).