Compositions – Electrically conductive or emissive compositions – Metal compound containing
Patent
1985-01-10
1987-07-28
Lone, Werren B.
Compositions
Electrically conductive or emissive compositions
Metal compound containing
549457, 558260, 568665, 568817, A61K 746, C11B 90
Patent
active
046830839
DESCRIPTION:
BRIEF SUMMARY
The invention is concerned with mixtures of tricyclo[5.2.1.0.sup.2,6 ]decane-derivatives and the use of these materials as perfumes or as aromas. These compounds are of the general formula A: ##STR2## R.sup.1 and R.sup.2 are a methyl group or a hydrogen atom, one of the substituents being a methyl group and the other a hydrogen atom, substituents being a methyl group and the other a hydrogen atom, at C-5 and a hydrogen atom at C-4, -alkyl, C.sub.1 -C.sub.6 -alkenyl-, C.sub.1 -C.sub.4 -alkoxymethyl, C.sub.1 -C.sub.2 alkoxycarbonyl-, formylmethyl-, or di-C.sub.1 -C.sub.4 -alkoxyethyl group, and alternatively two C--C-single bonds.
The dimer of cyclopentadiene (1), dicyclopentadiene (2), is an important starting material for the production of perfume materials. The esters 3b-c (preparation: Zeilanov et al., Chem. Abstracts, 68, 49319d) obtained by the addition of carboxylic acids (e.g. acetic acid, propionic acid) are used in large amounts world-wide as perfume materials. The formate 3a is described in U.K. Pat. No. 815,232 (6.24.1959) and the dimethylacrylate 3d in U.S. Pat. No. 3,593,745 (8/10/1971). Further perfume materials from dicyclopentadiene were together described by Ohloff and Rode-Sawal (in: H. Aebi, E. Baumgartner, H. P. Fiedler and G. Ohloff, "Nosmetika, Riechstoffe und Lebensmittelzusatzstoffe", G. Thieme Verlag, stutugart 1978, pp. 55-57). ##STR3##
Little is known about the products of methylcyclopentadiene (4). In European Pat. appln. No. 0 039 232 were claimed as scents (perfume materials) dimethyltricyclodecane-derivatives of the general formula 5 obtained from the dimeric methylcyclopentadiene (4), the broken line representing an optional double bond. The methyl group in the norbornane part should alternatively be the R.sub.1 or R.sub.2 group and the methyl group in the cyclopentene part should alternatively be the R.sub.4, R.sub.5 or R.sub.6 group. The respective non-substituted positions R.sub.1, R.sub.2, R.sub.4-6 should be occupied by hydrogen. The molecular group Y should be a carbonyl-, hydroxyl-, acetate-, propionate-, or a C.sub.3 - or C.sub.4 - either group. The products consist of isomeric mixtures. ##STR4##
German Pat. No. OLS 3 120 700 Al (2/25/1982) describes tricyclodecane-derivatives of general formula 7 and their use as scents.
The preparation of the new compounds of general formula A started from dimeric methylcyclopentadiene.
Methylcyclopentadiene (preparation: review W. T. Ford, J.Org. Chem. 25, 3979 (1971)) exists as a mixture of three double-bonded isomers 4a, b, c. According to S. McLean and P. Haynes (Tetrahedron 21, 2313 (1965)) it exists in equilibrium as 44.5% of 1-methyl-isomer 4a, 54.5% of C-2-isomer 4b and only about 1% of c-5-isomer 4c.
By the dimerization of anequilibrium mixture of methylcyclopentadiene a plurality of products can theoretically be prepared. By this hypothesis, products with angular methyl groups are sterically unfavorable and do not arise in significant amounts, and that product derived from 4c (<1%) can be ignored, so that ##STR5## the dimerised methylcyclopentadiene (gaschromatogram: FIG. 1) comprises the structural isomers 8a-h. The .sup.1 H-NMR-spectrum (FIG. 2) indicates signal groups in the range of olefinic protons (5-6 ppm), which correspond to their integral 2,2 protons. The signals at 1.25 and 1.50 ppm can by analogy with dicyclopentadiene (Sadtler-NMR-spectra collection No. 6494M) be classified as the protons of the C.sub.1 -bridge. Only the relatively low-intensity signals at 1.23 and 1.35 ppm can be classified as the bridging methyl group of 8a-d. These findings and the intensities of the olefinic signals point to the preponderant presence of isomers 8e-h (about 85%), while 8a-d exists as only about 15%. ##STR6##
The selective hydrogenation of the norbornane part of the isomeric dimethylcyclopentadienes 8a-h is by a modification of a method of Ch. A. Brown for the selective hydrogenation of dicyclopentadiene (2) (Ch. A. Brown, Che. Commun. 1969, 952; H. C. Brown and Ch. A. Brown, J. Am. Chem. Soc., 85, 1004 (1963). Using nick
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Brunke Ernst-Joachim
Struwe Hartmut
Dragoco Gerberding and Co. GmbH
Lone Werren B.
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