Basf Aktiengesellschaft

Karl Von Fraunberg

Werner Hoffmann

Joachim Paust

Hardo Siegel

Walter Himmele

Manfred Baumann

Sigberg Pfohl

Werner Hoffman

Norbert Mueller

New 1-acyl- and 1-hydroxymethyl-cyclododecanes and -cyclododecenes. The new 1-acyl-cyclododecenes and -cyclododecanes are obtained by a Rupe or Meyer-Schuster rearrangement, with or without subsequent hydrogenation in the presence of Ni, Pd and Pt catalysts. The 1-acyl-cyclododecenes and -cyclododecanes are valuable scents of the basic type of the sought-after macrocyclic musk scents. Furthermore, they are used for the manufacture of numerous other new 1-substituted or 1-and 2-substituted cyclododecenes and cyclododecanes having good scent characteristics.

Musk-like scents and their manufacture

2-Halomethyl-, 2-alkoxymethyl- and 2-acyloxymethyl-3-methyl-3-formyl-bicyclo[2.2.1]heptane and -hept-5-ene and a process for their preparation. The new compounds are obtained by reacting cyclopentadiene or dicyclopentadiene with the corresponding 4-halo-, 4-alkoxy- or 4-acyloxy-2-methyl-crotonaldehydes under the conventional conditions for Diels-Alder reactions, with or without subsequent catalytic hydrogenation of the Diels-Alder adduct obtained. The new compounds provide an industrially easily realized and advantageous method of synthesis of the sought-after essential ingredients of natural sandalwood oils.

Bicyclic aldehydes

New polycyclic Diels-Alder adducts which are formed on reaction of 8-vinyl-tricyclo-[5,2,1,0.sup.2,6 ]-dec-8-ene or 8-hydroxy-8-vinyl-tricyclo-[5,2,1,0.sup.2,6 ]-decane with alkenes or alkynes having one or two activating substituents, e.g., --COOH, --COOCH.sub.3, --COOC.sub.2 H.sub.5, --CHO, --COCH.sub.3, --COC.sub.2 H.sub.5 or --CN. They have green, fresh, fruity and in some cases woody odors with long-lasting tenacity and/or fixing properties. They can be used as constituents of perfumes and of compositions for perfuming body care products, detergents and other consumer products.

Polycyclic scents

The new product 3-oximino-4-oxo-2,5-dimethyl-tetrahydrofuran is manufactured by oximation of the new product 3-carboxy-4-oxo-2,5-dimethyl-tetrahydrofuran with aqueous nitrous acid, nitrite esters or nitrosyl chloride. Because of its fine caramel-like fragrance it may be used for the manufacture of scents and flavor materials. In addition it presents an advantageous method of synthesis of the sought-after flavor material 4-oxo-3-hydroxy-2,5-dimethyl-4,5-dihydrofuran (furaneol).

3-Oximino-4-oxo-2,5-dimethyl-tetrahydrofuran

Pinanes substituted by a group X in the 3-position which group is formyl, or its alkyl-acetals or alkyl-hemiacetals, carboxylic acid, carboxylic acid chloride, carboxylic acid amide, hydroxymethyl or aminomethyl substituted in a specific manner at the nitrogen, the optical isomers of these compounds and a process for their manufacture by hydroformylation of .alpha.-pinene in the presence of rhodium catalysts, and conversion of the 3-formylpinane first produced into the above derivatives by conventional methods.

Pinane derivatives

Cyclopentene derivatives (I) ##STR1## where R.sup.1 is isopropyl or isopropenyl, R.sup.2 is alkyl of 1 to 3 carbon atoms, X is --CHO, a dialkyl acetal or 1,2- or 1,3-alkylene acetal thereof where the acetal radical is of 2 to 6 carbon atoms, --CH.sub.2 OH or --CH.sub.2 OCOR.sup.3 where R.sup.3 is hydrogen or alkyl or alkenyl of up to 3 carbon atoms. The manufacture of I from the corresponding halomethyl cyclopentenes and aldehydes R.sup.2 --CH(CH.sub.3)--CHO in the presence of a base and a quaternary ammonium salt, followed if desired by acetalization or conversion of the --CHO group to the --CH.sub.2 OH or --CH.sub.2 O--CO--R.sup.3 groups. The compounds are useful as fragrance materials.

Cyclopentene derivatives

New macrocyclic ketolactones, especially 15-methyl-15-ethyl- and 15,15-dimethyl-12-oxo-15-hydroxytetradecanecarboxylic acid lactone. The new ketolactones have an intense and delicate woody musky odor and may be employed as scents and fixatives.

Ketolactones

Cyclopentene derivatives of the general formula ##STR1## where Hal is chlorine, bromine or iodine.

1-Methyl-2-halogenomethyl-3-isopropenyl-cyclopent-1-enes

.gamma.,.delta.-Unsaturated non-cyclic aliphatic ketones are prepared by reacting specific .alpha.,.beta.-unsaturated ketones with vinylmagnesium halide in the presence of inorganic copper compounds at temperatures below 0.degree. C. The reaction products are valuable intermediates in the synthesis of a number of perfumes. For example, the compound 3,3-dimethyl-1-hexen-5-one which may be prepared from mesityl oxide and vinylmagnesium chloride is an intermediate for lavandulyl compounds such as lavandulol and lavandulyl acetate.

Manufacture of .gamma.,.delta.-unsaturated ketones

A process for the manufacture of lavandulol and its esters, starting from the new compound 3,5,5-trimethyl-1,6-heptadien-3-ol, which is converted by conventional methods to 3,5,5-trimethyl-hepta-2,6-dien-1-ol or its esters, which are rearranged to lavandulol or lavandulyl esters by heating at from 150.degree. to 250.degree. C. Using the new process, the desirable product lavandulol, and its esters, which are also of great interest as scents, and even previously unknown lavandulyl esters, can be manufactured simply, in goods yields and in excellent purity, from easily obtainable starting compounds. Both the new starting compound 3,5,5-trimethyl-hepta-1,6-dien-3-ol and the new 3,5,5-trimethyl-hepta-2,6-dien-1-yl esters, obtained as intermediates, are scents and can be employed in the perfumery industry.

Manufacture of lavandulol and its esters

A process for resolving racemic .alpha.-hydroxy-.beta.,.beta.-dimethyl-.gamma.-butyrolactone, referred to as D,L-pantolactone, into its optical antipodes, based on the separation of diastereomeric salts of D,L-pantoic acid (.alpha.,.gamma.-dihydroxy-.beta.,.beta.-dimethylbutyric acid), produced from D,L-pantolactone, by means of (-)-3-aminomethylpinane, (+)-3-aminomethylpinane or one of their acid addition salts, as a new resolving agent.

Growing community of inventors

Bobenheim, Germany

Karl Von Fraunberg