Abstract:
4-Substituted but-3-ene-1-carboxylic acids and their esters R.sup.1 R.sup.2 C.dbd.CH--CH.sub.2 --CO--O--R.sup.3 (I, where R.sup.1 is an organic radical, R.sup.2 is H or R.sup.1, or R.sup.1 and R.sup.2 together form a 5-membered to 20-membered ring, and R.sup.3 is H or lower alkyl) are prepared by carbonylation of R.sup.1 R.sup.2 C(OH)--CH.dbd.CH.sub.2 (II) in the presence of an alcohol R.sup.3' --OH (III, where R.sup.3' is lower alkyl) or, for the preparation of the acids I alone, in the absence of an alcohol III, at from 50.degree. to 150.degree. C. and under from 200 to 700 bar, using a complex of a palladium halide and a tertiary organic phosphine.
Abstract:
1-Formyl-2,6,6-trimethyl-cyclohex-1-ene derivatives of the formula I ##STR1## where R is --H or --CH.sub.3 and A is O or NOH are prepared by nitrosylating the corresponding 1-formyl-2,6,6-trimethyl-cyclohex-1-ene or -cyclohex-2-ene and, where appropriate, hydrolyzing the resulting oxime (where A is NOH) to the corresponding ketone (where A is O).The compounds I, except where R is H and A is O, are novel.
Abstract:
An improved process for the preparation of unsaturated ketones of the general formula I ##STR1## where R.sup.1 is --CH.sub.3, ##STR2## and R.sup.2 and R.sup.3 are different and each is H or --CH.sub.3, by reacting an aldehyde of the general formula II ##STR3## with a molar excess of acetone or methyl ethyl ketone at an elevated temperature in the presence of an aqueous alkali metal hydroxide solution, wherein (a) all the reactants are mixed thoroughly, (b) the temperature is kept at from 10 to 120.degree. C. above the boiling point of the lowest-boiling component and (c) the pressure is kept at from p to 100 bar, where p is the vapor pressure of the mixture at the reaction temperature.The products methylpseudoionone, dimethylpseudoionone, pseudoirone, methylpseudoirone and dimethylpseudoirone are useful scents and scent intermediates. In addition, pseudoionone is an important intermediate for the industrial preparation of vitamin A, and 6-methyl-hepta-3,5-dien-2-one is a sought-after aromatic.
Abstract:
Process for the preparation of the compounds of the formulae Ia and Ib ##STR1## wherein A. 2,4,4-trimethylcyclohex-2-en-1-one oxime of the formula IIb ##STR2## is treated with a strong aqueous acid at from 30.degree. to 80.degree. C., preferably 40.degree. to 70.degree. C.,B. the resulting ketone of the formula IIIb ##STR3## is oxidized in a conventional manner, and C. if desired, the resulting compound Ib is isomerized in a conventional manner.Compounds of the formula A ##STR4## where R is one of the following radicals: --CH(OH)--CH.sub.2 --CH.dbd.CH.sub.2 (IIIb), --CH(OH)--CH.sub.3 (IIIc), --CH.sub.2 OH (IIId), --CH(OH)--CH.dbd.CH.sub.2 (IIIe), --CH(OCOCH.sub.3)--CH.sub.3 (IIIf), --CH.sub.2 --OCOCH.sub.3 (IIIg), --CO--CH.sub.2 --CH.dbd.CH.sub.2 (Ib), --CO--CH.sub.3 (Ic) and --CO--CH.dbd.CH.sub.2 (Ie).The compounds IIIb to IIIg, Ib, Ic and Ie are useful scents and aromas, and furthermore may become important intermediates for novel carotenoids. They can be prepared in a relatively simple manner from compounds which are very readily available.
Abstract:
An improved process for the preparation of cyclocitrals of the general formula I ##STR1## via the novel N-methylaldimines of the general formula II ##STR2## and the novel N-methylaldimines of the formula II. The cyclocitrals of the formula I are obtained in yields of 80-90%, based on citral employed. The compounds I and II are important intermediates for the preparation of fragrances and carotinoids, such as vitamin A, and products related thereto.
Abstract:
Process for the preparation of the compounds of the formulae Ia and Ib ##STR1## wherein A. 2,4,4-trimethylcyclohex-2-en-1-one oxime of the formula IIb ##STR2## is treated with a strong aqueous acid at from 30.degree. to 80.degree. C., preferably from 40.degree. to 70.degree. C.,B. the resulting ketone of the formula IIIb ##STR3## is oxidized in a conventional manner, and C. if desired, the resulting compound Ib is isomerized in a conventional manner.Compounds of the formula A ##STR4## where R is one of the following radicals: --CH(OH)--CH.sub.2 --CH.dbd.CH.sub.2 (IIIb), --CH(OH)--CH.sub.3 (IIIc), --CH.sub.2 OH (IIId), --CH(OH)--CH.dbd.CH.sub.2 (IIIe), --CH(OCOCH.sub.3)--CH.sub.3 (IIIf), --CH.sub.2 --OCOCH.sub.3 (IIIg), --CO--CH.sub.2 --CH.dbd.CH.sub.2 (Ib), --CO--CH.sub.3 (Ic), and --CO--CH.dbd.CH.sub.2 (Ie).The compounds IIIb to IIIg, Ib, Ic and Ie are useful scents and aromas, and furthermore may become important intermediates for novel carotenoids. They can be prepared in a relatively simple manner from compounds which are very readily available.
Abstract:
Novel disubstituted bicyclo[2.2.1]heptanes of the general formula I ##STR1## where R.sup.1 is C.sub.1 -C.sub.3 -alkyl, R.sup.2 is C.sub.1 -C.sub.8 -alkyl or-alkenyl, R.sup.3 and R.sup.4 together are .dbd.O, .dbd.CH--CN, .dbd.CH--CO--OCH.sub.3 or .dbd.CH--CO--OC.sub.2 H.sup.5, or R.sup.3 is hydrogen, --CH.sub.3, --CH.dbd.CH.sub.2 or --C.tbd.CH when R.sup.4 is --OH or --O--CO--CH.sub.3, or R.sup.3 is H when R.sup.4 is --CH.sub.2 --CO--OCH.sub.3, --CH.sub.2 --CO--OC.sub.2 H.sub.5 or --CH.sub.2 --C.tbd.N and one or both of the dashed lines may be a further bond, are obtained by subjecting cyclopentadiene to a Diels-Alder reaction with an unsaturated ketone, this reaction being catalyzed by a Lewis acid, and then subjecting the compound of the formula Ia ##STR2## initially formed to a reduction, a Grignard reaction or a reaction with diethylphosphonoacetonitrile or ethyl phosphonoacetate and NaH.They can be used as scents and/or aromas or as intermediates for scents.
Abstract:
A process for the preparation of a tetralin derivative of the formula ##STR1## where X is a --CH.sub.2 --, --CH(OH)-- or --CO-- group, R.sup.1 is one of the groups --COCH.sub.3, --CH(OR.sup.3).sub.2 or --CHO, R.sup.2 is hydrogen or methyl and R.sup.3 is alkyl of 1 to 4 carbon atoms, by electrochemical oxidation of a compound of the formula ##STR2## where R.sup.4 is methyl or ethyl and X and R.sup.2 have the abovementioned meanings, and novel tetralin derivatives.
Abstract:
Cycloalkylidene derivatives of the general formulae Ia to Ic ##STR1## where the dashed line is a possible additional chemical bond, the radicals R.sup.1 are identical or different C.sub.1 -C.sub.4 -alkenyl groups, R.sup.2 and R.sup.3 are each methyl or ethyl, R.sup.4 is hydrogen or one of the radicals R.sup.1, X is oxygen, methylene or a chemical bond, m is from 0 to 3 or, when X is methylene, is from 1 to 3, or, when X is methylene and R.sup.1 is methyl, is from 2 to 3 and n is from 0 to 3, are used as fragrance materials.
Abstract:
N,N'-disubstituted piperazines of the general formula I ##STR1## where the group is unsaturated (.dbd.) or saturated (--) and the substituents R.sup.1, R.sup.2 and A have the following meanings:A is --, --CH.dbd., --CH.sub.2 --, --CH.sub.2 --CH.sub.2 --,R.sup.1 is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkylcycloalkyl, cycloalkenylalkyl, alkylcycloalkenyl, bicycloalkyl, bicycloalkylalkyl or alkylbicycloalkyl, these radicals being unsubstituted or substituted by hydroxy, halogen, alkoxy or trialkylsilyl,R.sup.1 is further heterocycloalkyl with oxygen and/or sulfur, heterocycloalkylmethyl with oxygen and/or sulfur, alkyl-substituted heterocycloalkylmethyl with oxygen and/or sulfur, andR.sup.2 is alkyl, alkoxy, trimethylsilyl, cycloalkyl, alkylthio,and plant-physiologically tolerated salts thereof, and fungicides containing these compounds.