Basf Aktiengesellschaft

Hans-Martin Weitz

Rolf Hartmuth Fischer

Juergen Hartig

Rolf Schnabel

Klaus Volkamer

Ulrich Wagner

Joachim Paust

Rolf Platz

Alfred Lindner

Ludwig Vogel

Klaus-Juergen Schneider

Wolfgang Hoelderich

Dieter Lenke

Wolf D Mross

Franz J Broecker

Eckhard Hetzel

Klaus Broellos

Franz Merger

Hardo Siegel

Laszlo Marosi

Hans-Henning Vogel

Wolfgang Reiss

Otto Hertel

Dieter Stockburger

Klaus-Dieter Malsch

Klaus Schmieder

Kurt Kahr

Eckart Schubert

Harald Schwentker

Klaus-Jurgen Schneider

Hans H Pohl

Gerd Kissau

Toni Pfeiffer

Friedhelm Bandermann

Detlef Bender

Helmuth Grube

Klaus Brollos

1,4-Diacyloxybut-2-enes and 3,4-diacyloxybut-1-enes are converted into one another in the gas phase or liquid phase at from 100.degree. to 350.degree. C. under atmospheric or superatmospheric pressure in the presence of a zeolite as a catalyst.

Isomerization of diacyloxybutenes

A catalyst containing copper and silica is prepared by a process in which an aqueous alkali metal silicate solution containing from 1 to 26% by weight of SiO.sub.2 is brought to a pH of from 0.5 to 2.0 with nitric acid, an aqueous copper nitrate solution containing from 5 to 15% by weight of Cu is added, after the addition of the nitric acid, so that a clear solution containing from 0.18 to 3.0 moles of Cu per mole of SiO.sub.2 is formed, the resulting solution is mixed with an aqueous alkali metal carbonate solution at from 40.degree. to 80.degree. C., the pH of the mixture being kept at from 7.5 to 8.5, and the precipitated material is separated off, dried, calcined by heating at from 250.degree. to 400.degree. C. and pressed in a conventional manner to give catalyst moldings. The catalyst thus obtained is used for the hydrogenation of dialkyl dicarboxylates to diols.

Preparation of a catalyst containing copper and silica

Acyloxy-2-butenes of the formula ##STR1## where R.sup.1, R.sup.3 and R.sup.4 are each hydrogen or alkyl of 1 to 5 carbon atoms, R.sup.2 is alkyl of 1 to 5 carbon atoms, R.sup.5 is hydrogen, alkyl of 1 to 5 carbon atoms or R.sup.6 --CO--O, and R.sup.6 and R.sup.7 are each hydrogen, alkyl of 1 to 5 carbon atoms, phenyl or cyclohexyl, the preparation of these acyloxy-2-butenes by reaction of 1-acyloxy-1,3-butadienes of the formula ##STR2## with carboxylic acids of the formula R.sup.7 --COOH and oxygen at 50.degree.-180.degree. C. in the presence of catalysts containing palladium or platinum, and the use of the compounds of the formula I, where R.sup.1, R.sup.3, R.sup.4 and R.sup.5 are hydrogen, R.sup.2 and R.sup.6 are methyl and R.sup.7 is methyl or ethyl, for the preparation of 4-acyloxytiglic aldehydes.

Acyloxy-2-butenes and their preparation

2-Methylalk-2-enals of the formula ##STR1## where R.sup.1 and R.sup.2 are each hydrogen, alkyl or an aromatic radical, are prepared by isomerization of an acrolein derivative of the formula ##STR2## with a zeolite catalyst, an aluminum silicate and/or an aluminum phosphate.

Preparation of 2-methylalk-2-enals

Butane-1,4-diol is prepared by catalytic hydrogenation of dibutyl succinate by a process in which hydrogenation is terminated before complete conversion is reached, butanol is distilled off from the reaction mixture, the liquid distillation residue is cooled to below 108.degree. C., the upper phase, which is formed as a result of phase separation and essentially consists of dibutyl succinate, is recycled to the hydrogenation, and the butane-1,4-diol is obtained from the lower phase, which essentially consists of this compound, by fractional distillation under reduced pressure.

Preparation of butane-1,4-diol

.omega.,.omega.-Diacyloxy-2,6-dimethyl-octatrienoates and -octatrienals, as novel bifunctional asymmetric C.sub.10 building blocks for terpene syntheses, which possess a formyl or alkoxycarbonyl group at one chain end and 2 geminal acyloxy groups at the other, and a process for their preparation from readily obtainable industrial C.sub.5 building blocks and their use for the synthesis of terpene compounds by carbonyl olefination under conventional conditions.

.omega.,.omega.-Diacyloxy-2,6-dimethyl-octatrienoates and -octatrienals,

Acyloxyalkadienoates of the formula ##STR1## where R.sup.1, R.sup.2, R.sup.3, R.sup.6 and R.sup.7 are each hydrogen or a hydrocarbon radical, and R.sup.1 may furthermore be R.sup.6 --O--CO--, R.sup.4 is hydrogen or a hydrocarbon radical, but may only be hydrogen if x is 0, R.sup.5 is hydrogen, or is ##STR2## if x is 0, and x is 0 or 1, and their preparation.

Acyloxyalkadienoates and their preparation

2-alkyl-4,4-diacyloxybut-2-enals of the formula ##STR1## where R.sup.1 is alkyl and R.sup.2 and R.sup.3 are each hydrogen or an aliphatic, cycloaliphatic or aromatic radical, are prepared by a process wherein a 2-alkyl-2,4-diacyloxybut-3-enal of the formula ##STR2## is treated with an aliphatic carboxylic acid.

Preparation of 2-alkyl-4,4-diacyloxybut-2-enals

But-2-ene-1,4-diones substituted in the 1,4-positions, of the formula ##STR1## where R.sup.1 and R.sup.2 are each an aliphatic hydrocarbon radical of 1 to 17 carbon atoms, are prepared by a process in which a 2,5-disubstituted furan of the formula ##STR2## where R.sup.1 and R.sup.2 have the above meaning, is oxidized with a percarboxylic acid in the presence of a carboxylic acid.

Preparation of but-2-ene-1,4-diones substituted in the 1,4-positions

2-Alkyl-2,4-diacyloxy-but-3-enals of the formula ##STR1## where R.sup.1 is alkyl and R.sup.2 is hydrogen, alkyl, a cycloaliphatic radical or an aromatic radical, are prepared by reacting a buta-1,3-diene of the formula ##STR2## with an oxygen donor. The new compounds are valuable intermediates in the preparation of terpenes, e.g. retinal, .beta.-carotin and apocarotinoids.

2-Alkyl-2,4-diacyloxy-but-3-enals

1,4-diacyloxybutenes are prepared by reacting a 1,3-butadiene with a carboxylic acid and oxygen in the presence of a catalyst in a reactor, by a process in which the 3,4-diacyloxybutene formed as a by-product in the reaction is separated off from the reaction mixture, and some or all of this 3,4-diacyloxybutene is recycled to the reactor.

Preparation of diacyloxybutenes

A process for preparing diacyloxyalkadienes of the formula ##STR1## where R.sup.1 to R.sup.6 are each hydrogen or a hydrocarbon radical, which contain one or more hydrocarbon radicals having one or more non-conjugated double bonds, by reacting an aliphatic triene of the formula ##STR2## in which R.sup.1 to R.sup.6 have the same meanings given above with a carboxylic acid of the formula

Preparation of diacyloxyalkadienes

A process for the preparation of a diacyloxyhexadiene of the formula ##STR1## where X is R.sup.9 -CO- and R.sup.1 to R.sup.9 are hydrogen or alkyl of 1 to 3 carbon atoms, by reacting a hexatriene of the formula ##STR2## with oxygen and a carboxylic acid of the formula R.sup.9 COOH in the presence of a catalyst which contains palladium, platinum or a salt of these metals.

Preparation of diacyloxyhexadienes from hexatrienes

A process for the preparation of .alpha.,.beta.-unsaturated aldehydes by reacting a 1,4-diacyloxyalk-2-ene, which is substituted in the 2-position by an aliphatic radical, with water in the presence of an acid, and of 2,7-dimethylocta-2,6-dienal.

Preparation of .alpha.,.beta.-unsaturated aldehydes and

3-Alkyl-3-acyloxy-4-hydroxybut-1-enes are prepared by a process in which a 3-alkyl-3,4-epoxybut-1-ene is treated with a carboxylic acid and a copper salt of a carboxylic acid.

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Bad Durkheim, Germany

Hans-Martin Weitz