Roche Vitamins Inc.

Hoffmann-la Roche Inc.

August Ruttimann

Bruno Burdet

Paul Nosberger

Theodor Siegfried

George H Buchi

Jean-Marie Santer

A process for the manufacture of polyene aldehydes comprises reacting a polyene O,O-ethylene acetal with a 1-alkoxy-1,3-diene in the presence of a Lewis acid or Bronsted acid, hydrolyzing the resulting condensation product and cleaving off alcohol under basic or acidic conditions from the polyene derivative produced at this stage. The novel polyene O,O-ethylene acetals as well as the likewise novel condensation products in this process form further aspects of the invention. The final products are primarily carotenoids which find corresponding use, e.g. as colorants and pigments for foodstuffs, animal products etc.

Manufacture of polyene aldehydes

A process for the manufacture of a .gamma.-acetoxy-tiglic aldehyde by reacting a .gamma.-bromotiglic aldehyde or a .gamma.-chlorotiglic aldehyde with sodium acetate or potassium acetate in an organic solvent in the presence of a phase transfer catalyst.

Process for the manufacture of a .gamma. -acetoxy-tiglic aldehyde

A novel process for the manufacture of a .gamma.-halotiglic aldehyde HalH.sub.2 C-CH.dbd.C(CH.sub.3)-CHO [I], wherein Hal signifies chlorine or bromine, comprises haloalkoxylating a 1-alkoxy-2-methyl-1,3-butadiene H.sub.2 C.dbd.CH-C (CH.sub.3).dbd.CH-OR.sup.1 [II], wherein R.sup.1 signifies C.sub.1-4 -alkyl, using a particular halogenating agent in a C.sub.1-4 -alkanol (R.sup.2 OH) and hydrolyzing the thus-obtained .gamma.-halotiglic aldehyde dialkyl acetal HalH.sub.2 C-CH.dbd.C(CH.sub.3)-CH (OR.sup.1)(OR.sup.2) [III] to the desired .gamma.-chloro- or .gamma.-bromotiglic aldehyde I. The halogenating agent used in this process is selected from an alkali metal hypochlorite, an alkali metal hypobromite, an alkaline earth metal hypochlorite, an alkaline earth metal hypobromite, tert.butyl hypochlorite, N-bromoacetamide, 1.3-dichloro-5,5-dimethylhydantoin and 1,3-dibromo-5,5-dimethylhydantoin. Further aspects of the present invention are the use of the thus manufactured .gamma.-halotiglic aldehyde for the production of .gamma.-acetoxy-tiglic aldehyde or of a Wittig aldehyde halide Hal-Ph.sub.3 P.sup.+ CH.sub.2 -CH.dbd.C(CH.sub.3)-CHO [VII], wherein Hal signifies chlorine or bromine and Ph a process for the catalytic dealkoxylation of the 1,1,3-trialkoxy-2-methyl-butane CH.sub.3 -CH(ORl)-CH(CH.sub.3)-CH(OR.sup.1).sub.2 [VI] to the corresponding 1-alkoxy-2-methyl-1,3-butadiene II in the gas phase using an aluminium silicate of medium specific surface as the catalyst. The products I, .gamma.-acetoxy-tiglic aldehyde and VII are known, important intermediates for the production of various apocarotenoids and diapocarotenoids as well as of Vitamin A.

Process for the catalytic dealkoxylation of

A process for the manufacture of polyene esters or polyene acids comprises reacting a polyene O,O-dialkylacetal of di(O,O-dialkylacetal) with a vinylketene acetal or analogue thereof in the presence of a Lewis acid, hydrolyzing the reaction mixture depending on the vinylketene acetal used, subsequently cleaving alcohol under strongly basic conditions from the polyene derivative produced at this stage and, where the desired ester or carboxy group is still not present, performing the respective conversion. Certain intermediates in this process form a further aspect of the invention. The final products are primarily carotenoids which can be used appropriately, e.g. as colorants and pigments for foodstuffs, animal products etc.

Process for manufacturing polyene esters and acids

To manufacture polyene aldehydes and polyene dialdehydes a polyene O,O-dialkyl acetal or polyene di(O,O-dialkyl acetal) is reacted with a 1-alkoxy-1,3-diene in the presence of a Lewis acid or a Bronsted acid. The reaction mixture is then hydrolyzed and the alcohol is cleaved under basic conditions from the polyene derivative produced by the reacting. Those intermediates in this process from which the alcohol is to be cleaved are novel. The final products are primarily carotenoids which can be used as colorants and pigments for foodstuffs, animal products, and the like.

Process for manufacturing polyene aldehydes

A novel process for the manufacture of a .gamma.-halotiglic aldehyde HalH.sub.2 C--CH.dbd.C(CH.sub.3)--CHO �I!, wherein Hal signifies chlorine or bromine, comprises haloalkoxylating a 1-alkoxy-2-methyl-1,3-butadiene H.sub.2 C.dbd.CH--C(CH.sub.3).dbd.CH--OR.sup.1 �II!, wherein R.sup.1 signifies C.sub.1-4 -alkyl, using a particular halogenating agent in a C.sub.1-4 -alkanol (R.sup.2 OH) and hydrolyzing the thus-obtained .gamma.-halotiglic aldehyde dialkyl acetal HalH.sub.2 C--CH.dbd.C(CH.sub.3)--CH(OR.sup.1)(OR.sup.2) �III! to the desired .gamma.-chloro- or .gamma.-bromotiglic aldehyde I. The halogenating agent used in this process is selected from an alkali metal hypochlorite, an alkali metal hypobromite, an alkaline earth metal hypochlorite, an alkaline earth metal hypobromite, tert.butyl hypochlorite, N-bromoacetamide, 1.3-dichloro-5,5-dimethylhydantoin and 1,3-dibromo-5,5-dimethylhydantoin. Further aspects of the present invention are the use of the thus-manufactured .gamma.-halotiglic aldehyde for the production of .gamma.-acetoxy-tiglic aldehyde or of a Wittig aldehyde halide Hal-Ph.sub.3 P.sup.+ CH.sub.2 --CH.dbd.C(CH.sub.3)--CHO �VII!, wherein Hal signifies chlorine or bromine and Ph signifies phenyl, as well as a process for the catalytic dealkoxylation of the 1,1,3-trialkoxy-2-methyl-butane CH.sub.3 --CH(OR.sup.1)--CH(CH.sub.3)--CH(OR.sup.1).sub.2 �VI! to the corresponding 1-alkoxy-2-methyl-1,3-butadiene II in the gas phase using an aluminium silicate of medium specific surface as the catalyst. The products I, .gamma.-acetoxy-tiglic aldehyde and VII are known, important intermediates for the production of various apocarotenoids and diapocarotenoids as well as of Vitamin A.

Process for the manufacture of a gamma-halotiglic aldehyde

Novel processes and intermediates useful for the manufacture of the Wittig ester salts are disclosed. The Wittig ester salts are known as important C.sub.5 building blocks for the manufacture of various polyenecarboxylic acid esters in the field of carotenoid chemistry.

Method for the production of (3-alkoxycarbonyl-2-butenyl)

A novel process for the manufacture of quinone derivatives is described. In this process a compound of the formula ##STR1## is reacted with a compound of the formula ##STR2## and the resulting compound of the formula ##STR3## is subjected to a retro-Diels-Alder reaction. The substituents R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the significance given in the description.

Process for the manufacture of quinone derivatives

A novel process for the manufacture of quinone derivatives which are suitable as intermediates for the manufacture of (2RS,4'R,8'R)-tocopherol is described. In this process a quinone of the formula ##STR1## is reacted with a phytyl derivative of the formula ##STR2## If desired, the thus-obtained compound of the formula ##STR3## is subsequently converted into the compound of the formula ##STR4## and, if desired, this compound is converted into the compound of the formula ##STR5## The compound of formula V is known and can be converted into (2RS,4'R,8'R)-tocopherol in a known manner.

Alpha-tocopherol intermediates

A novel process for the manufacture of quinone derivatives which are suitable as intermediates for the manufacture of (2RS,4'R,8'R)-tocopherol is described. In this process a quinone of the formula ##STR1## is reacted with a phytyl derivative of the formula ##STR2## If desired, the thus obtained compound of the formula ##STR3## is subsequently converted into the compound of the formula ##STR4##

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Arlesheim, Switzerland

August Ruttimann