Montedison S.p.a.

Anic S.p.a.

Montedison Fibre S.p.a.

Istituto Donegani S.p.a.

Gian P Chiusoli

Luciano Pallini

Giuseppe Salerno

Giorgio Bottaccio

Marcello Marchi

William Giroldini

Roberto Santi

Giuseppe Cometti

Enzo Alneri

Giulio Lana

Giuliana Terenghi

Mirco Costa

Alfredo Musco

Process for the preparation of (omega-carbalkoxy-nor.alkyl) dialkylamines having a linear alkyl chain, comprising the steps of amination of allyl compounds in which at least an allyl carbon atom is a part of a cyclopropane ring which contains one or two carboxyl or carbalkoxy groups on the carbon atom which is adjacent to the allyl carbon, or is a part of a lactone ring, in the presence of catalysts consisting of triarylphosphine complexes of palladium, or trialkyl phosphite complexes of nickel, and the subsequent hydrogenation of the unsaturated amine thus obtained. By so doing, interesting linear amines are obtained, which contain carboxyl units or carbalkoxy units, said amines being useful as additives for the industry of synthetic fibres (viscosity stabilizers for polycaprolactam).

Process for the preparation of

This invention relates to a process for preparing dienoic acids. In particular, the present invention relates to a catalytic process for preparing octadienoic acids from 3-butenoic acids and butadiene. More particularly the present invention is directed to the preparation of octadienoic acids haing the two double bonds in position 3,6 and 2,6 in respect of the carboxylic carbon, starting from 3-butenoic acids and butadiene in the presence of complex catalysts of Rhodium or of Nickel.

Process for preparing dienoic acids

Optically active methyl esters of arylpropionic acids are prepared by reaction of the corresponding vinylaromatic compounds with carbon monoxide and methyl alcohol in the presence of a palladium catalyst system consisting of a palladium compound associated with optically active diphenyl-neomenthylphosphine and with trifluoroacetic acid, at substantially atmospheric pressure and at a temperature comprised between 20.degree. and 80.degree. C. There is dealt with particular regioselective and enantioselective catalysis conditions. The products obtained consist of esters of arylpropionic acids or of the corresponding acids obtainable from them, and are useful intermediates in the synthesis of organic compounds, particularly of pharmaceutical products.

Process for the preparation of methyl esters of arylpropionic acids

There is disclosed and claimed a process for preparing aryl- and heteroarylhexadienoic acids which is characterized in that an aryl- or heteroarylacetylene having the formula: R--C.tbd.CH, wherein R is an aryl or heteroaryl group, optionally substituted and having in the aggregate up to 20 carbon atoms, is reacted with 3-butenoic acid CH.sub.2 .dbd.CH--CH.sub.2 --COOH, in an alcoholic medium, at temperatures maintained between 50.degree. C. and 120.degree. C., approximately, in the presence of a catalyst selected from among the phosphinic complexes of rhodium having the formulas: III, Rh(PR'.sub.3).sub.n L.sub.m X associated with alkaline salts of carboxylic acids having up to 4 carbon atoms, and IV, Rh(PR'.sub.3).sub.n L.sub.p.sup.+ Y.sup.-, wherein R' is a hydrocarbyl group having up to 12 carbon atoms; 'L' is a linear or cyclic olefin selected from among the olefins having from 2 to 10 carbon atoms and the chelating olefins having from 6 to 8 carbon atoms, n is an integer from 1 to 3, m is an integer from 0 to 2 and such that n+m=2 or 3, and p is an integer from 0 to 3 and such that n+p=3 or 4; X is an anion selected from among the haloid anions, preferably the hydrochloric anion, and the anions of carboxylic acids having up to 4 carbon atoms and Y is a sparingly coordinating anion, preferably selected from PF.sub.6.sup.- and BF.sub.4.sup.-. The compounds obtained are used as intermediates for organic syntheses, with particular regard to the so-called 'fine chemicals' such as, for example, additives for polymers and paints, plasticizers, and the like.

Process for preparing aryl- or heteroarylhexadienoic acids

Dienoic acids are prepared by reaction of salts of 3-butenoic acid and vinyl halides, in the presence of catalysts which are phosphinic complexes of rhodium or nickel.

Octadienyl esters of 2-ethylidene-hepta-3,5-dienoic and 2-vinyl-hepta-3,5-dienoic acids of formula C.sub.8 H.sub.11 COOC.sub.8 H.sub.13 and .delta.-lactone of formula ##STR1## or 2-ethylidene-hepta-6-ene-5-olide, are prepared by reaction of 1,3-butadiene with CO.sub.2 at a temperature comprised between about 20.degree. and 150.degree. C. and at a total pressure between about 10 and 500 atm in the presence of a phosphinic complex of palladium having the formula Pd[P(R).sub.3 ].sub.x, wherein x is an integer from 2 to 4, and (R).sub.3 is a homogeneous or heterogeneous group consisting of alkyls, cycloalkyls having up to 8 carbon atoms and of phenyls, also substituted, in an inert atmosphere. The obtained products are 'per se' new and are valuable intermediates for synthesis of chemicals (fungicides, pesticides, etc.) and in particular as effective plasticizers.

Synthesis of unsaturated esters and lactone from butadiene and carbon

A process is disclosed for the carboxylation of organic substrates or reactants containing at least one active hydrogen atom by reaction with CO.sub.2 and alkaline phenates in an organic medium, characterized in that the reaction is conducted in the presence of simple or substituted alkaline phenates in at least an aprotic medium which is at least a partial solvent for the phenate, and selected from the class consisting of cyclic ethers, aliphatic, cycloaliphatic and heterocyclic tertiary amines, and cyclic sulphones, and at temperatures between about 40.degree. and 60.degree. C. The alkaline phenate is selected from the class consisting of the Li, Na, K salts of the phenols of the general formula: ##STR1## WHEREIN R is hydrogen or an alkyl or an alkoxy group, linear or branched, having up to 20 carbon atoms, or a phenyl group, n varies from 1 to 5, and M is the alkali metal. The starting organic substrate or reactant is selected from the class consisting of ketones, esters, nitroparaffins and nitriles. The alkaline phenate may be prepared 'in situ' from the corresponding phenol and alkaline hydroxide with azeotropic elimination by means of solvent of the water thus formed.

Process for the carboxylation of organic substrates with carbon dioxide

Carboxylable substrates i.e., ketones, esters, nitroparaffins and nitriles, containing activated hydrogen atoms are carboxylated by reaction with alkaline phenates and CO.sub.2 in at least one hydrocarbon solvent selected from aliphatic, alicyclic, aromatic and alkyl-aromatic hydrocarbon solvents.

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Parma, Italy

Gian P Chiusoli