Atochem

Centre National De La Recherche Scientifique

Societe Nationale Des Poudres Et Explosifs

Yves Fort

Paul J Caubere

Marie-Christine Berthe

Agnes Ortar

Olivier Tillement

Jean-Marie Dubois

Jean-Claude C Gautier

Jean-Claude Mondet

A material composed of ultrafine particles, comprising at least a metal element M having catalytic properties and at least a metal element M&prime; having a standard oxidation potential less than that of M, part at least of M&prime; atoms being in oxidized form, the average size of the particles being less than 50 nm, at least 80% in number of the particles having an average size less than 10 nm. One particle of the material is constituted by at least a metal element M with oxidation level 0, or by at least a metal element M&prime; in oxidized form, or by at least a metal element M&prime; with oxidation level 0, or by the combination of at least two species selected from the three previous species. The material is useful as a catalyst for hydrogenation or coupling reactions.

Material constituted by ultrafine metallic and oxide particles

The invention concerns ultrafine polymetallic particles obtained from reducing a mixture of salts dissolved in an organic solvent by an alkali or alkaline earth metal hydride, at a temperature not higher than the solvent reflux temperature, the mixture of dissolved salts comprising at least a salt of a metal having a standard oxidant potential E&deg; at 25&deg; C. higher than &minus;1.18 V. The invention is applicable to the hydrogenation of olefins and the coupling of halogenated aromatic derivatives.

Ultrafine polymetallic particles, preparation and use for hydrogenating olefins and for coupling halogenated aromatic derivatives

Thiocyanoalkyl esters of hydroxy-substituted (meth)acrylic acids are prepared by a process which includes the step of reacting an acrylic compound with an aldehyde of the formula CHOHR' wherein R' is a straight-chain or branched alkyl optionally substituted by hydroxyl, alkoxy or ester substitutents; straight-chain, branched or cyclic alkenyl; aryl radicals, optionally substituted by halogen, nitro or alkoxy, unsaturated heterocyclic radicals; alkylaryl; or arylalkyl radicals.

Method of preparing thiocyanoalkyl esters of hydroxy-substituted

A process for the preparation of an acrylic or methacrylic compound of formula (I): ##STR1## wherein R is a hydrogen atom or methyl and n is an integer ranging from 2 to 20 inclusive, comprising reacting a halogeno-n-alkyl acrylate or methacrylate of the formula: ##STR2## in which n is as defined above and X is a halogen atom, with a thiocyanate salt in an organic solvent and in the presence of an effective phase-transferring amount of at least one phase-transfer agent.

Process for preparing thiocyanoalkyl esters of (meth)acrylic acid

Monomers of the formulae: ##STR1## and ##STR2## as well as polymers and copolymers thereof wherein n=2-20; R=H, CH.sub.3 or CHOHR' where R'=straight-chain or branched alkyl, optionally substituted by hydroxyl, alkoxy or ester substituents, straight-chain, branched or cyclic alkenyl, aryl, optionally substituted by halogenated, nitro or alkoxy substituents, unsaturated heterocycle, alkylaryl and arylalkyl, R=CH.sub.3 in formula (I) in the case of monomers and homopolymers wherein n=2 and in the case of monomers wherein n=4.

Process for the preparation of triazines

Process for the preparation of the acrylates chosen from those of formula ##STR1## those of formula ##STR2## and those of the formula ##STR3## useful in the production of new polymers and copolymers.

Acrylates containing an alcohol, aldehyde and/or ether functional group,

An unsaturated (meth) acrylic compound of formula: ##STR1## (X=O, S, NH, NR.sup.3 (R.sup.3 =C.sub.1-12 -alkyl) or O--(CH.sub.2).sub.n (where n=1-16 approximately); R.sup.2 =C.sub.2-20 straight-chain or branched alkyl, monocyclic or polycyclic cycloalkyl or heterocycloalkyl, or alkylaryl hydrocarbon chain, comprising an olefinic double bond in the chain, or at the end of the chain in the case of alkyl or alkylaryl, or an exocyclic or endocyclic olefinic double bond in the case of monocyclic or polycyclic cycloalkyl or heterocycloalkyl; and R.sup.1 =H or C.sub.1-5 -alkyl), is reacted at 10.degree.-60.degree. C. with at least one oxidising compound (hydrogen peroxide) in the presence of at least one catalyst (alkali metal molybdates and tungstates) and in the presence of at least one phase transfer agent and when R.sup.2 =polycyclic cycloalkyl or hetercycloalkyl, an organic peracid or hydrogen peroxide in the presence of at least one heteropolyacid. To open the epoxide function, the epoxide obtained is reacted with a compound chosen from strong inorganic acids, boron trifluoride etherate complexes, acid salts in the presence of the corresponding acid, halides of trialkylsilanes or trialkoxysilanes, and ketones in the presence of cationic resins.

Process for selective epoxidation of unsaturated (meth)acrylates, new

Process for the epoxidation of an unsaturated (meth)acrylic compound of formula: ##STR1## in which R.sub.1 is chosen from H and C.sub.1 -C.sub.5 -alkyl; R.sub.2 is chosen from H, alkyl and aryl; R.sub.3 is a straight-chain, branched or cyclic alkylene or oxyalkylene radical having from 1 to 12 carbon atoms, it being possible for one of the carbon atoms of R.sub.2, when the latter is an alkyl radical, to be linked to one of the carbon atoms of R.sub.3 to form a ring; and A is chosen from O, S, NH and NR.sub.4, R.sub.4 being a C.sub.1 -C.sub.12 -alkyl group; by the action of hydrogen peroxide on the said unsaturated (meth)acrylic compound, at a temperature of between 10.degree. C. and 50.degree. C., in the presence of at least one catalyst chosen from the alkali metal molybdates and the alkali metal pertungstates and in the presence of at least one phase transfer agent.

Process for selective epoxidation of unsaturated (meth)acrylic compounds

Monomers of the formulae: ##STR1## as well as polymers and copolymers thereof wherein n=2-20; R=H, CH.sub.3 or CHOHR' where R'=straight-chain or branched alkyl, optionally substituted by hydroxyl, alkoxy or ester substituents, straight-chain, branched or cyclic alkenyl, aryl, optionally substituted by halogenated, nitro or alkoxy substituents, unsaturated heterocycle, alkylaryl and arylalkyl, R=CH.sub.3 in formula (I) in the case of monomers and homopolymers wherein n=2 and in the case of monomers wherein n=4.

Triazines substituted with thioalkylmethacrylate groups

(Meth)acrylic compounds carrying a thiocyanate group

Acrylates of the formula ##STR1## in which: R is a radical chosen from alkyl radicals containing from 1 to 12 carbon atoms, cycloalkyl radicals containing from 5 to 12 carbon atoms, and aryl, arylalkyl and alkylaryl radicals,

Acrylates, containing an alcohol, aldehyde and/or ether functional

An unsaturated (meth)acrylic compound of formula: ##STR1## (X.dbd.O, S, NH, NR.sup.3 (R.sup.3 =C.sub.1-12 -alkyl) or O--(CH.sub.2).sub.n (where n=1-16 approximately); R.sup.2 =C.sub.2-20 straight-chain or branched alkyl, monocyclic or polycyclic cycloalkyl or heterocycloalkyl, or alkylaryl hydrocarbon chain, comprising an olefinic double bond in the chain, or at the end of the chain in the case of alkyl or alkylaryl, or an exocyclic or endocyclic olefinic double bond in the case of monocyclic or polycyclic cycloalkyl or heterocycloalkyl; and R.sup.1 =H or C.sub.1-5 -alkyl), is reacted at 10.degree.-60.degree. C. with at least one oxidizing compound (hydrogen peroxide) in the presence of at least one catalyst (alkali metal molybdates and tungstates) and in the presence of at least one phase transfer agent and when R.sup.2 =polycyclic cycloalkyl or hetercycloalkyl, an organic peracid or hydrogen peroxide in the presence of at least one heteropolyacid. To open the epoxide function, the epoxide obtained is reacted with a compound chosen from strong inorganic acids, boron trifluoride etherate complexes, acid salts in the presence of the corresponding acid, halides of trialkylsilanes or trialkoxysilanes, and ketones in the presence of cationic resins.

Selective epoxidation of unsaturated (meth)acrylates, new functional

These acrylates are those of formulae: ##STR1## where R=C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, aryl, arylalkyl or alkylaryl; Y=C.sub.1 -C.sub.12 alkyl, C.sub.6 -C.sub.12 aryl, heterocyclic radical whose ring contains from 5 to 10 members and whose heteroatom is chosen from N, O and S, an alkylaryl in which the alkyl part contains from 1 to 4 carbon atoms, Y not being able to denote 1,4-phenylene when R denotes methyl; and Z=hydrocarbon radical containing at least 2 C forming with O and the 2 adjacent Cs a ring containing from 4 to 8 members. To prepare them, an acrylate of formula CH.sub.2 .dbd.CH--COOR is reacted with a dialdehyde OHC--Y--CHO in the presence of an effective quantity of at least one functionalisation catalyst. The invention also relates to the preparation of new polymers and copolymers from the said acrylates.

The present invention relates to a process for the synthesis of monohaloalkanoylferrocenes of general formula (I) ##STR1## in which X=Cl, Br, n is an integer such that 2.ltoreq.n.ltoreq.7, R.sub.1 and R.sub.2 =H, C.sub.1 -C.sub.8 alkyl chain. A ferrocene derivative of general formula (II) ##STR2## in which R.sub.1 and R.sub.2 have the abovementioned meaning, is reacted at a temperature -5.degree. C.&lt;.theta..sub.r &lt;+15.degree. C., in the presence of AlCl.sub.3 with a halide or the anhydride of an acid of general formula (III) HOOC--(CH.sub.2).sub.n --X, X and n having the abovementioned meaning. An acylating solution obtained by mixing AlCl.sub.2 and the acid halide or anhydride in CH.sub.2 Cl.sub.2, whose temperature .theta..sub.a is such that 5.degree. C..ltoreq..theta..sub.r -.theta..sub.a .ltoreq.15.degree. C., is progressively added to a solution of the ferrocene derivative (II) in CH.sub.2 Cl.sub.2. The molar ratio of the acid halide or anhydride to the ferrocene derivative is between 0.99 and 1.01 and that of AlCl.sub.3 to the ferrocene derivative between 1.05 and 1.11. The mixture is then hydrolyzed and the crude product (I) is recovered by filtration followed by evaporation of CH.sub.2 Cl.sub.2. This process enables a crude synthetic product to be obtained in a yield and with a purity which are high. The monohaloalkanoylferrocenes (I) are synthesis intermediates in pharmacy and in self-propulsion.

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Vandoeuvre les Nancy, France

Yves Fort