Exxon Research and Engineering Company

Exxon Chemical Patents, Inc.

Istvan T Horvath

Jacob I Emert

Richard Henry Schlosberg

Warren A Thaler

Stephen Zushma

David A Young

Raymond A Cook

Gabor Kiss

Frank Hershkowitz

Harry William Deckman

Michael Gerard Matturro

Anthony M Dean

Jozsef Rabai

John M Millar

Stoichiometric and catalytic chemical transformations may be carried out in solution using novel fluorous multiphase systems (FMS). The term 'fluorous' is defined as a carbon-fluorine bond rich organic molecule which is generated by replacing hydrogen atoms bonded to carbon atoms with fluorine. The novel complexes suitable for use as fluorous catalysts and reagents in the present invention contain sufficient number of fluorous moieties to render them preferentially soluble in the appropriate fluorous solvent without impairing the ability of the catalyst or reagent to be effective or participate in the corresponding reaction. Thus, a variety of fluorous compositions may be prepared according to the present invention, included among them are complexes selected from the group consisting of perfluoroalkylphthalocyaninato metal complexes wherein the metal is selected from ruthenium, iron, cobalt, osmium, rhodium and iridium; (perfluoro-alkyl) 5, 10, 15, 20-tetrakis-pentafluorophenyl porphyrin metal complexes selected from ClM{P[(CH.sub.2).sub.n (CF.sub.2) CF.sub.3 ].sub.3 }.sub.3, ClM{P[O(CH.sub.2).sub.n (CF.sub.2).sub.m CF.sub.3 ].sub.3 }.sub.3, HM(CO).sub.x {P[(CH.sub.2).sub.n (CF.sub.2) .sub.m CF.sub.3 ].sub.3 }.sub.4-x, and HM(CO).sub.x {P[O(CH.sub.2).sub.n (CF.sub.2).sub.m CF.sub.3 ].sub.3 }.sub.4-x, wherein in each occurrence M is selected from cobalt, rhodium, iron, osmium, and iridium, x ranges from 1-3, (CH.sub.2).sub.n may be present or absent and when present n ranges from 1-5, and m ranges from 4-20.

Fluorous multiphase system

A polymer having a terminal hydroxyl, aldehyde or alkylamino substituent which may be used directly or in a derivative form as a dispersant for both fuel and lubricating oil compositions, wherein the polymer has a M.sub.n of about 300 to 10,000, and is derived from a polyolefin which is derived from a polyene (diene, e.g.), monomer of the formula H.sub.2 C.dbd.CHR.sup.4, wherein R.sup.4 is hydrogen or a straight or branched chain alkyl radical. Preferably, the polyolefin has at least about 30% terminal vinylidene unsaturation. Particularly desirable amine derivatives can be formed by either a single step aminomethylation process or a two step hydroformylation and reductive amination process.

Polymers having terminal hydroxyl, aldehyde, or alkylamino substituents

A saturated polymer having a terminal aldehyde or hydroxy substituent which may be used directly or in a derivative form as a dispersant for both fuel and lubricating oil compositions, wherein the saturated polymer has a M.sub.n of about 300 to 10,000, and is derived from a polyolefin which is derived from a monomer of the formula H.sub.2 C.dbd.CHR.sup.4, wherein R.sup.4 is hydrogen or a straight or branched chain alkyl radical, and wherein the polyolefin has at least about 30% terminal vinylidene unsaturation. Particularly desirable amine derivatives can be formed by either a single step aminomethylation process or a two step hydroformylation and reductive amination process.

Saturated polyolefins having terminal aldehyde or hydroxy substituents

A saturated polymer having a terminal aldehyde or hydroxy substituent which may be used directly or in a derivative form as a dispersant for both fuel and lubricating oil compositions, wherein the saturated polymer has a M.sub.n of about 300 to 10,000, and is derived from a polyolefin which is derived from a monomer of the formula H.sub.2 C=CHR.sup.4, wherein R.sup.4 is hydrogen or a straight or branched chain alkyl radical, and wherein the polyolefin has at least about 30% terminal vinylidene unsaturation. Particularly desirable amine derivatives can be formed by either a single step aminomethylation process or a two step hydroformylation and reductive amination process.

The invention is a process for production of C.sub.3 to C.sub.6 aldehydes by hydroformylating a mixture containing: (a) C.sub.2 to C.sub.5 olefins and mixtures thereof, and (b) (i) C.sub.2 to C.sub.5 alkynes and mixtures thereof or (ii) C.sub.3 to C.sub.5 cumulated dienes and mixtures thereof or (iii) mixtures of (i) and (ii), with CO, H.sub.2 and a solution of a rhodium complex catalyst produced by complexing Rh and an organophosphorus compound at a concentration of Rh in solution from 1 to 1000 ppm by weight. Alternatively, the solution of rhodium complex catalyst can have a P/Rh atom ratio of at least 30. Alternatively, the solution of rhodium complex catalyst can have a P/Rh atom ratio greater than the value R.sub.L defined by the formula: ##EQU1## in which R.sub.B is the P/Rh ratio sufficient for a catalytically active Rh complex, pKa.sub.TPP is the pKa value for triphenylphosphine, pKa.sub.L is the pKa value for the triorganophosphorus compound, R is the gas constant, and .DELTA.S.sub.B is 35(N-1) cal/mole/.degree.K., N is the number of P-Rh attachments per ligand molecule. The process has utility for the hydroformylation of streams that contain olefins and alkynes.

Direct hydroformylation of a multi-component synthesis gas containing

Polymers having terminal hydroxyl aldehyde, or alkylamino substitutents

The invention is a process for hydroformylating multicomponent syngas feed streams containing CO, H.sub.2, C.sub.2 to C.sub.5 olefins and mixtures thereof and C.sub.2 to C.sub.5 alkynes and mixtures thereof by contacting the multicomponent syngas feed stream with a solution of an oil soluble rhodium complex catalyst produced by complexing in solution a low valence Rh and an oil soluble triorganophoshorous compound wherein the catalyst has a P/Rh ratio of at least 30, a concentration of Rh in solution from about 1 to about 1000 ppm by weight, a total concentration of coordinatively active P of at least about 0.01 mol/l, and a ratio of [P]/p.sub.co of at least 0.1 mmol/l/kPa, wherein [P] is the total concentration of coordinatively active phosphorous in the solution, and p.sub.co is the partial pressure of CO, to produce the corresponding C.sub.3 to C.sub.6 aldehydes. The process has utility for the hydroformylation of streams that contain olefins and alkynes.

Stoichiometric and catalytic chemical transformations may be carried out in solution using novel fluorous multiphase systems (FMS). The term 'fluorous' is defined as a carbon-fluorine bond rich organic molecule. The FMS consists of a fluorous phase containing a fluorous solvent, typically a fluorocarbon or a fluorohydrocarbon and a reagent or a catalyst containing a sufficient number of fluorous moieties to render it preferentially soluble in the fluorous solvent without impairing the ability of the catalyst or reagent to be effective in the reaction and while maintaining the reaction in a liquid or fluid phase. The nonfluorous solvent may be any suitable organic or nonorganic solvent(s) with limited or no solubility in the fluorous solvent that is effective for dissolving the reactant(s) and most desirably, for separating the resulting product(s). Typically, such solvents have a Hildebrand solubility parameter of at least about 18.0 MPa1/2. Appropriate fluorous moieties are linear, branched and carbocyclic fluorocarbon alkyl chains with high carbon numbers. FMS reagents and catalysts can be prepared by (1) fluorination (i.e., replacement of C--H bonds with fluorine); (2) fluorofunctionalization, e.g., the attachment of fluorous moieties to the reagents or catalysts; or (3) by total synthesis. The invention is useful in separations technology and in catalyst design and synthesis.

Fluorous multiphase systems

The invention relates to a process for selectively producing alkyl halides from alkanes, such as methane and ethane at low temperatures and low pressures. Optional hydrolysis to the corresponding alcohols may follow. The process involves adding an alkane and an added halogen source to an aqueous solution in a homogeneous system in the presence of a transition metal halide containing complex, for a time, under conditions and in effective amounts that will permit the formation of alkyl monohalides.

Low temperature conversion of alkanes

The invention relates to a process for selectively producing alkyl halides from alkanes, such as methane and ethane at relatively mild temperatures and pressures in an organic liquid phase in the presence of halogen and transition metal complex. The alkane may be neat if in a liquid form, or may be solubilized with a suitable organic solvent, if the alkane not a liquid at reaction conditions. The reaction is for a time, under conditions of temperature and pressure and in effective amounts that will permit the formation of alkyl halides. Optional hydrolysis to the corresponding alcohols may follow. The alkyl halides have utility as precursors for alternative fuels, such as methanol.

Low temperature halogenation of alkanes

The present invention provides a catalyst for hydrogenation of aromatic compounds, which comprises a hydrophilic support material; and a stationary aqueous acid phase supported by the hydrophilic support material, the aqueous acid having a transition metal catalyst dissolved therein, Preferably, the solid hydrophilic support material is an acidic material, such as an acid-treated clay. The foregoing catalyst is particularly useful in hydrogenating aromatic hydrocarbons.

Stationary aqueous acid phase transition metal catalysts for reduction

The present invention provides a catalyst for hydrogenation of aromatic compounds, which comprises a hydrophilic support material; and a stationary aqueous acid phase supported by the hydrophilic support material, the aqueous acid having a transition metal catalyst dissolved therein. Preferably, the solid hydrophilic support material is an acidic material, such as an acid-treated clay. The foregoing catalyst is particularly useful in hydrogenating aromatic hydrocarbons.

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High Bridge, NJ, United States of America

Istvan T Horvath