E.i. Dupont De Nemours and Company

Los Alamos National Security, LLC

Ralph Thomas Baker

Allen Capron Sievert

Viacheslav Alexandrovich Petrov

Richard P Beatty

Robert Lewis Wallace, Jr

Velliyur Nott Mallikarjuna Rao

William Brown Farnham

Ralph Newton Miller

Velliyur Nott Rao

Richard J Keaton

Frederick N Tebbe

Sigridur Soley Kristjansdottir

Frances Helen Stephens

Johanna Marie Blacquiere

Velliyurnott Mallikarjuna Rao

Velliyur N Mallikarjuna Rao

A liquid phase process is disclosed for producing halogenated alkane adducts of the formula CARRCBRR(where A, B, R, R, R, and Rare as defined in the specification) which involves contacting a corresponding halogenated alkane, AB, with a corresponding olefin, CRR&#x2550;CRRin a dinitrile or cyclic carbonate ester solvent which divides the reaction mixture into two liquid phases and in the presence of a catalyst system containing (i) at least one catalyst selected from monovalent and divalent copper; and optionally (ii) a promoter selected from aromatic or aliphatic heterocyclic compounds which contain at least one carbon-nitrogen double bond in the heterocyclic ring. When hydrochlorofluorocarbons are formed, the chlorine content may be reduced by reacting the hydrochlorofluorocarbons with HF. Azeotropes of CClFCHCFwith HF and azeotropes of CFCHCHFwith HF are also disclosed; as are process for producing such azeotropes.

Process for the manufacture of halocarbons and selected compounds and azeotropes with HF

A method of dehydrogenating an amine-borane using an acid-catalyzed reaction. The method generates hydrogen and produces a solid polymeric [RRB&#x2014;NRR]product. The method of dehydrogenating amine-boranes may be used to generate Hfor portable power sources.

Acid-catalyzed dehydrogenation of amine-boranes

A method of dehydrogenating an amine-borane having the formula RHN&#x2014;BHRusing base metal catalyst. The method generates hydrogen and produces at least one of a [RHN&#x2014;BHR]oligomer and a [RN&#x2014;BR]oligomer. The method of dehydrogenating amine-boranes may be used to generate Hfor portable power sources, such as, but not limited to, fuel cells.

Base metal dehydrogenation of amine-boranes

A liquid phase process is disclosed for producing halogenated alkane adducts of the formula CARRCBRR(where A, B, R, R, R, and Rare as defined in the specification) which involves contacting a corresponding halogenated alkane, AB, with a corresponding olefin, CRR&#x2550;CRRin a dinitrile or cyclic carbonate ester solvent which divides the reaction mixture into two liquid phases and in the presence of a catalyst system containing (i) at least one catalyst selected from monovalent and divalent copper; and optionally (ii) a promoter selected from aromatic or aliphatic heterocyclic compounds which contain at least one carbon-nitrogen double bond in the heterocyclic ring. When hydrochlorofluorocarbons are formed, the chlorine content may be reduced by reacting the hydrochlorofluorocarbons with HF. New compounds disclosed include CFCFCClCHCCl, CFCClCHCHCl and CFCClCHCHClF. These compounds are useful as intermediates for producing hydrofluorocarbons. Azeotropes of CClFCHCFwith HF and azeotropes of CFCHCHFwith HF are also disclosed; as are process for producing such azeotropes. A process for purification of certain hydrofluorocarbons and/or chloro-precursors thereof from mixtures of such compounds with HF is also disclosed.

The invention relates to azeotropic compositions of halogenated propanes with HF.

A liquid phase process is disclosed for producing halogenated alkane adducts of the formula: CAR,R,CBR,R,(where A, B, R,, R,, R,, and R,are as defined in the specification) which involves contacting a corresponding halogenated alkane, AB, with a corresponding olefin, CR,R,&boxH;C,R,in a dinitrile or cyclic carbonate ester solvent which divides the reaction mixture into two liquid phases and in the presence of a catalyst system containing: (i) at least one catalyst selected from monovalent and divalent copper; and optionally (ii) a promoter selected from aromatic or aliphatic heterocyclic compounds which contain at least one carbon-nitrogen double bond in the heterocyclic ring. When hydrochlorofluorocarbons are formed, the chlorine content may be reduced by reacting the hydrochlorofluorocarbons with HF. New compounds disclosed include CF,CF,CCl,CH,CCl,, CF,CCl,CH,CH,Cl and CF,CCl,CH,CHClF. These compounds are useful as intermediates for producing hydrofluorocarbons. Azeotropes of CClF,CH,CF,with HF and azeotropes of CF,CH,CHF,with HF are also disclosed; as are processes for producing such azeotropes. A process for purification of certain hydrofluorocarbons and/or chloroprecursors thereof from mixtures of such compounds with HF is also disclosed.

Processes involving certain nickel metallacycles with phosphite ligands are disclosed as useful for the manufacture of selected substituted hydrocarbons. Also disclosed are selected compounds including both nickel and phosphite ligands.

Process for the manufacture of fluorine-substituted hydrocarbons

Nickel catalyzed addition of -NH- containing compounds to vinyl and aryl

Process for the manufacture of halocarbons

A process is disclosed for the manufacture of product compounds of the formula HC(R.sup.1).sub.2 C(R.sup.1).sub.2 C(R.sup.2).sub.2 C(R.sup.2).sub.2 H wherein each R.sup.1 is independently selected from the group consisting of H, F, Cl, CN, R, OR, CO.sub.2 R, C(O)R, OC(O)R, R.sup.f, OR.sup.f, CO.sub.2 R.sup.f C(O)R.sup.f and OC(O)R.sup.f where R is a hydrocarbyl group and R.sup.f is a C.sub.1 to C.sub.10 polyfluoroalkyl group, provided that at least one R.sup.1 is F, and wherein each R.sup.2 is independently selected from the group consisting of H, F, Cl, CN, R, OR, CO.sub.2 R, C(O)R, OC(O)R, R.sup.f, OR.sup.f, CO.sub.2 R.sup.f, C(O)R.sup.f, OC(O)R.sup.f and difunctional linkages where an R.sup.2 group on each of two adjacent carbon atoms together form a link selected from the group consisting of --CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 CH(CH.sub.3)--, --CH.sub.2 CH(CH.sub.3)CH.sub.2 --, --C(O)OC(O)--, and norborndiyl. The process involves reacting a metallacycle of the formula L.sub.m M(1,4-C(R.sup.1).sub.2 C(R.sup.1).sub.2 C(R.sup.2).sub.2 C(R.sup.2).sub.2 --) wherein R.sup.1 and R.sup.2 are as defined above, and wherein M is a metal selected from the group consisting of Group 8, Group 9 and Group 10 metals, each L is a ligand selected from the group consisting of Group 14, Group 15 and Group 16 ligands, and m is an integer from 1 to 4, in the liquid phase with hydrogen. Also disclosed are certain compositions comprising product compounds within the above product compound formula and certain metallacycle compounds within the above metallacycle formula.

Process for the manufacture of selected halogenated hydrocarbons

A process is disclosed for the manufacture of product compounds of the formula HC(R.sup.1).sub.2 C(R.sup.1).sub.2 C(R.sup.2).sub.2 C(R.sup.2).sub.2 H wherein each R.sup.1 is independently selected from the group consisting of H, F, Cl, CN, R, OR, CO.sub.2 R, C(O)R, OC(O)R, R.sup.f, OR.sup.f, CO.sub.2 R.sup.f C(O)R.sup.f and OC(O)R.sup.f where R is a hydrocarbyl group and R.sup.f is a C.sub.1 to C.sub.10 polyfluoroalkyl group, provided that at least one R.sup.1 is F, and wherein each R.sup.2 is independently selected from the group consisting of H, F, Cl, CN, R, OR, CO.sub.2 R, C(O)R, OC(O)R, R.sup.f, OR.sup.f, CO.sub.2 R.sup.f, C(O)R.sup.f, OC(O)R.sup.f and difunctional linkages where an R.sup.2 group on each of two adjacent carbon atoms together form a link selected from the group consisting of --CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 CH(CH.sub.3 --, --CH.sub.2 CH(CH.sub.3)CH.sub.2 --, --C(O)OC(O)--, and norborndiyl. The process involves reacting a metallacycle of the formula L.sub.m M(1,4-C(R.sup.1).sub.2 C(R.sup.1).sub.2 C(R.sup.2).sub.2 C(R.sup.2).sub.2 --) wherein R.sup.1 and R.sup.2 are as defined above, and wherein M is a metal selected from the group consisting of Group 8, Group 9 and Group 10 metals, each L is a ligand selected from the group consisting of Group 14, Group 15 and Group 16 ligands, and m is an integer from 1 to 4, in the liquid phase with hydrogen. Also disclosed are certain compositions comprising product compounds within the above product compound formula and certain metallacycle compounds within the above metallacycle formula.

Process for the manufacturing of selected halogenated hydrocarbons

A process is disclosed for the manufacture of product compounds of the formula HC(R.sup.1).sub.2 C(R.sup.1).sub.2 C(R.sup.2).sub.2 H wherein each R.sup.1 is independently selected from the group consisting of H, F, Cl, CN, R, OR, CO.sub.2 R, C(O)R, OC(O)R, R.sup.f, OR.sup.f, CO.sub.2 R.sup.f, C(O)R.sup.f and OC(O)R.sup.f where R is a hydrocarbyl group and R.sup.f is a C.sub.1 to C.sub.10 polyfluoroalkyl group, provided that at least one R.sup.1 is F, and wherein each R.sup.2 is independently selected from the group consisting of H, F, Cl, CN, R, OR, CO.sub.2 R, C(O)R, OC(O)R, R.sup.f, OR.sup.f, CO.sub.2 R.sup.f, C(O)R.sup.f, OC(O)R.sup.f and difunctional linkages where an R.sup.2 group on each of two adjacent carbon atoms together form a link selected from the group consisting of --CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 CH(CH.sub.3)--, --CH.sub.2 CH(CH.sub.3)CH.sub.2 --, --C(O)OC(O)--, and norborndiyl. The process involves reacting a metallacycle of the formula L.sub.m M(1,4-C(R.sup.1).sub.2 C(R.sup.1).sub.2 C(R.sup.2).sub.2 C(R.sup.2).sub.2 --) wherein R.sup.1 and R.sup.2 are as defined above, and wherein M is a metal selected from the group consisting of Group 8, Group 9 and Group 10 metals, each L is a ligand selected from the group consisting of Group 14, Group 15 and Group 16 ligands, and m is an integer from 1 to 4, in the liquid phase with hydrogen. Also disclosed are certain compositions comprising product compounds within the above product compound formula and certain metallacycle compounds within the above metallacycle formula.

Borides and boride precursors deposited from solution

This invention relates to a liquid phase process for the preparation of R.sub.f CHXY by the homogeneous catalytic hydrodechlorination of R.sub.f CClXY wherein X and Y are independently H, F, Cl or R.sub.f ' provided X and Y are not both Cl, R.sub.f and R.sub.f ' are independently F, CF.sub.3, (CF.sub.2).sub.n Cl or (CF.sub.2).sub.n CF.sub.3, and n is 1-4, by reacting the R.sub.f CClXY with hydrogen while in solution with a Periodic Table Group 6-10 metal complex catalyst which contains tertiary Periodic Table Group 15 ligands without added base.

Homogeneous catalytic hydrodechlorination of chlorocarbons

This invention relates to a liquid phase process for the preparation of R.sub.f CHCl.sub.2 by the selective homogeneous catalytic hydrodechlorination of R.sub.f CCl.sub.3 wherein R.sub.f is F, CF.sub.3, (CF.sub.2).sub.n Cl or (CF.sub.2).sub.n CF.sub.3 by reacting the compound with hydrogen while in solution with a Periodic Table Group 8-10 metal complex catalyst which contains tertiary Periodic Table Group 15 ligands, without added base.

Growing community of inventors

Los Alamos, NM, United States of America

Ralph Thomas Baker