Abstract: Arylolefinic compounds are prepared by reacting aryl halide with an olefinic compound in the presence of a polar liquid reaction medium containing (a) secondary or tertiary amine as a hydrogen halide acceptor (b) a catalyst system formed from (i) Pd or Pd(0) compound, and/or Pd(I) salt or Pd(II) salt, and (ii) a tertiary phosphine ligand, and (c) a reaction accelerating amount of water in the range of about 0.5 to about 5 weight percent of the total weight of the reaction mixture. The arylolefinic compounds can be converted to an arylcarboxylic acid by hydrocarboxylation with CO in a reaction medium freed of amine and containing water and a Pd catalyst system as above in which a copper component may be included, and which preferably includes an ether such as THF.

Abstract: In a process for carrying out an exothermal reaction, selected from the addition reaction of organomagnesium halide compounds to carbonyl compounds and the ensuing hydrolysis of the addition product, a considerable fraction of the heat liberated during the reaction is removed by evaporation of the solvent.

Abstract: There is disclosed a method of preparing benzyl metal compounds represented by general formula (2), comprising reacting a phenyl metal compound represented by general formula (1) with toluene, in the presence of a catalytic amount of amine. According to this method, benzyl metal compounds can be prepared at a high yield, and in an industrially advantageous manner. Further, there is also disclosed a method of preparing 4-phenyl-1-butenes, comprising reacting the benzyl metal compound obtained in the method, with an allyl halide. ##STR1## wherein M represents an alkali metal, ##STR2## wherein M has the same meaning as the above.

Abstract: A process for producing dispersions of atmospherically stable, coated alkali metal particles and atmospherically stable, coated alkali metal powders by agitating a mixture of molten alkali metal in a hydrocarbon oil at dispersion speeds, optionally in the presence of a dispersing agent, contacting the molten alkali metal-hydrocarbon oil dispersion, above or below the surface of the dispersion, with up to 3 weight percent anhydrous carbon dioxide while agitating the dispersion for at least 1 minute. The dispersion in oil can be used directly in chemical reactions. The bulk of the oil can be removed from the dispersions to produce oil wet particles, the oil wet particles car be washed with a low boiling hydrocarbon to produce hydrocarbon wet particles which can be dried to produce atmospherically stable powders of coated metal particles. The dispersed particles in oil, the oil wet particles, the hydrocarbon wet particles and the atmospherically stable powders can each be used in chemical reactions.

Abstract: The present invention relates to polyvalent metal salts of a phosphoric diester represented by formula (1) and organo(poly)siloxanes modified with a polyvalent metal salt of a phosphoric diester having the structural units represented by formulae (9) and (10): ##STR1## wherein R.sup.1 represents a C1 to C20 linear or branched alkyl group, R.sup.2 and R.sup.4 are the same or different and independently represent a C2 to C3 linear or branched alkylene group, R.sup.3 represents a C3 to C20 linear or C5 to C20 branched alkylene group, A represents a group --COO-- or --O--, x and y are the same or different from each other and independently represent an integer of 0 to 10, L represents a C1 to C40 linear or branched alkyl group or a group, R.sup.1 --(OR.sup.2).sub.x --A--R.sup.3 (OR.sup.4).sub.y -- wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, A, x and y have the same meaning as defined herein before, M represents a divalent or polyvalent metal atom, and m represents the same value as the valence of M.

Abstract: A process for preparing metallocene complexes of the general ##STR1## in which the substituents have the following meanings:M is titanium, zirconium, hafnium, vanadium, niobium or tantalum,X is fluorine, chlorine, bromine, iodine, hydrogen, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl or --OR.sup.5,where R.sup.5 is C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, alkylaryl, aryl-alkyl, fluoroalkyl or fluoroaryl with, in each case, 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,R.sup.1 to R.sup.4 and R.sup.6 to R.sup.9 are hydrogen, C.sub.1 -C.sub.10 -alkyl, 5- to 7-membered cycloalkyl which can in turn carry C.sub.1 -C.sub.10 -alkyls as substituents, or C.sub.6 -C.sub.15 -aryl or aryl-alkyl, it also being possible where appropriate for two adjacent radicals together to be cyclic groups having 4 to 15 carbon atoms, or Si(R.sup.10).sub.3 withR.sup.10 being C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl or C.sub.3 -C.sub.

Abstract: A process for the preparation of hydrocarbon solutions of monofunctional ether initiators of the following general structure:M--Q.sub.n --Z--OA(R.sup.1 R.sup.2 R.sup.3)wherein M is defined as an alkali metal, selected from the group consisting of lithium, sodium and potassium, Q is an aromatic substituted saturated hydrocarbyl group produced by the incorporation of one or more alkenyl substituted aromatic hydrocarbons containing 8-25 carbon atoms into the M--Z linkage; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; A is an element selected from carbon and silicon; R.sup.1, R.sup.2, and R.sup.

Abstract: In producing (.+-.)-2-(6-methoxy-2-naphthyl)propionic acid or precursor thereof from 2-bromo-6-methoxynaphthalene, use is made of 2-bromo-6-methoxynaphthalene formed by (a) methylating 6-bromo-2-naphthol with methyl chloride in a solvent comprising one or more compounds, RZ, where R is a hydrogen atom or an alkyl group, and Z is --OH or --CN provided that if Z is --CN, R is alkyl, and in the presence of a strong base; and (b) recovering and purifying 2-bromo-6-methoxynaphthalene so formed.

Abstract: This dialkylmagnesium is represented by the formula R--(CH.sub.2 --CH.sub.2).sub.n --Mg--(CH.sub.2 --CH.sub.2).sub.n' --R', (E--O--E').sub.x, where R and R' each independently represent a C.sub.1 -C.sub.20 hydrocarbon residue, branched or not, substituted or not, of the alkyl, cycloalkyl or aralkyl type; n and n', identical or substantially identical, represent an average number of --CH.sub.2 --CH.sub.2 -- linkages such that the average number of carbon atoms in each of the two chains borne by Mg is greater than 20; E and E', identical or different, each represent an alkyl radical, linear or cyclical, branched or not; and 0.ltoreq.x.ltoreq.2, x being the average value of the number of moles of E--O--E' ether complexed to the dialkylmagnesium. In order to prepare a dialkylmagnesium of this type, ethylene is polymerized in an anhydrous, de-oxygenated hydrocarbonaceous solution by means of a catalyst Cp*.sub.2 MCl.sub.2 Li(OEt.sub.2).sub.

Abstract: A process for producing dispersions of atmospherically stable, coated alkali metal particles and atmospherically stable, coated alkali metal powders by agitating a mixture of molten alkali metal in a hydrocarbon oil at dispersion speeds, optionally in the presence of a dispersing agent, contacting the molten alkali metal-hydrocarbon oil dispersion, above or below the surface of the dispersion, with up to 3 weight percent anhydrous carbon dioxide while agitating the dispersion for at least 1 minute. The dispersion in oil can be used directly in chemical reactions. The bulk of the oil can be removed from the dispersions to produce oil wet particles, the oil wet particles can be washed with a low boiling hydrocarbon to produce hydrocarbon wet particles which can be dried to produce atmospherically stable powders of coated metal particle The dispersed particles in oil, the oil wet particles, the hydrocarbon wet particles and the atmospherically stable powders can each be used in chemical reactions.

Abstract: A process for the preparation of an efficient industrial organolithium diinitiator, comprising the reaction of two equivalents of a mono-organolithium initiator with one equivalent of 1,3-diisopropenyl benzene at a temperature in the range of from -20.degree. to 60.degree. C., in an apolar hydrocarbon solvent, and in the presence of a monofunctional tertiary amine in a molar ratio relative to mono-organolithium initiator from 0.5 to 2, followed by addition to the reaction mixture of a small amount of conjugated diene monomer, at a temperature in the range of from 0.degree. to 30.degree. C., to form a solution of an .alpha.,.omega.-dilithio poly(conjugated diene), having an apparent molecular weight in the range of from 1000 to 3000.

Abstract: The present invention provides processes for making alkynyl ketones and precursors thereof, using less expensive reagents and/or hydrocarbon solvents and/or higher temperatures.

Abstract: The invention relates to a polyacetylene-lithium insertion compound, its use in a storage battery and a process for the preparation of polymer-lithium insertion compounds.This insertion compound contains at least six CH groups per lithium atom and has a monoclinic structure. Polymer-lithium compounds can be obtained by the compression of a polymer mixture, such as polyacetylene, and lithium, e.g. under 30 to 250 MPa and at ambient temperature.The compound can be used as a negative electrode (5) in a lithium storage battery having an oxide, sulphide or oxysulphide positive electrode (9) and a lithium ion-conducting electrolyte (8).

Abstract: A method of preparing polymetalated compositions and the use of such polymetalated compounds as catalysts in polymerization reactions are described. The process comprises reacting (A-1) an allenic compound of the formula R.sup.2 --CH.dbd.C.dbd.CH.sub.2 wherein R.sup.2 is hydrogen or an aliphatic group containing from 1 to about 10 carbon atoms with (A-2) an organometallic compound R.sup.o M in a mole ratio of about 1:2 to about 1:6 wherein R.sup.o is a hydrocarbyl group and M is an alkali metal.A method of preparing a hydrocarbon-soluble polymetalated compositions also is described, and this process comprises the steps of(A) preparing an intermediate by reacting (A-1) an allenic compound of the formula R.sup.2 --CH.dbd.C.dbd.CH.sub.2 wherein R.sup.2 is hydrogen or an aliphatic group containing from 1 to about 10 carbon atoms with (A-2) an organometallic compound R.sup.o M in a mole ratio of about 1:2 to about 1:6 wherein R.sup.

Abstract: A process to produce an ethylene-bridged-metallocene-transition-metal compound that has an omega-alkenyl substitution on said ethylene bridge is provided. Said process comprises: contacting a diolefin compound with a peracid compound to form an omega-alkenyl oxirane compound; contacting said omega-alkenyl oxirane compound with an organometal compound to form an organo-omega-alkenyl-alcohol compound; contacting said organo-omega-alkenyl-alcohol compound with an organosulfur compound to form an organo-omega-alkenyl-organosulfur ester compound; contacting said organo-omega-alkenyl-organosulfur ester compound with an organometal to form an orgaomega-alkenyl-organo compound; contacting said organo-omega-alkenyl-organo compound with a transition metal compound to form a organo-omega-alkenyl-organo-transition compound. Additionally, processes to polymerize olefins using these compounds is provided.

Abstract: A process for the preparation of hydrocarbon solutions of monofunctional ether initiators of the following general structure:M--Q.sub.n --Z--OA(R.sup.1 R.sup.2 R.sup.3)wherein M is defined as an alkali metal, selected from the group consisting of lithium, sodium and potassium, Q is a saturated or unsaturated hydrocarbyl group derived by incorporation of a compound selected from the group consisting of conjugated diene hydrocarbons and alkenylsubstituted aromatic hydrocarbons; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; A is an element selected from carbon and silicon; R.sup.1, R.sup.2, and R.sup.

Abstract: Preparation of a monolithium acetylide/ammonia complex by the reaction of lithium amide and acetylene in ammonia, by carrying out the reaction at a temperature of from -10.degree. to 30.degree. C.

Abstract: Procedures are disclosed which preclude significant safety hazards in the production of bulk quantities pentafluorophenyl lithium. A pentafluorophenyl compound is reacted with an alkyl lithium compound in a reaction zone, preferably temperature controlled, under conditions such that only a small amount of a predetermined quantity of pentafluorophenyl lithium product is present in the reaction zone at any time. The product may be directly discharged from the reaction zone for combination with another reactant.

Abstract: A process for preparing functionalized alkyllithium compounds includes reacting in an inert solvent a protected functionalized alkyl halide with an alkali metal in the presence of a catalytic compound of the formula(RR.sup.1 R.sup.2 M.sup.a).sub.y A(R.sup.3).sub.xwherein R, R.sup.1 and R.sup.2 are each independently selected from the group consisting of hydrogen, halogen, alkyl or alkenyl groups containing one to thirteen carbon atoms; R.sup.3 is independently selected from aryl groups containing 6 to 18 carbon atoms, four to six-membered heterocyclic carbon containing groups containing one to two heteroatoms selected from oxygen, nitrogen and sulfur; hydroxyalkyl, alkoxyalkyl, monoalkylaminoalkyl, dialkylaminoalkyl and dialkylphosphinoalkyl groups containing two to thirteen carbon atoms; M.sup.

Abstract: An improved process for producing high purity solutions of aryllithium compounds comprising reacting a particulate alkali metal having a particle size in the range of 10 to 300 microns, with an aryl halide in a normally liquid etheral solvent of the formula ROR.sup.1, wherein R and R.sup.1 are selected from the group of alkyl radicals containing from 3 to 6 carbon atoms, in the presence of a Lewis base compound selected from compounds of the formula: R.sup.2 AR.sup.3 (R.sup.4).sub.z and ##STR1## wherein A is selected from oxygen, nitrogen, phosphorus or sulfur; R.sup.2, R.sup.3, and R.sup.4 are selected from alkyl radicals containing from 1 to 6 carbon atoms; R.sup.5 and R.sup.6 are independently selected from hydrogen or alkyl radicals containing one to six carbon atoms; y is an integer from 4 to 6; but when A is oxygen or sulfur, z is zero; and when A is nitrogen or phosphorus, z is one, and provided there is a mole ratio of ether to aryl halide of at least 1.

Abstract: The present invention is directed toward anionic polymerization initiators which are soluble in acyclic alkane solvents. The initiators include a solubilized lithio amine having the general formula (A)Li(SOL).sub.y. SOL is a solubilizing component and A is an alkyl, dialkyl or cycloalkyl amine radical or a cyclic amine and y is from about 1 to 4. The cyclic amine has an alkylene, oxy- or amino-alkylene group having from about 3 to about 16 methylene groups. The invention is also directed toward polymers and other products made using the initiator, and methods therefor. Further, the invention contemplates a polymer, a polymer composition and products therefrom, which include a functional group from the reaction product of an amine and an organolithium compound. The resulting polymers may be terminated with a terminating, coupling or linking agent, which may provide the polymer with a multifunctionality.

Abstract: The present invention provides anionic polymerization initiators, comprising lithium amino magnesiate complexes, resulting in diene polymer and copolymer elastomers. The invention initiators have stable living ends at high polymerization temperatures and produce polymers containing a high level of tertiary amine functionality. Such polymers exhibit an increased efficiency in coupling termination reactions, and elastomers and products prepared from such polymers exhibit reduced hysteresis properties. Methods are also provided for preparing the initiators, the polymers and the elastomers.

Abstract: A multifunctional initiator is prepared by contacting an organo-alkali metal compound with a silane represented by the formula: ##STR1## wherein the R' are generally lower alkyl groups such as methyl and the R" is generally an .paren open-st.CH.sub.2 .paren close-st..sub.n group with n=2. Superior results are obtained presumably because of the separation of the vinyl groups and the greater solubility of the compound because of the R' groups. The resulting catalyst initiates polymerization of monomers such as conjugated dienes and monovinyl substituted aromatic compounds to give relatively monodispersed polymers with little or no crosslinking.

Abstract: A process for the preparation of hydrocarbon solutions of monofunctional ether initiators of the following general structure:M--Z--O--C(R.sup.1 R.sup.2 R.sup.3)wherein M is an alkali metal; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; and R.sup.1, R.sup.2, and R.sup.3 are independently selected from hydrogen, alkyl, substituted alkyl, aryl or substituted aryl groups, and their employment as initiators in the anionic polymerization of olefin containing monomers in an inert, hydrocarbon solvent comprising reacting an omega-protected-1-haloalkyl with lithium metal dispersion having a particle size between 10 and 300 millimicrons in size, at a temperature between 35.degree. and 130.degree. C. in an alkane solvent containing 5 to 10 carbon atoms.

Abstract: The subject invention discloses a process for preparing an initiator which contains a plurality of lithium atoms and which is particularly useful for initiating the polymerization of diolefin monomers into rubbery polymers; said process being comprised of reacting an alkyl lithium compound with an unsaturated hydrocarbon containing allylic, benzylic or aryl hydrogen atoms, wherein said process is conducted in the presence of a member selected from the group consisting of alkali metal alkoxides, alkali metal phenoxides, and chelating tertiary alkyl 1,2-ethylene diamines. After the initiators of this invention have been prepared they can be employed to initiate the polymerization of diolefin monomers into rubbery polymers. They can, of course, also be employed to initiate the copolymerization of diolefin monomers and vinyl aromatic monomers into rubbery polymers. These rubbery polymers can then be used in making tire tread compounds for automobiles and trucks.

Abstract: The magnesium complexes of cyclic hydrocarbons and conjugated dienes, such as 1,2-dimethylenecycloalkanes and 1,3-butadienes, are readily prepared in high yields using highly reactive magnesium. Reactions of these (2-butene-1,4-diyl)magnesium reagents with electrophiles such as dibromoalkanes, alkylditosylates, alkylditriflates, bromoalkylnitriles, esters, or amides serve as a convenient method for synthesizing carbocyclic systems. Significantly, carbocycles prepared by this method contain functional groups such as the exocyclic double bond or a keto group in one of the rings which could be used for further elaboration of these molecules. Furthermore, fused bicyclic systems containing a substituted five-membered ring can be conveniently prepared at high temperatures by the reactions of (2-butene-1,4-diyl)magnesium complexes with carboxylic esters or acid halides whereas low temperatures lead to regioselective synthesis of .beta.,.gamma.-unsaturated ketones. Additionally, .gamma.-lactones, including spiro .

Abstract: Process for the preparation of an efficient industrial .alpha., .omega.-dilithio poly(conjugated diene) diinitiator having a peak molecular weight in the range of from 1000 to 3000, comprising the reaction of mono-organolithium initiator with diisopropenyl benzene in an apolar hydrocarbon solvent, optionally in the presence of a tertiary amine, followed by addition to the reaction mixture of a small amount of conjugated diene monomer and at least 15 vol % of an aromatic ether activator at a temperature in the range of from 0.degree. to 30.degree. C.; the use of said .alpha., .omega.-dithio initiator for the manufacture of symmetrical block copolymers by anionic polymerization, from monovinylaromatic, conjugated diene and/or polar vinyl compound monomers; and block copolymers so obtained having a combination of a narrow molecular weight distribution (Mw/Mn.ltoreq.1.20) and relatively low vinyl content (.ltoreq.18%).

Abstract: A process for preparing easily separable solutions of organolithium compounds comprising the steps of reacting lithium metal, in the form of cast or extruded ingots or pieces cut therefrom, with an organo halide in mole ratios ranging from 3:1 to 20:1 in a solvent selected form a group of liquid hydrocarbons, alkyl ethers, and mixtures thereof under an inert atmosphere for one to ten hours with moderate stirring, cooling the resulting product, and separating the solution of the organolithium compound from the reacted lithium metal and by-product lithium chloride in the reactor.

Abstract: An anionic polymerization initiator includes the C-lithio reaction product of an organolithium compound and a tertiary-amino allyllithium or a tertiary-amino xylyllithium. When used in an anionic polymerization, a functional group from the initiator is incorporated onto the head of the growing polymer and a lithium atom is incorporated at the "living" end of the polymer chain prior to quenching. The initiator may be used to polymerize a monomer(s) including diolefin monomers, monovinyl aromatic monomers and trienes, and the living ends of the polymers are effectively maintained even at temperatures of up to 300.degree. F. and higher. Such polymers exhibit an increased efficiency in coupling termination reactions, and products prepared from such polymers exhibit improved hysteresis characteristics. Products such as tires and the like can be prepared from such polymers and from vulcanizable elastomer compositions employing the polymers.

Abstract: Solutions of triorganotin lithium are described having low residual concentrations (preferably less than 2,000 ppm) of halide. These are produced by a two-step process.Triorganotin halide is reacted with lithium to produce hexaorgano ditin and a precipitate of lithium halide. The lithium halide precipitate is removed by filtration and/or use of highly concentrated reaction conditions. Then the hexaorgano ditin is further reacted with lithium to form the triorgano substituted tin lithium. The lithium halide is less soluble in hot tetrahydrofuran (THF) and/or more concentrated solutions. THF is a preferred solvent for the reaction. The low-temperature reactions described result in low amounts of inactive and/or undesirable byproducts. These triorganotin lithium compounds are useful as anionic initiators that result in polymers with terminal tin compounds, e.g., triorganotin, attached to the terminal end of the polymer where initiation occurred.

Abstract: The magnesium complexes of cyclic hydrocarbons containing conjugated dienes, such as 1,2-dimethylenecycloalkanes, and 1,3-butadienes, are readily prepared in high yields using highly reactive magnesium. Reactions of these (2-butene-1,4 diyl)magnesium reagents with electrophiles such as dibromoalkanes, alkylditosylates, alkylditriflates, bromoalkylnitriles, esters, or amides serve as a convenient method for synthesizing carbocyclic systems. Significantly, carbocycles prepared by this method contain functional groups such as the exocyclic double bond or a keto group in one of the rings which could be used for further elaboration of these molecules. Furthermore, fused bicyclic systems containing a substituted five-membered ring can be conveniently prepared at high temperatures by the reactions of (2-butene-1,4-diyl)magnesium complexes with carboxylic esters or acid halides whereas low temperatures lead to regioselective synthesis of .beta.,.gamma.-unsaturated ketones. Additionally, .gamma.

Abstract: Processes for preparing a polymerization initiator precursor compound are disclosed wherein a first process involves dimerizing a halogen-diarylpropane compound to form a tetraarylhexane compound. A second process involves reacting a diaryl-propanol compound with a halogen-diarylpropane compound to form a bis(diaryl-propyl) ether compound. A third process involves reacting a halogen-diarylpropane compound with allyl halogen to form a diaryl-hexene compound.

Abstract: There is disclosed a process for purification a gaseous organometallic compound containing impurities by bringing the compound into contact with a catalyst comprising a copper or nickel component as the essential ingredient to remove oxygen contained in the compound. The above-mentioned process is capable removal of oxygen in an organometallic compound as low as 0.1 ppm and further to a ultralow concentration of 0.01 ppm, which removal has heretofore been impossible, and thereby the production of a ultrapure organometallic compound has been made possible.

Abstract: Dehydrated compositions are obtained by: combining a hydrous composition, e.g., a hydrous electrolyte salt, with inert fluorochemical liquid; heating the resulting mixture in a vessel to volatilize water and inert fluorochemical liquid therein until the water content of the mixture is reduced to a desired level; optionally treating the resulting dehydrated mixture with another chemical material, e.g., a polar organic solvent; and optionally subjecting the dehydrated mixture or the treated dehydrated mixture to further treatment, e.g., separation of the mixture. Liquid electrolytes suitable for use in battery applications can be prepared by this method.

Abstract: A soluble highly reactive form of calcium, prepared from Ca(II) salts and a reducing agent in ethereal, polyethereal, or hydrocarbon solvents, is presented. This form of calcium can be used in the preparation of organocalcium reagents. The organocalcium reagents resulting from the reaction of the soluble highly reactive calcium with organic compounds containing either halide, cyanide, a 1,3-diene, or a polyunsaturated functionality, are stable, useful reagents for organic synthesis. The organocalcium halide reagents undergo Grignard-type reactions. They also undergo reactions with Cu(I) salts to form organocalcium cuprate reagents. The organocalcium cuprate reagents undergo a variety of cross-coupling reactions. The soluble highly reactive calcium reacts with 1,3-dienes to yield the corresponding 2-butene-1,4-diylcalcium complexes. These bis-organocalcium reagents can undergo dialkylation reactions with .alpha.,.omega.

Abstract: Disclosed is a production method, wherein, with pentafluorobenzene represented by C.sub.6 HF.sub.5, 0.5 to 1.5 equivalents of organometallic compound represented by a general formulaR.sub.2-n MgXn(wherein n denotes a real number of 0 or 1, X denotes a halogen atom, R denotes a hydrocarbon group with carbon atoms of 1 to 10, and said hydrocarbon group may contain functional groups unaffecting the reaction) are mixed within a temperature range from -40.degree. to 250.degree. C. in an ether type solvent or a mixed nonaqueous solvent of ether type solvent with hydrocarbon type solvent and reacted at 25.degree. C. or higher to obtain pentafluorophenylmagnesium derivatives represented by a following general formula(C.sub.6 F.sub.5).sub.2-n MgXn(wherein n denotes a real number of 0 or 1 and X denotes a halogen atom).

Abstract: Cyclopentadienyl derivatives are deprotonated by a process whereby the cyclopentadienyl derivatives are reacted with a Grignard reagent in an inert solvent which contains from about 0.5 to 1.5 equivalents per equivalent of cyclopentadienyl derivative of a cyclic ether or an acyclic polyether, so as to form a dianionic salt of said cyclopentadienyl derivative.

Abstract: A catalytic process for alkylating an alkali metal selected from lithium, sodium and potassium with an alkyl halide containing 3 to 20 carbon atoms comprising conducting the reaction in the presence of a catalytic compound represented by the formula(RR.sup.1 R.sup.2 M.sup.a).sub.y A(R.sup.3).sub.xwherein R, R.sup.1 and R.sup.2 are independently selected from hydrogen, halogen, alkyl, alkenyl, cycloalkyl, and aryl groups, R.sup.3 is independently selected from alkyl groups containing 1 to 10 carbon atoms, alkylene groups containing 2 to 5 carbon atoms, aryl groups containing 6 to 18 carbon atoms, four to six-membered heterocyclic carbon containing groups containing one to two hetero atoms selected from oxygen, nitrogen, and sulfur; hydroxyalkyl, alkoxyalkyl and monoalkylaminoalkyl and dialkylaminoalkyl groups containing 2 to 13 carbon atoms; M.sup.

Abstract: A high temperature process for producing alkyllithium compounds in high yields of at least 90% and high purity comprising reacting, in a liquid hydrocarbon solvent, an alkyl halide containing 3 to 16 carbon atoms and mixtures thereof with lithium metal particles of less than 300 microns in size at a temperature between 35.degree. and 125.degree. C. and recovering the alkyllithium compound.

Abstract: Calcium-substituted polymeric reagents are provided. These reagents can be prepared via the oxidative addition of a soluble highly reactive calcium species to organic and inorganic polymers containing alkyl, aryl, or alkylaryl pendent groups substituted with halide atoms, cyanide molecules, 1,3-dienes, or any conjugated polyunsaturated system. Preferably, the polymer is a cross-linked p-bromopolystyrene, p-chloropolystyrene, p-fluoropolystyrene, or chloromethylated polystyrene. Preferably, the soluble highly reactive calcium species is prepared from the reduction of Ca(II) salts with an alkali metal arene, such as lithium biphenylide. These calcium-substituted polymeric reagents react with a variety of electrophiles to yield functionalized polymers. Reaction with Cu(I) salts yields calcium-substituted polymeric cuprate reagents, which can react, for example, with acid chlorides to form ketones, alkyl halides containing functionality, and undergo 1,4-conjugate addition with .alpha.,.beta.

Abstract: In a process for the stabilization of a solution of ethylmagnesium carbonate in ethanol, which has been prepared by the reaction of a suspension of magnesium ethylate in ethanol with carbon dioxide, 0.2 to 1.0% by weight of water, based on the ethylmagnesium carbonate solution, is added to the solution or its starting materials.

Abstract: The present invention relates to a novel compound, its use as an initiator in anionic polymerizations yielding norbornene-terminated homopolymers of block copolymers, and the further use of said norbornene-terminated polymers as macromonomers in the preparation of graft copolymers.

Abstract: Organic-solvent soluble magnesium hydrides or formulas ##STR1## are prepared by catalytically hydrogenating finely powdered magnesium, optionally in the presence of a magnesium halide, in an organic solvent in the presence of their MgH.sub.2 -free counterparts in whichQ is an alkyl, alkenyl, alkoxy, dialkylamino, aralkyl, aryl or diarylamino group, each with up to 18 carbon atoms,R is an alkenyl, aralkyl or aryl group, each with up to 18 carbon atoms,X is chlorine, bromine, or iodine, ##STR2## is a chelating ligand, E is --CH.sub.2, --N(R)-- or --O--,is an alkylene radical of the formula --(CH.sub.2).sub.p,D is a dialkylamino, diarylamino or alkoxy group, each with up to 18 carbon atoms,M is aluminum or boron,m is 1, 2, or 3, and1<n.ltoreq.50.

Abstract: A vulcanizable elastomeric compound and products such as pneumatic tires and the like, are formed from a functionalized polymer having a functional group derived from the polymerization initiator. The polymerization initiator is selected from the group consisting of ##STR1## where R.sup.1 and R.sup.2 are the same or different and are selected from the group consisting of alkyls having from 1 to about 12 carbon atoms, cycloalkyls having from 3 to about 14 carbon atoms, and aryls having from 6 to about 20 carbon atoms. Methods of the present invention include preparing the initiator, preparing functionalized polymers and, reducing the hysteresis of vulcanizable elastomeric compounds.

Abstract: The magnesium complexes of cyclic hydrocarbons, such as 1,2-dimethylenecycloalkanes, are readily prepared in high yields using highly reactive magnesium. Reactions of these (2-butene-1,4-diyl)magnesium reagents with electrophiles such as dibromoalkanes, alkylditosylates, or bromoalkylnitriles serve as a convenient method for synthesizing spirocyclic systems. Significantly, spirocarbocycles prepared by thisThe present invention was made with Government support under Contract No. GM35153 awarded by the National Institute of Health. The Government has certain rights in the invention.

Abstract: A method for the preparation of dialkylmagnesium compounds is disclosed, wherein magnesium hydride is reacted with an olefin in the presence of a halide of sub-groups IV to VIII of the Periodic Table and in the presence of an ether as reaction medium at a temperature of about between 1 to 300 bar and in a temperature range of about 0.degree. to 200.degree. C. According to the disclosed invention, the magnesium hydride is activated by grinding to a particle size of .ltoreq.10 .mu.m and the method is carried out in the absence of complex catalysts. The grinding of the magnesium hydride takes place prior to the reaction with the olefin, but may also be conducted during the reaction.

Abstract: A soluble highly reactive form of calcium, prepared from Ca(II) salts and a reducing agent in ethereal, polyethereal, or hydrocarbon solvents, is presented. This form of calcium can be used in the preparation of organocalcium reagents. The organocalcium reagents resulting from the reaction of the soluble highly reactive calcium with organic compounds containing either halide, cyanide, a 1,3-diene, or a polyunsaturated functionality, are stable, useful reagents for organic synthesis. The organocalcium halide reagents undergo Grignard-type reactions. They also undergo reactions with Cu(I) salts to form organocalcium cuprate reagents. The organocalcium cuprate reagents undergo a variety of cross-coupling reactions. The soluble highly reactive calcium reacts with 1,3-dienes to yield the corresponding 2-butene-1,4-diylcalcium complexes. These bis-organocalcium reagents can undergo dialkylation reactions with .alpha.,.omega.

Abstract: A catalytic process for alkylating an alkali metal selected from lithium, sodium and potassium with an alkyl halide containing 3 to 20 carbon atoms comprising conducting the reaction in the presence of a catalytic compound represented by the formula(RR.sup.1 R.sup.2 M.sup.a)yA(R.sup.3)xwherein R, R.sup.1 and R.sup.2 are independently selected from hydrogen, halogen, alkyl, alkenyl, cycloalkyl, and aryl groups, R.sup.3 is independently selected from aryl groups containing 6 to 18 carbon atoms, four to six-membered heterocyclic carbon containing groups containing one to two hetero atoms selected from oxygen, nitrogen, and sulfur; hydroxyalkyl, alkoxyalkyl and monoalkylaminoalkyl and dialkylaminoalkyl groups containing 2 to 13 carbon atoms; M.sup.a is selected from silicon, carbon, germanium, and tin, A is selected from oxygen, sulfur, nitrogen and phosphorus, and x and y independently have values from zero to three.

Abstract: Calcium-substituted polymeric reagents are provided. These reagents can be prepared via the oxidative addition of a soluble highly reactive calcium species to organic and inorganic polymers containing alkyl, aryl, or alkylaryl pendent groups substituted with halide atoms, cyanide molecules, 1,3-dienes, or any conjugated polyunsaturated system. Preferably, the polymer is a cross-linked p-bromopolystyrene, p-chloropolystyrene, p-fluoropolystyrene, or chloromethylated polystyrene. Preferably, the soluble highly reactive calcium species is prepared from the reduction of Ca(II) salts with an alkali metal arene, such as lithium biphenylide. These calcium-substituted polymeric reagents react with a variety of electrophiles to yield functionalized polymers. Reaction with Cu(I) salts yields calcium-substituted polymeric cuprate reagents, which can react, for example, with acid chlorides to form ketones, alkyl halides containing functionality, and undergo 1,4-conjugate addition with .alpha.,.beta.

Abstract: A process for the preparation of alkyllithium compounds including 2-alkyl-substituted alkyllithium compounds by reacting in a liquid organic solvent, in an inert atmosphere a C.sub.2 to C.sub.18 saturated, acyclic, primary alkyl halide including 2-alkyl-substituted alkyl halides with a dispersion of particulate lithium and sodium metals in which there is 5 to 50 mole percent sodium based on the lithium content at a temperature of 0.degree. to a temperature up to but not exceeding the decomposition temperature of the product.