Abstract: The present invention relates to a new catalytic system, which is a Lindlar type catalyst, wherein the supporting material (CaCO3) has an average particle size (d50) of more than 10 Pm, as well as to the use of such a catalytic system for the partial hydrogenation of a carbon-carbon triple bond (to a carbon-carbon double bond).

Abstract: This invention provides a process for obtaining propargyl bromide in high yield from propargyl alcohol and phosphorus bromide, in the form of a stable composition with alkylbromide.

Abstract: A method of synthesizing an alkyl cyclopentadiene compound is disclosed. The method includes contacting at least one cyclopentadienyl anion source and at least one alkyl group source to form at least one alkyl cyclopentadiene compound. The method further includes extracting the alkyl cyclopentadiene compound with a hydrocarbon solvent. The alkyl cyclopentadiene compound may be converted to a metallocene catalyst compound.

Abstract: Selectively fluorinated molecules are important as materials, pharmaceuticals, and agrochemicals, but their synthesis by simple, mild, laboratory methods is challenging. We report a straightforward method for the cross-coupling of a difluoromethyl group with readily available reagents to form difluoromethylarenes. The reaction of electron-neutral, electronrich, and sterically hindered aryl and vinyl iodides with the combination of Cul, CsF and TMSCF2H leads to the formation of difluoromethylarenes in high yield with good functional group compatibility. This transformation is surprising, in part, because of the prior observation of the instability of CuCF2H.

Abstract: Provided is a method for producing a chlorohydrocarbon having conjugated double bonds by stereoselectively chlorinating an alcohol having conjugated double bonds. More specifically, provided is a method for producing a chlorohydrocarbon having conjugated double bonds, the method including a step of chlorinating an alcohol having conjugated double bonds with a chlorinating agent in a solvent in the presence of a base and in the absence of metal salt for chlorination of the alcohol, and the alcohol being represented by the formula (1): RCH?CHCH?CH—Z—OH??(1) wherein R represents a hydrogen atom or a linear, branched or cyclic C1-17 monovalent hydrocarbon group which may have at least one double bond or at least one triple bond; and Z represents a linear, branched or cyclic C1-17 divalent hydrocarbon group which may have at least one double bond or at least one triple bond.

Abstract: A method of the present invention, for producing an iodizing agent, includes the step of electrolyzing iodine molecules in a solution by using an acid as a supporting electrolyte. This realizes (i) a method of producing an iodine cation suitable for use as an iodizing agent that does not require a sophisticated separation operation after iodizing reaction is completed, and (ii) an electrolyte used in the method. Further, a method of the present invention, for producing an aromatic iodine compound, includes the step of causing an iodizing agent, and an aromatic compound whose nucleus has one or more substituent groups and two or more hydrogen atoms, to react with each other under the presence of a certain ether compound. This realizes such a method of producing an aromatic iodine compound that position selectivity in iodizing reaction of an aromatic compound is improved.

Abstract: A method of synthesizing an alkyl cyclopentadiene compound is disclosed. The method includes contacting at least one cyclopentadienyl anion source and at least one alkyl group source to form at least one alkyl cyclopentadiene compound. The method further includes extracting the alkyl cyclopentadiene compound with a hydrocarbon solvent. The alkyl cyclopentadiene compound may be converted to a metallocene catalyst compound.

Abstract: A method of the present invention, for producing an iodizing agent, includes the step of electrolyzing iodine molecules in a solution by using an acid as a supporting electrolyte. This realizes (i) a method of producing an iodine cation suitable for use as an iodizing agent that does not require a sophisticated separation operation after iodizing reaction is completed, and (ii) an electrolyte used in the method. Further, a method of the present invention, for producing an aromatic iodine compound, includes the step of causing an iodizing agent, and an aromatic compound whose nucleus has one or more substituent groups and two or more hydrogen atoms, to react with each other under the presence of a certain ether compound. This realizes such a method of producing an aromatic iodine compound that position selectivity in iodizing reaction of an aromatic compound is improved.

Abstract: The present invention relates to a process for preparing (meth)acrylates, which comprises the transesterification of an alcohol with a low-boiling ester of (meth)acrylic acid in the presence of catalysts, with the alcohol liberated from the low-boiling ester of (meth)acrylic acid being separated off by distillation, characterized in that the molar ratio of low-boiling ester of (meth)acrylic acid to starting alcohol present in the reaction mixture is increased during the reaction by addition of low-boiling ester of (meth)acrylic acid. The process of the invention makes a particularly inexpensive preparation of (meth)acrylates having a very high purity possible.

Abstract: The invention relates to a process for the manufacture of vinyl chloride monomer comprising the preparation of acetylene from one or more renewable starting materials and then the reaction of the acetylene with hydrogen chloride in order to form vinyl chloride monomer. The invention also relates to the vinyl chloride monomer obtained and to its use.

Abstract: Disclosed are: an advantageous production process for a carotenoid intermediate; and others. Specifically disclosed are: a process for producing a dialcohol represented by formula (1), which is characterized by reacting a Grignard reagent with an acetylene gas in an organic solvent at a temperature of 30° C. or higher to prepare an ethynyl magnesium halide and subsequently reacting the ethynyl magnesium halide with methacrolein; a process for producing an allylhalide compound represented by formula (3) [wherein X represents a halogen atom: and the wavy line means the compound is either of E/Z geometric isomers or a mixture thereof], which is characterized by reducing a dialcohol represented by formula (1) with hydrogen to produce a triene alcohol represented by formula (2) [wherein the wavy line is as defined above] and halogenating the triene alcohol; and an allylchloride compound represented by formula (4) [wherein the wavy line is as defined above].

Abstract: A method of the present invention, for producing an iodizing agent, includes the step of electrolyzing iodine molecules in a solution by using an acid as a supporting electrolyte. This realizes (i) a method of producing an iodine cation suitable for use as an iodizing agent that does not require a sophisticated separation operation after iodizing reaction is completed, and (ii) an electrolyte used in the method. Further, a method of the present invention, for producing an aromatic iodine compound, includes the step of causing an iodizing agent, and an aromatic compound whose nucleus has one or more substituent groups and two or more hydrogen atoms, to react with each other under the presence of a certain ether compound. This realizes such a method of producing an aromatic iodine compound that position selectivity in iodizing reaction of an aromatic compound is improved.

Abstract: The present invention relates to a process for preparing chlorinated or partly chlorinated carbonyl compounds, which comprises reacting unchlorinated or partly chlorinated carbonyl compounds with a chlorinating agent in a jet loop reactor.

Abstract: A multiple stage apparatus and process using aerodynamic reactors and aero-coalescers in sequence for the selective capture and removal of purified carbon dioxide gas, the sequential capture and removal of mercury, metal and particulate aerosols by a recycling chemical generation-regeneration system using alkali metal chloride solution following multiple oxidations of mercury vapor, and nitric oxide in sequence, selective capture and removal of sulfur dioxide and nitrogen dioxide by two stage absorption by a recycling chemical generation-regeneration system using alkali metal hydroxide-carbonate-bicarbonate solution together with sequential oxidation to alkali metal sulfate and alkali metal nitrate compounds through evaporation and crystallization. Carbon dioxide capture and recovery is achieved in sequence by selective thermal decarbonation from an alkaline liquid followed by recovery as a purified gas stream.

Abstract: Iodohydroxylated olefins can be prepared by treating an olefin with an aqueous solution of an iodine monohalide selected from iodine monochloride and iodine monobromide.

Abstract: Propargyl bromide is effectively stabilized against shock or thermal decomposition by use therewith of an environmentally acceptable inert liquid solvent that forms an azeotrope with propargyl bromide.

Abstract: This invention provides a process of producing propargyl bromide in the absence of a base. The process comprises: A) bringing together in a reaction zone under an inert atmosphere and in the absence of a base and in the presence of an inert diluent, a feed of phosphorus tribromide and a separate feed of propargyl alcohol thereby forming a reaction mixture; B) while mechanically agitating the mixture being formed in A), maintaining the temperature of the mixture in the range of about 0° C. to about 25° C. to form a product mixture, and then C) raising the temperature of the product mixture to a temperature in the range of about 40° C. to about 60° C. while stirring the product mixture for a ride period of at least about 2.5 hours. Such process can be conducted as a batch process, as a semi-batch process, or as a continuous process.

Abstract: 1-chloropropylethyne is prepared by dehydrochlorination with a base of 1-chloro-1-cyclopropylethene, which is itself prepared by treating 1-cyclopropylethanone with dichlorotriarylphosphorane or dichlorotrialkylphosphorane in the presence of a base.

Abstract: The present invention provides a method and catalyst composition for carbonylating aromatic hydroxy compounds, comprising the step of contacting at least one aromatic hydroxy compound with oxygen and carbon monoxide in the presence of a carbonylation catalyst composition comprising an effective amount of at least one Group 8, 9, or 10 metal source, an effective amount of a combination of inorganic co-catalysts comprising at least one Group 4 metal source and at least one Group 11 metal source, an effective amount of at least one salt co-catalyst with an anion selected from the group consisting of carboxylate, benzoate, acetate, sulfate, and nitrate, wherein the carbonylation catalyst composition is free of a halide source.

Abstract: In a process for production of allyl chloride whereby allyl alcohol and hydrogen chloride are reacted in the presence of a catalyst and the resulting allyl chloride is distilled off from the reaction system, the by-production of diallyl ether is suppressed by lowering the molar concentration ratio of hydrogen chloride with respect to allyl alcohol in the reaction solution ([AAL]½/[HCL]).

Abstract: In a process for chlorinating ketones which, apart from the carbonyl group, are inert in respect of triarylphosphine dichlorides, except for cyclopropyl methyl ketone, in which the ketones are reacted with a chlorinating agent in the presence of triarylphosphine oxides, the amount of triarylphosphine oxide is from 0.1 to 10 mol %, based on the amount of ketone. The ketones preferably have a least one CH-acid proton in the &agr; position to the carbonyl group.

Abstract: In a continuous process for preparing propargyl chloride by reacting propargyl alcohol with a chlorinating agent in the presence of a catalyst, the chlorinating agent, propargyl alcohol and from 0.1 to 10 mol % of the catalyst, based on the amount of propargyl alcohol, are continuously metered into a reaction zone and reacted at from 40 to 70° C.

Abstract: The present invention relates to a process for preparing alkyl, alkenyl and alkynyl chlorides from alcohols by reaction with a chlorinating agent in the presence of a catalyst, wherein the catalyst is a urea compound.

Abstract: This invention provides an improved process for the preparation of chloroalkynes from alkynyl alcohols. The chloroalkynes can be employed to prepare alkynyl amines which are useful for the manufacture of biologically active materials. The present invention reduces the hazards of the chlorination reaction, eliminates or greatly reduces by-product formation, and provides certain environmental benefits.

Abstract: A method for preparing fatty acid chlorides. The method comprises reacting a silylation product of a fatty acid comprising at 1east 2 aliphatically unsaturated bonds per molecule and a chlorinating agent.

Abstract: An improvement is proposed for the removal of the precipitates of a phosphine oxide compound as a by-product from a mixture thereof with an olefin compound obtained by the Wittig reaction for the preparation of the olefin compound from a phosphorane compound and a carbonyl compound. Instead of the conventional procedure of filtration to remove the precipitates, the mixture in a hydrocarbon solvent, after replacement of a non-hydrocarbon solvent with a hydrocarbon solvent, if necessary, is admixed with a lower carboxylic acid such as acetic acid so that the precipitates of the phosphine oxide are dissolved forming a viscous fluid which is immiscible with the mixture of the olefin compound and the hydrocarbon solvent. The fluid containing the dissolved phosphine oxide compound can be easily removed by phase separation so that a great increase is obtained in the yield of the desired olefin compound.

Abstract: The preparation of an alkyl, alkenyl, or alkynyl chloride by the reaction of a corresponding alcohol with phosgene or thionyl chloride in the presence of a phosphine oxide acting as catalyst, wherein the catalyst used is an aliphatic, cycloaliphatic, or cyclic/aliphatic phosphine oxide.

Abstract: A terpene compound having the formula (III) is produced by reacting an allylic halide having the formula (I) with a Grignard reagent having the formula (II) in the presence of anhydrous zinc chloride and a copper compound or an organic zinc halide compound having the formula (IV) in the presence of a copper compound, provided that when A-A is C-C, R' is hydrogen and when A-A is C=C, X is chlorine.

Abstract: A pheromonal compound produced by the western corn rootworm has been identified as 8-methyl-2-decanol propanoate (8-M-2-DP) having the structural formula: ##STR1## A synthesis has been devised for racemic 8-M-2-DP which demonstrates activity toward the western corn rootworm comparable to its natural counterpart. Other diabroticites including the Mexican corn rootworm and the northern corn rootworm also respond to the synthetic compound. By attracting rootworms to field traps, 8-M-2-DP is a useful tool for the monitoring and control of these major agricultural pests.

Abstract: Chloro-olefins which contain a group of the formula ##STR1## where Y is chlorine or hydrogen, which are prepared by a process in which a trichloromethyl compound which contains a group of the general formula ##STR2## where X is hydrogen or an organic radical, is reduced with a chromium(II) salt in an aqueous medium.

Abstract: Halogenated, unsaturated alcohols are dehydrated by contacting the alcohol and a carrier gas with a silica alumina catalyst to form dienes of the formula: ##STR1## wherein each X is independently hydrogen, fluorine chlorine, or bromine with the proviso that no more than one of them is hydrogen, and each R is independently hydrogen, alkyl, aralkyl, alkaryl, or aryl.

Abstract: An improved process for the preparation of primary terpenoid alcohols, e.g. 6,7-dihydrogeraniol and phytol, and of their esters with formic acid. The terpenoid formates are obtained very advantageously by reacting the corresponding tert.-vinylcarbinols with more than 2 moles, per mole of vinylcarbinol, of aqueous formic acid of more than 70 percent strength by weight, or with anhydrous formic acid, at from 5.degree. to 100.degree. C. The primary terpenoid alcohols themselves are obtained from their formates by trans-esterification with a low-boiling alcohol in the presence of a catalytic amount of a strong base. The products are valuable compounds. For example, 6,7-dihydrogeraniol is used as a scent and phytol is used as a perfume fixative and as a starting material for the synthesis of naturally occurring materials.

Abstract: A method for the preparation of a first sulfone compound of the formula: ##STR1## wherein R.sub.a is ##STR2## where R.sub.b is Br and R.sub.c is H except that R.sub.b and R.sub.c together may be an electron pair when R.sub.6 is a radical of the formula: ##STR3## wherein X.sub.1 is independently chlorine, bromine or iodine and R.sub.1 and R.sub.2 are independently at each occurrence hydrogen or, substituted or unsubstituted, phenyl or alkyl where the substituents are halogen or alkoxy or additional --SO.sub.2 Br groups; provided that, each carbon atom of R.sub.1 or R.sub.2 which contains --SO.sub.2 Br also contains an X.sub.1 group and wherein R.sub.3 through R.sub.9 are independently --OZ,--C.sub.6 M.sub.5,--Z,--SiZ.sub.3 or --X.sub.2, where Z is hydrogen or substituted or unsubstituted phenyl, alkyl, alkenyl or alkynyl; X.sub.2 is chlorine, bromine, iodine or fluorine; M is independently at each occurrence Z or X.sub.2 ; R.sub.3 and R.sub.4 may together be an electron pair; two or more of R.sub.3, R.sub.

Abstract: A process for the preparation of a 1,1-dichloro-alkene of the formula ##STR1## in which R.sup.1 is hydrogen, or an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, andR.sup.2 is an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, orR.sup.1 and R.sup.2 together form an optionally branched and/or optionally benzo-fused hydrocarbon chain,comprising reacting a carbonyl compound of the formula ##STR2## with a trichloromethanephosphonic acid ester of the formula ##STR3## in which R.sup.3 each individually is an alkyl or phenyl radical, or together are alkanediyl,in the presence of at least an equimolar amount of magnesium. Advantageously,R.sup.1 is hydrogen,R.sup.2 is a C.sub.2 to C.sub.5 alkenyl radical or a radical of the formula ##STR4## Z is a cyano, acetal, carboxyl or C.sub.1 to C.sub.4 alkoxycarbonyl radical, or a radical of the formula COOM, andM is sodium or potassium,R.sup.3 each individually is a C.sub.1 to C.

Abstract: The invention relates to a new process for preparing unsaturated geminal dihalogen compounds. More particularly, the invention concerns a process for preparing compounds of the formula (I) ##STR1## wherein X is halogen,R.sup.1 is a straight or branched chained alkenyl group having 2 to 6 carbon atoms,by clearing the corresponding 1-substituted 2,2,2-trihaloethylesters.

Abstract: In the preparation of a 1,1-dihalogenoalkene of the formula ##STR1## in which R.sup.1 is a hydrogen atom or an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, andR.sup.2 is an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, orR.sup.1 and R.sup.2 together form an optionally branched and/or optionally benzo-fused hydrocarbon chain, andX.sup.1 and X.sup.2 each independently is a halogen atom,wherein a carbonyl compound of the formula ##STR2## is reacted with a trihalogenoacetate of the formula ##STR3## in which X.sup.3 is a halogen atom, andM.sup..sym. is an alkali metal ion or one equivalent of an alkaline earth metal ion,in the presence of an approximately equimolar amount of a phosphorus-containing compound, the improvement which comprises employing as said phosphorus-containing compound a phosphorous acid trialkyl ester or a phosphorous acid triamide and effecting the reaction at a temperature between about 0.

Abstract: The invention provides a novel and efficient method for the synthetic preparation of cis-nonen-6-yl chloride which is a useful intermediate compound for the syntheses of, for example, cis-nonen-6-yl acetate, cis-nonen-6-ol, cis-nonen-6-al and the like as flavors as well as cis-dodecen-9-yl acetate and cis-tetradecen-11-yl acetate known as sexual pheromone compounds of several noxious insects. The inventive method comprises reacting 1-bromo-3-chloropropane with the Grignard reagent of cis-hexen-3-yl chloride which is a chlorination product of cis-hexen-3-ol known by a trivial name of leaf alcohol. The reaction is preferably carried out in tetrahydrofuran in the presence of a catalyst which may be lithium copper dichloride or dilithium copper tetrachloride at 0.degree. to 40.degree. C.

Abstract: A process for the preparation of a 1,1-dichloroalkene of the formula ##STR1## in which R.sup.1 is hydrogen, or an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, andR.sup.2 is an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aralkenyl or aryl radical, orR.sup.1 and R.sup.2 together form an optionally branched and/or optionally benzo-fused hydrocarbon chain,comprising reacting a carbonyl compound of the formula ##STR2## with a trichloromethanephosphonic acid ester of the formula ##STR3## in which R.sup.3 each individually is an alkyl or phenyl radical, or the two radicals R.sup.3 together are alkanediyl,in the presence of at least an equimolar amount of a phosphorous acid triamide of the formulaP(NR.sup.4.sub.2).sub.3in whichR.sup.4 each independently is an alkyl radical, or the two radicals R.sup.4 together are alkanediyl.Advantageously,R.sup.1 is hydrogen,R.sup.2 a C.sub.2 to C.sub.

Abstract: A process for the preparation of a 1,1-dichloroalkene of the formula ##STR1## in which R.sup.1 is hydrogen or an optionally substituted alkyl, alkenyl, alkynyl, aralkyl or aryl radical, andR.sup.2 is an optionally substituted alkyl, alkenyl, alkynyl, aralkyl, aralkenyl or aryl radical, or cycloalkyl which is optionally substituted by halogen, alkyl, alkanoyl, carbamoyl, cyano or phenyl, orR.sup.1 and R.sup.2 together form a hydrocarbon chain which is optionally branched and/or optionally contains a fused benzene ring,comprising reacting an aldehyde or ketone of the formula ##STR2## with a dichloromethane-phosphonic acid ester of the formula ##STR3## in which R.sup.3 each independently is alkyl or phenyl or the two radicals R.sup.3 together are alkanediyl,in the presence of a base at a temperature between about -50.degree. and +50.degree. C.

Abstract: A process for the preparation of dihalovinyl compounds of the formula ##STR1## wherein each Hal is fluorine, chlorine or bromine, R.sup.1 is an optionally substituted hydrocarbyl group, R.sup.2 is a methyl group or a hydrogen atom, or R.sup.1 and R.sup.2 together with the carbon atom to which they are attached form cycloalkylidene group, which process comprises treating a trihalo compound of the formula ##STR2## wherein Hal, R.sup.1 and R.sup.2 have the above meanings and R.sup.3 is a hydrogen atom or ##STR3## in which M is an alkali atom, with PHal.sub.3.

Abstract: A novel compound cis-6-undecene-1-chloride is prepared by reacting cis-3-octene-1-chloride with metallic magnesium to give a Grignard reagent of the chloride and then reacting the Grignard reagent with 1-bromo-3-chloropropane in the presence of a lithium copper chloride as a catalyst. The inventive compound is a useful intermediate compound for the synthetic preparation of several kinds of so-called sexual pheromone compounds of noxious insects. As an example of such sexual pheromone compounds, the synthetic preparation of cis-9-tetradecenyl acetate is described.

Abstract: In the process for the production of a halogenoalkene of the formula ##STR1## in which R.sup.1 is an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl or aryl radical or an optionally substituted heterocyclic radical,R.sup.2 represents a halogen atom, a cyano group, an optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, aralkenyl, aryl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl or aminocarbonyl radical or an optionally substituted heterocyclic radical, andX is a halogen atom,in which an .alpha.-hydroxy-phosphonic acid ester of the formula ##STR2## in which R.sup.3 each independently is an alkyl or phenyl radical, or the two radicals R.sup.3 together are an alkanediyl (alkylene) radical,is reacted with a phosphorus-containing olefinating agent of the formula ##STR3## in which Z.sup.1 is the phosphorus-containing radical ##STR4## R.sup.4 and R.sup.5 each independently is an alkyl, phenyl, alkoxy or phenoxy radical or together are an alkanedioxy radical, andR.

Abstract: A process for asymmetrically hydrogenating through the use of microorganisms a double bond connected to tertiary carbon atom in an olefinic aliphatic compound to produce a tertiary, optically active aliphatic compound useful as an intermediate for optically active Vitamins E and K.

Abstract: 1-[3-Methyl-3,5,5-trialkoxy-pent-1-yn-1-yl]-2,6-dimethyl-cyclohex-1-enes, which may or may not be methyl-substituted in the 2- and/or 6-position, are obtained by reacting the corresponding 1-[3-methyl-but-1-yn-3-en-1-yl]-2,6-dimethyl-cyclohex-1-enes with orthoformic acid esters in the presence of acid condensing agents. The new compounds provide a new method of access to the compounds of carotinoid chemistry, especially to vitamin A, which avoids the conventional expensive synthesis via phosphorus ylide compounds.

Abstract: 1,1,1-Trihalogeno-4-methyl pentenes and 1,1-dihalogeno-4-methyl-1,3-pentadienes are produced. These compounds are of value as intermediates for the production of pyrethrin analogs which are of use as insecticides or agricultural chemicals.