Organic Hydroperoxide Reactant Patents (Class 549/529)
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Patent number: 5349072Abstract: In reacting tertiary butyl hydroperoxide in solution in tertiary butyl alcohol with propylene to produce propylene oxide and tertiary butyl alcohol in a reactor system comprising a first isothermal segment and a second adiabatic segment about 60 to 80 wt % of the tertiary butyl hydroperoxide is converted in the isothermal segment to provide an intermediate reaction mixture, a recycle stream comprising about 25 to 100 wt. % of the combined weight of the propylene and the tertiary butyl alcohol solution is removed from the intermediate reaction mixture and recycled to the first isothermal segment and the remainder of the intermediate reaction mixture is passed through the adiabatic segment where an additional 20 to 40 wt. % of the tertiary butyl hydroperoxide is converted.Type: GrantFiled: July 6, 1993Date of Patent: September 20, 1994Assignee: Texaco Chemical CompanyInventors: Kyle L. Preston, Chung-Nan T. Wu, Mark E. Taylor, Mark A. Mueller
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Patent number: 5336790Abstract: A process for recovery of molybdenum from residual fractions derived from an epoxidation reaction of propylene with tertiary butyl hydroperoxide in liquid phase with tertiary butyl alcohol, in the presence of soluble molybdenum, which process comprises:Fractionating epoxidation reaction product for obtaining a liquid fraction containing essentially all molybdenum from the reaction product;Contacting the liquid fraction with anhydrous ammonia for forming a precipitate containing the major portion of the molybdenum and a liquid phase containing 500 ppm or less molybdenum;Separating the liquid phase from the precipitated solid;Evaporating the liquid phase under conditions of elevated temperatures and reduced pressure in the presence of 1 to 3% water for separation into an evaporator overhead vapor essentially free of molybdenum and an evaporator concentrate comprising essentially all of the molybdenum fed to the evaporator;Rapidly cooling evaporator concentrate from about evaporation temperature to about room teType: GrantFiled: November 18, 1993Date of Patent: August 9, 1994Assignee: Texaco Chemical CompanyInventors: Edward T. Marquis, Howard F. Payton, Robert A. Meyer
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Patent number: 5334768Abstract: The invention relates to a process for the preparation of cycloalkanone and optionally cycloalkanol by causing a mixture containing cycloalkylhydroperoxide to react with cycloalkene under the influence of a catalyst, characterised in that the reaction is carried out with a short measure of cycloalkene relative to the cycloalkylhydroperoxide, under such conditions that virtually all of the cycloalkene reacts to cycloalkene oxide and optionally cycloalkanol and/or cycloalkanone, after which the mixture, optionally after decomposition of cycloalkylhydroperoxide and distillation of cycloalkane, is subjected to a first separation, in which cycloalkene oxide--and optionally other components--is separated, after which the cycloalkene oxide in the separated mixture is isomerised to substantially cycloalkanone, after which the cycloalkanone obtained--and optionally cycloalkanol--is recovered.Type: GrantFiled: February 3, 1993Date of Patent: August 2, 1994Assignee: DSM N.V.Inventors: Johannes G. van Hinsberg, Cornelis G. M. van de Moesdijk, Ivo Spaargaren, Otto E. Sielcken
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Patent number: 5331084Abstract: Fluorine-substituted epoxides of the formula ##STR1## in which the substituents R.sub.1 to R.sub.4, independently of one another, have the following meanings:R.sub.1 to R.sub.4 =H, fluorine, C.sub.1 - to C.sub.18 -alkyl in which some or all of the hydrogens may be substituted by fluorine, and at least one of the substituents R.sub.1 to R.sub.4 is a completely fluorinated alkyl or an alkyl of the formula--(CH.sub.2).sub.m --(C.sub.n F.sub.2n+1),in which m is 1 or 2, and n is an integer from 1 to 17, and x is 0 or 1.Furthermore, a method for the preparation of fluorine-substituted epoxides is described.Type: GrantFiled: February 12, 1993Date of Patent: July 19, 1994Assignee: Hoechst AktiengesellschaftInventors: Jurgen Kulpe, Heinz Strutz
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Patent number: 5319114Abstract: Olefins are selectively converted to epoxides by reacting with an organic hydroperoxide in the presence of a heterogeneous catalyst comprised of a carbon molecular sieve containing a Group IVA, VA, VIA, or VIIA transition metal such as molybdenum.Type: GrantFiled: September 23, 1993Date of Patent: June 7, 1994Assignee: Arco Chemical Technology, L. P.Inventors: Anne M. Gaffney, Manish K. Nandi, Rangasamy Pitchai, Yuan-Zhang Han
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Patent number: 5310956Abstract: The present invention is optically active epoxides and its production characterized in that the process comprises reacting alkenyl ethylene glycols with 0.5 to 2.0 equivalents of a titanium-tetraalkoxyde, a peroxide and an L-(+)- or D-(-)-dialkyl tartrate at a temperature of -78.degree. to 50.degree. C. to asymmetrically oxidize the alkenyl ethylene glycols. The production of the present invention is an excellent method for producing chiral epoxides in which steric configuration of three asymmetric points can be perfectly controlled, the reaction is performed by mild conditions and the chemical yield and the optical yield are extremely high. The optically active epoxides which can be efficiently produced by the production of the present invention are useful as stating materials of several kinds of compounds.Type: GrantFiled: May 19, 1993Date of Patent: May 10, 1994Assignee: Chisso CorporationInventors: Seiichi Takano, Kunio Ogasawara
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Patent number: 5286884Abstract: A method and apparatus for continuously catalytically exothermally reacting propylene with tertiary butyl hydroperoxide in a reaction mixture stream comprising a tertiary butyl alcohol solution of catalyst, reacting propylene, reacting tertiary butyl hydroperoxide, propylene oxide and reaction by-products by thermosyphonically circulating the reaction mixture stream around a thermosyphonic reactor loop; continuously removing heat from the circulating stream in a downflow heat exchange zone in the reactor and continuously passing the circulating stream of reaction mixture through an adiabatic zone such as an upflow reaction zone of progressively increasing temperature while withdrawing or displacing a product stream in an amount sufficient to maintain a predetermined volume of reaction mixture in the reactor and whereby the density of the reaction mixture in the heat exchange zone will be greater than the density of the reaction mixture in the adiabatic zone whereby continuous thermosyphonic circulation can beType: GrantFiled: July 24, 1992Date of Patent: February 15, 1994Assignee: Texaco Chemical CompanyInventors: Roderick S. Cowley, Darrell D. Kinzler
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Patent number: 5276235Abstract: In the co-production of propylene oxide and styrene monomer, there is produced a sodium-containing heavy residue stream previously suitable only as a low grade fuel. In accordance with the invention, the heavy residue stream is contacted with acid having a molar concentration with respect to water above that which corresponds to the product salt solubility limit, and the resulting mixture is phase separated into an aqueous sodium salt-containing slurry phase and an organic phase reduced in sodium.Type: GrantFiled: February 19, 1993Date of Patent: January 4, 1994Assignee: ARCO Chemical Technology, L.P.Inventor: Walter S. Dubner
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Patent number: 5274139Abstract: A method of effecting a reaction between oxygen and an organic substance comprising the stages of:a. forming a reaction mixture comprising an N-alkylpyrrolidinone, at least one organic substance capable of reaction with oxygen and a hydroperoxide decomposition catalytically effective amount of a transition metal oxidation catalyst under a partial pressure of oxygen of at least about 16 psig, the molar ratio of organic substance to N-alkylpyrrolidinone being at least about 1:100;b. subjecting the reaction mixture to conditions such that an oxidation reaction occurs, whereby:(1) at least a portion of the N-alkylpyrrolidinone is oxidized, in situ, to the corresponding hydroperoxide;(2) the hydroperoxide is subsequently decomposed by the catalytic action of the transition metal oxidation catalyst to the corresponding N-alkylsuccinimide, the decomposition resulting in the production of active oxygen which reacts with the organic substance;c.Type: GrantFiled: February 26, 1993Date of Patent: December 28, 1993Assignee: University of FloridaInventors: Russell S. Drago, Douglas E. Patton
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Patent number: 5274138Abstract: An epoxidation reaction wherein: an olefin and an organic hydroperoxide, preferably, propylene and tertiary butyl hydroperoxide are reacted in a primary reaction zone in a liquid phase with an organic solvent, preferably tertiary butyl alcohol, in the presence of a soluble molybdenum catalyst at a ratio of propylene to tertiary butyl hydroperoxide of from about 0.9:1 to about 3:1, at a reaction temperature from about 100.degree. C. to about 140.degree. C.Type: GrantFiled: January 21, 1993Date of Patent: December 28, 1993Assignee: Texaco Chemical CompanyInventors: Kenneth P. Keating, Edward T. Marquis, Mark A. Mueller
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Patent number: 5268489Abstract: Unsaturated cycloaliphatic esters like higher hydrocarbyl, functionally substituted or polyunsaturated cyclohex-3-ene carboxylates, made directly by cycloaddition of dienes with dienophillic (meth/eth)acrylates, and their derivatives like epoxides and urethanes, provide useful thermal and radiation curable coatings, inks, sealants, adhesives, solvents, acid scavengers, and intermediates for other uses.Type: GrantFiled: February 5, 1993Date of Patent: December 7, 1993Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Joseph V. Koleske, John N. Argyropoulos, Oliver W. Smith
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Patent number: 5254704Abstract: The present invention is optically active epoxides and its production characterized in that the process comprises reacting alkenyl ethylene glycols with 0.5 to 2.0 equivalents of a titanium-tetraalkoxyde, a peroxide and an L-(+)- or D-(-)-dialkyl tartrate at a temperature of -78.degree. to 50.degree. C. to asymmetrically oxidize the alkenyl ethylene glycols. The production of the present invention is an excellent method for producing chiral epoxides in which steric configuration of three asymmetric points can be perfectly controlled, the reaction is performed by mild conditions and the chemical yield and the optical yield are extremely high. The optically active epoxides which can be efficiently produced by the production of the present invention are useful as stating materials of several kinds of compounds.Type: GrantFiled: May 20, 1992Date of Patent: October 19, 1993Assignee: Chisso CorporationInventors: Seiichi Takano, Kunio Ogasawara
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Patent number: 5208352Abstract: An improved process for preparing the R- and S-isomers of 2-hydroxymethyl-2-octadecyloxymethyl-tetrahydrofuran, a critical step of which involves the preparation of the R- and S-isomers of 2-[3-(1-methoxy-1-methylethoxy)]propyl-oxiranemethanol employing metal-catalyzed Sharpless epoxidation. In addition, the invention relates to the use of the R- and S-isomers of 2-hydroxymethyl-2-octadecyloxymethyl-tetrahydrofuran in preparing stereoisomers of pharmacologically active compounds, and to the R- and S-isomers of 2-[3-(1-methoxy-1-methylethoxy)]-propyl-oxiranemethanol as novel compounds.Type: GrantFiled: April 2, 1992Date of Patent: May 4, 1993Assignee: Sandoz Ltd.Inventors: Chung-Pin Chen, Prasad K. Kapa, William J. Houlihan
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Patent number: 5175316Abstract: The preparation of cyclohexene oxide, cyclohexanol and cyclohexanone involvesa) oxidizing cyclohexane using a gas containing molecular oxygen to form cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone,b) jointly separating the mixture from a) and c) by distillation, andc) reaction of the cyclohexyl hydroperoxide fraction from b) with cyclohexene in the presence of a transition-metal compound from group 4 to 6, forming cyclohexene oxide, and separating the product mixture in b).Type: GrantFiled: February 10, 1992Date of Patent: December 29, 1992Assignee: BASF AktiengesellschaftInventors: David Agar, Paul-Michael Bever, Hans H. Schuster, Gerald Neubauer
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Patent number: 5171868Abstract: Caustic requirements are substantially reduced in the treatment of epoxidate from olefin/ethylbenzene hydroperoxide epoxidation by treating the epoxidate products with an aqueous stream comprised of alkali metal carbonate, separating a phenol-containing 1-phenyl ethanol fraction from the treated expodiate, separating phenol from the 1-phenyl ethanol fraction by treatment with basic anion exchange resin, regenerating the resin with aqueous alkali metal hydroxide, and converting alkali metal hydroxide from the resin regeneration to alkali metal carbonate for use in the epoxidate treatment.Type: GrantFiled: April 15, 1992Date of Patent: December 15, 1992Assignee: ARCO Chemical Technology, L.P.Inventors: Rajendra S. Albal, Robert N. Cochran, T. Ben Hsu
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Patent number: 5166371Abstract: Prochiral ethylenically unsaturated substrates are converted to chiral epoxides by reaction with optically active hydroperoxides in the presence of transition metal catalysts. For example, chiral glycidol is obtained by asymmetric epoxidation of allyl alcohol using optically active ethyl benzene hydroperoxide and a titaniuym alkoxide/tartrate catalyst. The chiral epoxide products are versatile synthetic intermediates.Type: GrantFiled: August 9, 1991Date of Patent: November 24, 1992Assignee: Arco Chemical Technology, L.P.Inventors: Wilfred P. Shum, Haven S. Kesling, Jr., John G. Zajacek
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Patent number: 5155243Abstract: The present invention provides a composition represented by the formula ##STR1## (wherein x is an integer of 3 to 7, y is an integer of 0 to 50, and R.sub.a and R.sub.b are H, methyl group, or propyl group and each of the R.sub.a and R.sub.b groups may be replaced with any of the other groups simultaneously)and useful as a raw material or modifier for resins for use in coating compositions, adhesives, epoxy resins, and the like, and further provides a process for producing a composition comprising compounds represented by the above formula (I) which process is characterized in that a compound represented by the formula ##STR2## is reacted with a lactone at 30.degree. to 20.degree. C. or compounds represented by the formula ##STR3## (wherein x, y, R.sub.a, and R.sub.b have the meanings as defined above) are epoxidized at 0.degree. to 80.degree. C. using a peroxide.Type: GrantFiled: October 15, 1991Date of Patent: October 13, 1992Assignee: Daicel Chemical Industries, Ltd.Inventors: Takaaki Fujiwa, Tomohisa Isobe
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Patent number: 5151530Abstract: The distillation product fraction obtained from an isobutane oxidation reaction product after the removal of unreacted isobutane will contain tertiary butyl hydroperoxide, tertiary butyl alcohol and carboxylic acid contaminants such as formic acid, acetic acid and isobutyric acid. It has been discovered that when the distillation product fraction is treated with about 1/2 to 1 equivalents of calcium oxide and/or calcium hydroxide based on the carboxylic acid content of the distillate product fraction, a portion of the carboxylic acid contaminants will precipitate thus partially purifying the distillation product fraction so that, thereafter, molybdenum precipitation will be substantially inhibited when the thus-treated distillation product fraction is used as a feedstock for an epoxidation reaction wherein tertiary butyl hydroperoxide is reacted with an olefin in the presence of a soluble molybdenum catalyst to provide an olefin epoxide and additional tertiary butyl hydroperoxide.Type: GrantFiled: September 25, 1991Date of Patent: September 29, 1992Assignee: Texaco Chemical CompanyInventors: Edward T. Marquis, John R. Sanderson, Robert A. Meyer
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Patent number: 5128492Abstract: An epoxidation reaction product formed by the molybdenum catalyzed reaction of propylene with tertiary butyl hydroperoxide to provide propylene oxide and tertiary butyl alcohol is separated by distillation into a propylene fraction, a propylene oxide fraction, a tertiary butyl alcohol fraction and a heavy liquid distillation fraction composed primarily of tertiary butyl hydroperoxide, tertiary butyl alcohol, dissolved molybdenum catalyst, and impurities including lower aliphatic C.sub.1 -C.sub.4 carboxylic acids, and the heavy liquid distillation fraction is saturated with hydrogen to precipitate the molybdenum therefrom for recovery.Type: GrantFiled: May 20, 1991Date of Patent: July 7, 1992Assignee: Texaco Chemical CompanyInventors: William A. Smith, Robert A. Meyer, Edward T. Marquis
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Patent number: 5126505Abstract: The invention relates to improved recovery of cycloalkanol/cycloalkanone from epoxidation mixtures which result from olefin epoxidation with cycloalkyl hydroperoxide by hydrolysis of ketal compounds contained in the mixtures.Type: GrantFiled: October 18, 1990Date of Patent: June 30, 1992Assignee: Arco Chemical Technology, L.P.Inventor: Te Chang
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Patent number: 5118822Abstract: Olefins are oxidized to epoxide compounds by contacting the olefins with organic hydroperoxides in the presence of rhenium catalysts comprised of perrhenate anions and organopnicogen-containing cations. High yields of epoxides are attained, particularly when the olefin substrate bears an aromatic substituent.Type: GrantFiled: September 30, 1991Date of Patent: June 2, 1992Assignee: Arco Chemical Technology, L.P.Inventors: Wilfred P. Shum, Haven S. Kesling, Jr.
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Patent number: 5107001Abstract: Present invention relates to the production of propylene oxide by reaction of propylene with a C.sub.4 or higher hydroperoxide wherein at least a portion of the propylene is derived from the hydroperoxide moiety.Type: GrantFiled: September 7, 1990Date of Patent: April 21, 1992Assignee: Arco Chemical Technology, L.P.Inventors: Morris Gelb, David W. Leyshon, John A. Sofranko, C. Andrew Jones
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Patent number: 5107067Abstract: Complexes made by reacting an ammonium-containing molybdenum compound with an alkylene glycol in the presence of water at an elevated temperature are described. Mild stripping of the water subsequent to complex formation is preferred. If some of the water is left in the complex, it may serve as an excellent olefin epoxidation catalyst. The ratio of moles of alkylene glycol to gram atoms of molybdenum in the complex forming reaction ranges from 7:1 to 20:1. Ethylene glycol and propylene glycol are the particularly preferred alkylene glycols.Type: GrantFiled: May 12, 1989Date of Patent: April 21, 1992Assignee: Texaco Inc.Inventors: Edward T. Marquis, Kenneth P. Keating, John R. Sanderson, William A. Smith
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Patent number: 5103027Abstract: Olefins are oxidized to epoxide compounds by contacting the olefins with organic hydroperoxides in the presence of oxorhenium porphyrin complex catalysts. High yields of epoxides are attained, particularly when the olefin substrate bears an aromatic substituent.Type: GrantFiled: July 23, 1991Date of Patent: April 7, 1992Assignee: Arco Chemical Technology, L.P.Inventors: Wilfred P. Shum, Haven S. Kesling, Jr.
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Patent number: 5101052Abstract: An epoxidation reaction product formed by the molybdenum catalyzed reaction of propylene with tertiary butyl hydroperoxide to provide propylene oxide and tertiary butyl alcohol is separated by distillation into a propylene fraction, a propylene oxide fraction, a tertiary butyl alcohol fraction and a heavy liquid distillation fraction composed primarily of tertiary butyl hydroperoxide, tertiary butyl alcohol, dissolved molybdenum catalyst, and impurities including lower aliphatic C.sub.1 -C.sub.4 carboxylic acids, and the heavy liquid distillation fraction is saturated with ammonia to precipitate the molybdenum therefrom for recovery.Type: GrantFiled: May 20, 1991Date of Patent: March 31, 1992Assignee: Texaco Chemical CompanyInventors: Robert A. Meyer, Edward T. Marquis
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Patent number: 5093506Abstract: The distillation product fraction obtained from an isobutane oxidation reaction product after the removal of unreacted isobutane will contain tertiary butyl hydroperoxide, tertiary butyl alcohol and carboxylic acid contaminants such as formic acid, acetic acid and isobutyric acid. It has been discovered that when the distillation product fraction is treated with about 1/2 to 1 equivalents of calcium oxide and/or calcium hydroxide based on the carboxylic acid content of the distillate product fraction, a portion of the carboxylic acid contaminants will precipitate thus partially purifying the distillation product fraction so that, thereafter, molybdenum precipitation will be substantially inhibited when the thus-treated distillation product fraction is used as a feedstock for an epoxidation reaction wherein tertiary butyl hydroperoxide is reacted with an olefin in the presence of a soluble molybdenum catalyst to provide an olefin epoxide and additional tertiary butyl hydroperoxide.Type: GrantFiled: August 30, 1989Date of Patent: March 3, 1992Assignee: Texaco Chemical CompanyInventors: Edward T. Marquis, John R. Sanderson, Robert A. Meyer
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Patent number: 5093509Abstract: An epoxidation reaction product formed by the molybdenum catalyzed reaction of propylene with tertiary butyl hydroperoxide to provide propylene oxide and tertiary butyl alcohol is separated by distillation into a propylene fraction, a propylene oxide fraction, a tertiary butyl alcohol fraction and a heavy liquid distillation fraction composed primarily of tertiary butyl hydroperoxide, tertiary butyl alcohol, dissolved molybdenum catalyst, and impurities including lower aliphatic C.sub.1 -C.sub.4 carboxylic acids, and the dissolved molybdenum content of the heavy distillation fraction is adjusted to about 300 to 500 ppm of dissolved molybdenum, if necessary, by treatment with a precipitating agent and contacted with a solid adsorbent consisting essentially of a synthetic, porous, high surface area amorphous magnesium silicate.Type: GrantFiled: May 20, 1991Date of Patent: March 3, 1992Assignee: Texaco Chemical CompanyInventors: Robert A. Meyer, Edward T. Marquis
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Patent number: 5081267Abstract: The present invention relates to the epoxidation of olefinic compounds by reaction with an organic hydroperoxide in the presence of a solid, heterogeneous catalyst comprised of molybdenum oxide finely dispersed in silica or of both molybdenum oxide and titanium oxide finely dispersed in silica.Type: GrantFiled: September 13, 1990Date of Patent: January 14, 1992Assignee: Arco Chemical Technology, Inc.Inventors: M. Rameswaran, Robert N. Cochran
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Patent number: 5041569Abstract: Styrene oxide is prepared by reacting styrene and hydrogen peroxide in a heterogeneous system in the presence of a bis(tri-n-alkyltinoxy)molybdic acid and an amine represented by the following general formula: ##STR1## wherein R.sub.1, R.sub.2 and R.sub.3 each independently represent H, CH.sub.3, C.sub.2 H.sub.5, C.sub.3 H.sub.7, C.sub.4 H.sub.9, or HOCH.sub.2 CH.sub.2.Type: GrantFiled: January 17, 1990Date of Patent: August 20, 1991Assignee: Tokai Denka Kogyo Kabushiki KaishaInventors: Saburo Enomoto, Masami Inoue, Osami Ohura, Tutomu Kamiyama, Hirohisa Nitoh
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Patent number: 5017712Abstract: Production of novel hydrocarbon-soluble salts, especially adapted for use as catalysts in the epoxidation of olefinic compounds with an organic hydroperoxide, by reaction of an ammonium molybdate with a carboxylic acid in the presence of an organic amine at specified elevated temperatures while removing water.Type: GrantFiled: July 8, 1988Date of Patent: May 21, 1991Assignee: Arco Chemical Technology, Inc.Inventors: Masahiro Usui, Yasuhiko Higashio
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Patent number: 5011953Abstract: Disclosed herein is a method for preparing epichlorohydrins by reacting allyl chlorides with an alkyl hydroperoxide in the presence of a modified catalyst formed by substituting specific substituents for 1 to 50% of the silanol groups of a catalyst having titanium atoms bound to a silicon dioxide carrier via oxygen atoms and having on the same carrier 1 to 6 silanol groups per square nanometer thereof.Type: GrantFiled: November 8, 1989Date of Patent: April 30, 1991Assignee: Mitsui Toatsu Chemicals, IncorporatedInventors: Takehisa Nakanishi, Eiji Koga, Isao Fukada
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Patent number: 4994586Abstract: A novel method for preparing an epoxy compound is disclosed which comprises the step of reacting an olefin compound having 4 to 16 carbon atoms with an organic hydroperoxide in an inactive solvent in the presence of a molybdenum compound and at least one metal halide selected from the group consisting of halides of alkali metals and alkaline earth metals, in order to form the corresponding epoxy compound. Typical examples of the aforesaid metal halide include sodium chloride, potassium iodide, sodium bromide and barium chloride. According to the present invention, the epoxy compound having 4 to 16 carbon atoms can be prepared in an extremely high yield.Type: GrantFiled: May 25, 1989Date of Patent: February 19, 1991Assignee: Mitsui Toatsu Chemicals, IncorporatedInventors: Nobumasa Arashiba, Takashi Shimizu, Masaru Takeshita, Akira Otsu
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Patent number: 4992566Abstract: Tertiary butyl hydroperoxide and tertiary butyl alcohol are recovered from the reaction product formed by reacting excess propylene with tertiary butyl hydroperoxide in solution in tertiary butyl alcohol in the presence of a soluble molybdenum catalyst, by fractionating the reaction produce to provide distillate propylene, propylene oxide, and tertiary butyl alcohol fractions and a heavy distillation fraction comprising tertiary butyl hydroperoxide, tertiary butyl alcohol and impurities, including dissolved molybdenum catalyst, the tertiary butyl hydroperoxide and tertiary butyl alcohol being recovered from the heavy distillation fraction by vacuum evaporation under evaporation conditions including a temperature of about 25.degree. to about 160.degree. C. and a pressure of about 2 to about 200 mm Hg. in order to provide a lighter condensate fraction comprising about 60 to about 95 wt. % of the heavy distillation fraction and containing from about 70 to about 95 wt.Type: GrantFiled: August 31, 1989Date of Patent: February 12, 1991Assignee: Texaco Chemical CompanyInventors: Edward T. Marquis, Kenneth P. Keating, John R. Sanderson, Robert A. Meyer
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Patent number: 4988830Abstract: Present invention relates to the production of propylene oxide by reaction of propylene with a C.sub.4 or higher hydroperoxide wherein at least a portion of the propylene is derived from the hydroperoxide moiety.Type: GrantFiled: July 28, 1989Date of Patent: January 29, 1991Assignee: Arco Chemical Technology, Inc.Inventors: Morris Gelb, David W. Leyshon, John A. Sofranko, C. Andrew Jones
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Patent number: 4980485Abstract: Optically active periplanone-B is manufactured through oxidizing (1RS, 4S, 5E)-isopropyl-7-methylene-5-cyclodecene-1-ol. The oxidized product is regioselectively enolized and then sulfenylated. The sulfenylated product is oxidized and then subjected to decomposition of the sulfoxide. The decomposed product is epoxidated, and the epoxidated product is converted into an enolate which is then oxidized. The oxidized product is oxidized and then regio- and stereoselectively epoxidated to obtain optically active periplanone-B.Type: GrantFiled: September 26, 1989Date of Patent: December 25, 1990Assignee: Japan Tobacco Inc.Inventors: Kenji Mori, Takeshi Kitahara, Koshi Koseki
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Patent number: 4977285Abstract: A heavy distillation fraction comprising tertiary butyl hydroperoxide, tertiary butyl alcohol, impurities and dissolved molybdenum catalyst resulting from the removel of propylene, propylene oxide and tertiary butyl alcohol from an epoxidation reaction product is mixed with about 5 to about 10 wt. %, based on the weight of the heavy liquid distilation fraction, of a lower aliphatic alcohol containing from 1 to 3 carbon atoms to provide a charge mixture, and the charge mixture is:charged to a falling film evaporator and separator therein, under evaporator operating conditions including a temperature within the range of about 20.degree. to about 150.degree. C. and a pressure of about 1 to about 200 mm Hg., into an overhead vaporized fraction comprising substantially all of the aliphatic alcohol and from about 80 to about 95 wt. % of the heavy distillation fraction charged to the falling film evaporator.Type: GrantFiled: December 8, 1989Date of Patent: December 11, 1990Assignee: Texaco Chemical CompanyInventors: Edward T. Marquis, Kenneth P. Keating, Robert A. Meyer, John R. Sanderson
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Patent number: 4946973Abstract: The stereoselective expoxidation of cyclic 4-hydroxy olefins is disclosed. These methods involve contacting the cyclic 4-hydroxy olefin with peroxycarboximidic acid, which is preferably generated in situ by contacting an organic nitrile with aqueous hydrogen peroxide. The invention provides unexpectedly high yields of the corresponding cis-epoxides.Type: GrantFiled: September 20, 1988Date of Patent: August 7, 1990Assignee: Union Camp CorporationInventor: Walter C. Frank
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Patent number: 4939281Abstract: A process for substantially completely removing a minor amount of molybdenum dissolved in a substantially anhydrous organic solution, such as a heavy distillation fraction resulting from the removal of unreacted propylene, propylene oxide and tertiary butyl alcohol from an epoxidation reaction mixture:wherein from about 1 to about 10 wt. % of an aqueous solution of sodium meta borate containing from about 1 to about 10 wt. % of dissolved sodium meta borate is added to an organic solution containing dissolved molybdenum catalyst in an amount sufficient to provide a molar excess of sodium meta borate, based on the gram atoms of dissolved molybdenum in said organic solution, to provide a mixture,wherein the mixture is maintained at a temperature ranging from about ambient temperature up to about 100.degree. C. at a pressure of about 0 to about 1,000 psig. for about 0.Type: GrantFiled: June 19, 1989Date of Patent: July 3, 1990Assignee: Texaco Chemical Co.Inventors: Edward T. Marquis, John R. Sanderson, Kenneth P. Keating
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Patent number: 4935101Abstract: Water-insoluble crystallizable epoxy alcohols such as phenyl glycidol are recovered from epoxidation reaction mixtures by washing the mixture with water, concentrating the mixture by distillation under vacuum to remove unreacted hydroperoxide and alcohol co-product, and crystallizing the epoxy alcohol from solution. Minimal decomposition of the epoxy alcohol is observed.Type: GrantFiled: October 13, 1989Date of Patent: June 19, 1990Assignee: Arco Chemical Technology, Inc.Inventors: Wilfred P. Shum, Christopher J. Sowa
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Patent number: 4900850Abstract: It has been discovered in accordance with the present invention that a tertiary butyl alcohol/ditertiary butyl peroxide azeotrope may be recovered from a product containing tertiary butyl alcohol and ditertiary butyl perioxide by distilling the tertiary butyl alcohol product to obtain an overhead fraction containing substantially all of the ditertiary butyl peroxide as a ditertiary butyl peroxide/tertiary butyl alcohol azeotrope and other contaminants.It has been further discovered in accordance with the present invention that the ditertiary butyl peroxide can be recovered from the distillate fraction by extraction with water (e.g., in a countercurrent water extraction tower) to provide a ditertiary butyl peroxide product of any desired degree of purity.Type: GrantFiled: December 23, 1986Date of Patent: February 13, 1990Assignee: Texaco Inc.Inventors: John R. Sanderson, Robert A. Meyer
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Patent number: 4900847Abstract: Improved method for epoxidation of ethylenic alcohols is provided employing catalytic amounts of a titanium-glycol catalyst and a peroxide under mild conditions which provide for the continuous maintenance of an anhydrous medium during catalyst formation and during the course of the reaction. Conveniently, molecular sieves may be employed.Type: GrantFiled: February 24, 1986Date of Patent: February 13, 1990Assignee: Massachusetts Institute of TechnologyInventors: Robert M. Hanson, Soo Y Ko, Karl B. Sharpless
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Patent number: 4891437Abstract: A hydroperoxide charge stock (t-butyl hydroperoxide or t-amyl hydroperoxide) is reacted with a C.sub.3 to C.sub.20 olefin charge stock in liquid phase in a reaction zone in the presence of a catalytically effective amount of a soluble molybdenum catalyst to form a product olefin epoxide corresponding to the olefin charge stock and a product alcohol corresponding to the hydroperoxide charge (t-butyl alcohol or t-amyl alcohol), which process is improved in accordance with the present invention by maintaining a reaction medium composed of more than 60 wt % of polar components (hydroperoxide charge stock, product alcohol and product epoxide) in the reaction zone by charging to the reaction zone at least about a 30 wt % solution of the hydroperoxide charge stock in the corresponding product alcohol and charging said olefin charge stock to said reaction zone in an amount relative to the amount of said charged solution of charged hydroperoxide in product alcohol sufficient to provide a ratio of from about 0.Type: GrantFiled: December 16, 1987Date of Patent: January 2, 1990Assignee: Texaco Inc.Inventors: Edward T. Marquis, Kenneth P. Keating, John F. Knifton, William A. Smith, John R. Sanderson, Jonathan Lustri
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Patent number: 4876372Abstract: The present invention is directed to a method for preparing epichlorohydrins by epoxidizing allyl chlorides with an organic hydroperoxide, and the epoxidation reaction is performed in the presence of a catalyst having titanium atoms bound to a silicon dioxide carrier and having silanol groups on the same carrier, whereby epichlorohydrins are obtained in high yield.Type: GrantFiled: April 13, 1988Date of Patent: October 24, 1989Assignee: Mitsui Toatsu Chemicals, IncorporatedInventors: Takehisa Nakanishi, Eizi Koga, Isao Fukada
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Patent number: 4864041Abstract: A novel process for the homogenous oxidation of organic substrates is disclosed. This process uses a transition metal-substituted polyoxometalate catalyst, which in the presence of an oxygen donor, catalyses the carbon-hydrogen bond (e.g., alkane) hydroxylation reaction and/or epoxidation reaction of the organic substrate.Type: GrantFiled: February 4, 1987Date of Patent: September 5, 1989Assignee: Emory UniversityInventor: Craig L. Hill
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Patent number: 4845251Abstract: Complexes are made by reacting a solid ammoniummolybdate and a solid alkali metal molybdate with ethylene -glycol. Stripping of water of reaction subsequent to complex formation is preferred. The ratio of moles of alkylene glycol to total gram atoms of molybdenum should be in the range from about 7:1 to about 20:1 and the ratio of gram atoms of molybdenum in the ammonium molybdate to gram atoms of molybdenum in the alkali metal molybdenum should be in the range of about 1:1 to about 20:1. Solutions of the complexes are excellent catalysts for the reaction of propylene with an organic hydroperoxide such as tertiary butyl hydroperoxide to form propylene oxide and tertiary butyl alcohol.Type: GrantFiled: May 28, 1987Date of Patent: July 4, 1989Assignee: Texaco Inc.Inventors: Edward T. Marquis, John R. Sanderson, Kenneth P. Keating
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Patent number: 4814511Abstract: Cyclohexyl hydroperoxide containing reaction mixtures obtained by oxidation of cyclohexane with molecular oxygen or molecular oxygen containing gases in the liquid phase at from 130.degree. to 200.degree. C. and under from 5 to 125 bar are worked up by reaction with cycloolefins at elevated temperature in the presence of catalysts to react cyclohexyl hydroperoxide with cyclohexene at elevated temperatures in the presence of cyclohexene-soluble compounds of transition metals of groups 4 or 5 or 6 of the periodic table or of one or more cyclohexane-insoluble compounds of a transition metal of group 4 or 5 or 6, or in the presence of selenium, tellurium or a boride, and the resulting cyclohexene oxide at elevated temperatures to cyclohexanol in the presence of hydrogenation catalysts.Type: GrantFiled: October 23, 1987Date of Patent: March 21, 1989Assignee: BASF AktiengesellschaftInventors: Gerald Neubauer, Rolf Schnabel, Juergen Hartig, Josef Ritz
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Patent number: 4810809Abstract: It has been discovered in accordance in accordance with the present invention that a tertiary butyl alcohol/ditertiary butyl peroxide azeotrope may be recovered from a product containing tertiary butyl alcohol and ditertiary butyl peroxide by distilling the tertiary butyl alcohol product to obtain an overhead fraction containing substantially all of the ditertiary butyl peroxide/tertiary butyl alcohol azeotrope and other contaminants.It has been further discovered in accordance with the present invention that the ditertiary butyl peroxide can be recovered from the distillate fraction by extraction with ethylene glycol (e.g., in a countercurrent ethylene glycol extraction tower) to provide a ditertiary butyl peroxide product of any desired degree of purity.Type: GrantFiled: December 23, 1986Date of Patent: March 7, 1989Assignee: Texaco Inc.Inventors: John R. Sanderson, Robert A. Meyer, William A. Smith, Edward T. Marquis
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Patent number: 4788303Abstract: A process is disclosed for preparation of novel epoxy-substituted aralkyl isocyanates by reaction of tertiary aralkyl olefins and an epoxidizing agent at a temperature of from -35.degree. C. to about 50.degree. C. The compounds are useful as intermediates to produce curing agents for polyfunctional active hydrogen-containing compounds, e.g., by reaction with polyols to produce epoxy-pendant urethanes and then with polyamines, and the like.Type: GrantFiled: December 14, 1987Date of Patent: November 29, 1988Assignee: American Cyanamid CompanyInventor: Paul S. Waterman
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Patent number: 4772731Abstract: Production of novel molybdenum dioxo dialkyleneglycolate compositions, especially adapted for use as catalysts in the epoxidation of olefinic compounds with an organic hydroperoxide, by reaction of molybdenum trioxide with particular dialkylene glycol compounds at specified elevated temperatures while removing water.Type: GrantFiled: December 24, 1986Date of Patent: September 20, 1988Assignee: ARCO Chemical CompanyInventors: Wilfred P. Shum, Charles F. Cooper
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Patent number: 4764628Abstract: Asymmetric epoxidation of allylic alcohols using carboxylic acid treated phenethyl hydroperoxide oxidate and titanium tartrate catalyst gave optically active glycidols following an enantioselection rule opposite to that observed from the Sharpless epoxidation (U.S. Pat. No. 4,471,130). Overall yield and enantiomeric excess of the glycidol made are dependent on the amount of carboxylic acid present in the oxidate feed. This novel finding provides a direct epoxidation route to (R)-glycidol using the less expensive natural L-(+)-dialkyl tartrate ligand.Type: GrantFiled: September 14, 1987Date of Patent: August 16, 1988Assignee: ARCO Chemical CompanyInventor: Wilfred P. Shum