Showing papers on "Epoxide published in 1971"
TL;DR: The simplicity of the present assay permits the use of epoxide hydrase a a marker enzyme for microsomal membranes in hepatic microsomes increases during maturation of rats and following pretreatment of rats with phenobarbital or 3-methylcholanthrene.
407 citations
319 citations
TL;DR: Washed rat liver microsomes that had been heated for 5 minutes at 50°C were incubated at room temperature for 30 seconds with 3 H-dibenz(a,h)-anthracene, TPNH, MgCl 2 , and unlabeled 5,6-epoxy-diphenracene to reveal the presence of an epoxide.
172 citations
122 citations
TL;DR: A microsomal epoxide hydrase, which catalyzes the hydration of styrene oxide to form styrene glycol, has been purified from guinea pig liver using microsomes with cutscum and further purification by (NH4)2SO4 precipitation, Sephadex G-25 chromatography, and calcium phosphate gel adsorption and desorption resulted in an overall 40-fold increase in specific activity.
97 citations
TL;DR: A soluble preparation of epoxide hydrase, purified from guinea pig microsomes, catalyzes hydration of a wide variety of epoxides including styrene oxide, indicating either the presence of a single epoxide Hydrase with broad substrate specificity or a group of ep oxide hydrases which have been purified to the same extent.
93 citations
Patent•
18 May 1971
TL;DR: In this article, a blend of EPOIDE MATERIALs is presented, which, though ESSENTIALLY free to VOLATILE SOLVENTS, is LIQUID and TRACTABLE for COATING and RELATED applications at or near room temperature.
Abstract: A BLEND OF EPOXIDE MATERIAL IS PROVIDED WHICH, ALTHOUGH ESSENTIALLY FREE TO VOLATILE SOLVENTS, IS LIQUID AND TRACTABLE FOR COATING AND RELATED APPLICATIONS AT OR NEAR ROOM TEMPERATURE. THE EPOXIDE MATERIALS INCLUDE AN EPOXY PREPOLYMER OF THE TYPE OF GLYCIDYL-BISPHENOL A RESINS, EPOXIDIZED NOVOLAKS, POLYGLYCIDYL ETHERS AND ALICYCCLIC DIEPOXIDES, BLENDED WITH A BIS(EPOXYCYCLOALKYL) ESTER AND IN MANY CASES ALSO WITH A LOW VISCOSITY MONOEPOXIDE IN LIMITED PROPORTIONS. THE COMPOSITIONS PREFERABLY INCLUDE ADDITIONALLY A CATIONIC POLYMERIZATION INITIATOR, PREFERABLY A RADIATION-SENSITIVE CATALYST PRECURSOR, AND EPOXIDE POLYMERS ARE PRODUCED BY COATING SUCH COMPOSIONS ON A SUBSTRATE, FOLLOWED BY APPLICATION OF ENERGY THROUGH HEAING OR PREFERABLY THROUGH IRRADIATION, TO EFFECT SUBSTANTIAL POLYMERIZATION OF THE EPOXIDIC MATERALS OF THE COATING.
42 citations
Patent•
01 Nov 1971TL;DR: In this article, the epoxide adducts are derived from polyepoxide compounds which on an average contain more than one epoxide group in the molecule, and less than one equivalent of NH groups for every epoxide equivalent of the poly-epoxide compound, i.e., a binuclear, five or six-membered, unsubstituted or substituted N-heterocyclic compound with an endocycyclic NH group in each nucleus.
Abstract: New ''''advanced'''' adducts, containing epoxide groups, from (1) polyepoxide compounds which on an average contain more than one epoxide group in the molecule, and (2) less than one equivalent of NH groups for every epoxide equivalent of the polyepoxide compound (1) of a binuclear, five or six-membered, unsubstituted or substituted N-heterocyclic compound with an endocyclic NH group in each nucleus, the heterocyclic rings being linked by a divalent aliphatic, cycloaliphatic or araliphatic radical, preferably an alkylene radical, which may be interrupted by oxygen atoms, e.g. the reaction product of 2 mols of diomethanediglycidyl ether and 1 mol of 1,1''-methylene-bis-(5,5-dimethylhydantoin). The epoxide resins ''''advanced'''' by means of such nitrogen compounds have a good storage stability and excellent electrical properties.
25 citations
Patent•
18 May 1971
TL;DR: In this paper, the authors discuss the role of a cyclic amide in the action of a CATIONIC CATALYST, and discuss a variety of other types of amides, such as an N-SUBSTITUTed 2-PYRIDONE, or a 2-pYRROLIDINONE MONOMER or POLYMER in the 1-POSITION.
Abstract: POLYMERIZATION OF EPOXIDE MONOMERS AND PREPOLYMERS, AND OF OTHER MATERIALS POLYMERIZABLE THROUGH THE ACTION OF CATIONIC CATALYSTS, IS CONTROLLED BY PROVIDING, IN ASSOCIATION WITH A RADIATION-SENSITIVE CATALYST PRECURSOR, A GELATION INHIBITOR IN THE FORM OF A CYCLIC AMIDE, SUCH AS AN N-SUBSTITUTED 2-PYRIDONE, OR A 2-PYRROLIDINONE MONOMER OR POLYMER SUBSTITUTED IN THE 1-POSITION.
25 citations
TL;DR: In this paper, the synthesis of yomogi alcohol (2, 5, 5-trimethylhepta-3, 6-dien-2-ol, 2) is described, and experiments directed towards its allylic rearrangement to artemisia alcohol detervatives have been carried out.
Abstract: The synthesis of yomogi alcohol (2, 5, 5-trimethylhepta-3,6-dien-2-ol, 2) is described, and experiments directed towards its allylic rearrangement to artemisia alcohol detervatives have been carried out. Acidic reagents open the ring of yomogi alcohol epoxide (16) at with participation of the 6,7-double-bond, a shift of the vinyl group results to yield a compound with the santolinyl skeleton. The same reagents are without effect when this double bond reduced. Action of butyllithium of the benzaldehyde acetal (41) of 2, 5-dimethyl-4-vinyl-2, dihydroxy-hex-5-ene (28), obtained by acid-catalyzed ring opening of yomogi alcohol epoxide in the presence of benzaldehyde, leads to santolinatriene (42).
This vinyl shift is not observed in the case of O-acetyl yomogi alcohol epoxide (46), from white a compound believed to be an oxetan 48 (R COCH3) is formed with concomitent shift of the acetate group. Further unusual reactions of the oxetan are described, and some observation about the epoxidation of sterically hindered allyl alcohols and their acetates are made.
23 citations
TL;DR: Several mono and bistrithiocarbonates were synthesized by the reaction of the corresponding mono and bisepoxides with carbon disulfide in the presence of potassium hydroxide as mentioned in this paper.
Abstract: Several mono and bistrithiocarbonates were synthesized by the reaction of the correspondingmono and bisepoxides with carbon disulfide in the presence of potassiumhydroxide. These trithiocarbonates were successfully obtained even in the presenceof a catalytic amount of potassium hydroxide. Potassium methoxide instead of potassiumhydroxide as catalyst also gave trithiocarbonate in good yield.
Patent•
08 Mar 1971TL;DR: In this article, the authors discuss the process for the manufacturing of Crystaline, and the use of linear polygonal structures in the process of constructing a CRYSTALLINE factory.
Abstract: THE INVENTION RELATES TO PROCESS FOR THE MANUFACTURE OF CRYSTALLINE, PREDOMINANTLY LINEAR POLYADDUCTS, CHARACTERIZED IN THAT A LONG-CHAIN DICARBOXYLIC ACID OF THE FORMULA HOOC-A-COOH IN WHICH A REPRESENTS A PREDOMINANTLY LINEAR RESIDUE IN WHICH POLYMETHYLENE CHAINS ALTERNATE IN A REGULAR MANER WITH ETHER OXYGEN ATOMS OR CARBOXYLIC ACID ESTER GROUPS, THE QUOTIENT Z:Q (IN WHICH Z REPRESENTS THE NUMBER OF CARBON ATOMS IN THE RECURRENT STRUCTURAL UNIT OF RESIDUE A AND Q THE NUMBER OF OXYGEN BRIDGES IN THE RECURRENT STRUCTURAL UNIT OF RESIDUE A) BEING AT LEAST 5 AND PREFERABLY AT LEAST 6, AND THE TOTAL NUMBER OF CARBON ATOMS IN ALTERNATING CARBON CHAINS IN RESIDUE A) BEING AT LEAST 50, IS REACTED AT AN ELEVATED TEMPERATURE WITH DIEPOXY COMPOUNDS TO FORM POLYADDUCTTS, USING FOR EVERY EQUIVALENT OF EPOXIDE GROUPS 0.7 TO 1."2, PREFERABLY 0.9 TO 1.0 EQUIVALENT OF CARBOXYL GROUPS.
TL;DR: In this paper, the authors investigated the topology of the substrate rearrangement of 3β,4β-epoxycarane and the results compared with those obtained earlier with 3α,4α-epoxidecarane.
TL;DR: Evidence for the inhibition of the enzymatic hydrolysis of 2 β, 3β-EC with 2β, 3α-dihydroxy-5α-cholestane could indicate that the enzyme formation from an epoxide proceeds through a protonation mechanism.
TL;DR: The reaction of tertiary phosphine dichlorides and dibromides with epoxides gives vicinal dihalides as discussed by the authors, which are mixtures of cis and trans isomers in which the cis isomer is formed by backside attack of halogen at both epoxide carbons.
Patent•
09 Sep 1971TL;DR: In this article, a synergistic catalytic effect is realized in the esterification reaction between an organic carboxylic acid and a vicinal epoxide by using a catalyst system comprising: (a) a compound containing an amino and/or ammonium nitrogen atom, in combination with (b) a soluble compound containing a ionizable atom of iron or chromium.
Abstract: A synergistic catalytic effect is realized in the esterification reaction between an organic carboxylic acid and a vicinal epoxide by using a catalyst system comprising: (a) a compound containing an amino and/or ammonium nitrogen atom, in combination with (b) a soluble compound containing an ionizable atom of iron or chromium.
Patent•
13 Sep 1971
TL;DR: In this paper, the authors present a scenario where the SUCCESSOR of SULFONIC ACID GROUPS with OXIDE or SIMILAR EPOXIDE is used to form the CORRESPONDING ESTER of Sulfonic ACID.
Abstract: ORGANIC POLYMERS SUCH AS POLYETHYLENE, POLYSTYRENE AND POLYPROPYLENE ARE RENDERED ADHESIVE, ANTISTATIC AND HIGHLY IMPERMEABLE TO OLEPHILIC MATERIALS AND LOW MOLECULAR WEIGHT GASES SUCH AS OXYGEN AND CARBON DIOXIDE BY INITIALLY SURFACE SULFONATING THE ORGANIC POLYMER AND SUBSEQUENTLY REACTING THE SUBSTITUENT SULFONIC ACID GROUPS WITH ALKYLENE OXIDE OR SIMILAR EPOXIDE TO FORM THE CORRESPONDING ESTER OF SULFONIC ACID.
Patent•
09 Aug 1971TL;DR: In this paper, the authors consider the case where R4, R5, R6 and R7 form a HETEROCYCLIC RING, or R4 and R5 BOTH represent METHYL GROUPS and R6 DENOTES an ALKYL HYDROCARBON GROUP of 6-18 CARBON ATOMS or a BENZYL GROUP.
Abstract: CURABLE COMPOSITIONS COMPRISES AN EPOXIDE RESIN AND A COMPLEX OF FORMULA BCL3.NR4R5R6 WHERE R4, R5 AND R6 TOGETHER WITH THE NITROGEN ATOM FORM A HETEROCYCLIC RING, OR R4 AND R5 BOTH REPRESENT METHYL GROUPS AND R6 DENOTES AN ALKYL OR ARALKYL GROUP OF AT LEAST 6 AND AT MOST 18 CARBON ATOMS. PREFFERED COMPOSITIONS CONTAIN COMPLEXES IN WHICH NR4R5R6 DENOTES PYRIDINE, AND THOSE IN WHICH R6 DENOTES AN ALKYL HYDROCARBON GROUP OF 6-18 CARBON ATOMS OR A BENZYL GROUP. THE COMPLEXES ACT AS LATENT HARDNESS.
TL;DR: In this article, an alternate copolymerization of carbon dioxide with optically active propylene oxide using a diethylzinc-water system as catalyst was investigated, and it was shown that the ring opening of propylene dioxide takes place predominantly at the methylene-Oxygen linkage in the copolymersization, which suggests the anionic nature of the reaction.
Abstract: Alternate copolymerization of carbon dioxide with optically active propylene oxide using a diethylzinc–water system as catalyst was investigated. The hydrolysis of the copolymer, poly(propylene carbonate), followed by subsequent treatment with p-nitrobenzoyl chloride, transformed the epoxide unit of the copolymer into the form of propylene glycol bis-p-nitrobenzoate. The determination of the optical activity of this ester led to the conclusion that the ring opening of propylene oxide takes place predominantly at the methylene–Oxygen linkage in the copolymerization, which suggests the anionic nature of the reaction. The optical rotatory behavior of the copolymer is also described.
TL;DR: In an aprotischem medium (benzene), cyclone 3 adds diazomethane to form the Δ1-pyrazoline 4a, which by thermolysis in xylene gives the cyclopropane 7a and in the higher boiling tetralin the phenol 8a as discussed by the authors.
Abstract: Das Cyclon 3 addiert in aprotischem Medium (Benzol) Diazomethan zum Δ1-Pyrazolin 4a das bei der Thermolyse in Xylol vorwiegend das Cyclopropanderivat 7a, im hohersiedenden Tetralin das Phenol 8a lieferte. Saure Zersetzung von 4a gab das isomere Phenol 6a, das in konz. Schwefelsaure Ringschlus zum Fluorenon 9a erlitt. In protischem Losungsmittel (Methanol) reagierte unter N2-Abspaltung die CO-Gruppe, wobei teils unter Ringerweiterung ein drittes Phenol 13a, teils das Epoxid 11a entstand; letzteres lieferte in saurem Medium das 6-Hydroxy-fulven 12. — Die Umsetzung von 3 mit Diazoathan verlief weitgehend analog, doch entstanden einige Produkte bevorzugt, so namentlich 5b und 14b. Phenyldiazomethan und Diazoessigester lieferten mit 3 in Benzol nur die stabilen Δ2-Pyrazoline 5c und 5d. — Methanol, Athanol oder Wasser addieren sich an eine CC-Doppelbindung von 3 zu Verbindungen 17, wobei nicht nur Alkalihydroxid oder Triathylamin, sondern auch Phenyl-diazomethan und Benzoyldiazomethane als „basische” Katalysatoren dienen konnen. Einige Umsetzungen von 17 bzw. 20 werden beschrieben.
Reactions of Cyclopentadienones with Diazoalkanes, 7 Experiments with Dimethyl 2-Oxo-4.5-diphenylcyclopentadiene-1.3-dicarboxylate
In an aprotic medium (benzene) the cyclone 3 adds diazomethane to form the Δ1-pyrazoline 4a, which by thermolysis in xylene gives the cyclopropane 7a and in the higher boiling tetralin the phenol 8a. Acidolysis of 4a yielded the isomeric phenol 6a, which is cyclized by conc. H2SO4 to the fluorenone 9a. Reaction of 3 with diazomethane in a protic medium (methanol) results in the elimination of N2 and formation of a third phenol 13a and an epoxide 11a; in an acid medium the latter was rearranged to the fulvene 12. — Reaction of 3 with diazoethane proceeded in a similar way, but some products were formed preferentially, such as 5b and 14b. Phenyldiazomethane and ethyl diazoacetate reacted with 3 to give only the stable Δ2-pyrazolines 5c and 5d, respectively. — Methanol, ethanol or water are added to one CC-double bond of 3 to yield products 17. In this reaction not only alkali hydroxide or triethyl amine but also phenyldiazomethane, diazoacetic ester and benzoyldiazomethanes can serve as „basic” catalysts. Some reactions of 17 and 20 are described.
TL;DR: Treatment of methyl 2-benzamido with dimethyloxosulfonium methylide gave met the 3-C-formyl derivative 10. Ring opening of 2 with sodium acetate in buffered N,N-dimethylformamide gave the 3C-(acetoxymethyl)a
TL;DR: In this article, the acid-catalyzed cycloadditions of isocyanide with carbonyl compounds and with Schiff bases with the aid of BF3.Et2o were reported.
Patent•
18 May 1971
TL;DR: In this article, a radiation-sensitive catalyst precursor, a gelation inhibitor in the form of an nitrile compound such as acetonitrile present in small amounts up to several percent by weight, is presented.
Abstract: Polymerization of epoxide monomers and prepolymers, and of other materials polymerizable through the action of cationic catalysts, is controlled in compositions essentially free of volatile solvents by providing in such compositions, in association with a radiation-sensitive catalyst precursor, a gelation inhibitor in the form of an nitrile compound such as acetonitrile present in small amounts up to several percent by weight.
TL;DR: The absolute configuration of the predominant Cecropia hormone, methyl 12,14-dihomojuvenate, has been determined to be methyl (E,E)-(10R,11S)-(+)-10,11-epoxy-7-ethyl-3, 11-dimethyl-2, 6-tridecadienoate (I).
Abstract: The absolute configuration of the predominant Cecropia hormone, methyl 12,14-dihomojuvenate, has been determined to be methyl (E,E)-(10R,11S)-(+)-10,11-epoxy-7-ethyl-3,11-dimethyl-2, 6-tridecadienoate (I). The less abundant hormone, methyl 12-homojuvenate, can be presumed by analogy to have the corresponding 3,7,11-trimethyldienoate structure (II). The assignment has been established with microamounts of substance by applying Horeau's method to the glycol derivative (III) of the hormone.
The course of the perchloric acid-catalyzed epoxide ring opening of I was checked by conducting the conversion in 18O-labeled water. It has been ascertained that the configuration at the secondary hydroxyl group of the resulting III remained unchanged. On the other hand, the hydration proceeded with a surprisingly high rate of cis opening.
TL;DR: Ethereal hydrogen chloride has been used to convert trans-1-acetyl- and 1-benzoyl-2-(o-nitrophenyl)ethylene oxides into the corresponding 6-chloro-1,3-dihydroxyquinolin-4-ones as discussed by the authors.
Abstract: Ethereal hydrogen chloride converts trans-1-acetyl- and 1-benzoyl-2-(o-nitrophenyl)ethylene oxides (1c and a) in low yield into the corresponding 6-chloro-1,3-dihydroxyquinolin-4-ones (2a and c). In contrast, reaction of the cis-benzoyl epoxide (1b) or of the 1,1-diacylethylene oxides (1d and e) with ethereal hydrogen chloride affords high yields of the compounds (2a and c). In the presence of hydroquinone these reactions give the chlorine-free 1,3-dihydroxyquinolones (2b and d). The course and mechanism of the reactions are discussed.Manganese dioxide oxidation of the 1-hydroxyquinolones (2a—d) and of the reduction products (3a and b) affords the hitherto unknown quinoline-3,4-quinones (7a—d) and (8a and b).
Patent•
27 Aug 1971TL;DR: PIGMENTED AROMATIC POLYCARBONates as mentioned in this paper are a type of modularity which can contain from about 5 to about 100 percent by weight relative to the weight of the PIGMENT of COPOLYMERS CONTAINING EPOXIDE GROUPS.
Abstract: PIGMENTED AROMATIC POLYCARBONATES ARE PROVIDED WHICH CONTAIN FROM ABOUT 5 TO ABOUT 100 PERCENT BY WEIGHT RELATIVE TO THE WEIGHT OF THE PIGMENT OF COPOLYMERS CONTAINING EPOXIDE GROUPS OR OF A VINYL POLYMER FREE OF EPOXIDE GROUPS.
Patent•
21 Jan 1971
TL;DR: In this paper, a 4,4''-ISOPROPYLIDENE BIS PHENOL, (B) DILAURYL THIODIPROPIONATE, and (C) EPOXIDIZED SOYBEAN OIL.
Abstract: AN EXAMPLE IS ETHYLENE-PROPYLENE-DICYCLOPENTADIENE TERPOLYMER RUBBER STABILIZED WITH (A) 4,4''-ISOPROPYLIDENE BIS PHENOL, (B) DILAURYL THIODIPROPIONATE, AND (C) EPOXIDIZED SOYBEAN OIL. (A) A PHENOL; (B) AN ORGANIC SULFIDE OR THIOESTER; AND (C) AN EPOXIDE OR PHOSPHITE ESTER. HYDROCARBON ELASTOMERS OF LOW UNSATURATION (E.G., EPDM, BUTYL RUBBER) OR HIGH UNSATURATION (E.G., SBR) ARE STABILIZED AGAINST OXIDATION BY THE USE OF A TERNARY SYNERGISTIC COMBINATION OF:
TL;DR: In this paper, the same epoxide was treated with HCl in EtOH, and the results showed that the reaction converted the compound into the 15,17(21)-diene and the 28-nor-21α-methyl-12,17-diene, respectively.