Showing papers on "Cyclohexanone published in 1973"
TL;DR: A detailed study of the low frequency dielectric relaxation of dilute solutions of benzophenone, cyclohexanone and fenchone in o-terphenyl in the supercooled liquid state was performed in this paper.
Abstract: A detailed study of the low frequency dielectric relaxation of dilute solutions of benzophenone, cyclohexanone and fenchone in o-terphenyl in the supercooled liquid state shows (i) that only a part of µ2 is relaxed by the low frequency cooperative process (ii) the cooperative process is quantitatively similar in frequency/temperature location and shape to that observed for anthrone, phthalic anhydride and camphor in o-terphenyl, (iii) the shape of the dielectric loss curves may be represented by the Williams–Watts empirical relaxation function and (iv) that the defect diffusion model for cooperative relaxation proposed by Phillips, Barlow and Lamb gives a quantitative representation of the derived experimental dipole correlation function for benzophenone, and is also fairly satisfactory for cyclohexanone and fenchone.
45 citations
TL;DR: The enol acetates of cyclohexanone and cyclopentanone react with PhSeBr and AgOCOCF3 at low temperature to give, after work-up and oxidation (NaIO4), cycloenhex-2.1.
Abstract: The enol acetates of cyclohexanone and cyclopentanone react with PhSeBr and AgOCOCF3 at low temperature to give, after work-up and oxidation (NaIO4), cyclohex-2-en-1-one and cyclopent-2-en-1-one.
40 citations
39 citations
DSM1
TL;DR: In this paper, a method is described for the determination of trace amounts of cyclohexanone in concentrated solutions of cycloenanone oxime in toluene, which is achieved by liquid-liquid chromatography using a phase pair obtained from a mixture of 2,2,4-trimethylpentane, ethanol and water.
31 citations
TL;DR: The mass spectra of a series of 2,6-bis-benzylidenecyclohexanones have been determined at 70 1/eV as discussed by the authors.
Abstract: The mass spectra of a series of some substituted 2-benzylidenecyclohexanones and a series of substituted 2,6-bis-benzylidenecyclohexanones have been determined at 70 eV. The major fragmentation pathways include an intramolecular aromatic substitution reaction leading to the loss of an ortho-substituent with the formation of a stable benzopyrylium ion, loss of carbon monoxide and ethylene from the parent ion and also further ions derived from subsequent cleavages of the cyclohexanone ring. The structural and electronic factors involved in the aromatic substitution reaction were examined by comparing the M – H/M and M – Cl/M ratios determined from the spectra of the various substrates.
28 citations
22 citations
TL;DR: In this article, various ketones, such as deoxybenzoin, propiophenone, phenylacetone, benzylacetones, cyclohexanone and 2-methylcyclohexenone, and aldehyde such as 3-phenylpropionaldehyde were smoothly converted to the corresponding vinyl sulfides in good yields by the treatments with thiols in the presence of TiCl4.
Abstract: Various ketones, such as deoxybenzoin, propiophenone, phenylacetone, benzylacetone, cyclohexanone and 2-methylcyclohexanone, and aldehyde such as 3-phenylpropionaldehyde were smoothly converted to the corresponding vinyl sulfides in good yields by the treatments with thiols in the presence of TiCl4.
16 citations
Patent•
23 Feb 1973TL;DR: A palladium catalyst on an aluminum spinel carrier was used to selectively hydrogenate phenol to cyclohexanone as mentioned in this paper, which was used for the first time in the 1990s.
Abstract: A palladium catalyst on an aluminum spinel carrier is used to selectively hydrogenate phenol to cyclohexanone.
16 citations
TL;DR: The rate of cyclohexanone catalyzed by manganese salt increases remarkably in the presence of acetic acid, and is about one hundred times as high as the limiting rate of oxidation kp2(RH)2/2kt as discussed by the authors.
Abstract: The rate of oxidation of cyclohexanone catalyzed by manganese salt increases remarkably in the presence of acetic acid, and is about one hundred times as high as the limiting rate of oxidation kp2(RH)2/2kt. However, manganese concentration does not affect the rate of oxidation much in a wide range. The oxidation of cyclohexanone by manganic ion should be the rate determining step, since the rate of oxidation, which is of first order in cyclohexanone but independent of manganous ion, corresponds to the rate of oxygen absorption of cyclohexanone with the same manganese concentration. The oxidation of cyclohexanone by manganic ion seems to proceed through enol intermediates, since the rate of oxidation increases in the presence of alkali acetates. The rate equation including enolization step and the subsequent oxidation of enol intermediate with manganic ion agrees with the experimental results. A remarkable synergistic effect of metal salts was observed in a mixture of manganese and cobalt. The oxidation pr...
15 citations
TL;DR: Fischer ring closure of enehydrazines 1 and 4 with cyclohexanone leads to oxo-octa-hydrocarbazoles 2, however, follows both possible pathways to 9 and 10 as mentioned in this paper.
Abstract: Beim Fischer-Ringschlus mit Cyclohexanon erhalt man aus den Enhydrazinen 1 und 4 die Oxo-octahydrocarbazole 2, am 8 dagegen beobachtet man beide denkbaren Reaktionswege zu 9 und 10. Alle Produkte wurden mit Chloranil dehydriert.
Enehydrazines, 7. Carbazole Derivatives from Enehydrazines
Fischer ring closure of the enehydrazines 1 and 4 with cyclohexanone leads to the oxo-octa-hydrocarbazoles 2. 8, however, follows both possible pathways to 9 and 10. All products were dehydrogenated with chloranil.
13 citations
TL;DR: In this paper, the gas-phase decomposition of 1,2-epoxycyclohexane has been studied over the temperature range 680-740 K at pressures between 1.6 and 6 torr.
Abstract: The kinetics of the gas-phase decomposition of 1,2-epoxycyclohexane has been studied over the temperature range 680–740 K at pressures between 1.6 and 6 torr. Isomerization to cyclohexanone and 2-cyclohexen-1-ol accounts for ca. 97% of the primary reaction products and occurs by first-order, homogeneous, nonradical processes:
TL;DR: Condensations of 3-hydroxybenzylhydrazine with acetone, cyclohexanone, and 1-methyl-4-piperidone in the presence of acid gave the 1,1-disubstituted 1,2,3,4-tetrahydrophthalazines as mentioned in this paper.
Abstract: Condensations of 3-hydroxybenzylhydrazine with acetone, ethyl methyl ketone, diethyl ketone, cyclohexanone, and 1-methyl-4-piperidone in the presence of acid gave the 1,1-disubstituted 1,2,3,4-tetrahydrophthalazines (2)–(6). On the other hand, the reactions of 3-hydroxybenzoylhydrazine (7) with acetone, cyclohexanone, and benzalde-hyde gave the Schiff's bases (8)–(10).
TL;DR: The photolytic behavior of 1-nitro-1-nitrosoc-cyclohexane with red light in the absence of oxygen occurs by homolytic C-NO fission, and generates a radical pair: NO and the α-nitrogen-cyclosoc-hexyl radical.
TL;DR: In this article, the authors reported the study of ceric ammonium nitrate (CAN) oxidation of cyclic ketones, and suggested that structurally constrained ketones would behave similarly, thus CAN oxidation may provide an alternative to the classical Baeyer-Villiger reaction which generally utilizes a peracid.
TL;DR: For example, this paper showed strong intramolecular bonding with relatively weak intermolecular interactions in 1a and 2a, and relatively weak intra-and inter-mergentleman interaction in 1b, 2b, 3, and 4, respectively.
Abstract: Addition of fluoral at the α-carbon of 3-pentanone, cyclohexanone, 4-methyl-2-pentanone, and acetone gives 1,1,1-trifluoro-2-hydroxy-3-methyl-4-hexanone (1a and b, diastereomers), 2-(1-hydroxy-2,2,2-trifluoroethyl)cyclohexanone (2a and b, diastereomers), 1,1,1-trifluoro-2-hydroxy-6-methyl-4-heptanone (3), and 1,1,1-trifluoro-2-hydroxy-4-pentanone (4), respectively. Hydrogen-bonding studies, based on proton and fluorine n.m.r. measurements, show strong intramolecular bonding with relatively weak intermolecular interactions in 1a and 2a, and intermolecular bonding in 1b, 2b, 3, and 4.
TL;DR: In this paper, the reduction of several 2-benzyl-1,2-epiminocyclohexanes with lithium aluminum hydride gave the corresponding 1-Benzyl 1,2,1, 2-EICOhexanes.
Abstract: Reduction of several 2-benzylidenecyclohexanone oximes with lithium aluminum hydride gave the corresponding 1-benzyl-1,2-epiminocyclohexanes. Reduction of 2-benzylidenecyclohexanone oxime with lith...
TL;DR: With the aid of a catalytic amount of palladium chloride, triethylsilane reacted with ketones such as acetone, methyl ethyl ketone and cyclohexanone at room temperature to afford a mixture of triethylsilyl enol ether and triethyl silyl ether.
Abstract: With the aid of a catalytic amount of palladium chloride, triethylsilane reacted with ketones such as acetone, methyl ethyl ketone and cyclohexanone at room temperature to afford a mixture of triethylsilyl enol ether and triethylsilyl ether. When a small amount of thiophenol was added to the system, the reaction was completed within much shorter time and the formation of the enol ether became the predominant reaction path. These results showed that the method is a convenient method for synthesizing silyl enol ethers from a variety of aliphatic ketones.
Patent•
21 Nov 1973
TL;DR: In this article, a catalytic process for alkylating ketones carrying at least one methyl or methylene group in α-position to the carbonyl group is described.
Abstract: Catalytic process for alkylating ketones carrying at least one methyl or methylene group in α-position to the carbonyl group by reacting them with primary alcohols in the presence of copper and/or silver catalysts.
Patent•
02 Apr 1973TL;DR: In this paper, the present invention relates to the production of the crotoner of cyclohexanone and its conversion to orthophenylphenol, and is related to the present paper.
Abstract: The present invention relates to the production of the crotoner of cyclohexanone and to its conversion to orthophenylphenol.
TL;DR: In this paper, it was shown that irradiation of enamide (Ia) in the presence of iodine afforded hexahydrophenanthridone (V), which was also obtained from the 6-bromo-enamide (VI) upon irradiation.
Abstract: Irradiation of methanolic solutions of N-benzoylenamines [(I), (VIII), and (IX)] of cyclohexanone and 2-sub-stituted cyclohexanones (R = Me or CO2Et) resulted in stereoselective photocyclisation to give trans-octahydrophenanthridones [(II), (X), and (XI)]. However irradiation of the enamide (Ia) in the presence of iodine afforded the hexahydrophenanthridone (V), which was also obtained from the 6-bromo-enamide (VI) upon irradiation. The conjugated oxo-enamides (XIV) afforded the hexahydrophenanthridones (XV) even under non-oxidative conditions.
Patent•
21 Jun 1973
TL;DR: A process of obtaining esters from a waste salt solution from the production of cyclohexanone containing adipic acid, Epsilon -hydroxycaproic acid and monocarboxylic acids having chain lengths up to at least five carbon atoms is described in this paper.
Abstract: A process of obtaining esters from a waste salt solution from the production of cyclohexanone containing adipic acid, Epsilon -hydroxycaproic acid, and monocarboxylic acids having chain lengths up to at least five carbon atoms, comprising acidifying the salt solution to form an aqueous phase and an organic phase containing the organic acids and separating said phases, esterifying the organic phase with a lower alcohol to form an ester mixture of the corresponding esters of the said organic acid components of said organic phase, separating from said ester mxiture, a mixture containing the esters of adipic acid and of Epsilon -hydroxycaproic acid, and extracting with water the ester of Epsilon -hydroxycaproic acid from the said mixture with adipate.
Patent•
23 Apr 1973
TL;DR: In this paper, the authors proposed a stabilizer composition which essentially contains: A. ORGANOTIN SULFUR-CONTAINING COMPOUND, FOR EXAMPLE, orGANOTin MERCAPTIDES, ORGANOTE-ACIDS, ORGOTIN MERCAPTOACID ESTERS, ORGO-SULFIDES, OrGANOTHIO-STANNOIC ACIDS and the Like, and B. AN ALKALI METAL BISULFITE ADDITION PRODUCT, including ALDEHYDE OR KETONE AL
Abstract: A resin stabilizer composition which essentially contains: A. AN ORGANOTIN SULFUR-CONTAINING COMPOUND, FOR EXAMPLE, ORGANOTIN MERCAPTIDES, ORGANOTIN MERCAPTO-ACIDS, ORGANOTIN MERCAPTOACID ESTERS, ORGANOTIN SULFIDES, ORGANOTHIOSTANNOIC ACIDS AND THE LIKE, AND B. AN ALKALI METAL BISULFITE ADDITION PRODUCT, INCLUDING ALDEHYDE OR KETONE ALKALI METAL BISULFITES, FOR EXAMPLE, ACETONE SODIUM BISULFITE, CYCLOHEXANONE SODIUM BISULFITE, GLYOXAL SODIUM BISULFITE, FORMALDEHYDE SODIUM BISULFITE, ACETALDEHYDE SODIUM BISULFITE AND CYCLOHEXANONE POTASSIUM BISULFITE. These compositions synergistically contribute to the long term heat stability of vinyl halide resins. Among other advantages, the stabilizing efficiencies of such compositions are excellent and clarity in molded vinyl halide resins can be achieved with these stabilizer compositions.
TL;DR: In this paper, a computer simulation of the sodium borohydride reduction of an alkyl-substituted cyclohexanone in isopropanol has shown the following apparently contradictory experimental observations to be compatible: (1) the kinetics are experimentally indistinguishable from second-order, with the first hydride transfer rate determining.
TL;DR: In this paper, a cyclohexanone oxime with sulfur trioxide-1,4-dioxane complex under mild conditions was isolated as stable salts with various Lewis bases.
Abstract: Cyclohexanone oxime hydrogen sulfate, prepared by the reaction of cyclohexanone oxime with sulfur trioxide–1,4-dioxane complex under mild conditions, was isolated as stable salts with various Lewis bases. It was found that a Beckmann rearrangement of the oxime hydrogen sulfate to 3,4,5,6-tetrahydro-2H-azepin-7-ol hydrogen sulfate was retarded by the weak Lewis base 1,4-dioxane and prevented by a stronger Lewis base aniline. The rearrangement of the oxime hydrogen sulfate was also found to be promoted by Lewis acids such as sulfur trioxide, tin tetrachloride or zinc chloride. Hydrogen chloride retarded the rearrangement. Alcoholysis of the oxime hydrogen sulfate gave cyclohexanone oxime and monoalkyl sulfate quantitatively, while hydrolysis of the oxime hydrogen sulfate gave cyclohexanone, cyclohexanone oxime and e-caprolactam.
Patent•
07 Nov 1973
TL;DR: In this paper, cyclohexanone is dissolved in DMSO and contacted with a sulfonated copolymer of styrene and divinyl benzene to produce caprolactam in a continuous process.
Abstract: Organic sulfoxides such as dimethylsulfoxide are used in the transformation of alicyclic ketoximes into the corresponding lactams according to the Beckmann rearrangement in the presence of a strong acid cation exchange resin as disclosed. Thus cyclohexanone is dissolved in DMSO and contacted with a sulfonated copolymer of styrene and divinyl benzene to produce caprolactam in a continuous process.
TL;DR: In this paper, the ultraviolet irradiation of 3,3-pentamethyleneoxaziridine (1) gave two classes of photo-products: cyclohexanol and n-capronamide, the formation of which proceeds preferentially through the excited triplet state of 1.
Abstract: The ultraviolet irradiation of 3,3-pentamethyleneoxaziridine (1) gave two classes of photo-products: (a) cyclohexanol and n-capronamide, the formation of which proceeds preferentially through the excited triplet state of 1, and (b) e-caprolactam, dicyclohexylideneazine, and cyclohexanone, which are mainly furnished via the singlet state of 1. The correlation of the selectivity of (a)-class products with the triplet-state energy of the quenchers used made it possible to estimate that the lowest triplet energy of 1 was approximately 60 kcal/mol. The sensitized photolysis of 1 using sensitizers, the triplet-state energy of which was more than nearly 60 kcal/mol, gave n-capronamide predominantly. The photolytic decomposition rate of 1 was compared with those of 2-methyl-3,3-tetramethyleneoxaziridine (2), 2-methyl-3,3-pentamethyleneoxaziridine (3), and cyclohexanone oxime. The mechanism of the photolysis of 1, including homolytic N–O bond rupture, was also discussed.
Patent•
24 Feb 1973
TL;DR: Adipic acid is sepd. from the soln. and then the distilled is distilled as discussed by the authors, where organic acid mixt. is mixed with 6-12C aliphatic ketones and heated to >=60 degrees C pref.
Abstract: Adipic acid is sepd. from catalyst compst. and 4C- and 5C- dicarboxylic acids in the filtrates obtd. following oxidn. of cyclohexanone and/or cyclohexanol with HNO3 at elevated temp. using V-contg. catalysts, cooling of the reaction prod. centrifuging of the solid obtd. and concn. of the filtrate with simultaneous removal of HNO3 and H2O. The organic acid mixt. is mixed with 6-12C aliphatic ketones and heated to >=60 degrees C pref. is not >95 degrees C, the pptd. catalyst compts. are sepd. from the soln. and then the soln. is distilled.
Patent•
13 Sep 1973TL;DR: In this article, a process for the purification of cyclohexanone which comprises removing impurities from the crude product by adding inorganic or organic acids or ion exchangers is described.
Abstract: Object of the invention is a process for the purification of cyclohexanone which comprises removing impurities from the crude product by adding inorganic or organic acids or ion exchangers. The impurities are degraded and can now be readily separated off by distillation.
Patent•
10 Oct 1973
TL;DR: In this article, a method for the preparation of mixed tricyclohexylidene peroxide and DICYCLO-HIDENE peroxide with an organic solvent and a strong acid catalyst is presented.
Abstract: A method for the preparation of mixed tricyclohexylidene peroxide and dicyclohexylidene peroxide or dicyclohexylidene peroxide alone comprising reacting a peroxide selected from the group consisting of 1-hydroperoxy 1''-hydroxydicyclohexyl peroxide and 1,1''-dihydroperoxydicyclohexyl peroxide with an organic solvent and a strong acid catalyst. Another method is disclosed for the preparation of tricyclohexylidene peroxide and dicyclohexylidene peroxide or tricyclohexylidene alone comprising reacting a peroxide selected from the group consisting of 1hydroperoxy 1''-hydroxydicyclohexyl peroxide and 1,1''dihydroperoxydicyclohexyl peroxide with a liquid carboxylic acid and strong acid catalyst. Also disclosed are new and useful improvements in the method for the preparation of 1-hydroperoxy1''-hydroxydicyclohexyl peroxide comprising reacting cyclohexanone with aqueous hydrogen peroxide and a strong acid catalyst.