Showing papers on "Cyclohexanone published in 1974"
Patent•
11 Apr 1974TL;DR: In this paper, the process of oxidizing cyclohexane to produce cycloenanone and cycloenhexanol in the weight ratio of 0.5 to 1.5 was described.
Abstract: The process of oxidizing cyclohexane to produce cyclohexanone and cyclohexanol in the weight ratio of 0.5 to 1.5 of cyclohexanone to cyclohexanol, said process comprising contacting a stream of liquid cyclohexane with oxygen in each of at least three successive oxidation stages by introducing into each stage a mixture of gases comprising molecular oxygen and inert gas, said oxygen being introduced in amounts that may range from an amount that will substantially all react with the cyclohexane under the particular conditions involved to an amount in excess of the amount required to react with the cyclohexane, said excess being such that the overall oxygen consumed in the oxidation zone is not more than 95 mole percent of the amount fed under the particular conditions involved, in the presence of a binary catalyst system comprising 0.02 to 0.9 ppm chromium and 0.1 to 5 ppm cobalt at a temperature of from 130° to 200° C. and a pressure of from 60 to 350 psig, reacting any cyclohexylhydroperoxide that may be formed in the presence of said binary catalyst system and recovering a product of cyclohexanone and cyclohexanol in the above ratio.
51 citations
TL;DR: In this paper, cyclohexanone and one of its methyl-substituted derivatives (2, 3-, or 4-methylcyclochenanone) were hydrogenated competitively in pairs in cyclochexane solvent at 30 °C over group VIII metal catalysts.
40 citations
Patent•
20 Sep 1974TL;DR: In this article, 2,6-dimethylphenol reacts with ammonia in the presence of cyclohexanone, water and a supported palladium catalyst to form 2, 6-dimethylaniline.
Abstract: Hydroxy aromatics are aminated to form the corresponding aromatic amine by reaction at 200°-400°C with ammonia in the presence of a cyclohexanone and water in contact with a hydrogen transfer catalyst. For example, 2,6-dimethylphenol reacts with ammonia in the presence of cyclohexanone, water and a supported palladium catalyst to form 2,6-dimethylaniline.
24 citations
TL;DR: The metabolism of ethanol in vivo was studied by measurements of tritium isotope effects and extent of hydrogen transfer from ethanol to a reducible substrate of liver alcohol dehydrogenase, and the major metabolite in bile was cyclohexyl glucuronide.
Abstract: The metabolism of ethanol in vivo was studied by measurements of tritium isotope effects and extent of hydrogen transfer from ethanol to a reducible substrate of liver alcohol dehydrogenase. The specific radioactivity of ethanol in bile increased by a factor of two in 6–8 h following administration of [1-3H]ethanol, 11 mmol/kg. This indicates a tritium isotope effect of about 1.6 on the association of [1-3H]ethanol to the alcohol dehydrogenase-NAD complex or on the rate of conversion of the ternary complex.
Cyclohexanone was used as the reducible substrate of liver alcohol dehydrogenase. The major metabolite in bile was cyclohexyl glucuronide. During the simultaneous metabolism of [1,1 -2H2]-ethanol with a deuterium excess of 95 atoms % the cyclohexanol formed had a deuterium excess of about 65 atoms %. This dilution cannot be explained by the isotope effect and is most likely due to the reversible dissociation of the enzyme-NADH complex resulting in exchange with a less-labelled free-NADH pool.
Ethanol metabolism increased the rate of cyclohexanone elimination, probably by increasing the concentration of alcohol dehydrogenase-NADH complex. A large dose of cyclohexanone decreased the ethanol-elimination rate, possible due to competitive inhibition.
24 citations
Patent•
31 May 1974TL;DR: Aromatic hydroxy compounds (e.g., 2,6-dimethylphenol) are converted to the corresponding aromatic amine by reaction with ammonia at elevated temperatures in the presence of a cyclohexanone promoter and a catalyst comprising metallic palladium bonded to a phosphinated polystyrene resin this article.
Abstract: Aromatic hydroxy compounds (e.g., 2,6-dimethylphenol) are converted to the corresponding aromatic amine (e.g., 2,6-dimethylaniline) by reaction with ammonia at elevated temperatures in the presence of a cyclohexanone promoter and a catalyst comprising metallic palladium bonded to a phosphinated polystyrene resin.
16 citations
TL;DR: Evidence was obtained that indicated that the bacterium degraded cyclohexanone via 2-hydroxycyclohexane-1-one.
Abstract: A species of the genus Nocardia that could utilize cyclohexanone as a sole carbon source was isolated from soil. Cyclohexanone-grown cultures grew readily on cyclohexanol, cis, trans-cyclohexane-1,2-diol, cis-cyclohexane-1,2-diol, adipic acid and 2-hydroxycyclohexane-1-one without a noticeable lag period. The bacterium also grew on pimelic acid but only after a lag period of 4 days. Resting cell suspensions of cyclohexanone-grown cells were found to oxidize cyclohexanone, cyclohexanol, cyclohexane-1,2-dione, cis, trans-cyclohexane-1,2-diol and 2-hydroxycyclohexane-1-one at high \({\text{Q}}_{{\text{O}}_{\text{2}} }\) values. Evidence was obtained that indicated that the bacterium degraded cyclohexanone via 2-hydroxycyclohexane-1-one.
15 citations
TL;DR: Tris(triphenylphosphine)cobalt trihydride (I) is a direct precursor of a catalyst complex for a hydrogen transfer between cyclohexanone and isopropyl alcohol.
14 citations
TL;DR: The 1,4-Diketones are produced on treatment of monoketones with nickel peroxide; reaction occurs more readily with cyclic than with acyclic ketones, except in the case of activated (e.g. benzylic) ketones and less readily at a branched site as discussed by the authors.
Abstract: 1,4-Diketones are produced on treatment of monoketones with nickel peroxide; reaction occurs more readily with cyclic than with acyclic ketones, except in the case of activated (e.g. benzylic) ketones, and less readily at a branched site. Cyclohexanone gives, in addition to bicyclohexyl-2,2′-dione, variable amounts of 2-(cyclohex-1-enyloxy)cyclohexanone via the enol form of the ketone.
13 citations
TL;DR: In this paper, the photolysis of 1-chloro-1-nitrosocyclohexane was studied in aprotic solvents and showed that the primary photochemical step consists in C-NO bond cleavage.
Abstract: Detailed studies of the photolysis of 1-chloro-1-nitrosocyclohexane are presented. Photolysis in methanol solutions gave hydrochloric acid, methyl nitrite, 1,1-dimethoxycyclohexane, cyclohexanone, and cyclohexanone oxime. 1-Methoxycyclohexene and 6-hydroxyimino-1-methoxycyclohexene were minor products. Photolysis in aprotic solvents afforded 1-chlorocyclohexene, cyclohexanone, and 1,1-dichlorocyclohexane with small amounts of α-chlorocyclohexanone and 1-chloro-1-nitrocyclohexane at low concentrations whereas at high concentrations substantial amounts of cyclohexanone oxime were found. Evidence based on the variation of product distribution with solvent, concentration, and added radical scavengers is presented, which shows that the primary photochemical step consists in C–NO bond cleavage in all solvents. α-Chloronitrones are postulated as intermediates. The importance of solvolysis and other secondary ionic reactions is emphasised. Other studies of the photolysis of geminal chloronitrosoadamantane, 3-chloro-3-nitrosopentane, and 2-chloro-2-nitrosobutane in alcohols are briefly re-examined in the light of the proposed mechanism. In none of these cases have we found any evidence for a carbonyl-like photoreduction.
11 citations
11 citations
TL;DR: In this article, the addition of methyl-substituted 4-t-butylcyclohexanone was studied, providing that the β-axial methyl and α-exact methyl groups hindered the axial and equatorial attacks respectively.
Abstract: The addition to the methyl-substituted 4-t-butylcyclohexanone was studied, providing that the β-axial methyl and α-axial methyl groups hindered the axial and equatorial attacks respectively. The results obtained with fused-ring system ketones (four decalones) were explained by considering the similar stereochemical influence of 2-and 3-methylene substituents as corresponding methyl substituents. A rapid conformation equilibrium was also considered for cis-decalones. In addition, the axial attack, especially at a molar ratio of two or more, was found to be hindered by the α-equatorial methyl group. This hindrance was explained by assuming the half-chair form of the cyclohexanone ring in the transition state.
TL;DR: In this paper, the photolysis of azocyclohexane in an oxygen atmosphere and in the presence of cyclohexene yields cycloenyl hydroperoxide and cycloxide as principal products and no chain process is involved.
Abstract: The photolysis of azocyclohexane involves excited molecules which can be deactivated by collision or decompose into cyclohexyl radicals and nitrogen. Arrhenius parameters for reaction (11) have been estimated, cyclo-C6H11·+(cyclo-C6H11)N2 [graphic omitted] cyclo-C6 H12+ cyclo-C6H11N2-cyclo-C6H10˙k11= 105.6±0.1 exp(–6600 ± 1000 cal mol–1/RT) dm3 mol–1 s–1 and a disproportionation/combination rate constant ratio of 0.99 ± 0.10 for cyclohexyl radicals has been determined.The photolysis of azocyclohexane in an oxygen atmosphere and in the presence of cyclohexane yields cyclohexyl hydroperoxide and cyclohexanone as principal products. The results show that these are formed through a radical/radical reaction and no chain process is involved. Evidence is presented to show that the minor products, cyclohexene and water, are formed via a cyclohexyl-trioxyl radical cyclo-C6H11O3˙.
TL;DR: In this article, the reaction of tetrahydrofuran and cyclohexanone to polyfluorocyclohexanes was investigated and no polyfluoroaromatic species were found in the products.
TL;DR: Amino substituted 1, 2, 3, 4, 4-tetrahydronaphthalene and 5, 6, 7, 8, TTE-6-(methylamino)-6-phenylquinoline derivatives were synthesized as discussed by the authors.
Abstract: Amino substituted 1, 2, 3, 4-tetrahydronaphthalene and 5, 6, 7, 8-tetrahydroquinoline derivatives (1, 2, 3, 4-tetrahydro-6-methoxy-N-methyl-2-phenyl-2-naphthylamine, 1, 2, 3, 4-tetrahydro-6-methoxy-N, N-dimethyl-2-phenyl-2-naphthylamine, 5, 6, 7, 8-tetrahydro-6-(methylamino)-6-phenylquinoline and 5, 6, 7, 8-tetrahydro-6-(dimethylamino)-6-phenylquinoline) were synthesized. Thus, Michael adducts of methyl vinyl ketone and acrylonitrile to methyl 5-cyano-2-oxo-5-phenylcyclohexanecarboxylate (I) were used for formation of skeleton of naphthalene and quinoline, respectively. Quinoline derivative was also obtained by condensation of cyclohexanone derivative with 3-aminoacrolein. Amino function was derived from nitrile via Hofmann reaction of amide. Furthermore, an interesting tricyclic compound, 3, 8a-ethano-3, 4, 4a, 8a, 5, 6-hexahydro-3-phenyl-2, 7 (1H, 8H)-quinolinedione, was obtained on cyclization reaction of a Michael adduct (IIa).
TL;DR: It has been shown by radiotracer studies that in the presence of copper and nickel cyclohexanol gives phenol exclusively via cycloenhexanone, whereas in the case of platinum there is a direct pathway for the dehydrogenation of cyclochexanol into phenol.
Abstract: It has been shown by radiotracer studies that in the presence of copper and nickel cyclohexanol gives phenol exclusively via cyclohexanone, whereas in the presence of platinum there is a direct pathway for the dehydrogenation of cyclohexanol into phenol.
TL;DR: In this paper, active hydrogen compounds such as hydroquinone (HQ), cyclohexanone (CH), acetophenone (AP), and 4,4′-methylene bis-N-methylaniline (MNA) were polymerized with formaldehyde (F) and secondary diamines to produce Mannich base polyamine polymers.
Abstract: Active hydrogen compounds such as hydroquinone (HQ), cyclohexanone (CH), acetophenone (AP), and 4,4′-methylene bis-N-methylaniline (MNA) polymerized with formaldehyde (F) and secondary diamines to produce Mannich base polyamine polymers. The HQ-containing polymers were oxidized to benzoquinone (BQ)-containing polymers and their redox properties were investigated in the desulfurization of hydrogen sulfide.
TL;DR: In this article, cyclohexanone tosylhydrazone was reduced with NaBH4 and B2H6 in aprotic solvents; results indicate that the reduction affords cyclhexyl-tosylhydrazine or an equivalent organometallic adduct.
Abstract: Cyclohexanone tosylhydrazone was reduced with NaBH4 and B2H6 in aprotic solvents; results indicate that the reduction affords cyclohexyl-tosylhydrazine or an equivalent organometallic adduct confirming the mechanism previously proposed by us in the case of NaBH4 in protic solvents.
TL;DR: In this paper, active methylene compounds such as cyclohexanone and acetophenone are carboxylated by the reaction with carbon dioxide in the presence of ferric ethoxide under mild conditions to give β-ketoacids.
Abstract: Active methylene compounds such as cyclohexanone and acetophenone are carboxylated by the reaction with carbon dioxide in the presence of ferric ethoxide under mild conditions to give β-ketoacids.
Patent•
04 Nov 1974
TL;DR: In this article, it was shown that the glycol ethers of succinic, glutaric and adipic acids show a great increase in their water miscibility when they are mixed with either 6-hydroxycaproic acid methyl ester, one or more of the glycoacetates, diglycol ether, and glycol acid acetates.
Abstract: The dimethyl ethers of succinic, glutaric and adipic acids show a great increase in their water miscibility when they are mixed with either 6-hydroxycaproic acid methyl ester, one or more of the glycol ethers, diglycol ethers and glycol ether acetates, or both 6-hydroxycaproic acid methyl ester and one or more of the glycol ethers, diglycol ethers and glycol ether acetates. These dimethyl esters are, accordingly, substituents for the glycol ether derivatives in water-miscible solvents for film-forming resins. They may provide up to 80% by weight of the non-water components of the solvent. They may be produced at the same time as the methyl ester of 6-hydroxycaproic acid in a single esterification step by esterifying a fraction of acids derived from the waste salt solutions of cyclohexanone manufacture, as described in a related application, Ser. No. 372,021, now U.S. Pat. No. 3,859,335.
TL;DR: In this paper, the first-order rate constants for the formation of cyclohexanone and 2-cyclohexen-1-ol from 1,2-epoxycycloencylhexane and 1.6-d4 have been determined over the temperature range of 677-746°K.
Abstract: First-order rate constants for formation of cyclohexanone and 2-cyclohexen-1-ol from 1,2-epoxycyclohexane and 1,2-epoxycyclohexane-3,3,6,6-d4 have been determined over the temperature range of 677–746°K. The observed kinetic isotope effects are used in an attempt to determine the mechanism for formation of products. A distinction between a biradical and a concerted mechanism for the alcohol formation could not be made. However, if a common biradical is the precursor of both cyclohexanone and 2-cyclohexenl-ol then the rate of ring closure of this biradical must be much faster than the rates of hydrogen transfer to give the ketone and the alcohol.
TL;DR: In this paper, the bicycloalkyl 2,2,2′-diones obtained from oxidation by nickel peroxide of cyclopentanone, cyclohexanone and cycloheptanone with hydrogen peroxide afforded the corresponding symmetrical dihydroxy-peroxides (3,6-dihydroxy-1,2dioxans).
Abstract: Treatment of the bicycloalkyl-2,2′-diones obtained from oxidation by nickel peroxide of cyclopentanone, cyclohexanone, 4-methylcyclohexanone, and cycloheptanone with hydrogen peroxide afforded the corresponding symmetrical dihydroxy-peroxides (3,6-dihydroxy-1,2-dioxans). Perhydrodibenzo[c,e][1,2]dioxin-4a,6a-diol gave (i) mainly dodec-6-enedioic acid on reaction with iron (II) sulphate, (ii) the same acid, together with branched-chain dicarboxylic acids, on photolysis, and (iii) a mixture of lactones from treatment with formic acid. Bicyclohexyl-2,2′-dione and t-butyl hydroperoxide yielded a symmetrical bis-t-butylperoxyperhydrodibenzofuran.
TL;DR: An inactive reduced UDP-galactose-4-epimerase complex, which is prepared by reduction with NaBH4 in the presence of substrates and is known to contain DPNH and UDP-hexoses in tightly bound form, is largely reoxidized and partially reactivated in the Presence of 0.4 m cyclo hexanone or cyclohexanol.
Patent•
17 Oct 1974
TL;DR: In this paper, a 4-stage process for the production of catechol, starting with a mixture of cyclohexanol-cyclohexanone ("KA-oil"), is provided.
Abstract: A 4-stage process for the production of catechol, starting with a mixture of cyclohexanol-cyclohexanone ("KA-oil"), is provided herein whereby the starting mixture is first hydrotreated to convert the cyclohexanone to cyclohexanol, the cyclohexanol dehydrated to form cyclohexene which, in turn, is oxidized to 1,2-epoxy-3-hydroxy-cyclohexane. Dehydrogenation of this latter compound yields catechol. Volatiles and residue from the second stage are advantageously recycled to the KA-oil feed stream, and H 2 from the last stage recycled to the hydrotreating step.
TL;DR: In this article, the 2-cyclohexyl cyclohexenyl cycloenylcycloenylhexanone (2-Chen-hexenylon) was de-cycled in the presence of 5% palladium-on-charcoal at temperatures 280, 300, and 320 °C, the reaction time being 1/2-8 hr.
Abstract: The dehydrogenation reaction of 2-(1-cyclohexenyl)cyclohexanone was carried out in the presence of 5% palladium-on-charcoal at temperatures 280, 300, and 320 °C, the reaction time being 1/2—8 hr. o-Cyclohexylphenol and o-phenylphenol were obtained as dehydrogenation products, and dibenzofuran as the cyclization product via o-phenylphenol. In a short reaction time, 2-cyclohexylcyclohexanone was formed together with the dehydrogenation products. The compound disappeared, the amount of two phenols and dibenzofuran increasing with reaction time. The dehydrogenation process is discussed.
Patent•
26 Apr 1974
TL;DR: In this paper, the reaction is carried out neat or in the liquid phase using an alicyclic ester reaction solvent having a boiling point ranging from about 150° to 250° C.
Abstract: Alkoxy phenols such as o-methoxyphenol (guaiacol) and o-ethoxyphenol are prepared from substituted cycloaliphatic ketones by dehydrogenation thereof in the presence of a Group VIII noble metal catalyst, preferably palladium supported on carbon, at a temperature of 150° to 250° C. The reaction is carried out neat or in the liquid phase using an alicyclic ester reaction solvent having a boiling point ranging from about 150° to 250° C. The substituted cycloaliphatic ketone reactant, such as 2-chlorocyclohexanone is prepared by chlorination of cyclohexanone with subsequent conversion of the 2-chlorocyclohexanone to the alkoxy-cyclohexanone compound which is dehydrogenated.
TL;DR: In this article, the authors describe catalytic hydrogenation with molecular hydrogen dissolved under pressure in nonaqueous solutions containing the title compounds, achieved, during electrolysis, by transferring copper from the anode to the cathode.
Abstract: Catalytic hydrogenation with molecular hydrogen dissolved under pressure in non-aqueous solutions containing the title compounds is achieved, during electrolysis, by transferring copper from the anode to the cathode. The rate of hydrogenation and yield of conversion depend on the current density and temperature. Suitable choice of these variables allows complete conversion of aldehydes and ketones into primary and secondary alcohols, respectively.
Patent•
17 Jan 1974
TL;DR: In this article, the authors described a method for the induction of anesthesia in mammals by parenterally administering 2-(ethylamino)-2-(2-thienyl)cyclohexanone in combination with 4-(o-fluorophenyl)-6,8dihydro-1,3,8-trimethylpyrazolo(3,4-e)(1,4)diazepin -7(1H)-one in the proportions indicated above.
Abstract: Pharmaceutical compositions for anesthetic use comprising one part by weight of 2-(ethylamino)-2-(2-thienyl)cyclohexanone in combination with 0.1 to 10 parts by weight of 4-(o-fluorophenyl)6,8-dihydro-1,3,8-trimethyl-pyrazolo(3,4-e)(1,4)diazepin -7(1H)one. Methods for the induction of anesthesia in mammals by parenterally administering 2-(ethylamino)-2-(2thienyl)cyclohexanone in combination with 4-(o-fluorophenyl)-6,8dihydro-1,3,8-trimethylpyrazolo(3,4-e)(1,4)diazepin -7(1H)-one in the proportions indicated above. In the compositions and methods of the invention the substances can be used in either free base or acid-addition salt form.
Patent•
19 Apr 1974
TL;DR: In this article, the antifertility agents are prepared by diacylating 3-R-9-R''-1,5dioxaspiro(5.5)undecan-3,9-diamine (II) or mono-acylanating 9(Ac1NH)-3-R.9-r-R''.1, 5.5-dioxasimiro(1.5).
Abstract: 3-R-3-(Ac2NH)-9-R''-9-(Ac1NH)-1,5-dioxaspiro(5.5)undecane (I), where R and R'' are each hydrogen or lower-alkyl, Ac1 is loweralkanoyl or 4-Q1-benzoyl and Ac2 is 4-Q2-benzoyl where Q1 and Q2 each is lower-alkoxy or polyhalo-lower-alkoxy, are antifertility agents. The compounds are prepared by di-acylating 3-R-9-R''-1,5dioxaspiro(5.5)undecan-3,9-diamine (II) or mono-acylating 9(Ac1NH)-3-R-9-R''-1,5-dioxaspiro(5.5)undecan-3-amine (IV). IV and II are prepared by oxidizing 4-(Ac1NH)-4-R''-cyclohexanol (VI) to produce 4-(Ac1NH)-4-R''-cyclohexanone (VII), reacting VII with 2NO2-R-1,3-propanediol to produce 3-R-3-NO2-9-(Ac1NH)-9-R''-1,5dioxaspiro(5.5)undecane (VIII), reducing VIII to produce the corresponding 3-amine (IV) and hydrolyzing IV to the corresponding 3,9-diamine (II). Methods of preparing VI are shown.