65933-44-0

Upstream product

• 108-94-1 cyclohexanone 
• 67-56-1 methanol 
• 822-87-7 2-Chlorocyclohexanone 
• 149-73-5 trimethyl orthoformate 

Downstream Products

• 59892-15-8 3-chloro-2-methoxy-1-cyclohexene 
• 1259475-97-2 C₁₄H₂₅ClO₃Si 

Relevant academic research and scientific papers

Geminal acylation of α-heterosubstituted cyclohexanones and their ketals

Geminal acylation of derivatives of cyclohexanone with Br, Cl, F, and OCH3 in the α position, and of their corresponding dimethyl ketals, could not be accomplished to a significant extent following published procedures. The transformation was a

A safe, convenient and efficient one-pot synthesis of α-chloroketone acetals directly from ketones using iodobenzene dichloride

Various ketones, including aliphatic and aromatic ketones, can be directly converted into their corresponding α-chloroketone acetals in high to excellent yields using iodobenzene dichloride in ethylene glycol in the presence of 4 A molecular sieves at room temperature. Georg Thieme Verlag Stuttgart.

Nucleophilic substitution reactions of sulfur-substituted cyclohexanone acetals: An analysis of the factors controlling stereoselectivity

The reactions of cyclohexanone acetals substituted with thiophenyl groups (and other heteroatoms) at C-2 demonstrate the powerful influence that these substituents have on the stereoselectivity of nucleophilic substitution reactions. The trans selectivities of these reactions correlate with the behavior of the corresponding ketones. These experiments lend support to the possibility that the reactions of the acetals, which proceed via oxocarbenium ions, are operating under Felkin-Anh control.

Photo-cleavage of carbon-carbon bond of α-iodocycloalkanones giving ω,ω-dialkoxyalkanoic ester in alcohol

The irradiation at λ > 300 nm of α-iodocycloalkanones with a high- pressure mercury lamp in alcohols containing a small amount of water afforded the corresponding ω,ω-dialkoxyalkanoic ester (65-88%) by photochemical cleavage of the C(I)-C=O bond at room temperature. In the case of a commercial fluorescent lamp as the irradiating light source, photochemical ring-opening products were also obtained. The irradiation of 2α-iodo-5α- and 4β-iodo-5β-cholestan-3-ones in methanol gave methyl 2,2-dimethoxy-2,3- seco-5α-cholestan-3-oate and methyl 4,4-dimethoxy-3,4-seco-5β-cholestan-3- oate in 78 and 62% yields, respectively. The photochemical behavior of the cleavage reaction of α-iodocycloalkanones is also discussed on the basis of 2-hydroxycycloalkanone as an intermediate.

Organic Reactions of Sulfur Dioxide. Reactions with Nucleophilic Duoble Bonds Leading to the Isomerization, Aromatization, Selective Hydrogen-Deuterium Exchange, and Electron-Transfer Processes

Sulfur dioxide reacts readily with 1-alkoxycyclohexenes to give unstable 1,2,3,4,5a,6,7,8,9,9b-decahydro-4a,9a-dialkoxydibenzothiophene 5,5-dioxides, which, after elimination of alcohol, afford crystalline 1,2,3,4,5a,6,7,8,9-nonahydro-4a-alkoxydibenzothiophene 5,5-dioxides.These tricyclic sulfones undergo sulfur dioxide extrusion to give a 1:1 mixture of 2- and 6-cyclohex-1-enyl-1-alkoxy-1-cyclohexenes.This mixture of the 1,3- and 1,4-dienes reacts quantitatively with sulfur dioxide to give back the starting tricyclic sulfones.The apparent isomerization of the 1,4-diene to 1,3-isomer is an example of a quite general isomerization of a wide variety of olefins in sulfur dioxide.It appears that these reactions involve the allylic sulfinic acids as transient intermediates, which are capable of a very facile 1,3-thiaallylic rearrangement.When the reactions of those olefins that do undergo isomerization in liquid sulfur dioxide are carried out in the presence of deuterium oxide, a highly stereospecific hydrogen-deuterium exchange is observed.For example, optically active 1-methyl-4-isopropyl-cyclohexene affords 6,6-dideuterio-1-(trideuteroimethyl)-4-isopropylcyclohexene without appreciable racemization. 1,4-Cyclohexadienes react with liquid sulfur dioxide at room temperature to give quantitatively the aromatic hydrocarbon, elemental sulfur, and water. 1,4-Disubstituted 1,3-cyclohexadienes, on the other hand, under similar conditions provide only a small amount of the aromatic hydrocarbon, the main product being a polymeric hydrocarbon(s).Surprisingly, 1-methyl-4-isopropyl-1,3-cyclohexadiene in the presence of oxygen provided 1-methyl-4-isopropylbenzene exclusively.This reaction involves ascaridole as the intermediate, which then reacts with sulfur dioxide to give the aromatic hydrocarbon and sulfuric acid.When the reaction with oxygen is conducted at a low temperature, the ascaridole can be obtained in a quantitative yield.The mechanisms of olefin isomerization, hydrogen-deuterium exchange, and aromatization of cyclohexadienes are discussed.

Preparation of α-Nitro Olefins from α-Halo Ketoximes

α-Nitro olefins were synthesized from α-haloketones through oximation and subsequent oxidation with trifluoroperacetic acid.

STEREOCHEMICAL STUDIES-XXVI CONFORMATIONAL EQUILIBRIA OF KETALS OF 2-SUBSTITUTED CYCLOHEXANONES

The positions of the conformational equilibria in a series of 2-substituted cyclohexanone ketals have been determined by 1H NMR.For the ethylene ketals 6 the equatorial conformer has been found to be enthalpically preferred.The other ketal syst

Sulfuryl Chloride as a Reagent for Selective Chlorination of Symmetrical Ketones and Phenols

Cyclohexanone reacts with sulfuryl chloride in sulfur dioxide, ether, tetrahydrofuran, dioxane, and tetraglyme to give mixtures of mono- and dichlorocyclohexanones.However, when the reaction was carried out in sulfur dioxide solution containing a slight excess of methanol, only monochlorocyclohexanone was obtained in high yield.Almost as good selectivities are obtained in methylene chloride solution in the presence of methanol.A similar procedure with acetone affords monochloroacetone cleanly.While phenols do not react with sulfuryl chloride in methylene chloride even under reflux, the chlorination can be induced by the addition of various organic "bases", resulting in selective monochlorination.

Process for the preparation of selectively and symmetrically di-halogenated ketals

A method is disclosed wherein selectively halogenated ketals are prepared by treating ketones and ketals with halogen in an organic solvent under conditions of ordinary temperature and pressure. This process obviates the need for extreme times, temperatures, and complex equipment while resulting in higher yields than obtained heretofore.