The reaction of the potassium salt of trinitromethane with acetyl chloride and acetone

Conclusions On reacting the potassium salt of trinitromethane with acetyl chloride in abs acetone acylation of the trinitromethane anion does not occur and the main product of the reaction is 1,1,1-trinitro-2,2-dimethyl-pentan-4-one formed as a result of the addition of trinitromethane to mesityl oxide which arises from acetone in the process of reaction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2769–2771, December, 1967.     

Mass spectrometric synthesis. II. The reaction of catechol with acetone in a protic medium

The reaction of catechol with acetone, carried out in the chemical ionization chamber of a VG ZAB 2F mass spectrometer and in the presence of a protic medium (CH₅+), leads to 2,2-dimethyl-1,3-benzodioxole. This has been proved by exact measurements and collisionally activated dissociation mass analyzed ion kinetic energy spectra.     

A novel pyrrole synthesis via reaction of ketones with N-aminoimides

A new, mild synthesis of pyrroles using N-aminoimides and a ketone is described. The reaction has been utilized in the synthesis of dimeric morphinans containing a connecting pyrrole ring. The reaction appears to proceed through a diacylhydrazone intermediate, and it is suggested that the driving force behind the reaction is the facility with which a protonated imide moiety operates as a leaving group.     

An expedient synthesis of murrayaquinone A via a novel oxidative free radical reaction

Murrayaquinones A–D is a group of four bioactive carbazole-1,4-dione natural products isolated from the root bark of the plant Murraya eucrestifolia hayata. Murrayaquinone is synthesized in five steps starting from the commercially available 2,4,5-trimethoxybenzaldehyde with an overall yield of 45%. The novelty of this murrayaquinone synthesis is in the use of a Mn(OAc)₃ mediated oxidative radical reaction of a N-benzylaminoquinone derivative with 2-cyclohexen-1-one for the late-stage indole ring construction.     

Kinetics of the reaction of the potassium salt of trinitromethane with normal primary alkyl iodides in acetone

Conclusions The kinetics of the reaction of the potassium salt of trinitromethane with normal primary alkyl iodides was studied. The reaction proceeds according to a mechanism of bimolecular nucleophilic substitution (S_N2) and represents alkylation of the trinitromethane anion at the carbon atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 720–725, April, 1970.     

An anomalous by-product in the von pechmann reaction

During condensation of 4-chloro-2-methylphenol with diethyloxalacetate in sulfuric acid the spirodilactone 3 was observed as well as the desired coumarin 1 . Further reaction of 1 under the reaction conditions with 4-chloro-2-methylphenol did not produce 3 readily. These observations imply the formation of the intermediate 10 prior to production of the novel spirodilactone 3 .     

Three-component reaction of aldose sugars, aryl amines, and 1,3-diones: a novel synthesis of annulated pyrroles

Aldose sugars undergo smooth coupling with enamines, generated in situ from aryl amines and 1,3-diketones, in the presence of 10 mol % of InCl3 in water at 80 degrees C to furnish annulated pyrrole derivatives in relatively good to high yields. The use of InCl3, in combination with water, makes this procedure quite simple, more convenient, and environmentally friendly.     

Tunneling in the reaction of acetone with OH

Based on recent detailed quantum mechanical computations of the mechanism of the title reaction and, this paper presents kinetics analysis of the overall rate constant and its temperature dependence, for which ample experimental data are available for comparison. The analysis confirms that the principal channel is the formation of acetonyl radical + H(2)O, while the channel leading to acetic acid is of negligible importance. It is shown that the unusual temperature dependence of the overall rate constant, as observed experimentally, is well accounted for by standard RRKM treatment that includes tunneling. This treatment is applied at the microcanonical level, with chemically activated distribution of entrance species, i.e. using a stationary rather than a thermal distribution that incorporates collisional energy transfer and competition between the redissociation and exit channel. A similar procedure is applied to the isotopic reaction acetone-d6 + OH with equally satisfying results, so that the experimental temperature dependence of the KIE (kinetic isotope effect) is perfectly reproduced. This very good agreement between calculation and experiment is obtained without any fitting to experimental values and without any adjustment of the parameters of calculation.     

The reaction of isothiocyanates with 2-cyanoethanoic acid hydrazide. A novel synthesis of 1,3,4-thiadiazoles

Benzoyl and ethoxycarbonyl isothiocyanates reacted with 2-cyanoethanoic acid hydrazide 2 to afford 1-cyanoacetyl-4-substituted thiosemicarbazide ( 5a,b ). Compound 5a afforded the pyrazolo[1,5-a]-s-triazine derivative 6 on treatment with 5% potassium hydroxide, and cyclised to 2-benzoylamino-5-cyanomethyl-1,3,4-thiadiazole ( 8 ) when boiled under reflux in glacial acetic acid. Compound 8 condensed with aromatic aldehydes to yield the corresponding arylidene derivatives 9a-c . It undergoes coupling with aromatic diazonium salts to afford the hydrazones 11a-c . Similarly, it coupled with diazotised aminopyrazole to afford the cyclic product 12 .     

A novel synthesis of benzofuran and related compounds. I. The vilsmeier reaction of phenoxyacetonitriles

A novel synthesis of 2-benzofurancarboxylic acid derivatives by the Vilsmeier reaction of phenoxyacetonitriles is described.     

A novel and simple benzannulation reaction using the potassium salt of methyl mercaptoacetate for the synthesis of 3-aryl-2-methoxycarbonylacridines

A new benzannulation methodology has been developed and applied to the synthesis of 3-aryl-2-methoxycarbonylacridines.     

The reaction of malononitrile with thioglycolic acid. A novel procedure for the synthesis of thiazolone derivatives

Malononitrile (I) reacted with thioglycolic acid to yield the thiazolin-4-one derivatives II or III depending on the molar ratio of the reactants. Compound II reacted with benzaldehyde in refluxing pyridine to yield the arylidene derivative IV. On the other hand, the benzylidine bis derivative VIII was obtained when II was reacted with benzaldehyde in refluxing ethanol. The structure of IV was established via its synthesis from the reaction of benzylidenemalononitrile (VI) and thioglycolic acid in refluxing acetic acid. Similar to II, compound III condensed with benzaldehyde to yield the benzylidene derivative IX.