Showing papers on "Methyl vinyl ketone published in 1974"

The new michael reaction

Abstract: It was found that silyl enol ethers react with α,β-unsaturated ketones and esters in the presence of TiCl4 under mild (−78°C) conditions to give 1,5-dicarbonyl compounds in good yields. Further, it was also found that 1-phenyl-1,5-hexanedione and its monoacetal were obtained by the TiCl4-promoted reaction of methyl vinyl ketone ethylene acetal with α-trimethylsiloxystyrene.

Chemical oxidation of cyclophosphamide and 4-methylcyclophosphamide.

Abstract: Summary The oxidation of cyclophosphamide by Fenton9s reagent has been studied and the formation of acrolein as a product confirmed by gas chromatography-mass spectrometry. Oxidation of 4-methylcyclophosphamide generates methyl vinyl ketone. This is interpreted to indicate that the acrolein and methyl vinyl ketone arise from oxidation of position 4 of the ring of cyclophosphamide. The Fenton oxidation of both cyclophosphamide and 4-methylcylophosphamide generates cytotoxic material(s) which remains in the aqueous phase when the volatiles acrolein and methyl vinyl ketone are removed by gassing.

Synthesis of Nitrogen-containing Heterocyclic Compounds. XX. Improvement of One-step Synthesis of Phenanthrolines and Some Reactions of 4, 6-Phenanthroline

Abstract: 1, 9-Diazaanthracene (IV), 4-methyl-1, 9-diazaanthracene (V), 4, 6-phenanthroline (I), 1, 6-phenanthroline (III), and 5-methyl-1, 6-phenanthroline (II) were synthesized by the reaction of 2-, 3-, or 4-aminoquinolines with glycerol or methyl vinyl ketone, in the presence of sulfo-mix, ferrous sulfate, and boric acid. Methylation of I with methyl iodide afforded the monomethiodide (VI) in which methyl iodide was proved to have reacted with the nitrogen in 6-position. Chichibabin amination of I afforded 5-amino-4, 6-phenanthroline (VIII) and this amination was examined by comparison of reaction indices by the Huckel molecular orbital method.

Tetrahydronaphthylamines and Related Compounds. III. Synthesis of 1, 2, 3, 4-Tetrahydro-2-naphthylamine and 6-Amino-5, 6, 7, 8-tetrahydroquinoline Derivatives

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).

Stereoregularity of poly(alkyl α-chloroacrylates) and mechanism of isotactic polymerization

Abstract: The catalytic activity of the complexes prepared by the reaction of Grignard reagents with ketones, esters, and an epoxide as polymerization catalysts of methyl and ethyl α-chloroacrylates was investigated. The modifiers which gave isotactic polymers were α,β-unsaturated ketones such as benzalacetophenone, benzalacetone, dibenzalacetone, mesityl oxide, and methyl vinyl ketone, and α,β-unsaturated esters such as ethyl cinnamate, ethyl crotonate, and methyl acrylate. Catalysts with butyl ethyl ketone, propiophenone, and propylene oxide as modifiers produced atactic polymers but no isotactic polymers. It was revealed that the complex catalysts having a structure CCOMgX (X is halogen) gave isotactic polymers. The mechanism of isotactic polymerization was discussed. In addition, for radical polymerization of ethyl α-chloroacrylate, enthalpy and entropy differences between isotactic and syndiotactic additions were calculated to give ΔHi* − ΔHs* = 910 cal/mole and ΔSi* − ΔSs* = 0.82 eu.

Method for annelation of pyridinium rings on to nitrogen heterocycles

Abstract: Protonated heterocycles possessing an alkyl substituent on the carbon atom adjacent to the positive nitrogen react with methyl vinyl ketone to form adducts which can be converted into fused pyridinium salts.

Bis quinoline peri acids

Abstract: Preparation of a novel heterocyclic peri acid is initiated by reacting diaminodimethylbiphenyl with methyl vinyl ketone to produce tetramethyl biquinoline. The substituent methyl groups are oxidized subsequently to produce a tetraacid, or upon dehydration of the tetraacid, a dianhydride. The peri acids of this invention have the following structural formula: ##SPC1## Where R may be either ##EQU1## or (--COOH) 2 and R' is --H, --OCH 3 , ##SPC2##

Manufacture of d,l-methol

Abstract: Manufacture of piperitenone by mixing excess mesityl oxide with 10 to 70% by weight aqueous potassium hydroxide solution, heating the mixture to a temperature of between 20°C and the boiling point and introducing the methyl vinyl ketone into the heated mixture. d,1-methol is obtained directly, or via a mixture of methone and isomenthone, from the piperitenone which is obtained in good yield.

Method for annelation of pyridinium rings on to nitrogen heterocycles

Abstract: Protonated heterocycles possessing an alkyl substituent on the carbon atom adjacent to the positive nitrogen react with methyl vinyl ketone to form adducts which can be converted into fused pyridinium salts.