Superbasic System Research Articles

Reactions of Elemental Phosphorus and Phosphines with Electrophiles in Superbasic Systems: XIII. Phosphorylation of Phenylacetylene with Active Modifications of Elemental Phosphorus

Phosphorylation of phenylacetylene with white or activated red phosphorus (prepared from white phosphorus under the action of ionizing radiation) occurs in KOH-DMSO or KOH-HMPA systems with heat evolution and stereoselective formation of Z isomers of tristyrylphosphine and -phosphine oxide in yields of 48-49% and 10-15%, respectively. Under the comparable conditions the commercial red phosphorus is considerably less reactive toward phenylacetylene: The total yield of the above-mentioned products is 5%.

Nucleophilic addition to acetylenes in superbasic catalytic systems: XI. Transformations of alkali metal hydroxides during vinylation of 1-heptanol with acetylene under elevated pressure

Base-catalyzed addition of 1-heptanol to acetylene under elevated pressure of the latter is accompanied by side processes including formation of carboxylic acid salts (alkali metal heptanoates and acetates) with liberation of hydrogen and acetylene polymerization. The rate of acetylene absorption depends on the alkali metal nature and falls down in the series CsOH·H2O ≥ RbOH·H2O > 2KOH·H2O > NaOH > LiOH. Approximately the same order is observed for variation of the rate of deactivation of the catalyst owing to its transformation into metal carboxylate. Dehydration of the catalyst accelerates both vinylation and acetylene polymerization.

Synthesis and Thermal Stability of O-Vinylketoximes

The O-vinylketoximes 2 were synthesized from ketoximes 1 and acetylene in superbase systems in good to excellent yields. Their thermal stability was investigated.

An unusually fast nucleophilic addition of amidoximes to acetylene

The addition of amidoximes to acetylene in the presence of the KOH–DMSO superbase system afforded O-vinylamidoximes in 26–59% yields.

2-Iminothiopyrans from methylthiobutadiene and isothiocyanates

We have found a novel and simple approach to synthesis of 2-alkyl-3-(methylthio)-5,6-dihydro-2H-2-thiopyranimines by reactions of isothiocyanates with the carbanion of methylthiobutadiene, generatedin situ when treated with the superbasic system BuLi-t-BuOK. We have established that alkylation of the synthesized thiopyrans with methyliodide in the presence oft-BuOK leads to N-alkyl-1,2-di(methylthio)-2,4-pentadiene-1-imines.

Hydrogenation of unsaturated hydrocarbons over alkali-metal-modified zinc oxide

Superbasic catalytic systems have been obtained by evaporation of alkali metals onto a ZnO surface. The catalysts were characterized by IR and EPR spectroscopy. Similar to the case of alkali-metal-doped oxide insulators, surface colour centres Fs+, formed by the trapping of an alkali-atom electron in an oxide anionic vacancy, were identified as the source of the extremely strong one-electron donor properties. The studied catalysts exhibited a much higher activity in the hydrogenation of alkenes than the starting ZnO. A mechanism for propene hydrogenation over the superbasic alkali metal/ZnO system was proposed.

Synthesis ofN-allenylazoles from azoles and propargyl chloride or 1,2,3-trichloropropane in one preparative step

Reactions of imidazole and 1,2,4-triazole with propargyl chloride and its more accessible equivalent, 1,2,3-trichloropropane, in the superbasic KOH-DMSO system have been studied. The reactions afford the correspondingN-allenylazoles in one preparative step.

Step by Step Modeling of Superbasic Catalysts of the EDA Complex Type

A range of catalysts was synthesized; these catalysts contained species analogous to the structures appearing during the various elementary steps in the hydrogenation of alkenes over catalysts of extremely strong one-electron donor centers. The primary catalytic system, γ-Al2O3–metallic potassium, was modified by naphthalene, anthracene, and perylene vapors to form surface electron donor–acceptor (EDA) complexes. The specific EDA complexes were also prepared by the immobilization of potassium naphthenide on a γ-Al2O3surface in amounts relative to the number of surface hydroxyls. The investigated catalysts were tested in the isomerization of 1-pentene and 1-hexene and in the hydrogenation of ethene and propene. The catalytic importance of ion radical species of alkenes formed during their isomerization and hydrogenation over superbasic systems was demonstrated.

ChemInform Abstract: Reactions of Red Phosphorus with Electrophiles in Superbasic Systems. Part 6. Identification of the Products of Phosphorylation of Phenylacetylene with the System P‐KOH‐HMPA Under Conditions of Mechano‐ Chemical Activation.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Reactions of Elemental Phosphorus with Electrophiles in Superbasic Systems.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Chalcogenation in Multiphase Superbase Systems

Abstract Superbase-promoted chalcogenation of diverse electrophilic reagents with the chalcogens or their anions in multiphase superbase systems became possible owing to the fact that under the action of a very strong hard base such as the “naked” hydroxide ion the elemental chalcogens produce softer and more nucleophilic species which successfully compete for the electrophiles. This explains the paradox that electrophiles such as acetylene, vinylacetylene, phenylacetylene, diacetylene and organo halides, in the presence of strong bases prefer to react with the chalcogens or their anions rather than with the activated hydroxide ion. Ignorance of this fundamental fact for a long time hindered progress in the application of chalcogens for the direct synthesis of their organic derivatives.

N-allenylation of pyrroles using 1,2,3-trichloropropane

We have found that 1,2,3-trichloropropane is an efficient allenylating agent for pyrroles in the KOH/DMSO superbase system. Thus, l-propadienyl-2-phenylpyrrole (I) was obtained in 62% yield directly from 2-phenylpyrrole. The double dehydrochlorination, nucleophilic substitution of the chlorine atom by the pyrrolate anion, and prototropic isomerization of intermediate l-(2-propynyl)-2-phenylpyrrole to an allene were carried out in a single preparative step with almost 100% selectivity.

Hochaktive Katalysatorsysteme für die Vinylethersynthese aus Acetylen und Alkoholen—Kaliumalkoholat/Kronenether in Kohlenwasserstoffen

The activity of well-known alkaline-containing catalyst systems for the formation of vinyl ethers from alcohols and acetylenes can be remarkably increased by using a superbasic system: KOR-crown ether in an aprotic solvent (especially in hydrocarbons). To achieve a high catalytic activity a low concentration of alcohol in the hydrocarbon phase is essential. The results are discussed in terms of solvatation of alcoholate anion.

SUPERBASE-INDUCED GENERATION OF PHOSPHIDE AND PHOSPHINITE IONS AS APPLIED IN ORGANIC SYNTHESIS

Abstract A series of new direct reactions of red phosphorus (or white) with organyl halides, alkenes and acetylenes have been developed. Reactions occur in superbasic systems, such as alkali metal hydroxide-dipolar aprotic complexing solvent (DMSO, HMPA) or under phase-transfer conditions to afford earlier inaccessible triorganylphosphines and -phosphine oxides including unsaturated ones in good yields.

ChemInform Abstract: Reaction of Red Phosphorus with Electrophiles in Superbasic Systems. Part 2. Synthesis of Triorganylphosphine Oxides from Red Phosphorus and Organyl Halides.

ChemInform Abstract: Reaction of Red Phosphorus with Electrophiles in Superbasic Systems. Part 2. Synthesis of Triorganylphosphine Oxides from Red Phosphorus and Organyl Halides.

ChemInform Abstract: Reaction of Red Phosphorus with Electrophilic Reagents in Superbasic Systems.

ChemInform Abstract: Reaction of Red Phosphorus with Electrophilic Reagents in Superbasic Systems.

ChemInform Abstract: Reaction of Red Phosphorus with Electrophiles in Superbasic Systems. Part 1. Tris(Z‐styryl)phosphine and Its Derivatives.

AbstractReactions of the title phosphine (I), leading to the phosphine chalcogenides (II) and (IV), the phosphonium iodides (VI), and the complex (VIII) are performed as shown in the reaction scheme.

Reaction of Red Phosphorus with Electrophilic Reagents in Superbasic Systems

Abstract A new method for generating highly nucleophilic ions from red phosphorus in superbasic systems, such as alkali metal hydroxide-dipolar aprotic solvent (HMPA, DMSO) or solvent of moderate polarity (toluene) with or without a phase-transfer catalyst, has been developed and shown to cover non-standard convenient routes to triorganylphosphines, -phosphine oxides and their derivatives. This is illustrated by the following examples:

ChemInform Abstract: Mechanoactivation of the Superbasic System KOH‐DMSO: Efficient Application in the Reaction with Cyclohexanone.

ChemInformVolume 21, Issue 29 Isocyclic Compounds ChemInform Abstract: Mechanoactivation of the Superbasic System KOH-DMSO: Efficient Application in the Reaction with Cyclohexanone. B. A. TROFIMOV, B. A. TROFIMOV Irkutskii inst. org. khim. Sib. otd. AN SSSRSearch for more papers by this authorA. M. VASIL'TSOV, A. M. VASIL'TSOV Irkutskii inst. org. khim. Sib. otd. AN SSSRSearch for more papers by this authorA. I. MIKHALEVA, A. I. MIKHALEVA Irkutskii inst. org. khim. Sib. otd. AN SSSRSearch for more papers by this authorO. V. PETROVA, O. V. PETROVA Irkutskii inst. org. khim. Sib. otd. AN SSSRSearch for more papers by this authorA. V. POLYBENTSEV, A. V. POLYBENTSEV Irkutskii inst. org. khim. Sib. otd. AN SSSRSearch for more papers by this author B. A. TROFIMOV, B. A. TROFIMOV Irkutskii inst. org. khim. Sib. otd. AN SSSRSearch for more papers by this authorA. M. VASIL'TSOV, A. M. VASIL'TSOV Irkutskii inst. org. khim. Sib. otd. AN SSSRSearch for more papers by this authorA. I. MIKHALEVA, A. I. MIKHALEVA Irkutskii inst. org. khim. Sib. otd. AN SSSRSearch for more papers by this authorO. V. PETROVA, O. V. PETROVA Irkutskii inst. org. khim. Sib. otd. AN SSSRSearch for more papers by this authorA. V. POLYBENTSEV, A. V. POLYBENTSEV Irkutskii inst. org. khim. Sib. otd. AN SSSRSearch for more papers by this author First published: July 17, 1990 https://doi.org/10.1002/chin.199029111Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume21, Issue29July 17, 1990 RelatedInformation

Reaction of Red Phosphorus with Electrophilic Reagents in Superbasic Systems

Reaction of Red Phosphorus with Electrophilic Reagents in Superbasic Systems