Cleavage of 1,3-dioxo-2-silacyclanes and their oligomers by acid halides of carboxylic acids

Conclusions The cleavage of 1,3-dioxo-2-silacyclanes and their oligomers by the acid halides of carboxylic acids leads to a mixture of (-acetoxyaikoxy)chlorosilanes and the diacetates of the corresponding glycols.     

Cleavage of the Si-O bond in 1,3-dioxa-2-silacyclanes and their oligomers under the action of vinylethynylmagnesium bromide

Conclusions With the reaction between 2,2-dimethyl-1,3-dioxa-2-silacyclanes and vinylethynylmagnesium bromide as an example, it has been shown that under the action of an excess of a Iotsich complex cyclic alkoxysilanes and the oligomers corresponding to them undergo cleavage at both Si-O bonds forming the corresponding dialkynylsilanes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 943–944, April, 1967.     

Copper-mediated cross-coupling of functionalized arylmagnesium reagents with functionalized alkyl and benzylic halides

[reaction: see text]. Functionalized arylmagnesium halides, prepared via an iodine-magnesium exchange, undergo a smooth cross-coupling reaction with functionalized primary alkyl iodides and benzylic bromides in the presence of CuCN.2LiCl, either in stoichiometric (with trimethyl phosphite as an additive) or catalytic quantities.     

Synthesis of arylboronic acids via the reaction of borane with arylmagnesium halides

The reaction of borane complexes with arylmagnesium halides produces the corresponding arylborohydrides in high yield. The arylborohydrides are readily hydrolyzed to the arylboronic acids. The syntheses are conveniently carried out in one pot. The reaction mechanism was clarified via a boron-11 NMR study.     

The first example of Ge-Ge and Sn-Sn bond cleavage by arylmagnesium halides

Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2817–2818, November, 1996.     

Sulfenyl halides in the synthesis of heterocycles. 3. Interaction of perfluoro-1-ethyl-2-methyl-1-propenyl-iminochloromethanesulfenyl chloride with 1-allyl-2-methoxybenzene

Reaction of perfluoro-1-ethyl-2-methyl-1-propenyliminochloromethanesulfenyl chloride with 1-allyl-2-methoxybenzene in methylene chloride and nitromethane gives as the main products β-and β-chloro sulfides plus derivative of 2,3-dihydrobenzofuran. The reaction in nitromethane in the presence of lithium perchlorate gave a product of addition of sulfur-containing electrophiles to the double bond-a derivative of 1,3-thiazolidin-2-one-in preference to the cycloaddition product. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1558–1564, October, 2006.     

Interaction of N-vinylbenztriazole with halogens and hydrogen halides

Russian Chemical Bulletin -     

Interaction of schiff bases with indandione-1, 3

A new method was examined for the synthesis of multinuclear systems based on dihydroquinoline and quinoline, consisting of the interaction of arylidene--naphthylamines with indandione-1, 3. The reaction of arylidene anilines with indandione-1,3 leads to the formation of arylidenindandiones-1, 3.     

Interaction of polyfluoroalkyl-containing aziridinyl ketones with hydrogen halides

Polyfluoroalkyl-containing aziridinyl ketones, unlike their nonfluorinated analogs, react with hydrogen halides to give only -halo- -anvnoketones or their hydrogen halide salts. Thermal decomposition of the latter in the case where Hal = CI affords -chlorovinyl ketones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 684–686, March, 1996.     

Interaction of decacarbonyldimanganese and decacarbonyldirhenium with 1-aryl-3-cyanoprop-2-en-1-ones

The reactions of M₂(CO)₁₀ (M = Mn, Re) withtrans-1-aryl-3-cyanoprop-2-en-1-ones in the presence of Me₃NO proceed with replacement of the CO ligand and lead to complexeseq-(1-aryl-3-cyanoprop-2-en-1-on)nonacarbonyldimanganese andeq-(1-aryl-3-cyanoprop-2-en-1-on)nonacarbonyldirhenium complexes where the metals are bonded with the ligand through the nitrogen atom of the cyanogroup. The treatment of (1-phenyl-3-cyanoprop-2-en-1-on)nonacarbonyldirhenium with a second equivalent of the ligand resulted in the disubstituted complex,eq,eq-bis(1-phenyl-3-cyanoprop-2-en-1-on)octacarbonyldirhenium in a good yield. The structures of the obtained complexes are discussed on the basis of¹³C,¹H NMR, and IR-spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1485–1487, August, 1994.This work was supported in part by the Russian Foundation for Basic Research (grant No 93-03-4028).     

Reactions of 1,4-dioxa-2-silacyclohexanes with acetyl chloride

The reactions of 1,4-dioxa-2-silacyclohexanes with acetyl chloride lead to the cleavage of the Si−O bond to form chlorotriorganosilanes containing the acetoxy group in the organic radical at the silicon atom. Hydrolysis of these chlorosilanes affords bis(acetoxy-alkoxy(aryloxy)methyl)disiloxanes, while the reactions with cage copper sodium phenylsiloxane give dodecaphenyl[dodeca(acetoxyorganodimethylsilyloxy)]cyclododecasiloxanes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2527–2529, December, 1998.     

Interaction of silver halides with gelatin of like charge

Summary Interactions of gelatin with silver bromide and silver iodide sols of like charges have been studied as a function of gelatin concentration, pH, and addition of neutral electrolytes. Silver halide solsin statu nascendi and aged sols were used in the experiments. Solsin statu nascendi showed a scattering intensity maximum indicating coagulation, while aged sols did not. At higher pH values, the maximum appeared, if sufficient amounts of electrolyte and gelatin were present. It is suggested that gelatin reduces the effective surface charge density of the colloidal particles. Such silver halide sols of reduced charge are then coagulated by smaller amounts of electrolytes than the same sols in the absence of gelatin. For very large concentrations of gelatin, close to the gel point, coagulation occurred wheter sols were aged orin statu nascendi.

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Zusammenfassung Es wurde die Wechselwirkung zwischen Gelatine und AgBr- bzw. AgJ-Solen gleichen Ladungszeichens in Abhängigkeit von der Gelatinekonzentration, dem pH-Wert und der Konzentration an neutralen Elektrolyten untersucht. Zu den Untersuchungen wurden Solein statu nascendi und gealterte Sole verwendet. Bei Solenin statu nascendi trat ein Maximum in der Streuintensität auf, das Koagulationsvorgänge anzeigt; bei gealterten Solen wurde ein derartiges Maximum erst bei höherenPh-Werten beobachtet, wenn ausreichende Mengen an Elektrolyt und Gelatine vorhanden waren. Bei sehr hohen Gelatine-Konzentrationen (im Bereich um den Gelpunkt) tritt die Koagulation sowohl in gealterten wiein statu nascendi-Solen ein.Es wird angenommen, daß die Gelatine die wirksame Oberflächenladungsdichte der kolloidalen Partikel ver-ringert. Derartige Silberhalogenidesole mit verringerter Oberflächenladung werden dann durch geringere Mengen von Elektrolyt ausgefällt als dieselbe Sole bei Abwesenheit von Gelatine.

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With 8 figures

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Supported by the Federal Water Pollution Control Administration Grant WP-00815 and by the U. S. Army Research Office (Durham), Grant No. DA-ARO (D)-31-124-G 656.

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Presented at the 153. ACS National Meeting, Miami Beach, Florida, April 1967.

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Part of the M. S. Thesis byR. Nemeth     

Synthesis and conformation of some 2,4-dioxa- and 2,4-dioxa-3-silabicyclo[3.3.1]nonanes

The conformation of the title compounds established by ¹³C and ¹H NMR spectroscopy shows that replacement of the 2- and 4-methylene groups in bicyclo[3.3.1]nonane by ether oxygen atoms strongly destablizes the cc conformation: in 2-oxabicyclo[3.3.1]-nonane the cc and the bc conformers are about equally populated, whereas in 2,4-dioxabicyclo[3.3.1]nonane the bc conformation predominates. The 2,4-dioxa-3-silabicyclo[3.3.1]nonanes also occur predominantly inthe bc conformation. As in the carbocyclic bicyclo[3.3.1]nonanes both wings are strongly flattened. A stereoselective synthesis of 3-methylbicyclo[3.3.1]nonane, an important model compound in this study, is described.     

Ph~2C(OH)CH=CHSnAr~3的卤化物的合成、表征和性质

首次以非碳环醇(Z)-3-三芳基锡基-1,1-二苯基-2-丙烯基-1-醇[Ph~2C(OH)CH=CHSnAr~3]和卤素或拟卤素发生取代反应得到卤化物,并以此合成了氢氧化物、氧化物和配合物。通过元素分析、IR和^1HNMR等对上述17种新化合物的结构进行了表征,并提出了卤化物的性质。