Reaction of 2-chloro(bromo)-3-phenyl-1,3,2-oxazaphospholanes with acyl halides

Conclusions The 2-chloro(bromo)-3-phenyl-1,3,2-oxazaphospholanes react with acyl halides, with opening of the oxazaphospholane ring and the formation of alkyl dihalophosphite derivatives. The latter are heat unstable and when heated they decompose with the liberation of the N-phenyl-N-(-haloethyl)acetamide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2161–2163, September, 1977.     

Electrochemical oxidation of 1-chloro(bromo)-2,2,6,6-tetramethylpiperidines

Electrochemical oxidation of 1-haloamines of the 2,2,6,6-tetramethylpiperidine series results in the formation of relatively stable radical-cations, detected by the methods of cyclic voltammetry and ESR spectroscopy. The final products of electrochemical oxidation of these haloamines are stable nitroxyl radicals.     

2-Alkyl-3-chloro(bromo)tetrahydrofurans

The reaction ofRS(SR)-2,3-dibromo- and 2,3-dichlorotetrahydrofurans with ethylmagnesium bromide in ether was investigated. It was shown that the main reaction products are 2-ethyl-3-bromotetrahydrofuran (27%) and 3-bromo-2-(2-ethyl-3-tetrahydrofuryl)tetrahydrofuran (65%) in the first case and 2-ethyl-3-chlorotetrahydrofuran (33%) and 3-chloro-2-(3-chloro-2-tetrahydrofuryl)tetrahydrofuran (65%) in the second.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. I. M. Gubkin Moscow Institute of Petroleum and Gas, 111917 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1430–1434, June, 1992.     

Reaction of 9-hydroxy(chloro,bromo)-4-azafluorene to bis[9-chloro(bromo-4-aza-fluoren-9-yl]

4-Aza-fluoren-9-ol and 9-chloro(bromo)-4-azafluorenes are converted in high yields upon refluxing with thionyl chloride to form bis[9-chloro(bromo)-4-azafluoren-9-yl]. At about 20C, azafluorenol and thionyl chloride form 9-chloro-4-azafluorene. Mechanisms are proposed for these reactions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 72–74, January, 1990.     

A general synthesis of 2,5-diaryl-4-chloro (or bromo)oxazoles

Reaction between acyleyanides (ArCOCN) and aldehydes (ArCHO) in the presence of ether and hydrogen chloride (or hydrogen bromide) gives good yields of 2,5-diaryl-4-chloro (or bromo)oxazoles ( 2 ).     

Reaction of 2- and 4-(Acetoxymercuriomethyl)-1-phenylquinolinium Perchlorates with Sodium Ethoxide

Russian Journal of Organic Chemistry -     

Reaction of Epoxides with (Alkylthio)methyl Chloride

The reaction of (methylthio)methylchloride with 1,2-epoxybutane and styrene oxide furnishes eleven and eight compounds, respectively. The probable mechanism of their formation and their mass spectral characterization are presented in this article.     

The Diels-Alder Reaction of Dienes Derived from Substituted 3-(Phenyl-Thio)-3-Sulfolenes

Substituted 3-(phenylthio)-3-sulfolenes (3) and (4) are good precursors for 2-(phenylthio)-1,3-butadienes (5) and (6). The Diels-Alder reaction of the dienes derived from (3) and (4) with various dienophiles was studied. It was found that heating of sulfolenes (3) with methyl propiolate and N-phenylmaleimide afforded the Diels-Alder adducts of (5) directly and with complete regio- and stereospecificity. The same reaction with methyl vinyl ketone gave a mixture of endo and exo addition products. If sulfolenes (3) were first converted to the dienes (5) using lithium aluminum hydride and then reacted with methyl vinyl ketone in the presence of anhydrous zinc chloride, the stereoselectivity could be improved. Sulfolenes (4) also underwent cycloreversion/cycloaddition with methyl acrylate, methyl vinyl ketone, and N-phenylmaleimide, but gave mostly the double bond-isomerized cycloaddition products. The regiochemistry of cycloaddition was delicately dependent on the dienophiles used.     

Method for the preparation of 3β-chloro(bromo)-substituted steroids from the corresponding methyl ethers

Conclusions A stereospecific method was developed for obtaining 3-chloro(bromo)-substituted steroids by treating the appropriate methyl ethers with phosphorus pentahalide derivatives and BF₃·etherate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2825–2827, December, 1970.     

Palladium-catalyzed cross-coupling reactions of 2-iodo-4-(phenylchalcogenyl)-1-butenes

[reaction: see text] 2-Iodo-4-(phenylchalcogenyl)-1-butenes 2 or 3, which are derived from the ring-opening reaction of methylenecyclopropanes (MCPs) 1 by iodine, can be applied to some palladium-catalyzed cross-coupling reactions such as the Sonogashira, Heck, Kumada, Suzuki, and Negishi reactions under mild conditions to give the corresponding coupling products in good yields. These reactions proceeded smoothly at room temperature (20 degrees C) in most cases without any phosphine ligand and additive. The phenylchalcogenyl group plays an important role in the reactions and a plausible reaction mechanism has been proposed.     

Reaction of trihalo(phenylenedioxy)phosphoranes with acetylenes: X. specific features of the reactions of substituted 2,2,2-trichloro-1,3,2λ5-benzodioxaphospholes with 3-chloro(bromo, iodo)propynes

It was shown for the first time that 3-chloro-, 3-bromo-, and 3-iodopropynes can react with 2,2,2-trichloro-, 2,2,2-trichloro-5-methyl-, and 5,6-dibromo-2,2,2-trichloro-1,3,2λ⁵-benzodioxaphospholes to give derivatives of 4-(halomethyl)-2-chloro-2H-1,2λ⁵-benzoxaphosphinin-2-ones. The reaction involves nonselective chlorination of the phenylene substituent in different positions, and the resulting isomer ratio is temperature-dependent. In the reactions of 3-bromo-and 3-iodopropynes with 2,2,2-trichloro-1,3,2λ⁵-benzo-dioxaphosphole, a side process takes place, viz. nucleophilic substitution of bromine and iodine with chlorine. The structure of some of the prepared 4-(chloromethyl)-1,2-benzoxaphosphinines was studied by means of X-ray diffraction.     

(E)- and (Z)-1-benzenesulfonyl-4-trimethylsilyl-2-butenes as (E)-1-(1,3-butadienyl) synthons

(E)- and (Z)-1-benzenesulfonyl-4-trimethylsilyl-2-butenes (E/Z=9), prepared from 4-trimethylsilyl-1-buten-3-ol, $\text{n}$-butyllithium and benzenesulfenyl chloride and oxidation of the intermediate (E)- and (Z)-1-benzenesulfinyl-4-trimethylsilyl-2-butenes with hydrogen peroxide, react with $\text{n}$-butyllithium and then primary halides to give 4-benzenesulfonyl-1-trimethylsilyl-2-alkenes which are rapidly 1,4-debenzenesulfonyltrimethylsilated to (E)-1,3-alkadienes by tetra-$\text{n}$-butylammonium fluoride at O°C.     

Reaction of ethyl 3-(1-adamantyl)-3-oxopropanoate with fluorobenzoyl chlorides

Russian Journal of Organic Chemistry -     

Reaction of 3-(N-phenylamino)-1-p-tolylprop-2-en-1-one with Ru3(CO)12

Russian Chemical Bulletin -     

Reaction of 5-Substituted 2-(3-Chloropropanoylamino)benzophenone syn- and anti-Oximes with Sodium Hydroxide

Treatment of syn-oximes of 5-substituted 2-(3-chloropropanoylamino)benzophenones with equimolar amount of sodium hydroxide results in formation of syn-oximes of 5-substituted 2-propenoylamino-benzophenones. The corresponding anti isomers under the same conditions give a mixture of anti-oximes of 5-substituted 2-(propenoylamino)benzophenones and 18-membered 11,22-disubstituted 7,8,18,19-tetrahydrodibenzo[d,m][1,10,2,6,11,15]dioxatetraazacyclooctadecine-6,17(5H,16H)-diones.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 969–977.Original Russian Text Copyright © 2005 by Andronati, Simonov, Pavlovskii, Kulikov, Gdanec, Mazepa.     

Synthesis of Novel 1-Alkyl-2-chloro（alkoxy）-1H-indole 3-Carbaldehyde Oximes and Oxime-ethers（esters） Derivatives

A convenient synthesis of 1-alkyl-2-chloro-1H-indole-3-carbaldehyde oximes(5a―5d) and 1-alkyl-2-phenoxy-1H-indole-3-carbaldehyde oximes(6a―6d) from 2-indolone was completed via the Vilsmeier-Haack reac-tion,with N-alkylation and oximation as the key steps.An improved one-pot method for the synthesis of 1-alkyl-2-alkoxy-1H-indole-3-carbaldehyde oximes(7a―7h) from 1-alkyl-2-chloro-1H-indole-3-carbaldehydes(3a―3d) was described.The Williamson reactions and esterification reactions were performed and the oxime-...     

The Reaction of Quaternary Ammonium Salts Derived from 2-Aryl-3-(N,N-dimethylamino)-1-propenes with Oxygen Containing Nucleophiles

A variety of quaternary ammonium salts derived from 2-aryl-3-(N, N-dimethylamino)-1-propenes have been converted to the corresponding alkyl and fluoroalkyl ethers by displacement of the ammonium group. This procedure represents an efficient means for the construction of 2-aryl substituted allylic ethers.     

The Reaction of Quaternary Ammonium Salts Derived From 2 Aryl-3-(N,N-dimethylamino)-1-propenes with Some Enoiate Anions

A variety of quaternary ammonium salts derived from 2-aryl-3-(N,N-dimethylamino)-1-propenes have been reacted with enolate anions derived from several activated methylene compounds. The reactions represent clean and efficient methodology for the elaboration of the 2-aryl-1-propene system.