Selected Reaction of (Z)-Dimethyl α-(Bromomethyl) Fumarate with Secondary Amines

Regioselective reaction of (Z)-dimethyl α-(bromomethyl) fumarate 2 with bulky secondary amines in ether as solvent at room temperature, leads exclusively to the rearranged substitution α-(functional alkyl amino) acrylic esters 4a-i in high yields. The less and more bulky amine gives rise respectively to the two successive (S_N2′) and (S_N2) substitution derivatives 5j,k and 51.     

Reaction of α-Pinene with Haloacetic Acids

The reactions of -pinene with chloro-, bromo-, and trichloroacetic acids, accompanied by isomerization of -pinene, were studied.     

Synthesis of trifluoromethyl derivatives of pyrrole. Reaction of α,β-unsaturated trifluoromethyl ketones with sodium cyanide

An efficient preparative procedure was developed for the synthesis of 5-hydroxy-5-trifluoromethyl-2-pyrrolidones by the reaction of ,-unsaturated trifluoromethyl ketones with sodium cyanide. Dehydration of these reaction products under mild conditions afforded previously unknown 5-trifluoromethyl-3-pyrrolin-2-ones.     

Reaction of α-hydroxyiminoacetonitrile oxides with potassium thiocyanate

Potassium thiocyanate reacts with substituted -hydroxyiminoacetonitrile oxides in acetic acid to give, unexpectedly, 5-(carbamoyl)imino-²-1,4,2-oxathiazo-lines. The structure of 3-(1-adamantyl)-5-(carbamoyl)imino-²-1,4,2-oxathiazo-line has been confirmed by x-ray diffraction.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 885–889, April, 1991.     

Reaction of 1-(2-Oxocyclohexyl)ethane-1,1,2,2-tetracarbonitrile with α,β-Unsaturated Aldehydes

Russian Journal of General Chemistry - The reaction of 1-(2-oxocyclohexyl)ethane-1,1,2,2-tetracarbonitrile with crotonic aldehyde, cinnamic aldehyde, 2-furylacrolein, 3-phenyl-2-propinal,...     

Reaction of α-carbanions of lithium acylates with 1,2-dibromoethane

The reaction of 1,2-dibromoethane with α-carbanions of lithium acylates generated from acetic, butyric, isobutyric, and capronic acids with lithium diisopropylamide has been studied. Anion-radical and anionic pathways of the products formation have been discussed.     

The Reaction of 1-Aryl-2-(4-nitrophenylsulfonyl)ethanones with α,β-Unsaturated Esters

1-Aryl-2-(4-nitrophenylsulfonyl)ethanones (1) reacted with one equiv. of α,β-unsaturated esters at 60°C to afford the tandem addition-rearrangement products (3), while at 75°C 1a reacted with two equiv. of methyl acrylate and gave an unexpected addition-rearrangement-addition-annulation product which is dimethyl 4-hydroxyl-1-(4-nitrophenyl)-4-phenyl-1,3-cyclohexyldicarboxylate (4). A mechanism is suggested.     

The Reaction of 1-Nitro-4-(4-nitrophenylsulfonylmethyl)benzene with α,β-Unsaturated Esters

Under solid-liquid PTC conditions, treatment of 1-nitro-4-(4-nitrophenylsulfonyl-methyl)benzene(1) with α,β -unsaturated esters (2a-h) at 35–75°C gave tandem addition-rearrangement products(3a-h). While at higher temperature(75°C), addition-rearrangement-addition products (4a-b) were obtained when acrylates were used. Finally a possible mechanism is proposed.     

Reaction of 2-Alkoxypropenals with α-Hydroxyamino Oximes and 1,2-Bis(hydroxyamino)cyclohexane

Reactions of 2-alkoxypropenals with α-hydroxyamino oximes in neutral medium involve the aldehyde group of the former to afford both acyclic and cyclic azomethine oxides: N-(2-hydroxyiminoalkyl)-N-(2-alkoxy-2-propenylidene)amine oxides and 1-hydroxy-2,5-dihydroimidazole 3-oxides. The state of tautomeric equilibrium between the cyclic and acyclic products depends on the solvent nature and temperature. The reaction in acidic aqueous medium is accompanied by hydrolysis of the vinyl ether moiety in 2-alkoxy-propenals with formation of 2-oxopropionaldehyde which reacts with α-hydroxyamino oxime at the hydroxy-amino group to give substituted pyrazine 1,4-dioxides. The reaction of 2-alkoxypropenals with 1,2-bis-(hydroxyamino)cyclohexane leads to formation of 2-(1-alkoxyvinyl)-1,3-dihydroxyperhydrobenzimidazoles. The structure of the products was proved by IR, UV, and ¹H and ¹³C NMR spectroscopy and X-ray analysis.     

Reaction of Lithium Acylate α-Carbanions with Carbon Tetrabromide

Russian Journal of Organic Chemistry - Lithium acylate α-carbanions generated by metalation of acetic, butanoic, and 2-methylpropanoic acids with lithium diisopropylamide in THF under argon...     

Reaction of α-bromolevoglucosenone with 2,2-disubstituted 1,3-dinitropropanes

2,2-Bis(nitromethyl)decane and 4-methyl-2,2-bis(nitromethyl)pentane reacted with α-bromolevoglucosenone in the presence of a base under ultrasonic treatment to give the corresponding cyclopenta-fused derivatives. Analogous reactions of 1,1-bis(nitromethyl)cycloalkanes with α-bromolevoglucosenone afforded spiro compounds.     

Reaction of Lithium Acylate α-Carbanions with Carbon Tetrachloride

Russian Journal of Organic Chemistry - Metalation of acetic, butanoic, or 2-methylpropanoic acid with lithium diisopropylamide in tetrahydrofuran under argon gave the corresponding lithium acylate...     

Reaction of 2-cyanoethane-1,1,2-tricarboxamide with α-alkylacroleins

In the presence of catalytic amounts of triethylamine 2-cyanoethane-1,1,2-tricarboxamide forms Michael adducts with -alkylacroleins. After two intramolecular cyclizations, the adducts are converted into 5-alkyl-6-amino-4-hydroxy-7-carbamoyl-2-oxo-1-cyano-3-azabicyclo[3.2.1]oct-6-enes.I. N. Ul'yanov Chuvash State University, Cheboksary. Institute of Heteroorganic Compounds, Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1326–1330, October, 1996. Original article submitted June 6, 1996.     

Reaction of α-bromocarboxylic acids with hydrazine and dimethylhydrazine

Nucleofilic reaction of a series of α-bromocarboxylic acids with hydrazine and dimethylhydrazine is studied. High reactivity of α-bromocarboxylic acids is revealed and a series of α-hydrazinoarboxylic acids and N-(1-carboxyalkyl)-N,N-dimethylhydrazinium bromides are synthesized.     

The Reaction of (Phenyldimethylsilyl)dichloromethyllithium with Organoboranes. A Synthesis of α-Hydroxyorganosilanes and Ketones

The α-transfer reaction of organoboranes has been utilized to great advantage in the employment of organoboranes in synthesis.² We report here that this process can be used as illustrated in eq 1 to generate α-hydroxyorganosilanes, which can be converted to ketones. This procedure serves to incorporate two of the groups of the organoborane into the product as well as generating the hydroxyl group via oxidation of the newly formed carbon-boron bond.     

Reactions of phenylenedioxytrihalophosphoranes with arylacetylenes: XIII. Reaction of 5-tert-butyl-2,2,2-trihalo-1,3,2λ5-benzodioxaphospholes with acetylenes

Reactions of 5-tert-butyl-2,2,2-trichloro-, 2,2,2-tribromo-5-tert-butyl-, and 2,2-dibromo-5-tert-butyl-2-fluoro-1,3,2λ⁵-benzodioxaphospholes with aryl- and alkylacetylenes lead to quantitative formation of 2-halo-1,2λ⁵-benzoxaphosphinine 2-oxides which may be regarded as phosphorus analogs of natural heterocyclic compounds, coumarin and chromene. The major products (>70%) are 4-aryl-7-tert-butyl-2,6-dichloro-, 4-aryl-2-bromo-7-tert-butyl-, and 4-aryl-7-tert-butyl-2-fluoro-1,2λ⁵-benzoxaphosphinine 2-oxides. Hydrolysis of these compounds and their treatment with amines gives the corresponding 2-hydroxy and 2-amino derivatives, as well as ammonium salts. The structure of some compounds was proved by X-ray analysis.