Hydrogenation/Regioselective C‐Acylation Reaction of Diethyl Coumarin‐3‐phosphonate With NaBH4/Acid Anhydrides: A New One‐Pot Tandem Reaction

The one‐pot tandem reaction of diethyl coumarin‐3‐phosphonate 1 with a mixture of sodium borohydride/acid anhydrides gives mainly the corresponding hydrogenation/acylation product of diethyl 3‐acyl‐2‐oxochroman‐3‐ylphosphonates 3a–d in good yields. Different experimental conditions have been examined to get the best yields of the reaction products. From this reaction the hydrogenation product of diethyl 2‐oxochroman‐3‐ylphosphonate, 2, as well as the products of the consecutive hydrogenation, diethyl 2‐hydroxychroman‐3‐ylphosphonate (4) and diethyl 3‐[2‐hydroxyphenyl]‐1‐hydroxy‐propan‐2‐ylphosphonate (5), have been isolated.     

Reaction of diethyl acetonedicarboxylate with nitrosyl chloride

The reaction of diethyl acetonedicarboxylate with greater than two equivalents of nitrosyl chloride or the reaction of diethyl isonitrosoacetonedicarboxylate with one equivalent of nitrosyl chloride gave diethyl 4-hydroxyisoxazole-3,5-dicarboxylate in quantitative yield. Mechanistic possibilities are discussed.     

Reaction of Diethyl Vinylphosphonate with Benzimidazole and 2-Aminobenzimidazole

Benzimidazole reacted with diethyl vinylphosphonate to give diethyl 2-(1H-benzimidazol-1-yl)- ethylphosphonate. The addition of 2-aminobenzimidazole to vinylphosphonate involved the endocyclic nitrogen atom with formation of diethyl 2-(2-imino-2,3-dihydro-1H-benzimidazol-1-yl)ethylphosphonate.     

Reaction of 4,4-Dimethyl-1,3-dioxane with Dinitriles

The reaction of 4,4-dimethyl-1,3-dioxane with bis(2-cyano)diethyl ether or 1,2-di(beta-cyanoethoxy)ethane yields the corresponding bis[2-(4,4-dimethyl-5,6-dihydro-2-oxazinyl)]diethyl ether and 1,2-di{beta-[2-(4,4-dimethyl-5,6-dihydro-2-oxazinyl)]ethoxy}ethane which are readily hydrolyzed under the action of aqueous alkali to give 3-methyl-3-amino-1-butanol.     

Reaction of acetylacetone with diethylphosphorous acid

Conclusions The reaction of equimolar amounts of acetylacetone and diethylphosphorous acid at room temperature in the presence of sodium alcoholate gives the diethyl ester of 1-methyl-1-hydroxy-3-ketobutylphosphonic acid. When heated or when treated with water-removing agents the latter cleaves water with the formation of the diethyl ester of 1-methyl-3-keto-1-buten-1-yl-phosphonicacid. The reaction of two moles of diethyl-phosphorous acid with one mole of acetylacetone under the same conditions gave 2-oxo-2-ethoxy-3,5-dimethyl-3-hydroxy-5-diethoxyphosphono-1-oxa-2-phospholane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2757–2761, December, 1971.We wish to thank T. A. Zyablikova and É. I. Gol'dfarb, co-workers at the A. E. Arbuzov Institute of Organic and Physical Chemistry of the Academy of Sciences of the USSR, for taking the NMR spectra.     

The Pseudo‐Michael Reaction of 2‐Hydrazinylidene‐1‐Arylimidazolidines with Diethyl Ethoxymethylenemalonate

The pseudo‐Michael reaction of 2‐hydrazinylidene‐1‐arylimidazolidines with diethyl ethoxymethylenemalonate (DEEM) was investigated. The reaction yields the chain adduct, namely diethyl{[2‐(1‐arylimidazolidin‐2‐ylidene)hydrazinyl]methylidene}propanedioates. This is contrary to the pseudo‐Michael reaction of DEEM with 1‐aryl‐4,5‐dihydro‐1H‐imidazol‐2‐amines that does not allow isolation of chain derivatives and leads to cyclic imidazo[1,2‐a]pyrimidine derivatives while even at thermodynamic control. At first cyclization of diethyl{[2‐(1‐arylimidazolidin‐2‐ylidene)hydrazinyl]methylidene}propanedioates leads to ethyl 1‐aryl‐5(1H,8H)oxo‐2,3‐dihydro‐imidazo[2,1‐c][1,2,4]triazepine‐6‐carboxylates. 1,5‐Sigmatropic shift, following the cyclization, caused isomerization of 5(1H,8H)oxo‐2,3‐dihydro‐imidazo[2,1‐c][1,2,4]triazepine‐6‐carboxylates to ethyl 1‐aryl‐5(1H)hydroxy‐2,3‐dihydroimidazo[2,1‐c][1,2,4]triazepine‐6‐carboxylates. Presence of both isomers in the reaction product was detected in the NMR spectra. The structure of all the compounds was confirmed with spectroscopic studies (¹H NMR and MS). The structure of diethyl{[2‐(1‐phenylimidazolidin‐2‐ylidene)hydrazinyl]methylidene}propanedioate was also confirmed by X‐ray crystallography. In the addition reaction, thermodynamics and HOMO–LUMO orbitals of the reactants were studied by using quantum chemical calculations.     

Reaction of 3-aminoindole-2-carboxylic acids with diethyl acetylenedicarboxylate

-Carboline and indolo--carboline derivatives were obtained by reaction of the potassium salts of 3-aminoindole-2-carboxylic acids with diethyl acetylenedicarboxylate. A difference in the behavior of 3-aminoindole derivatives in the Michael reaction due to the nature of the substituent in the 5 position of the indole ring was established.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 82–84, January, 1977.     

Manganese(III) Acetate Initiated Oxidative Free Radical Reaction between 2-Anilino-1,4-naphthoquinones and Diethyl Malonate

A free radical reaction between 2-anilino-1,4-naphthoquinones and diethyl malonate initiated by manganese (III) acetate is described. This reaction provides a novel method for the synthesis of 5,6,11,12-tetra-hydro-6,11-dioxo-benzo[b]acridines. With a meta substituent on the anilino group, this reaction shows poor to high regioselectivity depending on the steric effect of the substituents on the anilino group and malonate.     

Reaction of Diethyl Chloroethynylphosphonate with 3-Amino-1,2,4-triazoles

Russian Journal of General Chemistry - A series of new 6-phosphonylated 1H-imidazo[2,1-c][1,2,4]triazoles was synthesized by the reaction of diethyl chloroethynylphosphonate with 2-substituted...     

Synthesis of Arylhydrazines by Reaction of Arylbromides with DEAD via Sonochemical Barbier Reaction

A series of arylhydrazines was synthesized from the reaction mixture of Mg powder, 1,2‐dibromoethane, aryl bromide and DEAD (diethyl azodicarboxylate) in THF under ultrasound. This sonochemical Barbier reaction provides an efficient and inexpensive preparation method for synthesis of arylhydrazines.     

Reaction of H-Phosphonate Diesters with Trityl Halides

Abstract

A study on the reaction of H-phosphonate diesten with trityl halides under different reaction conditions has been performed. The reactions were evaluated using 31P NMR spectroscopy. For the study we selected simple H-phosphonate diesters, i.r. diphenyl H-phosphonate and diethyl H-phosphonate. Depending on the reaction conditions used the products obtained differed substantially. Formation of C-phosphonate 1 vs 2 depended primarily on the kind of trityl derivative used for the reaction.     

Reaction of diethyl (phthalimidoacetyl)malonate with hydroxylamine

The reaction of diethyl (phthalimidoacetyl)malonate with hydroxylamine was investigated. Depending upon the reaction conditions, N-phthaloylglycinehydroxamic acid ( 2 ) and the cyclized product, 4-ethoxycarbonyl-5-hydroxy-3-(phthalimidomethyl)isoxazole ( 4 ), were obtained.     

Reaction of 3-Methyleneisocamphanone with Derivatives of Malonic Acid

Reaction of 3-methyleneisocamphanone with malononitrile, ethyl cyanoacetate or diethyl malonate in the presence of catalytic quantities of alkali or under catalysis with tetramethylguanidine in ethanol proceeds according to classical scheme of the Michael reaction and gives rise to 3-exo-(2,2-dicyanoethyl)-, 3-exo-(2-cyano-2-ethoxycarbonylethyl)-, or 3-exo-(2,2-diethoxycarbonylethyl)isocamphanone respectively. When the reaction with ethyl cyanoacetate and diethyl malonate is carried out in methanol occurs transalkylation of the ester groups resulting in the corresponding methyl esters, and in THF occurs hydrolysis to form carboxylic acids. In ethanol or methanol in the presence of equimolar or excess amounts of alkali compounds with cyano groups suffer cyclization into the corresponding 2-alkoxy-3-cyano- or 1-alkoxy-3-alkoxycarbonyl-7,7,8-trimethylbicyclo[2.2.1]hepteno[2.3-b]pyridines. In THF partially form analogous tricyclic 2-hydroxypyridines.     

4-Hydroxy-2-quinolones. 112. Reaction of 2-ethoxycarbonylmethyl-4H-3,1-benzoxazin-4-one with active methylene compounds

The reaction of 2-ethoxycarbonylmethyl-4H-3,1-benzoxazin-4-one with malononitrile in dry pyridine leads to 1-hydroxy-3,6-dioxo-4,6-dihydro-3H-pyrimido[1,2-a]quinoline-5-carbonitrile. Acetoacetic and cyanoacetic esters under analogous conditions form anilides of 4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acid while diethyl malonate gives N,N′-di-2-carboxyanilides of malonic acid. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 75–79, January, 2007.     

Reaction of 2,7-dialkyl- and 1,2.7-trialkyldecahydro-4-quinolones with triethylaluminum

The reaction of triethylaluminum with stereoisomeric 2,7-dimethyl- and 1,2,7-trimethyldecahydro-4-quinolones and their 7-tert-butyl-substituted analogs was studied. The reaction of triethylaluminum with ketones that have an equatorial 2-CH₃ group proceeds in two directions — reduction of the carbonyl group to an alcohol group and alkylation to give tertiary 4-ethyl-substituted alcohols — in benzene. depending on the reagent ratio. The stereochemistry of the reduction of the carbonyl group depends on the temperature. Only an alkylation product is formed in tetrahydrofuran (THF) and diethyl ether. The reaction of triethylaluminum with ketones that have an axial 2-CH₃ group depends on the nature of the solvent. Epimeric secondary alcohols are formed in toluene at various ratios of the reacting substances, whereas tertiary ethyl-substituted alcohols are formed in THF and diethyl ether.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 946–952, July, 1976.     

Reaction of aryl-substituted glycineamidines with oxalic acid derivatives

The reaction of N¹,N²-diaryl-N-arylglycineamidines with oxalyl chloride and diethyl oxalate leads to 1,4-diaryl-5-aryliminopiperazine-2,3-diones and 1,3-diaryl-4-aryliminoimidazolidin-2-ones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 230–232, January, 1991.     

Chemistry of heterocyclic N-oxides and related compounds. 10. Reaction of pyridine N-oxide with 4-methyl- and 4-phenyl-substituted hantzsch esters

The corresponding dehydrogenation products were obtained in the reaction of diethyl 1,4-dihydro-2,4,6-collidine-3,5-dicarboxylates and diethyl 1,4-dihydro-4-phenyl-2, 6-lutidine-3,5-dicarboxylate with pyridine N-oxide. The reaction with dihydrocollidine is accompanied by simultaneous demethylation in the 4 position and methylation of the pyridine ring.See [1] for Communication 9.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 652–654, May, 1979.     

Sequential Intramolecular Diels–Alder Reaction of 3‐Heteroaryl‐2‐propenylamides of Ethenetricarboxylate

The reaction of 1,1,2‐ethenetricarboxylic acid 1,1‐diethyl ester with E‐3‐(2‐furyl)‐2‐propenylamines under the amide condensation conditions (EDCI/HOBt/Et₃N) on heating at 80–110°C afforded cis‐fused tricyclic compounds, furo[2,3‐f]isoindoles as major product. On the other hand, the reaction with E‐3‐(3‐furyl)‐2‐propenylamines afforded trans‐fused tricyclic compounds predominantly. The formation of amide/[4 + 2] cycloaddition/hydrogen‐shift reactions proceed sequentially. The observed stereoselectivity of the fused rings has been investigated by the density functional theory calculations. The reaction of 1,1,2‐ethenetricarboxylic acid 1,1‐diethyl ester with 3‐(3‐pyridinyl)‐2‐propen‐1‐amine under the amide condensation conditions afforded HOBt‐incorporated 3,4‐trans‐pyrrolidine selectively. The chemoselectivity and stereoselectivity of the reactions with (3‐heteroaryl)‐2‐propen‐1‐amines depend on the nature of heteroarenes.     

Reaction of Mono- and Dihaloalkanes with Mixed Solutions of Chalcogens in Alkaline Reductive Systems

Sufur-selenium, sulfur-tellurium, selenium-tellurium, and sulfur-selenium-tellurium mixtures readily dissolve in the hydrazine hydrate-alkali system to form chalcogenide anions. Alkylation of the latter with ethyl bromide results in preferential formation of diethyl disulfide, diethyl diselenide, and diethyl ditelluride. Tellurium reacts with dichloromethane in the presence of sulfur, yielding poly(methylene ditelluride), the reaction in the presence of selenium gives rise to poly(methylene selenotellurides), while in the sulfurselenium-tellurium mixture polymers containing all the components are formed.     

4-Hydroxy-2-quinolones. 107. Reaction of triethyl methanetricarboxylate with indoline

The first stage of the reaction of triethyl methanetricarboxylate with indoline is the formation of the diethyl ester of 2-(indoline-1-carbonyl)malonic acid, which then, depending on the conditions selected, may be converted into the ethyl ester of 2-(indoline-1-carbonyl)-3-(indolin-1-yl)-3-oxopropionic acid, methanetri-N-(indolin-1-yl)carboxamide, or the ethyl ester or (indolin-1-yl)amide of 1-hydroxy-3-oxo-5,6-dihydro-3H-pyrrolo[3,2,1-ij]quinoline-2-carboxylic acid. __________ Translated From Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1191–1197, August, 2006.