Oxazinone Derivative Research Articles

Asymmetric synthesis of all four stereoisomers of 1-amino-3-hydroxy-cyclopentane-1-carboxylic acid

An asymmetric synthesis of all four stereoisomers of 1-amino-3-hydroxy-cyclopentane-1-carboxylic acid based on a chiral glycine equivalent, oxazinone derivative is presented. The crucial point of the performed reactions is the alkylation of (S)- and (R)-glycine equivalent with the respective stereoisomers of 4-(2-iodoethyl)-1,3,2-dioxathiolan-2-oxide using phosphazenic base t-BuP4.

ChemInform Abstract: Broensted Base‐Catalyzed Tandem Isomerization—Michael Reactions of Alkynes: Synthesis of Oxacycles and Azacycles.

AbstractAlkylidenetetrahydrofurans (II), ‐piperidines, ‐lactams, and an oxazinone derivative are prepared from the appropriate hydroxy‐ or amino‐substituted alkynes by use of the strong bicyclic guanidine base TBD as catalyst.

Synthetic utility of enaminoester moiety in heterocyclic synthesis

Thieno[2,3-b]pyridine-2-carboxylate was utilized to construct a variety of new heterocyclic systems such as thienopyrimidinone, thienopyridine and pyridothienoxazinone derivatives. Treatment of pyridothienoxazinone derivative with some other nitrogen nucleophiles afforded 3-substituted-pyridothienopyramidinone derivatives. Secondary amines such as morpholine, piperidine and N-methylaniline reacted smoothly with the oxazinone derivative. When the oxazinone derivative was allowed to react with ethanol containing few drops of pyridine or formamide as a basic catalyst and heated to reflux, afforded thienopyridine ester. All the compounds were fully characterized by means of IR, MS, 1 H NMR spectra and elemental analyses.

Synthesis, structure and reactivity of amino-benzodifurane derivatives

Abstract The reactivity of amino groups of some dialkyl esters of 2,6-diamino-benzo[1,2-b:4,5-b′]difuran-3,7-dicarboxylic acid towards acylic reactants was investigated. The easy and chemoselective obtainment of the N,N′-acetyl- and N,N′-benzoyl-derivatives makes the diamino compounds suitable monomers to prepare polymers with tunable chemo-physical behavior. Two novel polyamides, potentially useful for applications in the field of organic electronics, were synthesized and their properties examined. Single crystal X-ray analysis was performed on some of the prepared compounds, thus obtaining information on the extent of electronic conjugation. The obtainment of an oxazinone derivative by cyclization reaction of an N,N′-benzoyl ester was also described.

Anti-inflammatory activity of heterocyclic systems using abietic acid as starting material

A series of pyridines, pyrimidinone, oxazinones, and their derivatives were synthesized as anti-inflammatory agents using abietic acid (7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,4b,5,6,10,10a-decahydrophenanthrene-1-carboxylic acid) as the starting material. The arylidiene derivative was treated with cyanothioacetamide to give cyano pyridine-thione, which was reacted with ethyl chloroacetate to yield the corresponding cyano ester. The ester was hydrolysed to the sodium salt, which was reacted with acetic anhydride to afford 2-methyloxazinone, which was treated with ammonium acetate to afford 2-methylpyrimidinone followed by methylation with methyl iodide to yield 2,3-dimethyl- pyrimidinone. In addition, the oxazinone derivative was reacted with aniline or hydrazine hydrate to give 3-phenyl- or 3-aminopyrimidinones. The latter reacted with thiophene-2-carboxaldehyde or phenylisothiocyanate to afford Schiff’s bases or thiosemicarbazide derivatives. The pharmacological screening showed that many of these compounds have good anti-inflammatory activity comparable to Prednisolone® as reference drug.

Synthesis, Reactions, and Anti-inflammatory Activity of Heterocyclic Systems Fused to a Thiophene Moiety Using Citrazinic Acid As Synthon

A series of pyridines, pyrimidinones, and oxazinones were synthesized as anti-inflammatory agents using citrazinic acid (2,6-dihydroxyisonicotinic acid) as a starting material. Acryloyl pyridine was treated with cyanothioacetamide to give cyano pyridine-thione, which was reacted with ethyl chloroacetate to yield the corresponding amino ester. The ester was hydrolysed to the sodium salt, which was treated with acetic anhydride to afford 2-methyloxazinone, which was treated with ammonium acetate to afford 2-methylpyrimidinone followed by methylation with methyl iodide to yield 2,3-dimethylpyrimidinone. In addition, the oxazinone derivative was reacted with aniline or hydrazine hydrate to give 3-phenyl- or 3-aminopyrimidinones. The latter reacted with thiophene-2-carboxaldehyde or phenylisothiocyanate to afford Schiff’s bases or thiosemicarbazides. 3-Aminopyrimidinone was treated with phthalic anhydride or 1,2,4,5-benzenetetracarboxylic acid dianhydride or toluene-3,5-diisocyanate to afford the corresponding imide, bis-imide, and bis-semicarbazide derivatives. The pharmacological screening showed that many of these compounds have good anti-inflammatory activity comparable to Prednisolone® as reference drug.

Asymmetric synthesis of L‐[4‐13C]lysine by alkylation of oxazinone derivative as a chiral glycine equivalent

AbstractL‐[4‐13C]Lysine (2) was synthesized from sodium [2‐13C]acetate (3) and Dellaria's oxazinone 1 as a chiral glycine equivalent. Wittig reaction of the glycinal 7 and 13C‐labeled phosphonium ylide 5, prepared from sodium [2‐13C]acetate (3), gave the α, β‐unsaturated ester 8. The ester 8 was converted to the allylic bromide 10. Alkylation of the oxazinone 1 with 10 proceeded with high diastereoselectivity. Ethanolysis, hydrogenation of the double bond with diimide, removal of the chiral auxiliary, and hydrolysis gave L‐[4‐13C]lysine (2). Copyright © 2004 John Wiley & Sons, Ltd.

Highly enantioselective synthesis of a fluorescent amino acid

A high enantiomeric excess (>99.5%) synthesis of l-2-amino-3-(7-methoxy-4-coumaryl) propionic acid (l-Amp) is described. The two step synthesis route of this non-proteinogenic amino acid includes an oxazinone derivative as glycine enolate, which is alkylated with the fluorogenic group.

Synthesis of Novel Pyridothienopyrimidines, Pyridothienopyrimidothiazines, Pyridothienopyrimidobenzthiazoles and Triazolopyridothienopyrimidines

AbstractThe reaction of 3‐amino‐4,6‐dimethylthieno[2,3‐b]pyridine‐2‐carboxamide (1a) or its N‐aryl derivatives 1b‐d with carbon disulphide gave the pyridothienopyrimidines 2a‐d, whilst when the same reaction was carried out using N1‐arylidene‐3‐amino‐4,6‐dimethylthieno[2,3‐b]pyridine‐2‐carbohydrazides (1e‐h), pyridothienothiazine 3 was obtained. Also, refluxing of 1b‐d with acetic anhydride afforded oxazinone derivative 4. Compounds 2a and 2b‐d were also obtained by the treatment of thiazine 3 with ammonium acetate or aromatic amines, respectively. When compound 2a was allowed to react with arylidene malononitriles or ethyl α‐cyanocinnamate, novel pyrido[3″,2″:4′,5′]thieno[3′,2′:4,5]pyrimido[2,1‐b][1,3] thiazines 5a‐c were obtained. Treatment of 2b‐d with bromine in acetic acid furnished the disulphide derivatives 6a‐c. U.V. irradiation of 2b‐d resulted in the formation of pyrido[3″,2″:4′,5′]thieno[3′,2′:4,5]pyrimido[2,1‐b]benzthiazoles 7a‐c. The reaction of 2a‐d with some halocarbonyl compounds afforded the corresponding S‐substituted thiopyrido thienopyrimidines 8a‐j. Compound 8b was readily cyclized into the corresponding thiazolo[3″,2″‐a]‐pyrido[3′,2′:4,5]thieno[3,2‐d]pyrimidine 9 upon treatment with conc. sulphuric acid. Heating of 2a,b with hydrazine hydrate in pyridine afforded the hydrazino derivatives 11a,b. Reaction of ester 8c with hydrazine hydrate in ethanol gave acethydrazide 10. Compounds 10 and 11a,b were used as versatile synthons for other new pyridothienopyrimidines 12–15 as well as [1,2,4] triazolopyridothienopyrimidines 16–19.

SYNTHESIS OF THIENOQUINOLINES: PART I. SYNTHESIS OF NOVEL HETEROCYCLO-THIENO[2,3-b]QUINOLINE DERIVATIVES

Abstract Ethyl 3-amino-4-(p-chlorophenyl)-5,6,7,8-tetrahydrothieno[2,3-b]quinoline-2-carboxylate (IIa ) was hydrolysed to the sodium salt of the corresponding acid (III) which upon treatment with acetic anhydride furnished the oxazinone derivative IV. Recyclization of IV with ammonium acetate, hydrazine hydrate and/or aniline afforded the pyrimidine derivatives V, VIII and X respectively. Alkylation of V gave the N-alkylated products VI and VII. Compound VIII condensed with p-nitrobenzaldehyde to give the Schiff base IX. On the other hand, condensation of 3-amino-4-(p-chlorophenyl)-5,6,7,8-tetrahydrothieno-[2,3-b]quinoline-2-carbonitrile (IIb ) with triethyl ortho-formate gave methanimidate derivative XI which reacted with hydrazine hydrate to yield XII. Treatment of XII with formic acid gave s-triazolo compound XIII.3-Amino-4-(p-chlorophenyl)-5,6,7,8-tetrahydro-thieno[2,3-b]quinoline-2-carboxamide (IIc ) was also reacted with phenyl isothiocyanate, phenyl isocyanate, carbon disulfide and/or nitrous acid ...

Molecular Structure Analysis of Monoamine Oxidase Inhibitors IV. Crystal Structure of 3‐[4‐[(3‐nitrophenyl)‐methoxy] phenyl]‐6‐methoxymethyl‐2‐oxazinone: C19H20N2O6

AbstractThis paper is the fourth of a general study of structural properties of a series of new Monoamine Oxidase Inhibitors (MAOI's). The results of the X‐ray crystal structure analysis of an oxazinone derivative are related to and compared with those previously reported for oxazolidinone homologues.

Molecular Structure Analysis of Monoamine Oxidase Inhibitors III. Crystal Structure of 3‐[4 ‐[(3 ‐ Chlorophenyl)‐Methoxy] Phenyl]‐5‐(Methoxymethyl)‐2‐Oxazolidinone: C18H18NO4Cl.

This paper is the fourth of a general study of structural properties of a series of new Monoamine Oxidase Inhibitors (MAOI's). The results of the X-ray crystal structure analysis of an oxazinone derivative are related to and compared with those previously reported for oxazolidinone homologues.

Reaction of Group IV Organometallic Compounds. XXXI. The Reaction of N-Trimethylsilyl- and -stannyl(diphenylmethylene)amine with Diketene

Abstract Linear 1/1 adducts and oxazinone derivative were obtained by the reaction of N-trimethylsilyl- and -stannyl(diphenylmethylene)amine; Ph2C=N–MMe3 (M=Si, Sn) with diketene. Consecutive demetallation reaction by ethanethiol for the organostannyl 1/1 adduct, and by methanol for the organosilyl 1/1 adduct gave a piperidine derivative and an oxazinone derivative, respectively.