Phosphorus-substituted carbothioamides

Козлов, В. А.; Odinets, Irina L.; Churusova, Svetlana G.; Yarovenko, S. V.; Petrovskii, P. V.; Mastryukova, T. A.

doi:10.1023/b:rucb.0000037865.24497.d8

Cited by 6 publications

(6 citation statements)

References 5 publications

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“…Earlier, we have ob served a similar regularity, i.e., a gradual downfield shift in the 31 P NMR spectra caused by the introduction of the α substituent into phosphorus substituted CH acids, in studies of alkylation and cycloalkylation of nitriles and esters of (thio)phosphorylacetic acids with α,ω dihalo alkanes. 3, 14 The investigation of 2,6 bis(diphenylphos phoryl) 1,2,3,5,6,7 hexahydro s indacene 2,6 dicarbo nitrile (5a) by 31 P NMR spectroscopy demonstrated that this compound exists as cis and trans stereoisomers char acterized by singlets with ∆δ ~0.06. Although we failed to separate these stereoisomers by chromatography or frac tional crystallization, general considerations suggest that the less sterically hindered trans isomer is the major one (cis : trans ≈ 2 : 8).…”

Section: Methodsmentioning

confidence: 99%

Reactions of phosphoryl- and thiophosphorylacetonitriles with poly(bromomethyl)arenes containing closely-spaced bromomethyl groups. New types of phosphorus-substituted fused systems

et al. 2005

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Reactions of phosphoryl and thiophosphorylacetonitriles with poly(bromomethyl)arenes containing closely spaced bromomethyl groups under conditions of phase transfer catalysis occur as cycloalkylation to form new types of fused systems, in which aromatic rings are annelated with a five , six , or seven membered ring containing the exocyclic phosphorus containing and cyano substituents. The reaction pathway is independent of the reagent ratio. Under the same conditions, the reaction with 1,3,5 tris(bromomethyl) 2,4,6 trimethylbenzene affords products of monoalkylation at all electrophilic groups of the starting substrate. In the resulting compounds, the alkoxy groups at the phosphorus atom are easily transformed into the hydroxy groups via the corresponding silyl ethers to give the corresponding phosphorus acids, whereas the cyano group is chemically inert.

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Section: Methodsmentioning

confidence: 99%

Reactions of phosphoryl- and thiophosphorylacetonitriles with poly(bromomethyl)arenes containing closely-spaced bromomethyl groups. New types of phosphorus-substituted fused systems

et al. 2005

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“…Melting points are uncorrected. The starting thioacetamides 2 [10] and diethyl 2-anilino-1-cyano-2-thioxoethylphosphonate 4 [24] were obtained by the known procedures as reported. The assignment of the absorption bands in IR spectra was made according to [25,26].…”

Section: Experimental Generalmentioning

confidence: 99%

“…Recently we published a procedure [10], which would allow for synthesizing high yields of a wide range of phosphorussubstituted carboxylic acid thioamides, which may serve as starting substrates in this reaction.…”

Section: Introductionmentioning

confidence: 99%

Regioselective synthesis, structure and behavior in solutions of novel phosphorylated thiazolidin‐4‐ones

Козлов

Odinets

Lyssenko

et al. 2005

Heteroatom Chemistry

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“…9 Here we present data on their application as annulating agents in reactions with azines. Diethoxy and diphenylphosphorylthio acetamides 1a,b were chosen as the starting organophos phorus substrates and easily accessible 2,3 dichloro quinoxaline and N methylquinoxalinium iodide, as azine components.…”

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“…Thioamides 1a,b, 9 diethoxyphosphorylacetamide, 16 2,3 di chloroquinoxaline, 17 and N methylquinoxalinium iodide 18 were prepared according to known procedures. Their physicochemi cal constants were identical with the literature data.…”

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Phosphorylthioacetamides in the synthesis of annulated quinoxalines

et al. 2007

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Diethoxyphosphorylthioacetamide in the reaction with 2,3 dichloroquinoxaline acted as a thionating reagent, giving diethoxyphosphorylacetonitrile and 2 chloro 3 [(3 chloro 2 quinoxalinyl)thio]quinoxaline. Reactions of phosphorylthioacetamides with N methylquin oxalinium iodide in alcohol media in the presence of a base proceeded stereoselectively to afford cis 3 phosphoryl 1,3,3a,4,9,9a hexahydro 2H pyrrolo[2,3 b]quinoxaline 2 thiones.Key words: phosphorylthioacetamides, 2,3 dichloroquinoxaline, N methylquinoxalinium iodide, annulation, 1,3,3a,4,9,9a hexahydro 2H pyrrolo[2,3 b]quinoxaline 2 thiones.Thioamides of carboxylic acids are widely employed as key precursors for the synthesis of various five and six membered heterocycles. 1 In particular, azines con taining two and more heteroatoms are known to undergo annulation in the presence of thioamides of carboxylic acids (and some other bisnucleophilic reagents). This abil ity of azines is behind convenient routes to complex fused heterocyclic systems that are of particular interest from the viewpoint of biological activity. 2-4However, publications devoted to the reactivities of phosphorylthioacetamides are scarce. 5-8 To the best of our knowledge, they are mainly concerned with (1) alky lation reactions that occur at the sulfur atom 5,6 and sub sequently afford biologically active amidines, (2) the Hantzsch synthesis of phosphorus containing thiazoles, 7 and (3) regioselective condensation with dimethyl acetylenedicarboxylate yielding phosphorus containing thiazolidin 4 ones. 8 Limited data on the chemical prop erties of compounds of this class are largely due to the lack of convenient methods for their preparation.A recently developed, convenient method for the syn thesis of phosphorylthioacetamides with various types of the surrounding of the P atom made these organophos phorus compounds easily accessible. 9 Here we present data on their application as annulating agents in reactions with azines. Diethoxy and diphenylphosphorylthio acetamides 1a,b were chosen as the starting organophos phorus substrates and easily accessible 2,3 dichloro quinoxaline and N methylquinoxalinium iodide, as azine components.Condensation of thioamides RC(S)NH 2 (R = H, Me, and Ph) with 2,3 dichloroquinoxaline has been re ported 10-12 to give 2 substituted thiazolo[4,5 b]quinoxa lines, although the physicochemical constants of the re sulting 2 methyl derivative do not coincide (the melting points of the samples differ by more than 200 °C). Sur prisingly, thioamide 1a in a reaction with 2,3 dichloro quinoxaline 2 acted as a thionating agent. As a result of the reaction of equimolar amounts of the reactants in ethanol in the presence of triethylamine as an acceptor of HCl, 2 chloro 3 (3 chloroquinoxalin 2 ylthio)quin oxaline 3, the starting thioamide 1a, and diethoxy phosphorylacetonitrile were isolated instead of the ex pected thiazolo[4,5 b]quinoxaline (Scheme 1). Scheme 1

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Phosphorus-substituted carbothioamides

Cited by 6 publications

References 5 publications

Reactions of phosphoryl- and thiophosphorylacetonitriles with poly(bromomethyl)arenes containing closely-spaced bromomethyl groups. New types of phosphorus-substituted fused systems

Reactions of phosphoryl- and thiophosphorylacetonitriles with poly(bromomethyl)arenes containing closely-spaced bromomethyl groups. New types of phosphorus-substituted fused systems

Regioselective synthesis, structure and behavior in solutions of novel phosphorylated thiazolidin‐4‐ones

Phosphorylthioacetamides in the synthesis of annulated quinoxalines

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