A new reaction of vicinal sulfonyliminocarboxylates with phosphites

The reaction of alkyl trifluoro(organylsulfonylimino)propionates with phosphites occurs with NC transfer of the RSO₂ group and leads to sulfonyl-substituted trifluoroalanine derivatives. The novel rearrangement is interpreted as cheletropic 1,4-cycloaddition of the phosphite and subsequent 1,2-shift of the sulfonyl group in the intermediate cyclic phosphorane.     

Organophosphorus chemistry,XII. Reaction of furil with alkyl phosphites and ylide-phosphoranes

Summary The reaction of furil (1) with trialkyl phosphites2 yielded caged phosphorane derivatives of types3a-c. Dry hydrogen chloride gas converted3a-c into the respectivea-hydroxyvinyl-phosphates8a-c which are equally produced by reacting furil with the appropriate dialkyl phosphite7. The reaction of furil with ylide-phosphoranes10 proceeded according to the Wittig reaction mechanism to give the respective ethylenes11a-c. The new compounds have been characterized by their spectroscopic data (IR, PMR,³¹P-NMR, MS) and elementary analyses.Dedicated to Prof. M. Sidky on the occasion of his 60th birthday     

Synthesis and structure of the 1,2-isopropylidene-α-D-glucofuranose 3,5,6-bis-cyclophosphite complex with tungsten(0) pentacarbonyl

Metallocomplexes with optically active ligands are of considerable interest as catalysts of stereoselective processes. A complex of 1,2-isopropylidene-α-D-glucofuranose 3,5,6-bis-cyclophosphite with tungsten(0) pentacarbonyl has been synthesized for the first time and studied by X-ray crystallography.     

Synthesis of Some Dialkyl Bromo-Substituted Benzyl Phosphonates

Arbuzov reaction of bromo-substituted benzyl bromides and trialkyl phosphites in benzene gave high yields of dialkyl bromo-substituted benzyl phosphonates, and —CH₂CH₂CH₂CH₃). The structural assignments of these phosphonates were confirmed by ¹H nmr, ¹³C nmr, ir and mass spectral analysis.     

2-Cyanoacrylates in the conjugate addition of trifluoroacetic acid and nucleophilic reagents

In the presence of trifluoroacetic acid, ethyl 2-cyanoacrylate readily reacts with nucleophilic reagents, such as 2-chloro-1,3,2-benzodioxaphosphole, (EtO)₃P, (EtO)₂PCl, Ph₂PCl, Ph₃P, and thiourea. In these reactions the acid proton enters position 2 of the cyanoacrylate, whereas the nucleophilic component enters position 3, in accordance with the electron density distribution in the acrylate. In the absence of trifluoroacetic acid the above reagents, except 2-chloro-1,3,2-benzodioxaphosphole, cause ethyl 2-cyanoacrylate polymerization. The interaction of ethyl 2-cyanoacrylate with 2-chloro-1,3,2-benzodioxaphosphole and trifluoroacetic acid is the first example of a 2-cyanoacrylate taking part in the acid-initiated electrophilic conjugate addition of a weak nucleophile.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1245–1247, July, 1993.     

A first <Emphasis Type="Italic">P,N</Emphasis>-bidentate phosphite with a chiral ketimine fragment. Catalytic properties of its Rh<Superscript>I</Superscript> and Pd<Superscript>II</Superscript> complexes in comparison with those of phosphine analogs

A chiral P,N-bidentate aryl phosphite ligand containing peripheral (R)-(+)-camphor-derived ketimine and its rhodium(I) and palladium(II) chelate complexes were synthesized for the first time. These compounds were found to be suitable for asymmetric allylic substitution. The Pd-catalyzed sulfonylation of 1,3-diphenylallyl acetate with sodium p-toluenesulfinate gave the product in 73% ee; in the alkylation of the same substrate with dimethyl malonate, the ee was 94%. These ee values are higher than the enantioselectivity achieved with the known phosphine analogs.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1942–1945, September, 2004.     

Building three-dimensional metal phosphites from the corner-shared four-membered rings chain

Three new compounds, a one-dimensional (1D) zinc phosphite, (C₄H₈N₂H₄)[Zn(HPO₃)₂] (I), two three-dimensional (3D) metal phosphites (C₄H₈N₂H₄)[Zn₃(HPO₃)₄] (II) and (C₄H₈N₂H₄)[Zn_(3−x)Co_x(HPO₃)₄(H₂O)₂] (x≈0.83) (III) have been synthesized under hydrothermal conditions templated by piperazine and characterized by single-crystal X-ray diffraction, XRD, IR, UV-vis spectra and SQUID magnetometer. Compound I displays 1D chain-like structure, containing corner-shared (cs) four-membered rings. Interestingly, the structures of II and III show 1D chains similar to those observed in I. It is noteworthy that III represents the first cobalt-substituted zinc-phosphite. Crystal data: I, monoclinic, C2/c, a=17.748(2) Å, b=7.428(9) Å, c=8.8071(11) Å, β=105.345(3)°, V=1091.9 Å³, Z=4. II, Monoclinic P2₁/c, a=9.9435(4) Å, b=10.1438(3) Å, c=17.8164(5) Å, β=95.665(2)°, V=1788.27 Å³, Z=4, and III, Monoclinic P2₁/c, a=7.2338(2) Å, b=15.0238(5) Å, c=9.2153(3) Å, β=107.741(2)°, V=953.88(5) Å³, Z=2.     

Reaction of α-cyanoacrylic acid and cyanoacrylates with dialkyl and diaryl phosphites

-Cyanoacrylic acid and -cyanoacrylates add dialkyl and diaryl phosphites and diethyl thiophosphite at the C=C double bond in the absence of catalyst. This is an anti-Markovnikov reaction, which yields the corresponding phosphonates and thiophosphonates.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1913–1915, August, 1992.     

Synthesis of Some New Triphenylphosphanylidenes,Alkylphosphonates, and Heterocycles of Pyrazole Derivatives and Their Antimicrobial Activity

Abstract

The reaction of 5(4H)-pyrazolone with phosphorus ylides afforded new triphenylphosphanylidene alkanone derivatives. Moreover, its benzylidene derivative reacted with Wittig–Horner reagents to give the corresponding dialkoxyphosphoryl, alkyl phosphonate, and heterocyclic products. Treatment of pyrazole-4-carbaldehyde with Wittig–Horner reagents and trialkyl phosphites gave the respective alkyl phosphonate adducts. Mechanisms accounting for the formation of the new products are discussed. The biological activity of some of the newly synthesized compounds was also examined.     

A SYNTHETIC ROUTE TO 3-METHYLTHIO-2-ALKANONES STARTING FROM 3-ALKYL-2,4-PENTANEDIONES

Abstract

An efficient preparation of a 3-methylthio-2-alkanone (1) has been realized by the reaction of a 3-alkyl-2,4-pentanedione (8) with one mol-equiv of S-methyl methanethiosulfonate (4) in the presence of excess EtONa in EtOH. Furthermore, treatment of 8 with 4 and K₂CO₃ in refluxing acetone, followed by addition of MeOH and heating the resulting mixture, gave 1 in a high yield. These methods were applied to synthesis of pseudoionone.