Synthesis and properties of bis [N-Alkyl(aryl)-aminomethyl]phosphinic acids

Conclusions Reaction of primary aliphatic and aromatic amines with bischloromethylphosphinic acid yielded a series of bis(N-alkyl(aryl)aminomethyl)phosphinic acids and the methacroylamides of several of them were obtained.Translated from Izvestiya Akademii Nauk SSSR, Seriya Kkimicheskaya, No. 8, pp. 1860–1862, August, 1968.     

Synthesis of esters of bis(alkoxymethyl) phosphinic acids

Conclusions A method was developed for the production of esters of bis(alkoxymethyl)phosphonic acids, and some of these esters were synthesized.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 710–716, 1969.     

Synthesis of some derivatives of bis (N,N-dialkylaminomethyl)phosphinic acids

Conclusions A number of derivatives of bis(N,N-dialkylaminomethyl)phosphinic acids have been obtained by the reaction of dialkylamines with esters and amides of bis(chloromethyl) phosphinic acid.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1346–1348, June, 1967.     

Synthesis and fungicidal activity of aryl(arylamino)methylphosphonic acids

A series of aryl(arylamino)methylphosphonic acids were synthesized based on the previous work for the modification of alkylphosphonates. As key intermediates, α-aminophosphonates were synthesized with high yield by a three-component Kabachnik–Fields reaction under solvent-free conditions. The compounds were identified and characterized by infrared, ¹H NMR, ¹³C NMR, mass spectrum, and elemental analyses. Their fungicidal activities against typical fungi occurring in the Chinese agro-ecosystems were evaluated. The results of preliminary bioassays showed that some of the title compounds exhibited moderate fungicidal activities against tomato late blight and cucumber fusarium wilt. For example, compound 3b showed 78% inhibitory activity against tomato late blight, and compound 3h possessed 86% inhibitory activity against cucumber fusarium wilt.     

Dearomatizing anionic cyclizations of N-benzyl-N-methyldiphenylphosphinamides. Synthesis of gamma-(N-methylamino)phosphinic acids

The first dearomatizing anionic reaction of a phenyl ring promoted by an N-benzyl-N-methylphosphinamide group is described. The intermediate lithium species can be trapped with different electrophiles, affording tetrahydrobenzo[c]-1-aza-2lambda(5)-phospholes with excellent diastereoselectivity. The new process is a simple and very efficient entry to the stereoselective synthesis of functionalized gamma-(N-methylamino)phosphinic acids and esters.     

Synthesis of phosphinic analogs of sulfur-containing amino acids

Phosphinic analogs of the key compounds of the metabolism of methionine were synthesized. The compounds obtained were selectively oxidized either at the phosphinic group or at the sulfur-containing fragment. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1360–1363, July, 1999.     

Synthesis and antiviral activity of adamantyl-containing phosphonous and phosphinic acids

The method of adamantly-containing phosphonous and phosphinic acids preparation, based on radical addition of hypophosphorous acid and sodium hypophosphite to unsaturated derivatives of adamantane, has been developed. Unsymmetrical phosphinic acids have been prepared by reacting bistrimetylsilyl esters of phosphonous acids with halides. The obtained phosphinic acids exhibit antiviral activity against herpes simplex virus, influenza A (H5N1), respiratory syncytial virus, and adenovirus.     

Synthesis of phosphinic and phosphonic analogs of aromatic amino acids

The reaction of aryl and aralkyl aldoximes with hypophosphorous acid resulted in aminophosphinic acids, which were oxidized into the corresponding aminophosphonic acids. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 137–140, January, 1997.     

Acylation of α-(N-carbamoyl)alkylcuprates and alkyl- or aryl(halo)cuprates

α-(N-Carbamoyl)alkylcuprates [R₂CuLi·LiX or RCuXLi (X=CN, Cl)] when prepared from THF soluble CuX·2LiCl (X=Cl, CN) undergo a reliable and generally high yield reaction with aroyl, alkanoyl, and alkenoyl chlorides to provide a rapid and efficient synthesis of α-carbamoyl ketones. Cuprates prepared from acyclic, cyclic, and a functionalized carbamate can be utilized. Although yields are a function of cuprate reagent and substrate structure, nearly quantitative yields can be obtained with reagents generated from 2RLi+CuCN·2LiCl. The use of reagents generated from CuCl·2LiCl are more efficient in the α-(N-carbamoyl)alkyl ligand, although yields are slightly lower. Acylation of alkyl(chloro)cuprates generated from one equivalent of CuCl·2LiCl and organolithium or Grignard reagents provides an efficient and high yield procedure for ketone synthesis.     

Preparation and electronic spectra of some alkyl- and aryl(2,2′-bipyridine)platinum(II) complexes

A series of alkyl- and aryl-(2,2′-bipyridine)-platinum (II) complexes has been prepared by displacement of the diene ligand in the corresponding cyclooctadiene complexes with 2,2′-bipyridine. Dimethyl(1,10-phenanthroline)platinum(II) was prepared in an analogous way. The electronic spectra of the complexes contain metal to ligand charge transfer bands whose energy is dependent on the nature of the substituents on platinum and on the solvent. It is suggested that π-bonding is important in the phenyl—platinum bond.     

Synthesis of imidazole phosphinic acids as I4AA analogues

The GABA_C receptor has been identified as a potentially attractive target involved in a number of eye diseases. TPMPA is the best antagonist reported so far. The synthesis of two new pharmacophores based on imidazole phosphinic acid core structure will be presented.     

Synthesis of aryl(ferrocenyl)methanols via an enantioselective addition of arylboronic acids

Enantiomerically enriched ferrocenyl alcohols are important intermediates in the synthesis of a range of chiral ferrocene-derived ligands. We studied various possibilities for their synthesis by the catalytic enantioselective addition of arylboronic acids to ferrocenyl carbonyl compounds. The best system comprised of ferrocenyl oxazolinyl alcohol as a catalyst and an arylation reagent generated from a boronic acid and diethylzinc. Aryl ferrocenyl methanols were synthesized in yields of up to 97% and with enantiomeric purities of up to er 98:2.     

Synthesis and optical activity of aryl(N-trifluoromethylsulfonylimino)thiodifluoroacetic acids and their derivatives

Synthesis and NMR studies of a new type of optically active sulfur(IV) compounds—aryl(N-trifluoromethylsulfonylimino)thiodifluoroacetic acids and their derivatives are described.     

Synthesis of [2-(methoxyaryl)-1-methylethyl]phosphinic acids from red phosphorus and (allyl)(methoxy)benzenes

(Allyl)(methoxy)benzenes react with red phosphorus in the superbasic system KOH-DMSO in the presence of small amounts of water and hydroquinone (3 h, 130 °C) to regio- and chemoselectively give [2-(methoxyaryl)-1-methylethyl]phosphinic acids in preparative yields up to 52%. The reactions involve isomerization of allylbenzenes into (prop-1-enyl)benzenes.