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Alcohols and α-hydroxyphosphonates undergo the addition to (chloromethyl)phosphonic(-phosphinic) iso(thio)cyanates, yielding phosphorylated (thio)urethanes. The latter undergo cyclization to form, depending on their structure, saturated or unsaturated five-membered P,N,O,S-containing heterocycles.

The steric structure of 1,3,6,2-dioxazaphosphocanes and 1,3,6,2-dioxazasilocanes in solution was established by high-resolution 1H, 13C, and 31P NMR spectroscopy and PM3 calculations. It is shown that the preferred conformation of the eight-membered heterocycle is chair-chair (crown).

2-Alkoxy-4-oxo-5,6-benzo-1,3,2-dioxaphosphorinanes containing an electron-withdrawing fluorinated exocyclic substituent at the P atom react with aromatic aldimines to give 6,7-benzo-1,4,2-oxaza- phosphepines with a high regio- and stereoselectivity. The major diastereomers were isolated, and their configuration was determined by single crystal X-ray diffraction.

Phenyl α-aminoalkylphosphonates add to phenyl iso(thio)cyanates to give saturated heterocycles, 1,3,4-diazaphospholidin-2-(thi)ones. The reaction of diphenyl (α-methylamino)benzylphosphonate with diethyl isothiocyanatophosphate involves initial formation of 1,3,4-tiazaphospholidine-2-thiones containing exo- and endocyclic phosphorus atoms. These products are readily hydrolyzed in air, yielding diethyl isothio- cyanatophosphate and phenyl hydrogen (α-methylamino)benzylphosphonate. The final products of the reaction of chloromethyl isocyanatophosphonates with aminoalkylphosphonates are 1,3,4-oxazaphospholines. Phenyl aminoalkylphosphonates react with chloromethyl isocyanatophosphonates to give saturated heterocycles, 1,3,4-diazaphospholidines, whereas with chloromethyl isothiocyanatophosphonates 1,3,4-thiazaphospholines are formed.

The intramolecular version of nucleophilic additon of phosphites to imines was carried out for the first time taking as an example β-aldiminoalkylphosphites, formed from chlorophosphites and β-aldiminoalcohols [N-(benzylidene)-2-aminoethanol and R-(+)-N-(benzylidene)-2-aminobutanol-1]. In these reactions, stereoisomeric 1,4,2-oxazaphosphorines were obtained in good yields. R-(+)-N-(benzylidene)-2-aminobutanol-1 being used as a precursor, nucleophilic attack by P(III) atom on electrophilic C atom of the CN group proceeds stereospecifically with participation of only re-face of the two possible diastereotopic faces of the imine double bond to give the epimeric at phosphorus (3R,5R)-2-(β-chloroethyl)-2-oxo-3-phenyl-5-ethyl-1,4,2-oxazaphosphorines as precursors of nonracemic α-aminophosphonic acids. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:56–61, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10054

The reaction of 2-tert-butoxy-5,6-benzo-1,3,2-dioxaphosphinin-4-one with chloral involves expansion of the six-membered heteroring to form 2-hydroxy-3-trichloromethyl-6,7-benzo-1,4,2λ5-dioxaphosphepin-5-one 2-oxide as a single diastereomer. The product was chlorinated with thionyl chloride to obtain (RS,SR)-2-chloro-3-trichloromethyl-6,7-benzo-1,4,2λ5-dioxaphosphepin-5-one 2-oxide.

As shown by NMR and IR spectroscopy and high-resolution mass spectrometry, the major products of the reaction of 2,2,2,4,5,6,7-heptachlorobenzo[d]-1,3,2λ5-dioxaphosphole with phenylacetylene are a six-membered heterocyclic compound, 2-oxo-4-phenyl-2,5,6,7,8-pentachlorobenzo[e]-1,2λ5(2H)-oxaphosphorine, and the E and Z isomers of 2-(2,3,4,4,5-pentachlorocyclohexadienon-6-yl)-2-phenylvinylphosphonic dichloride. The molecular and supramolecular structure of the heterocycle and phosphorus-containing products of its hydrolysis were studied by single crystal X-ray diffraction.

Bis(chloromethyl)phosphinic (-phosphinothioic) iso(thio)cyanates add secondary amines to form N-phosphorylated (thio)ureas, which cyclize in the presence of a base to 1,3,4λ5-oxaza(thiaza)phospholines. Phosphorylated ureas obtained by addition of ammonia and primary amines to chloromethylphosphonic (-phosphinic) isocyanates cyclize to give 1,4,2-diazaphospholidines or 1,3,4-oxazaphospholines. Prototropic transformations in the series of 1,3,4λ5-oxazaphospholines were revealed; the electronic and steric structures of the tautomers were studied. Chloromethylphosphonothioic (-phosphinothioic) isothiocyanates add primary amines to give 1,3,4λ5-thiazaphospholines.

Trichloro(o-phenylenedioxy)phosphorane reacts with 1,2-alkadienylphosphonates with selective replacement of the alkoxy group in the phosphinoyl moiety, yielding the corresponding 1,2-alkadienylchloro- phosphonates and o-phenylene chlorophosphate.

New method of synthesis of six-membered heterocycles – 2-R-2-oxo-4-aryl-2H-benzo[e][1,2]-oxaphosphorin-3-enes has been developed. It includes the interaction of arylenedioxy trihalogenophosphoranes with arylacetylenes. The formation of phosphoryl group and P-C bond, ipso-substitution of the aromatic oxygen and halogenation of the benzene ring take place in this unusual reaction. The influence of the phosphorane structure on synthetic result is discussed. If both para positions at benzene ring of the phosphorane are occupated by halogens, the evolving of halogen molecule occurs. The structures of 2-R-2-oxo-4-aryl-2H-benzo[e][1,2]-oxaphosphorin-3-enes are determined by X-ray analysis.

The reaction of R-(+)-2-benzylideneaminobutan-1-ol with ethylene phosphorochloridite afforded phosphorus-epimeric (3R,5R)-2-(2-chloroethoxy)-5-ethyl-2-oxo-3-phenyl-1,4,2-oxazaphosphorinanes. The phosphorinane-ring closure proceeded stereospecifically and occurred only from one of the diastereofacial sides (re) of the C=N bond.

N,N'-Dimethyl-N,N'-bis(trimethylsilyl)methylphosphonic diamide reacts with chloral to form 1,2,3-trimethyl-4,4-dichloro-5-trimethylsiloxy-1,3,2-diazaphospholidine 2-oxide and with chloromethyldi- methylchlorosilane to form 1,2,3,4,4-pentamethyl-1,3-diaza-2-phospha-4-silacyclopentane 2-oxide.

The products of reaction ofo-phenylenedioxytrichlorophosphorane with arylacetylenes were identified as 4-aryl-2-chloro-2-oxo-5,6-(4-chlorobenzo)phosphorin-3-enes using1H,13C,31P NMR, and IR spectroscopy and high-resolution mass spectrometry.

We have established that direct phosphorus-selenium spin-spin coupling constants in cyclic compounds with P=Se exocyclic and P-C endocyclic bonds are found in the range1JPSe=−708 to −859 Hz; in this case, it is greater for the axial orientation of P=Se than for the equatorial orientation.

The products of reaction ofo-phenylenedioxytrichlorophosphorane with arylacetylenes were identified as 4-aryl-2-chloro-2-oxo-5,6-(4-chlorobenzo)phosphorin-3-enes using1H,13C,31P NMR, and IR spectroscopy and high-resolution mass spectrometry.

Reaction in a three-component system tetrachloro-o-benzoquinone-arylacetylene-phosphorus trichloride was investigated with the use of NMR and IR spectroscopy and high resolution mass spectrometry. It was established that prevailingly formed 4-aryl-2-oxo-2,5,6,7,8-pentachlorobenzo[e]-1,2-oxaphosphorin-3-enes which on hydrolysis furnished 2-aryl-2-(1-hydroxy-2,3,4,5-tetrachlorophenyl)vinylphosphonic acids.

Mixed-ligand NiIII complexes with α-nitroso-β-naphthol, β-nitroso-α-naphthol,o-ethylxanthate, andN,N-diethyldithiocarbamate as ligands have been studied by ESR in liquid and frozen solutions. The degrees of symmetry distortion for the first coordination sphere of these complexes have been determined. It is shown that the transition from planar square NiIIL2 complexes to more stable octahedral NiIIIL2L′ and NiIIILL2′ complexes occursvia the radical addition mechanism. A method for trapping short-lived radicals is suggested on the basis of the complex formation scheme.

The reactions of the cyclic derivatives of the two-coordinated phosphorus atom - 2-phenyl- and 2 -acetyl-2-H-l,2,3-diazaphospholes, dialkylphosphoe sulphenyklorides, dialkyldithio- and dialkylmonothiophosphates kads to the formation of the new P(III)-fUnctiohalized diazaphosphoknes.

NMR parameters of the phosphorus-containing molecules are known to be affected by the phosphorus coordination number. Very little has been published about the theory proper and about the correlation characteristics of this influence. In order to obtain some information about this problem we have synthesized a number of phospholene and oxaphospholene derivatives containing phosphorus in various valent states.

Using 1H, 13C, 31P, 77Se NMR it has been established that six-membered rings of 5-seleno-5-phenyl-2,2-dimetiiyl-l,3,5-dioxaphosphorinanes, 5-seleno-1,3,5-diazaphosphorinanes and 5-seleno-5-phenyl (alkyl)-2,2-dimethyl-1,3,2,5-dioxa-silaphosphorinanes in the solution are in chair conformation with the equatorial PSe group, whereas the eight-membered ring of 6-seleno-2,2,6-trimethyl-1,3,2,6-dioxa-silaphosphocane is mainly in the chair-chair conformation with the symmetry plane passing through the silicon atom and the axially oriented P=Se group. The selenium nuclear chemical shifts δ77se -266–416 ppm in these compounds depend on the size of the cycle, and on the effect of the substituent of the cycle. The phosphorus nuclear chemical shifts δ31pO-50 ppm depend on the phosphorus valence angle at the cycle and the electron infulence of the closest phosphorus substituents. For the stereoisomer pairs of the six-membered cycles the 31P nuclei in the isomer with the equatorial P=Se group have been shown to...

1. Feasibility has been demonstrated for the use of the1H {31P} DHSD method in studying the structure of complexes of Ni(II) and Co (II) with hydrazones in solution. 2. It has been confirmed by means of1H DHSD that Co (II) and Ni (II), with the salicyloylhydrazone of acetone and the benzoylhydrazone of benzaldehyde, form complexes with coordination number 4; with the benzoylhydrazone of salicylaldehyde and with the salicyloylhydrazones of 2-pyridinealdehyde and benzaldehyde, they form complexes with coordination number 6. 3. It has been established by means of NMR that complexes of Co(II) with acylhydrazones having a planar square unit, are capable of coordinating oxygen molecules.

Reactions of aromatic sulfites with N-acetoxymethyldimethylamine lead to formation of the Mannich phenol bases, aromatic acetates, and ammonium salts of Mannich bases with p-hydroxybenzenesulphonic acids.

On the basis of an analysis of a number of characteristics (NMR and IR spectra, dipole moments) of derivatives of 2-phospholenes and 3-phospholenes with tri- and tetracoordinated phosphorus, it was concluded that there is no p-π interaction of the unshared pair of electrons of phosphorus with the double bond of 2-phospholenes, and also that the electron-acceptor properties of the phosphorus fragment predominate regardless of the valence state of the phosphorus atom.

In contrast to aliphatic aldehydes, the reaction of 2,4,6-triisopropyl-1,3,5-dioxaphosphorinane and its sulfide with chloral and p-fluorobenzaldehyde, does not stop at the addition stage, but proceeds, with oxidation, to the formation of oxides.

1. Nonempirical calculations were carried out for the first time for substituted phosphorinanes. The conformer with an axial methyl group at the phosphorus atom predominates in 5-methyl-1,3,5-dioxaphosphorinanes as well as in the 5-oxa and 5-thio derivatives. The conformer with an equatorial methyl group at the phosphorus atoms and axial N-H bonds predominates in 5-thio-5-methyl-1,3,5-diazaphosphorinanes. 2. CNDO/2 and ab initio calculations for 5-methyl-1,3,5-dioxaphosphorinanes and its 5-oxo derviatives show the same trend for change in the energies of the favored conformers. 3. The conformer with an axial phenyl group oriented approximately in the symmetry plane of the molecule predominates in 5-phenyl-1,3,5-dioxaphosphorinanes and their 5-oxo derivatives, while the conformer with an equatorial phenyl group oriented approximately in the molecular symmetry plane is favored in 1,3,5-triphenyl-1,3,5-diazaphosphorinane.

In the liquid state and in solution, the dichloroanhydride ofα-chloroethylthiophosphonic acid exists as a two-conformer equilibrium with the P=S and C-Cl, and P=S and C-H bonds in trans orientation.

The possibility is discussed of using tautomerism to determine the conformational free energies of ring substituents, and the free energy of steric interaction of the substituents in the individual stereoisomers of 1-phenyl-3-carbomethoxyphosphorinan-4-one and its derivatives.

We determined the conformational free energy of a phenyl substituent on a tri- and tetracoordinated phosphorus atom in a 2,4,6-trimethyl-1,3,5-dioxaphosphorinane ring.

1. It was established by the PMR method that a two-component conformational equilibrium with approximately equal proportions of the trans and gauche rotamers is realized in solutions of the investigated β-halogenophenetoles in carbon tetrachloride. 2. The procedures for the empirical calculation of the3JHH constants are identically effective for the investigated compounds. 3. The spectral parameterA=N+1/3¦L¦ varies with variation of the temperature and the dielectric constant of the medium.

The strength of intramolecular hydrogen bonding in the o-(aminomethyl)phenols varies by some 5 kcal/mole, depending on the substituent at the nitrogen atom and in the benzene ring. Steric effects from the substituent determine the bonding strength.

1. The stereoisomers of 5-phenyl-5-oxo-2,4,6-trimethyl-1,3,5-dioxaphosphorinane have been obtained. 2. The stereoisomers obtained have equatorial CH3 groups and differ with respect to the orientation of the P=O bond. 3. The stereoisomer with the equatorial orientation of the P=O bond predominates at equilibrium.

Hydroxymethyldiphenylboryloxymethylphenylphosphine and 2,5-diphenyl-2-bora-1,3,5-di-oxaphosphorinane, in which the phenyl group at the phosphorus atom is predominantly found in the axial position, are formed in the reaction of di(hydroxymethyl)phenylphosphine with isobutyl diphenylborate.

In the conformational equilibrium of N,N-disubstituted 5-phenyl-1,3,5-diazaphosphorinanes and their oxides and sulfides forms can exist with an axial substituent on one of the heteroatoms, as well as a form with all equatorial substituents at the P and N atoms.

The interaction of dihydroxymethylphenylphosphine with the isobutyl ester of diphenylboric acid in the presence of nitriles proceeds in two stages, one of which is a reesterification reaction and the other is the addition of the nitriles to the P-C-O-B system of the reesterification product.

1. On the basis of1H and31P NMR data, derivatives of the 1,3,5-dioxaphosphorinanes have predominantly the chair conformation. In low-boiling isomers, the orientation of unshared electron pairs and P=O and P=S groups is equatorial, and in high-boiling isomers is axial. 2. The region of most probable values of the geminal SSCC2JPH has been determined as a function of orientation of the P=O and P=S groups. 3. Structures of the complexes Ni(acac)2 and Co(acac)2 with derivatives of 1,3,5-dioxaphosphorinanes have been studied. 4. Linear correlation of values of2JPH in the diamagnetic state and hfs constants of the protons in a paramagnetic complex has been established.

1. The geometrical structures of the chloroanhydrides of certain alkylsulfonic acids have been determined by study of vibrational and PMR spectra and measurements of dipole moments and Kerr constants. Increasing the size of the substituent at theα-carbon atom reduces the content of the conformer with trans orientation of the substituent relative to the phosphoryl group. 2. Comparison of the spectra of Cl2P(O)Alk and the spectra of complexes of these compounds with SnCl4, undissociated under the conditions of the present experiments, showed that band doubling in the 1250–1300 cm−1 region could not be entirely due to the establishment of a conformational equilibrium. 3. Free-atom interaction gives a satisfactory explanation of the geometrical structures established here.