Molecular structure of (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide. Synthesis of (3,5-diallylisocyanuratomethyl)phosphine sulfides

X-Ray study of the (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide showed that the phosphorylmethyl group is bonded to the nitrogen atom of the cycle. Reaction of the tris(chloromethyl)phosphine sulfide with sodium diallylisocyanurate gave (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide, and treatment of the tris(3,5-diallylisocyanuratomethyl)phosphine oxide with phosphorus pentasulfide gave a tris(3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1446–1448, August, 1993.     

New trigonal tris(phosphine oxides)

The reaction of 1,1,1-tris(chloromethyl)propane with diphenylphosphine under phase-transfer conditions afforded 1,1,1-tris(diphenylphosphinomethyl)propane, whose oxidation gave a previously unknown representative of trigonal tris(phosphine oxides), viz., stable 1,1,1-tris(diphenylphosphorylmethyl)propane. Its analogs, viz., bis(diphenylphosphoryl)diphenylphosphinomethane and tris(diphenylphosphoryl)methane, are unstable in air and decompose with the cleavage of the P-C bond.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1926–1929, September, 2004.     

Synthesis of acyclic pentaalkoxyphosphoranes from tris(hexafluoroisopropoxy)dihalophosphoranes and chloral

Tris(hexafluoroisopropoxy)-bis(1-halo-2,2,2-trichloroethoxy)phosphoranes were obtained by addition of chloral to tris(hexafluoroisopropoxy)dibromo- and dichlorophosphoranes. The intermediate tris(1,1,1,3,3,3-hexafluoroisopropoxy)-1,2,2,2-tetrachloroethoxychlorophosphorane was also isolated in this reaction.V. I. Ul'yanov-Lenin Kazan State University, 420008 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 683–687, March, 1992.     

Furfuryl-containing tertiary phosphine oxides and polymers based on some of them

The syntheses of dimethyl(furfuryloxymethyl)phosphine oxide (DPO), methylbis(furfuryloxymethyl)phosphine oxide (MPO), tris(furfuryloxymethyl)phosphine oxide (TPO), dimethyl(tetrahydrofurfuryloxymethyl)phosphine oxide (DTPO), methyl-bis(tetrahydrofurfuryloxymethyl)phosphine oxide (MTPO) and tris(tetrahydrofurfuryloxymethyl)phosphine oxide (TTPO) from dimethyl(chloromethyl)phosphine oxide, methyl-bis(chloromethyl)phosphine oxide, tris(chloromethyl)phosphine oxide and the furfuryl and tetrahydrofurfuryl sodium alkoxides via the Williamson reaction are reported. Phosphorus-containing furan polymers with reduced flammability are prepared by polymerizing MPO and TPO using p-toluenesulphonic acid as catalyst. The oxygen indexes of these polymers, as determined by ASTM D-2863, are 35.1 and 33.1% O₂, respectively; for the phosphorus-free polymer from difurfurylidene acetone, it is 23.0% O₂. It is shown that DPO can be used as an efficient fire-retardant for reducing the flammability of a polymer from difurfurylidenacetone.     

Tertiary Phosphine Oxides in Reaction with Benzaldehyde

Symmetrical and unsymmetrical tertiary phosphine oxides containing benzyl and 5-chloro-2-thienyl radicals stereoselectively react with benzaldehyde in the sodium amide-THF system to form the E isomers of 1-organyl-2-phenylethene and diorganylphosphinic acids in high yields. Triethyl, tris(2-phenyl- ethyl)-, and tris[(4-methoxyphenyl)methyl]phosphine oxides under the above-mentioned conditions do not react with benzaldehyde.     

Experimental and Theoretical Studies on Some Energetic Functionalized Trimethylamine Derivatives

The synthesis and structural properties (from X‐ray diffraction or B3LYP/6‐31G(d) calculations) of three energetic compounds derived from tris(chloromethyl)amine and of tris(chloromethyl)amine itself were investigated and compared to those of compounds with similar structures. The compounds have almost planar NC₃ units at their amine center, and the substituents bound to the CH₂ groups tend to be reactive towards further substitution. Multiple hyperconjugation was used to explain these observations.     

Über Tris(siloxymethyl)-, Tris(silylmercaptomethyl)- und Tris(silylmethyl)amine

By the reaction of alkali salts of triorgano-silanols, -silanethiols and trimethylsilylmethanol as well as of triorganosilyllithium compounds with tris(chloromethyl)amine, silyl derivatives of tris(hydroxymethyl)-, tris(mercaptomethyl)- and tris(methyl)amine were prepared.     

Reductive coupling of polyfunctionalized organobismuth and organolead arylating reagents in the synthesis of benzopyran derivatives

Benzopyran derivatives were synthesized in good yields by the reactions of tris[2-(chloromethyl)phenyl]bismuth diacetate and 2-(halomethyl)aryllead triacetates with phenols and naturally occurring 4-hydroxycoumarins in the presence of bases according to a three-step one-pot procedure. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2520–2529, November, 2005.     

PCl3- and organometallic-free synthesis of tris(2-picolyl)phosphine oxide from elemental phosphorus and 2-(chloromethyl)pyridine hydrochloride

In the superbase KOH/H₂O/toluene/phase-transfer catalyst system, 2-picolyl chloride, generated in situ from 2-(chloromethyl)pyridine hydrochloride, reacts with elemental phosphorus at 65–95?°C for 3?h to afford tris(2-picolyl)phosphine oxide in 50% yield. Single crystal X-ray analysis of the latter revealed one polymorph form of this tertiary phosphine oxide.     

Reactions of Elemental Phosphorus and Phosphine with Electrophiles in Superbasic Systems: XV. Phosphorylation of Allyl Halides with Elemental Phosphorus

Elemental phosphorus (red or white) reacts with allyl chloride and allyl bromide in a two-phase system aqueous KOH-organic solvent to form tertiary symmetrical and mixed phosphine oxides among which tris(prop-2-enyl)-, bis(prop-2-enyl)[(E)-prop-1-enyl]-, bis(prop-2-enyl)[(Z)-prop-1-enyl]-, (prop-2-enyl)[(E)-prop-1-enyl][(Z)-prop-1-enyl]-, bis[(E)-prop-1-enyl](prop-2-enyl)-, bis[(Z)-prop-1-enyl](prop-2-enyl)-, tris-[(E)-prop-1-enyl]-, and bis[(E)-prop-1-enyl][(Z)-prop-1-enyl]phosphine oxides were identified. The conditions (room temperature, 60% aqueous KOH-dioxane) allowing preparation from white phosphorus and allyl bromide of tris(prop-2-enyl)- and bis(prop-2-enyl)[(E)-prop-1-enyl]phosphine oxides as major products in the total yield of up to 96% were found.     

Beitrüge zur Chemie der Si-N-Bindung,XXII N,N′-Tetrakis(trimethylsilyl)methylendiamin

N.N′-Tetrakis-Tetrakis(trimethylsilyl)methylenediamine is prepared by the reaction of lithium-bis(trimethylsilyl)amide with tris(chloromethyl)amine.     

Crystal structure of tris(chloromethyl)phosphine oxide

In the crystalline phase, tris(chloromethyl)phosphine oxide is a tgg conformer (with a transoid Cl-C-P-C-Cl chain).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1554–1556, July, 1990.     

The mass spectra of some para substituted triarylphosphines and triarylphosphine oxides

The mass spectra are reported for a series of tris(p-alkylaryl)phosphines and the corresponding phosphine oxides. The phosphines all give [M]^+˙ as the base peak except when the phenyl groups are not para substituted. For the oxides [M–H]⁺ gives the base peak with one exception for which [M]^+˙ is the most abundant ion.     

Phosphorylnitrile oxides. 6. 1,3-cycloaddition with azomethines and nitriles

The 1,3-dipolar cycloaddition of diisopropoxyphosphorylnitrile oxide to Schiff bases gives 3-diisopropoxyphosphoryl-4-R-5-phenyl-1,2,4-oxadiazolines. The cycloaddition of phosphorylated nitrile oxides at the azomethine bond of hydrazones does not proceed due to the low dipolarophilic activity of the CH = N bond and high tendency of phosphorylnitrile oxidesto undergo dimerization and polymerization. The reaction of nitrile oxides with 2-hydroxybenzylidenaniline leads to the corresponding ester of diisopropoxyphosphorylformhydroxamic acid. The nitrile group undergoes cycloaddition only when activated. The reaction of a solution of phosphorylnitrile oxides in benzene with tetracyanoethylene gives the bisadduct at the two C = N bonds without affecting the C = C bond.Communication 5, see ref. [1].Kazan State Technological University, 420015 Kazan. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1261–1268, September, 1994. Original article submitted August 5, 1994.     

Reactions of Bis(chloromethyl)phosphinic(-Phosphinothioic) Chlorides with Silylated Carbamates and Trimethylsilyl N-Trimethylsilylacetimidoate

Bis(chloromethyl)phosphinic chloride reacts with trimethylsilyl methylcarbamate in benzene in the presence of a base to give trimethylsilyl bis(chloromethyl)phosphinate. The same reaction performed without a solvent and in the absence of a base yields trimethylsilyl bis(chloromethyl)phosphinate and bis(chloromethyl)phosphinic anhydride. Reaction of bis(chloromethyl)phosphinic chloride with trimethylsilyl diethylcarbamate yields N,N-diethylbis(chloromethyl)phosphinic amide. The reaction of bis(chloromethyl)phosphinic (-phosphinothioic) chlorides with trimethylsilyl N-trimethylsilylacetimidoate was studied.     

Chirality in the Absence of Rigid Stereogenic Elements: The Absolute Configuration of Residual Enantiomers of C3‐Symmetric Propellers

Two new tris(aryl)phosphane oxides existing as configurationally stable residual enantiomers have been synthesised and their racemates resolved by semipreparative HPLC on a chiral stationary phase (CSP HPLC). One of them, recognised as a conglomerate, could be resolved by fractional crystallisation at a preparative scale level. In this case, the absolute configuration of the propeller‐shaped molecule was determined by anomalous X‐ray scattering. The problem of the correlative assignment of the absolute configuration to all known C₃‐symmetric three‐bladed propeller‐shaped molecules existing as stable residual enantiomers is discussed. The configurational stability of the new chiral phosphane oxides and of the corresponding phosphanes was evaluated by CD signal decay kinetics and dynamic ¹H NMR spectroscopy. The racemisation barriers in phosphanes were found about 10 kcal mol^?1 lower than those found for the corresponding oxides, though geometry and inter‐ring gearing would be very similar in the two series. Configurational stability of residual tris(aryl)phosphanes was found to be influenced by the electronic availability of the phosphorus centre, as evaluated by electrochemical CV experiments.     

Synthesis of 9-(2,3-dihydroxy-1-propoxymethyl)guanine - a new potential antiviral agent

Coupling of tris(trimethylsilyl)guanine (4) with 1,2-di-$\text{O}$-acetyl-3-$\text{O}$chloromethyl glycerol (3), followed by removal of the protecting groups afforded 9-(2,3-dihydroxy-1-propoxy)guanine (1). Compound 1 exhibited potent antiviral activity.     

Reaction of Vinylpyridines with Active Modifications of Elemental Phosphorus in KOH/DMSO

The phosphorylation of 2-vinyl- and 4-vinylpyridines by white phosphorus and active modifications of red phosphorus (obtained by thermal polymerization of white phosphorus in the presence of graphite or the action of ionizing radiation in benzene) in the KOH/DMSO superbase system at room temperature leads to the formation of tris[2-(2-pyridyl)ethyl]- and tris[2-(4-pyridyl)ethyl]phosphine oxides in 58-72% yield. These oxides are promising ligands for design of metal complex catalysts. These vinylpyridines react less efficiently with ordinary red phosphorus and the yield of the corresponding tris(2-pyridylethyl)phosphine oxides does not exceed 10%.     

[3 + 2] Cycloaddition of nitrile oxides to dichloropropenes and 1,3-dichlorobut-2-ene: A regioselectivity issue

The reaction of nitrile oxides with 2,3-dichloroprop-1-ene, 1,3-dichloroprop-1-ene, and 1,3-dichlorobut-2-ene leads to 5-(chloromethyl)isoxazoles, 4-(chloromethyl)isoxazoles, or to mixtures of both regioisomers. The direction of cycloaddition and reactivity of substrate is determined by the steric hindrance at the terminal carbon atom of the alkene double bond. It has been found that the isomeric products of cycloaddition of nitrile oxides to 1,3-dichloropropene have significantly different dehydrochlorination capabilities. The experimental data on the regioselectivity of cycloaddition and the relative reactivity of substrates are in agreement with the results of quantum chemical calculations.