Synthesis of phosphonium 1,3,2,5-dioxaborataphosphorinanes

Conclusions Reaction of ammonium 2,2,5-triphenyl-4,6-disubstituted 1,3,2,5-dioxaborataphosphorinane oxides or the sodium salt of methoxy(diphenyl)borataoxybenzyl(hydroxybenzyl)phenylphosphine oxide with methyltriphenylphosphonium iodide yields methyltriphenylphosphonium 2,2,5-triphenyl-4,6-disubstituted 1,3,2,5-dioxaborataphosphorinane oxides.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2607–2609, November, 1988.     

Synthesis and properties of triethylammonium 2,2,5-triphenyl-1,3,2,5-dioxaborataphosphorinane

The reaction of bis(hydroxymethyl)phenylphosphine with isobutyl diphenylborate in the presence of triethylamine leads to the formation of triethylammonium 2,2,5-triphenyl-1,3,2,5-dioxaborataphosphorinane (1). The reaction of compound 1 with electrophilic reagents (O, S, Se, CH₂O, RHal) leads to quaternization of the phosphorus atom, giving the corresponding phosphine oxides, sulfides, and selenides and P,B-containing betaines. In the reactions of compound 1 with amines aminomethylphosphines of the diazaphosphorinane and diazadiphosphacyclooctane series are formed. Ammonium 1,3,2,5-dioxaborataphosphorinanes dissociate in solutions and enter into ion exchange with phosphonium iodides, leading to phosphonium 1,3,2,5-dioxaborataphosphorinanes. The latter, in the case of the aminomethylphosphonium cation, undergo intramolecular rearrangement with the formation of P,B-containing betaines and aminomethylphosphines.Deceased.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1398–1405, June, 1992.     

Displacement of aldehyde fragment in diphenylboryloxyalkylphosphines

Conclusion In the reaction of -diphenylboryloxyalkyl (imidoyl)phenylphosphines with chloral and triethylammonium 2,2,5-triphenyl-4,6-di-R-l,3,2,5-dioxaborataphosphorinane with substituted benzaldehydes, the aldehyde fragment is displaced without a change in the form of the molecule.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2510–2514, November, 1986.     

Tautomerism in 1,3,2,5-dioxaborataphosphorinanes and their analogs

In solutions ammonium 2,2,5-triphenyl-4,6-di-R-1,3,2,5-dioxaborataphosphorinanes are characterized by ioncomplex tautomerism. The complex form dissociates reversibly to a secondary phosphine and an aldehyde. The reaction of tris(hydroxymethyl) phosphine with isobutyl diphenylborate in the presence of formaldehyde and a tertiary amine gave 5,5'-spirobi (2,2-diphenyl-1,3,2,5-dioxaborataphosphorinanes).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1133–1139, May, 1990.     

Reactions of boryloxymethyl- and hydroxymethylphosphines with amines

Conclusions 5-(Hydroxymethyl)-2,2,5-triphenyl-1,3,2,5-dioxaborataphosphoniarinane reacts with diphenylamine and o-aminobenzoic acid with the formation of 5-(aminomethyl)-2,2,5-triphenyl-1,3,2,5-dioxaborataphosphoniarinanes, whereas 1,5,3,7-diammoniadiphosphacyclooctanes are formed with m- and p-aminobenzoic acids. With o-aminobenzoic acid, hydroxymethylphosphines and hydroxymethylphosphonium salts give the corresponding aminomethylphosphines and aminomethylphosphonium salts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1340–1343, June, 1989.Deceased.     

Borylation of α-hydroxyalkylphosphine oxides in the presence of strong bases

Lithium (sodium) 2,2,5-triphenyl-5-oxo-1,3,2,5-dioxaborataphosphorinanes, forming crystals with two molecules of water, are produced when bis(hydroxymethyl)phenylphosphine oxide is reacted with isobutyl diphenylborate in the presence of metallic sodium or lithium (sodium) alcoholate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 886–890, April, 1990.     

Synthesis of ammonium 1,3,2,5-dioxaborataphosphorinanes

Conclusions By reaction of bis(-hydroxyalkyl)phenylphosphines with isobutyl diphenylborinate in the presence of tertiary amines ammonium 2,2,5-triphenyl-4,6-p-1,3,2,5-dioxaborataphosphorinanes were obtained.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1641–1644, July, 1986.     

Synthesis of ammonium 5-oxo-1,3,2,5-dioxaborataphosphorinanes

Conclusions In the reaction of bis(-hydroxyalkyl)phenylphosphine oxides with isobutyl ester of diphenylboric acid in the presence of amines, ammonium 5-oxo-2,2,5-triphenyl-4,6-di-R-1,3,2,5-dioxaborataphosphorinanes were obtained.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2369–2372, October, 1985.     

Complexes of 2,5-diphenyl-1,3,2,5-dioxaboraphosphorinane and 1,3,5-triphenyl-1,3,5-diazaphosphorinane with molybdenum hexacarbonyl

The reaction of 2,5-diphenyl-1,3,2,5-dioxaboraphosphorinane (L) and 1,3,5-triphenyl-1,3,5-diazaphosphorinane (L) with molybdenum hexacarbonyl gave, respectively, Mo(CO)₄L₂ and Mo(CO)₅L complexes.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 201–203, January, 1992.     

Kinetics and Mechanism of the Isomerisation of 2,4,6-Triphenyl-4H-Thiopyran

Isomerisation of 2,4,6-triphenyl-4H-thiopyran into 2,4,6-triphenyl-2H-thiopyran has been studied kinetically and the rate of the reaction was determined in dimethylformamide. The first order rate constant could be expressed in terms of the Arrhenius parameters by the equation k_t = 2.85 × 10⁷ e^{?15820±110/RT}.     

Beiträge zur Chemie des Phosphors. 94. Tetraphenyl-cyclotetraphosphan, (PPh)4, und 1,2,3-Triphenyl-4-tert-butyl-cyclotetraphosphan, (PPh)3(PBut)

Contributions to the Chemistry of Phosphorus. 94. Tetraphenyl-cyclotetraphosphane, (PPh)₄, and 1,2,3-Triphenyl-4-tert-butyl-cyclotetraphosphane, (PPh)₃(PBu^t) The homocyclic four-membered phosphorus ring compounds tetraphenyl-cyclotetra-phosphane, (PPh)₄ ( 1 ), and l,2,3-triphenyl-4-tert-butyl-cyclotetraphosphane, (PPh)₃(PBu^t) ( 2 ), are obtained as main products by [3+l]-cyclocondensation of K(Ph)P? P(Ph)? P(Ph)K or Me₃Si(Ph)P? P(Ph)? P(Ph)SiMe₃ with PhPCl₂ or Bu^tPCl₂ respectively under suitable reaction conditions. At room temperature in solution 1 rearranges mostly to the oligomeric (PPh)₅, whereas 2 is remarkably stable. The ³¹P-NMR parameters of the mixed substituted four-membered ring compound 2 are reported and discussed.     

A Complex between C-Methylcalix[4]resorcinarene and Triethylammonium Nitrate

Abstract

The synthesis and crystal structure of the complex formed by the all-cis epimer of C-methylcalix[4]resorcinarene (1) and triethylammonium nitrate are reported. “1.(HNEt⁺ ₃)₄. (NO^? ₃)₄(2)”, crystallizes in the monoclinic space group P2₁/n, a=25.796(2), b=16.6048(11), c=29.5659(10) Å, β=94.636(4)°, V=12623(2) ų, Z=8. Refinement led to a final conventional R₁ value of 0.128 for 12428 reflections and 1473 parameters. The resorcinarene displays the usual bowl-type shape, with four hydroxyl protons involved in intramolecular hydrogen bonds, whereas the remaining four make hydrogen bonds with four bridging nitrate ions, which results in the formation of infinite chains. Those chains are arranged so as to form layers, between which the triethylammonium ions and the remaining nitrate ions are hydrogen-bonded one to another.     

Synthesis and structural features of 1,3,2,5-dioxaboraphosphorinane complexes with Pt(II) and Pd(II) salts

Complexes of composition L₂MCl₂ [M=Pt, R=H (I), Me (II), Ph (III)], and LMC1₂ [M=Pd, R=H (IV)] are prepared by reaction of 4,6-R₂-2,5-diphenyl-1,3,2,5-dioxaboraphosphorinanes (L) with MCl₂. Far-IR and³¹P NMR spectroscopy are used to demonstrate that I is cis whereas II and III are trans complexes in the solid. The conformational behavior of I is studied by³¹P and¹H NMR. The asymmetric form of I exhibits anomalous stability.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2309–2312, October, 1991.     

Säurekatalysierte Umlagerung von 7-Hydroxy-royleanon in ein 20(10→9) abeo-Abietan-Derivat und zwei Phenalenone

Acid-catalyzed rearrangement of 7-hydroxyroyleanone into a 20(10→9) abeo-abietane derivative and two phenalenones Short treatment of either horminone ( 1b ), taxoquinone ( 1a ), 6,7-dehydroroyleanone ( 3 ) or 6β-hydroxyroyleanone ( 1c ) with 80% H₂SO₄ at 0° leads to a mixture of rearranged products. Two of the structures, determined by X-ray-cristallography, were found to be (9R, 10R)-20(10→9)-abeo-12-hydroxy-5,7, 12-abietatriene-11,14-dione ( 4 ) and 9-isopropyl-2,2,5-trimethyl-8H-phenaleno[1,9-bc]furan-8-one ( 5 ), and the third compound, isolated in very small amounts, has been provisionally identified as 3-hydroxy-9-isopropyl-2,2,5-trimethyl-8H-phenaleno[1,9-bc]furan-8-one ( 6 ) from the spectroscopic data.     

First‐ and second‐ sphere coordination of the uranyl ion by bis­[2‐(2‐hydroxy­phenoxy)­ethoxy]­ethane

Uranyl nitrate hexahydrate reacts with bis­[2‐(2‐hydroxy­phenoxy)­ethoxy]­ethane (C₁₈H₂₂O₆), denoted LH₂ hereafter, in the presence of triethylamine to give ­triethylammonium aqua[2,2′‐(3,6‐dioxaoctane‐1,8‐diyldioxy)diphenolato‐κ²O,O′](nitrato‐κ²O,O′)dioxouranium(VI), (Et₃NH)[UO₂(H₂O)L(NO₃)], which possesses a symmetry plane. The uranyl ion is coordinated to the two phenoxide O atoms, a nitrate ion and a water mol­ecule (first sphere); the water mol­ecule is itself held in the crown ether chain by hydrogen‐bonding interactions, thus ensuring second‐sphere coordination by the ligand L.     

Synthesis and Structural Studies of New (Triphenylphosphine)(trialkoxysilanethiolato)gold(I) Complexes

Compounds of general formula Au{SSi(OR)₃}(PPh₃), R = Prⁱ ( 1 ), Bu^s ( 2 ) or Bu^t ( 3 ), have been obtained by reaction of AuCl(PPh₃) with triethylammonium salts of respective silanethiols, (RO)₃SiSH. Molecular and crystal structures of 1 , 2 , and 3 have been determined by the single crystal X‐ray structural analysis. Compounds 1 and 2 are the first structurally characterized metal derivatives of hydrolytically unstable trialkoxysilanethiols (PrⁱO)₃SiSH and (Bu^sO)₃SiSH.     

Efficient synthesis of functionalized spiro-2,5-dihydro-1,2-λ-oxaphospholes

The reaction of ethyl propiolate with triphenylphosphine (Ph₃P) in the presence of N-alkylisatins led to ethyl 2,2,2-triphenyl-2,5-dihydro-1,2-λ⁵-oxaphosphole-4-carboxylate-spiro-1-alkyl-1,3-dihydro-2H-indol-2-ones in good yield. The reaction of dialkyl acetylenedicarboxylates with Ph₃P in the presence of N-alkylisatins led to dialkyl 2,2,2-triphenyl-2,5-dihydro-1,2-λ⁵-oxaphosphole-3,4-dicarboxylate-spiro-1-alkyl-1,3-dihydro-2H-indol-2-ones and alkyl 4-(alkoxy)-5-oxo-2,5-dihydro-3-furancarboxylate-spiro-1-alkyl-1,3-dihydro-2H-indol-2-ones.     

Synthesis of Pyrazolo[3,4‐d]pyrimidin‐4‐ones Catalyzed by Br?nsted‐acidic Ionic Liquids as Highly Efficient and Reusable Catalysts

A convenient and efficient method for the synthesis of pyrazolo[3,4‐d]pyrimidin‐4‐ones via heterocyclization reaction of 5‐amino‐1H‐pyrazole‐4‐carboxamides with triethyl orthoesters using two Br?nsted‐acidic ionic liquids, 3‐methyl‐1‐(4‐sulfonic acid)butylimidazolium hydrogen sulfate [MIM⁺(CH₂)₄SO₃H][HSO₄^?] or N‐(4‐sulfonic acid)butyl triethylammonium hydrogen sulfate [Et₃N⁺(CH₂)₄SO₃H][HSO₄^?], as efficient homogeneous catalysts under solvent‐free conditions is described.     

Two tetrakis(benzoylacetonato)lanthanide species: synthesis,characterization and structures of tetrakis(benzoylacetonato)cerium(IV) and triethylammonium tetrakis(benzoylacetonato)lanthanate(III) tetrahydrate

Tetrakis(benzoylacetonato)cerium(IV), [Ce(bzac)₄] and triethylammonium tetrakis(benzoylacetonato)lanthanate(III) tetrahydrate, [Et₃NH][La(bzac)₄] · 4H₂O were prepared and characterized by TG and DCS measurements, IR spectroscopy, and X-ray structure analysis. The coordination polyhedron of cerium is a trigonal dodecahedron, while that of lanthanum is a distorted square antiprism. Thermal and spectroscopic measurements indicate that bonding of the ligand to metal is stronger in [Ce(bzac)₄] than in [La(bzac)₄]^?.