Phosphorus and Sulfur and the Related Elements

doi: 10.1080/03086648808079009pmid: N/A

Abstract This is a scanned image of the original Editorial Board page(s) for this issue.

Pilgram, Kurt H.

doi: 10.1080/03086648808079010pmid: N/A

Abstract The reaction of (3-(2-nitroaryl)-1,3,4-oxadiazol-2(3H)ones, 1, with phosphorus pentasulfide in refluxing xylene leads to the formation in good yields of 1,3,4-thiadiazolo(3,2-a)benzimidazoles, 3, which form water soluble methiodide salts. Chemical evidence in support of a reaction pathway is presented.

Appel, Rolf; Schulte, Peter; Knoch, Falk

doi: 10.1080/03086648808079011pmid: N/A

Abstract Synthesis and properties of up to now unknown P,P,P′,P′-Tetrakis(methylene)-[sgrave]3μ5-bisphosphoranes are reported.

McEwen, William E.; Tien, J.-H.; Rembetsy, L. M.; Kalbacher, B. J.; Lubinkowski, Jacek J.; Mari, F.; Devincenzo, S.; Salgueiro, R. M.; Hou, J.; Alvarez, J. A.

doi: 10.1080/03086648808079012pmid: N/A

Hacklin, Henrik; Röschenthaler, Gerd-Volker

doi: 10.1080/03086648808079013pmid: N/A

Abstract 1-Chlorophosphorinane (1) was obtained in a modified literature procedure by P-N-bond cleavage of 1-diethylaminophosphorinane using dichlorophenylphosphine. Compound 1 and sodium yielded the diphosphine 3, which resulted, also from the redox disproportionation of the intermediate 1-fluorophosphorinane. besides 1,1,1-trifluoro-λ5-phosphorinane. Bromine and iodine split the P-P-bond in 3 to furnish 1-bromo (4) and 1-iodophosphorinane (5). respectively. From 1 and LiOCH(CF3)2 or LiOCH2CF3, the phosphinites 6 and 7 were formed. 1-Chlorophosphorinan (1) wurde nach einer modifizierten Literaturmethode durch P‒N-Bindungsspaltung von 1-Diethylaminophosphorinan mit Dichlorphenylphosphin erhalten. Verbindung 1 und Natrium ergaben das Diphosphin 3, das auch neben 1,1,1-Trifluor-λ5-phosphorinan in einer Redoxdisproportionierungsreaktion aus dem nicht isolierbaren 1-Fluorphosphorinan entstand. Brom und Jod spalten die P‒P-Bindung in 3 unter Bildung von 1-Brom- (4) bzw. 1-Jod-phosphorinan (5). Aus 1 und LiOCH(CF3)2 oder LiOCH2CF3 waren die Phosphinite 6 und 7 zugänglich.

Symes, J.; Modro, T. A.; Niven, M. L.

doi: 10.1080/03086648808079014pmid: N/A

Abstract Cyclic mixed anhydride, N-methyl-2-benzoyloxy-2-oxo-1,3,2-oxazaphosphorinane (1a) has been synthesised and the rate of its fragmentation involving nitrogen migration from phosphorus to carbonyl carbon has been measured. (1a) was found to be ca. 60 times less reactive than the non-cyclic, O-methyl-N,N-dimethyl analogue. The crystal and molecular structure of (1a) has been determined using x-ray diffraction. Pna21, a=22.229(6), b=7.597(2), c=7.210(2) Å; V=1217.6(6) Å3. Final R=3.08% for 1037 reflections with I(rel) > 2[sgrave]I(rel) and 157 parameters. The observed conformation of the molecule of (1a) is very different from that required for the fragmentation to occur; in order to achieve the geometry postulated for the transition state significant rotations about the P‒O and O‒C bonds would be necessary and steric hindrance by the 4,6-axial hydrogens would be expected.

Benmaarouf-khallaayoun, Z.; Baboulene, M.; Speziale, V.; Lattes,

doi: 10.1080/03086648808079015pmid: N/A

Abstract This paper describes the synthesis of γ-halogenopropyl phosphoramidates I by hydroboration-halogenation reaction of N-phosphorylated allylamines II (phosphoramidates and phosphoramides). Only the use of allyl phosphoramidates leads to a good regioselectivity of the addition of boron atom on the terminal carbon atom of the allyl structure (compounds III). The absence of N→B complex formation permits a good reactivity of the trialkylboranes III and IV. The breaking of the P‒N bond, in acidic medium of the compounds I gives corresponding γ-halogenated amines V.

Troev, K.; Roundhill, D. M.

doi: 10.1080/03086648808079016pmid: N/A

Abstract In order to test the proposal that phosphorus-containing metal salts exist as ion pairs, in contrast to ammonium salts which exist as free-ions, an investigation of their solution structure by means of 31P and 1H NMR spectroscopy was carried out. The presence of an ionic bond in the molecule of both salts causes a decrease of both the phosphorus chemical shift and the P-H coupling constant. The change of 31P chemical shift and the P-H coupling constant depends on the type of the cation.

Schmid, George H.

doi: 10.1080/03086648808079017pmid: N/A

Abstract It is proposed that conventional nomenclature, based on that use for carbenium ions, be restored to the naming of thiiranium ions. Such a definition provides a general mechanistic classification for a large number of apparently diverse reactions while still allowing refinements to the mechanism in the form of thiiranium ion-pairs.

Reimschüssel, Wladyslaw; Abramczyk, Halina; Michalak, Jacek

doi: 10.1080/03086648808079018pmid: N/A

Abstract 2-Chloro-5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinane has been studied in CCl4, CHCl3 and CD3CN solutions by IR and Raman line shape analysis. Equilibrium process of dimerization and ring conversion in CCl4 solutions have been considered. On the contrary to the commonly expected dominance of the conformer with the equatorial oriented P˭O bond for 2-halo-2-oxo-1,3,2-dioxaphosphorinanes, it was found that for the 2-chloro derivative both conformers are nearly equally distributed. It has been shown that the interactions induced absorption is an important mechanism of relaxation in the studied compound and this mechanism gives significant contribution to the total IR band broadening, while the interaction induced light scattering is negligible. The obtained results show that the molecular dynamics method can be useful in studying cyclic compounds in solutions.