Phosphorus and Sulfur and the Related Elements

doi: 10.1080/03086648708080647pmid: N/A

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

Lamande, Lydia; Munoz, Aurelio

doi: 10.1080/03086648708080648pmid: N/A

Abstract Hydridophosphoranes prepared from α-hydroxyacids, react in presence of triethylamine, on sulfur, selenium, Lawesson's reagent, tosylazide giving triethylammonium salts of phosphoranes with exocyclic anionic group: ‒S−, ‒Se−, ‒PS2‒C6H4‒OCH3(p), ‒N˭SO2‒C6H4‒CH3(p). The compounds obtained with sulfur and selenium represent good models of intermediates of substitution reactions on thio or (and) seleno phosphoric (phosphonic) esters. Reacting with trimethylchlorosilane, conjugated bases of the preceeding hydridophosphoranes, gave instead of the corresponding trimethyl silyl phosphoranes, the isomeric phosphorous ester. Les phosphoranes à liaison P‒H préparés à partir des α-hydroxyacides réagissent en préence de triéthylamine, sur le soufre, le sélénium, le réactif de Lawesson, 1′ azoture de tosyle pour conduire à des phosphoranes portant les groupements anioniques: ‒S−, ‒Se−, ‒PS2‒C6H4‒OCH3SO2‒C6H4‒CH3(p). Les composés obtenus à partir du soufre et du sélénium représentent de bons modeéles d'intermédiaires de réactions de substitution nucléophile sur des esters thiolo et séléno phosphoriques (phosphoniques). Les bases conjuguées des phosphoranes précédents réagissent avec le chlorotriméthylsilane, donnant, au lieu du triméthylsilyl phosphorane correspondant, le phosphite isomére.

Maier, L.; Duerr, D.; Rempfler, H.

doi: 10.1080/03086648708080649pmid: N/A

Abstract In the Cadogan reaction of 1,2-dinitro-4-chlorobenzene with phosphites and phosphonites the 2-nitro group is substituted but in 1,2-dinitro-4-alkoxycarbonylbenzenes the 1-nitro group is replaced exclusively (Table I and II). Extension of the Cadogan reaction to 4-phenoxy and 4-pyridyloxy substituted 1,2-dinitrobenzenes produced mainly 5-phenoxy and 5-pyridyloxy substituted 2-nitrophenylphosphonates and -phosphinates some of which show high herbicidal and plant growth regulating activity (Table III to V and Figure 1 to 4). 4- and 6-phenoxy or pyridyloxy substituted 2-nitrophenylphosphonates are herbicidally inactive. The herbicidal activity decreases from the phenoxy-phenylphosphonates to -phosphinates to pyridyloxy-phenylphosphonates when the same substitution pattern is present. The methyl esters 3a, 4a and 5a are the most active compounds in all three series. We wish to thank Ciba-Geigy's Physical Science Center for the hydrogenation experiments, the combustion analyses and for the 31P and 13C NMR spectra, and Messieurs H. Spoerri, M. Walti and M. Hartmeyer for experimental help.

Castera, Pierre; Faucher, Jean-Paul; Granier, Michel; Labarre, Jean-François

doi: 10.1080/03086648708080650pmid: N/A

Abstract Singly, doubly and triply bridged polyazaheterophanes (1,2,3) have been synthesized from hexachlorocyclotriphosphazene, N3P3Cl6. 31P NMR spectra indicate that the molecules 2 exist in a single conformation when there are three differently populated conformations A, B and C, in molecules 3 at ambient temperature, A and (B + C) being separated by a high interconversion barrier (about 22 Kcal mole−1) whereas the barrier between B and C is much lower (about 4 Kcal mol−1).

Yousif, N. M.; Salama, M. A.

doi: 10.1080/03086648708080651pmid: N/A

Abstract Carboxylic acid chlorides react with 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4- disulfide to give the intermediates 2a,b; 2'a,b) which are useful as thioacylating agents. Compounds 2 react with amines under mild conditions to give the corresponding thioamides.

łopusiński, Andrzej; Potrzebowski, Marek

doi: 10.1080/03086648708080652pmid: N/A

Abstract The synthesis of new pseudohalogen thioxaphosphoranesulfenyl bromides by simple bromination of bis(dialkoxythiophosphoryl)disulfides is presented. The new bromides turned out to be excellent thiophosphorylating agents, as well as substrates for a novel, highly efficient preparation of dialkoxythioxaphosphoranesulfenyl chlorides 4.

Maier, Ludwig; Rist, G.

doi: 10.1080/03086648708080653pmid: N/A

Abstract The reaction of dimethyl-chloromethylphosphinoxide with the alkali salts of imidazole, pyrazole, triazole, benztriazole, 2-methyIimidazole, benzimidazole, tetrazole, and indazole yields the corresponding dimethyl-heterocyclic substituted methylphosphine oxides 1a-1i (Table I). These phosphine oxides easily undergo a Wittig-Horner reaction when treated with aldehydes and ketones and give a cis/trans = 1:1 mixture of the corresponding olefines 2a, 2a′, 2b, 2d and 2f. Several of these can be separated by flash chromatography into the pure cis and trans isomers. It was observed that only the cis compounds exhibit fungicidal activity against Erysiphe graminis.

Van Genderen, Marcel H. P.; Koole, Leo H.; Scheper, Bernd C. C. M. Olde; Van De Ven, Leo J. M.; Buck, Henk M.

doi: 10.1080/03086648708080654pmid: N/A

Abstract A high resolution 1HNMR study of several 4- and 5-coordinated (TBP) phosphorus compounds enabled us to determine the nature of the conformational transmission effect, which describes the influence of the phosphorus coordination on the molecular conformation. Of great use was the accurate determination of the J POMe coupling constant, with which the pseudorotational equilibrium around the pentacoordinated phosphorus can be described. It was determined that conformational transmission is purely electrostatic in origin, due to a larger charge density in the axis of the TBP structure. These findings were corroborated with quantumchemical calculations.

Deutsch, W. Francis; Hursthouse, Michael B.; Kiliç, Zeynel; Parkes, Harold G.; Shaw, Leylǎ S.; Shaw, Robert A.

doi: 10.1080/03086648708080655pmid: N/A

Abstract X-ray crystallographic and 13C NMR spectroscopic investigations demonstrate that 3 J(PNCC) spin-spin coupling constants are reduced when the nitrogen atoms deviate from planarity and the P‒N bond lengths increase.

Wladislaw, B.; Marzorati, L.; Uchôa, R. B.

doi: 10.1080/03086648708080656pmid: N/A

Abstract A versatile method of synthesis of p-substituted phenyl alkyl ketones, by decomposition of the alkylation products of the corresponding α-(methylthio)benzyl sulfones, is described. In a recent communication1 we reported that α-methylthio-p-substituted benzyl sulfones (1) undergo thermal decomposition to give the corresponding p-substituted benzaldehydes.