Zur Chemie von Sulfiden und Seleniden primärer Phosphane — Die (1‐Hydroxyalkyl)‐organyl‐phosphansulfide und ‐selenide, neue Verbindungsklassen

Abstract

Primäre Phosphane reagieren mit S8 oder Se8 und bilden neben einer großen Anzahl von Nebenprodukten Organylphosphanmonosulfide bzw. ‐selenide, RP(X)H2 (X = S, Se), die 31P‐NMR‐ spektroskopisch charakterisiert werden können. Die Bildung von Organylphosphanmonosulfiden ist auch bei der Umsetzung primärer Phosphane mit 2,4‐Diaryl‐1,3,2,4‐dithiadiphosphetan‐2,4‐disulfid nachweisbar. Praktisch ohne Nebenprodukte verläuft die Reaktion primärer Phosphane mit Schwefel oder Selen und einer Reihe von Ketonen. Es entstehen die meist kristallinen (1‐Hydroxyalkyl)‐organyl‐phosphansulfide bzw. ‐selenide, RP(X)(H)C(OH)R1R2. Die Röntgen‐Kristallstrukturanalyse des (1‐Hydroxy‐1‐methyl‐ethyl)‐phenyl‐phosphansulfids (R = Ph, R1 = R2 = Me) ergab, daß im Kristall intermolekulare OH …︁ S‐Wasserstoffbrückenbindungen (O …︁ S = 328 pm) zu einer kettenförmigen Anordnung der Moleküle führen. Aldehyde reagieren mit Phenylphosphan und Schwefel zu Bis(1‐hydroxyalkyl)‐phenyl‐phosphansulfiden, C6H5P(S)[CH(OH)R1]2. 1H, 13C und 31P‐NMR‐Untersuchungen gestatten den Nachweis und die Zuordnung von auftretenden Stereoisomeren. Quantenchemische Berechnungen spiegeln richtig wider, welche Carbonylverbindungen in der Lage sind, mit dem intermediär gebildeten Phosphansulfid zu reagieren und welche nicht.

Organo–Phosphorus–Sulfur Heterocycles by Reactions of Phenylphosphine with Ketones

“…31 P, 13 C, 1 H-NMR spectroscopy allowed for characterization of both diastereomers whereas recrystallization permitted the characterization of (1a,Z) (1,3,2,4-oxathiadiphospholane, 5,5-dimethyl-2,4-diphenyl-2,4-disulfide,(Z)-) by XRD. In addition, mechanistic studies allowed for the elucidation of synthetic intermediates to the heterocyclic intermediates including 1,3,2,4,5-dithiatriphospholane-2,4,5-triphenyl-,2-sulfide (2) ((PhP) 3 S 3 ) and 1,3,2,4-oxathiadiphospholane-5,5-dimethyl-2,4-diphenyl-2-sulfide (3a)/(3b) ((PhP S)(PhP)SOCMe 2 ).…”

“…As described by Uhlig et al 13 previously, the reaction of primary organophosphines, especially PhPH 2 , in mixtures of n-hydrocarbons and ketones as solvents with 1 equivalent of sulfur (S 8 ) produces acyclic α-hydroxymethylphosphansulfides of type (4) in reasonable yields ( Figure 1). However, this changes drastically if higher equivalents of sulfur are employed in such reactions.…”

“…The addition of acetone which had been stored over molecular sieves resulted in a mixture of products including the diastereomers [10] (1a,Z)/(1b,E) and small amounts of PhPHSC(Me) 2 OH, (4) as side product, known in the literature, as determined by 31 P-NMR. 13 For our initial purposes, acetone which had been stored over molecular sieves was used due to simplify NMR interpretations. Although reaction mechanistic clarification was done using only acetone, asymmetric ketones can be used as well.…”

“…In some cases, the addition of aldehydes or ketones to phosphorus compounds and the chalcogens leads to completely novel derivatives. Recently, we were able to describe a series of acyclic α-hydroxymethylphosphansulfides by reacting primary phosphines with 1 equivalent of sulfur in the presence of ketones and aldehydes, 13 whereas Woollins and coworkers described the formation of a 5-membered selenium-phosphorus ring by reacting pentaphenylcyclopentaphosphine with gray selenium in the presence of acetone. 10 We report here on the synthesis of a novel heterocyclic phosphorus-sulfur ring.…”

Oxidation of Substituted Phosphanylboranes with Chalcogens

“…[4] In the laboratory,t hey can easilyb eo xidized by using elemental chalcogens or organic oxidants. [5] Phosphorus-chalcogen-containing compounds have become valuable tools for organic synthesis, for example, phosphine oxides RR'HPO can be used as chiralp religands for enantioselective catalysis. [6] Another well-known example is Lawesson'sr eagent [(4-MeOC 6 H 4 )PS(m-S)] 2 ,w hich is widely used for the conversion of C=Oi nto C=Sg roups.…”