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Relevant academic research and scientific papers

Experimental Basicities of Superbasic Phosphonium Ylides and Phosphazenes

Experimental basicities of some of the strongest superbases ever measured (phosphonium ylides) are reported, and by employing these compounds, the experimental self-consistent basicity scale of superbases in THF, reaching a pKα (estimate of pKa) of 35 and spanning more than 30 pKa units, has been compiled. Basicities of 47 compounds (around half of which are newly synthesized) are included. The solution basicity of the well-known t-Bu-N=P4(dma)9 phosphazene superbase is now rigorously linked to the scale. The compiled scale is a useful tool for further basicity studies in THF as well as in other solvents, in particular, in acetonitrile. A good correlation between basicities in THF and acetonitrile spanning 25 orders of magnitude gives access to experimentally supported very high (pKa > 40) basicities in acetonitrile, which cannot be directly measured. Analysis of structure-basicity trends is presented.

Reductive cleavage of the carbon-phosphorus bond with alkali metals. II. Cleavage of mixed functionalized triarylphosphines; Birch reduction of arylphosphines

The reductive cleavage of mixed ortho- and para-functionalized triarylphosphines with Na/NH3 and Li/THF depends strongly on the nature and positions of the substituents.Reduction occurs readily with phosphines PhAr2P (4, 6 and 9) and Ph2ArP 19 when the corresponding phosphine Ar3P is not reduced.Cleavage of para-substituted compounds 7 and 9 leads to mixtures of secondary phosphines.By contrast, cleavage of mixed ortho-substituted triphenylphosphines is very selective.The functionalized phenyl group is split off in high yield when it carries CH3, (CH3)2N and CH3O substituents (2, 3, 5, 6, 8, 10, 11, 13, 14, 17, 19, 24, 25).Reaction of 4 is not selective due to loss of methoxy groups (1, 15, 16).The reactions of bis- and tris(diphenylphosphino)benzenes with Li/THF leads predominantly to cleavage of the diphenylphosphino group from the respective substrates.In a number of cases, the product of a Birch reduction with an isolated diene system is formed in NH3 (1, 9, 12, 21, 23) via a phosphino-stabilized cyclohexadienyl anion.This reduction does not occur in the aprotic solvent THF.Base-catalyzed isomerization leads to a conjugated double-bond system with a vinylphosphine moiety.We also report interesting large 4J(PP) couplings in 1,3-diphosphinobenzenes and complicated 13C resonances of para-substituted phosphines.

A Highly Basic and Nucleophilic Triphenylphosphine, Tris(2,4,6-trimethoxyphenyl)phosphine, and Related Compounds

A series of methoxy substituted triphenylphosphines, R3-nPhnP , and their tertiary phosphonium perchlorates have been prepared.The basicity of the title compound, (1), in acetone was f

A Highly Basic Triphenylphosphine, 3P

Tris(2,4,6-trimethoxyphenyl)phosphine was found to be highly basic (pKa, 11.2).

PHOSPHORORGANISCHE VERBINDUNGEN 101. TERTIAERE PHOSPHINE MIT ORTHOALKOXYPHENYL-GRUPPEN. Synthese und Eigenschaften

Alkylphenylethers, ortho-lithiated in good yields, are transformed according to scheme (1) to the triarylphosphines ArPPh2, Ar2PPh and Ar3P (Ar contains in all cases an ortho-alkoxy group) (Table 1.).Hydroquinonedialkylethers can be lithiated twice, forming the compounds 102 and 103.Table 2 summarizes some arylalkylethers (71 - 101) which were lithiated; table 7 presents 12 new arylalkylethers.The syntheses of triarylphosphines with one or two bulky groups (105 - 110) and of triarylphosphines with one or two 3,4-dialkoxyphenyl groups (111 - 114) are reported.The 31P-spectra of the compounds prepared are discussed with respect to the validity of the Tolman-rule.