Phosphine methyl derivatives

Carbamoyl methyl Phosphine Oxide Derivatives The physicochemical properties of various aryl derivatives of CMPO have been investigated at the Vernadsky Institute of Geochemistry and Analytical Chemistry. Extraction of americium and lanthanides from nitric acid with solutions of diphenyl- and dibutyl-(diethylcarbamoylmethyl) phosphine oxides (Ph2Et2-CMPO and Bu2Et2-CMPO) in dichloroethane have been investigated as a function of the concentrations of the extractants and nitric acid (110, 111). The observed dependences are characterized... 

The reaction of nickelocene with primary phosphines has allowed the preparation of the phosphido-bridged dimers (1) deprotonation and methylation of the phosphido moiety results in the formation ofthe methylated derivatives (2) (Scheme 1). A large series of pentamethylcyclopentadienyl (Cp ) derivatives have been prepared by reacting PEts with... 

No phosphonitrilic alkyls have been obtained. Stokes 85) continued the work of Couldridge 20) on the reaction of zinc ethyl with the tri-meric chloride at high temperatures a violent reaction took place, but no identifiable products could be isolated. It is probable that alkyl phosphines were formed. W. Philpott 2) found the trimeric chloride in ethereal solution to be unreactive to methyl Grignard reagents and to aluminum alkyls. Unsuccessful attempts have been made by H. T. Searle 2) to prepare the methyl derivatives by reaction of Me2PCls with ammonium chloride, either dry or in tetrachloroethane. Most of the expected hydrogen chloride is evolved, but ring closure does not take place. 

Garcia and Maitlis have reported tliat some d " ML 1 4-electron platinum phosphine fragments [PtL ] (L = PEtj, PMcj, Lj - PhjPCHjCHjPPhj dppe) reversibly insert into the C-S bond of thiophenes -T, BT and DBT as well as of some of their methylated derivatives- to yield the corresponding ring-opened products [PtLjlB C.S-Th)], as exemplified in Eq. 4.7 for DBT [38-44]. 

Studies have been reported on the attack of electrophiles on the P=0 and P=N— systems. It was found that there was a good correlation between the reactivity of a series of phosphonates and phosphinates and derivatives (112) towards triethyloxonium fluoroborate and the chemical shift of the methyl protons. Similarly, the reactivity of a similar series... 

This compound is a phosphine oxide derivative,with a methyl group replacing a hydrogen and two phenyl groups replacing two hydrogens. Its ncime is diphenylmethylphosphine oxide. 

Alkylphospholes have been shown to be much weaker bases than other tertiary phosphines a pA a of 0.5 was recorded for the 1-methyl derivative <69JA3308>. The site of proton attachment in nonaqueous systems has been investigated <86JCS(P2)629> and it was conclusively shown that if the protonation is allowed to occur at low temperature (—70°C) and with an acid whose anionic part is nonnucleophilic (e.g. CF3SO2OH) the proton attaches to phosphorus to form a lAf-phospholium ion. These ions are quite stable up to about — 30 °C, but decomposition occurs at room temperature (Equation (4)). 

A full report of the reaction between [(7v-C5H5)Fe(CO)2]2 and tetrakis(trifluoro-methyl)diphosphine (c/. Vol. 2, p. 311) has now appeared. The terminal phosphido-group in (62), which is formed from these reactants at 65—70 °C, or, less efficiently, from bis(trifluoromethyI)phosphine, retains a lone pair of electrons and thus undergoes a series of reactions (Scheme 4). The phosphine selenide derivative... 

In order to activate or enhance the activity of group III of the metabotropic glutamate receptors, new and potent phosphinic agonists were synthesized by Acher et al. in 2007 [54], Indeed, these presynaptic receptors inhibit the adenylate cyclase and the release process. y-Phosphinic acid derivative 49 is the key intermediate for the formation of compounds 51,52 and 53 (Scheme 7). Starting from a radical addition of hypophosphorous acid to the IV-CBz protected vinylglycine methyl ester 48, the phosphinic derivative compound 49 was obtained in 94%... 

Acid strengths are compared in Table 5.21. With given alkyl substituents, the acidity of a phosphinic acid is generally less than those of the corresponding phosphonic or phosphoric acids. For methyl derivatives the pA"j values lie in the order ... 

Colourless crystals of (6.973a), 3,5,8 trioxa-1-phosphabicyclo (2,2,2)octane, mp=88-89 C, can be made by heating tris(hydroxymethyl)phosphine with trimethyl orthofonnate in the presence of a little triethylamine (6.974). The methyl derivative, P(CH20)3 CMe can be obtained using MeC (OCHPa in this reaction. 

Tris phosphazenyl phosphine is obtained by reaction of the methyl derivative with phosphorus trichloride (7.488), and with phenyltetrafluorophosphorane, a tetrahedral cation and an octahedral anion are produced (7.489). With dimethyldifluorosilane fluorination occurs (7.490), but with dimethyldichlorosilane a ring cation is formed (7.491), and with some alcohols the product is phosphinimine (7.461). 

Of particular note, A[,A[-dimethylbenzylamines 5.4 are the most popular with 350 articles reported, followed by such other popular compounds as benzyl methyl derivatives 5.30 with 168,2-phenhylpyridines 5.14 with 135, dimethylantinopropyl (or propenyl) compounds 5.22 with 159, alkyl (or aryl) ethyl (or ethenyl) ketones 5.19 with 108, diallyl (or diaryl or propenyl) phosphines 5.25 with 206, and alkyl (or aryl) propionic acid esters 526 with 164. 

In this case, the benzoyl radical and a methyl radical produced through the fragmentation of a,a-dimethoxy benzyl radical both initiate pol5unerization. Other families include benzoin ethers, acetophenone derivatives, amino ketones, and phosphine oxide derivatives (1 ) (3,11). 

A few bisphospholane derivatives were converted to the corresponding bis(phosphine) monoxide derivatives making use of the protection of one of the P(III) centers as a phosphine borane (Schemes 10-1, 10-2 and 10-3). In one case (Scheme 10-1), an extra methyl group was also introduced. 

New synthetic methods, alternative synthetic pathways, total syntheses and biological applications have featured a progress in the area of phos-phonic and phosphinic acid derivatives. Among the biologically active compounds, a discovery of F-methyl phosphinic acids as organophosphoms... 

The diimine ligands 2-(phenylazo)pyridine and its p-methyl derivative [(33) R = H or Me] form bis complexes [Ru(LL)2XY]" with ruthenium(II). The complexes with X = Y = Cl, Br, or I (n = 0) react with tertiary phosphines by a second-order process with /c2 values apparently controlled by the bulk of the entering ligand. The complexes with X = py, Y = OH2, and X = Y = OH2 n = 2) react quite quickly with donor solvents such as acetronitrile or dimethyl sulfoxide the bis-aquo complex also reacts rapidly with pyridine. Complexes d5-[Ru(LL)2X2], when LL = an aryl-azooxime [(34) with R = aryl], readily lose HX on addition of a base such... 

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