Phosphines carbamoyl

In a closely related reaction, asymmetric reduction of 3-(2V-benzyl-7V-methylamino)propiophenone using H2, [Rh(COD)Cl]2 and the chiral phosphine (2S,4S-(l-(A-methyl-carbamoyl)-4-(dicyclohexylphosphino)-2-[diphenylphosphino)methyl]-pyrrolidine ((2S,4S)-MCCPM), followed by debenzylation and addition of the alcohol to l-chloro-4-(trifluoromethyl)benzene gave (R)-fluoxetine (4-(/ )). ... 

Recently, another class of neutral organophosphorus compounds, namely, N,N-dialkyl carbamoyl methyl phosphonate (CMP) (59) and its phosphine oxide analog (CMPO) have received attention due to their ability to extract even trivalent actinides from acidic solutions along with the hexa- and tetravalent actinide ions. These biden-tate phosphorus-based neutral extractants are reported to be stronger extractants as compared to TOPO (59-62). Pu(IV) and U(VI) are extracted as per the following extraction equilibria ... 

Bidentate oxygen-donor extractants include the neutral diamide compounds, such as the malonamides used in the French DIAMEX and DIAMEX-SANEX processes, RR N(C=0)-CHR"-(C=0)NRR the bisphosphine oxides, RR (P=0)- CIIR"-(P=0) RR the carbamoyl-(methyl)-phosphinates, R0R 0(P=0)-(CI I On o 0rr(C=0)NRR or the more efficient carbamoyl-methyl-phosphine oxides, RR (P=0)-CHR"-(C=0)... 

FIG U RE 3.1 n-Octyl-phenyl-W, W -di(/so )butyl-carbamoyl-methyl phosphine oxide (CMPO) used in the TRUEX process. 

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... 

When 59 or 60 are treated with a reducing agent such as hydrazine or triphenyl-phosphine, the Se-N bond is cleaved to give 2-(carbamoyl)phenyl diselenides [92], The ring cleavage with thiols leads to the selenosulfides [10, 97],... 

Carbamoyl ylids, 101, however, could be dehydrated via 102 R = H using triphenyl-phosphine dibromide and triethylamine (154). This reaction leads to an interesting class of push-pull ynamine phosphonium salts 103 (154), 72). 

Mit Arylisocyanaten reagiert Phosphin unter Bildung von Tri-carbamoyl-phosphinen 14 207,208) ... 

Horwitz, E.P. and Kalina, D.G., The extraction of Am(III) from nitric acid by octyl(phenyl)-iVJV-diisobutyl carbamoyl methyl phosphine oxide (CMPO)—tri butyl phosphate mixtures. Solv. Extr. Ion Exch., 1984, 2 179-200. 

Mathur, J.N., Murali, M.S., Ruikar, P.B., Nagar, M.S., Sipahimalani, A.T., Bauri, A.K., and Baneiji, A., Degradation, cleanup and reusability of octyl phenyl-A,A-diisobutyl carbamoyl methyl phosphine oxide during partitioning of minor actinides from high level waste (HLW) solutions. Sep. Set Tech., 1998, 33 2179-2196. 

Ramanujam, A., Dhami, P.S., Gopalakrishnan, V., Dudwadkar, N.L., Chitnis, R.R., and Mathur, J.N., Partitioning of actinides from high level waste of PUREX origin using octylphenyl-A,A-diisobutyl carbamoyl methyl phosphine oxide (CMPO) base supported Uquid membrane. Sep. Sci. Tech., 1999, 34 1717-1728. 

Extraction processes (TRUEX, PUREX, Talspeak, DIAMEX, PARC, etc.) generally involve complexation of transplutonium elements by alkyl phosphines, phosphine oxides, phosphoric acids, carbamoyl phosphonates, diamides, and thiophosphinates in aqueous/organic extractions, within derivatized solid supports, or on coated particles. There are excellent reviews of the processes and significant complexes by Mathur et al. and selected chapters in The Chemistry of the Actinide and Transactinide Elements to be published in 2003. " Work on the separation for nuclear waste management in the United States, France, and Russia have been reviewed. " ... 

JV-carbamoyl-substituted heterocyclic carbene/Pd(II) complexes in the presence of PPh3 and Cul are reported to mediate the cross-coupling of aryl iodides with terminal alkynes at very mild temperature [67]. The system is compatible with aryl bromides however, the temperature then required is 80 °C. In all reactions, the addition of 1 mol% of phosphine increased the yield of product. The role of the phosphine ligand is not completely understood but may facilitate the initial generation of a Pd(0) species. 

The reactions between ReBr(CO)5 or Re(CH2SiMe3)(CO)5 and amines RNH2 (R = Et, allyl, Pr ) affords the carbamoyl complexes Re(CONHR)(NH2R)(CO)4. These react with EtCOCl to form the cationic amine complexes [Re(CO)5(NH2R)]. The chelated iminoacyl Mn C(=NTol)C(CH2C6H4Cl)Nrol (CO)4 reacts with phosphines and phosphites to give substitution products rather than an pendant iminoacyl complex. ... 

The CMPO derivatives have been designed as efficient extractants for the trivalent lanthanide/ actinide group separation in the TRUEX process studied in the United States and Russia, see, for example, the review by Paiva and Malik (2004). Danonstration tests on the use of synergic mixtures of CMPO (Af,A-di-isopropyl carbamoyl methyl alkyl phenyl phosphine oxide) and chloroderivative CCD" for lanthanide/actinide extraction have been carried out in the development of the UNEX process, see Section 19.2.2 of this review. 

---