Third phase formation behaviour of tris(2-methylbutyl) phosphate and tri-n-alkyl phosphates in the extraction of mineral acids and tetravalent metal ions

The formation of third phase is a detrimental phenomenon witnessed in the nuclear separation processes during the extraction of certain metal salts by an organic solution, which comprises of a neutral extractant, tri-n-butyl phosphate dispersed in a non-polar diluent, n-dodecane (n-C12H26). In the present work, a comparative analysis on the third phase formation behaviour of three trialkyl phosphates, TBP, its linear and branched higher homologues tri-n-amyl phosphate and tris(2-methylbutyl) phosphate (T2MBP), respectively, have been provided which will be useful for the identification of an extractant with minimum third phase formation tendency. The organic phase splitting behaviour during the extraction of three mineral acids (HClO4, HCl and HNO3) and two tetravalent metal nitrates (Th(IV) and Zr(IV)) by trialkyl phosphates has been investigated to understand the influence of anionic and cationic components, respectively, in third phase formation of trialkyl phosphates. The effect of structure of the alkyl groups of trialkyl phosphate and chain length of diluents on third phase formation during Zr(IV) extraction from HNO3 media have also been studied. Overall, the third phase formation behaviour of T2MBP was found to be lower both for the extraction of mineral acid and Zr(IV), thereby indicating its potentiality for applications in various solvent extraction processes.

Regio- and Stereoselective (SN2) N-, O-, C- and S-Alkylation using Trialkyl Phosphates

Bimolecular nucleophilic substitution (S N 2) is one of the most known fundamental reactions in organic chemistry to generate new molecules from two molecules. In principle, a nucleophile attacks from the back side of an alkylating agent having a suitable leaving group, most commonly using a halide. However, alkyl halides are expensive, very harmful, toxic and not so stable which makes them problematic for laboratory use. In contrast, trialkyl phosphates are cheap, readily accessible, stable at room temperature, under air, and are easy to handle but rarely used as alkylating agents in organic synthesis. Here, we describe a mild, straightforward and powerful method for nucleophilic alkylation of various nucleophiles such as N-, O-, C- and S- using readily available trialkyl phosphate. The reaction proceeds smoothly with excellent yield and quantitative yield in many cases and covers a wide range of substrates. Further, the rare stereoselective transfer of secondary alkyl groups has been achieved with inversion of configuration of chiral centers (up to >99% ee).

Direct extraction of uranium from yellow cake and ore matrices using supercritical carbon dioxide

The study demonstrates the accomplishment of single step, direct supercritical fluid carbon dioxide (SC CO2) dissolution and extraction of uranium from crude matrices viz. yellow cakes (>90%) and rock phosphate ores (70%) employing adducts of trialkyl phosphates and nitric acid, thus avoiding free acid usage and eliminating number of process steps. Rock phosphate ore was made amenable for supercritical fluid extraction (SFE) system by unique strategy of pyrohydrolytic removal of fluorine. Pressure and temperature conditions, which were found to influence uranium extraction efficiency, were optimized at 150 atm. and 323 K. Two milliliter of adduct amount was found to be adequate. Adducts of branched alkyl phosphate, tri-isoamyl phosphate and tri-ethyl hexyl phosphate (TEHP), yield better purity in comparision to straight chain tri-butyl phosphate (TBP).

Selective N-Monoalkylation of Amide Derivatives with Trialkyl Phosphates

A highly selective and easily handled monoalkylation of primary amide derivatives by using trialkyl phosphates as alkylating reagents in cyclopentyl methyl ether (CPME) was developed. Various monoalkylated amide derivatives were efficiently synthesized by changing the alkyl moiety (e.g., methyl, ethyl, butyl, or benzyl) of the trialkyl phosphate. These phosphate reagents are relatively stable and easily available, and CPME is a useful solvent in process chemistry.

Experimental determination and model correlation for the solubilities of trialkyl phosphates in supercritical carbon dioxide

The solubilities of a series of trialkyl phosphates in supercritical carbon dioxide have been investigated.

Comparision in the solvent extraction behavior of uranium (VI) in some trialkyl phosphates in ionic liquid

Higher homologs of trialkyl phosphates (TAlP) are proposed for reprocessing of fast reactor fuels. Solvent extraction behavior of U(VI) from nitric acid medium was studied in some TAlP present in 1-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C

Haloalkylphosphorus Hydrolases Purified from Sphingomonas sp. Strain TDK1 and Sphingobium sp. Strain TCM1

ABSTRACTPhosphotriesterases catalyze the first step of organophosphorus triester degradation. The bacterial phosphotriesterases purified and characterized to date hydrolyze mainly aryl dialkyl phosphates, such as parathion, paraoxon, and chlorpyrifos. In this study, we purified and cloned two novel phosphotriesterases fromSphingomonassp. strain TDK1 andSphingobiumsp. strain TCM1 that hydrolyze tri(haloalkyl)phosphates, and we named these enzymes haloalkylphosphorus hydrolases (TDK-HAD and TCM-HAD, respectively). Both HADs are monomeric proteins with molecular masses of 59.6 (TDK-HAD) and 58.4 kDa (TCM-HAD). The enzyme activities were affected by the addition of divalent cations, and inductively coupled plasma mass spectrometry analysis suggested that zinc is a native cofactor for HADs. These enzymes hydrolyzed not only chlorinated organophosphates but also a brominated organophosphate [tris(2,3-dibromopropyl) phosphate], as well as triaryl phosphates (tricresyl and triphenyl phosphates). Paraoxon-methyl and paraoxon were efficiently degraded by TCM-HAD, whereas TDK-HAD showed weak activity toward these substrates. Dichlorvos was degraded only by TCM-HAD. The enzymes displayed weak or no activity against trialkyl phosphates and organophosphorothioates. The TCM-HAD and TDK-HAD genes were cloned and found to encode proteins of 583 and 574 amino acid residues, respectively. The primary structures of TCM-HAD and TDK-HAD were very similar, and the enzymes also shared sequence similarity with fenitrothion hydrolase (FedA) ofBurkholderiasp. strain NF100 and organophosphorus hydrolase (OphB) ofBurkholderiasp. strain JBA3. However, the substrate specificities and quaternary structures of the HADs were largely different from those of FedA and OphB. These results show that HADs from sphingomonads are novel members of the bacterial phosphotriesterase family.