2.2.3.3- tetrafluoropropoxy

Chloro-/V-[[chloro(2,2,3,3-tetrafluoropropoxy)phosphinyl]oxy]ethanimidoyl chloride... 

Although solvent samples have been observed for approximately one year without any solids formation, work was completed to define a new solvent composition that was thermodynamically stable with respect to solids formation and to expand the operating temperature with respect to third-phase formation.109 Chemical and physical data as a function of solvent component concentrations were collected. The data included BC6 solubility cesium distribution ratio under extraction, scrub, and strip conditions flowsheet robustness temperature range of third-phase formation dispersion numbers for the solvent against waste simulant, scrub and strip acids, and sodium hydroxide wash solutions solvent density viscosity and surface and interfacial tension. These data were mapped against a set of predefined performance criteria. The composition of 0.007 M BC6, 0.75 M l-(2,2,3,3-tetrafluoropropoxy)-3-(4-.sw-butylphenoxy)-2-propanol, and 0.003 M TOA in the diluent Isopar L provided the best match between the measured properties and the performance criteria. 

FIGURE 6.5 The structures of the FPEX solvent, consisting of 4,4, (5 )-di(fert-butylcyclohexano)-18-crown-6(DtBuCH18C6),calix[4]arene-bis(terf-octylbenzo-crown-6) (BOBCalixC6), and l-(2,2,3,3-tetrafluoropropoxy)-3-(4- ec-butylphenoxy)-2-propanol modifier (Cs-7SB). 

The CSSX process utilizes a novel solvent made up of four components calix[4]arene-bis-(4-fer/-octylbenzo-crown-6) known as BOBCalixC6 as extractant a lipophilic fluorinated alcohol, l-(2,2,3,3-tetrafluoropropoxy)-3-(4-. ec-butylphenoxy)-2-propanol known as Cs-7SB, as diluent modifier tri- -octylamine as a suppressor of impurity effects and the isoparaffinic diluent Isopar L, a mixture of branched hydrocarbons with an average chain-length of 12 carbons. Figure 3 shows the composition of the solvent as currently optimized for the SWPF application at the SRS [37,49], The chemistry of the solvent is well understood, with regards to both its fundamental properties and its performance under process conditions. All of the components are commercially available, and efficient synthetic and purification procedures have been worked out [17,18,37], Thus, these key components may be obtained from multiple chemical suppliers capable of specialty synthesis. 

Addition of arenethiols to ethanolic solutions of tetrakis[2,2,3,3-tetrafluoropropoxy] tellurium at — 50° precipitated quantitatively a mixture of bis[arylthio] tellurium compounds and diaryl disulfanes. Recrystallization from petroleum ether separated the two products2. 

Bis[4-Chlorophenylthio] Tellurium2 3.6 g (25 mmol) of 4-chlorobenzenethiol are dissolved in 25 ml of anhydrous ethanol, the solution is cooled to — 50°, and 3.25 g (5 mmol) of tetrakis[2,2,3,3-tetrafluoropropoxy] tellurium are added dropwise. The mixture is stirred for 10 min, filtered, the solid is washed with chilled (—20°) diethyl ether, dried under reduced pressure at <0°, and recrystallized from petroleum ether at low temperature yield 2.07g (100%), m.p. 105-107°. 

Bis[morphohno] lellurium Dichloridc3 To a stirred solution of 1.38 g (3 mmol) of bis[2,2,3,3-tetrafluoropropoxy] tellurium dichloride in 20 ml of anhydrous diethyl ether at 0° is added dropwise a solution of 1.03 g (6.5 mmol) of JV-trimethylsilylmorpholine in 10 ml of diethyl ether. The mixture is stirred at 5° for 1 h. The precipitate is filtered and washed with diethyl ether yield 80%. 

Heating of benzenesulfonimido 2,2,3,3-tetrafluoropropoxy tellurium fluoride and N-trimethylsilylmorpholine at 60° in benzene for 15 minutes gave rise to the moisture-sensitive benzenesulfonimino morpholino tetrafluoropropoxy telluriuml. 

Benzenesulfonimino Morpholino 2,2,3,3-Tetrafluoropropoxy Tellurium 1.5 g (3.55 mmol) of benzenesulfonimino tetrafluoropropoxy tellurium fluoride are suspended in 30 ml of anhydrous benzene, 0.48 g (3.0 mmol) of /V-trimcthylsilylmorpholine dissolved in benzene are added, and the mixture is heated at 60° for 15 min. The mixture is then filtered, the solvent is distilled from the filtrate under reduced pressure, and the wall of the flask is scratched to induce the oily residue to crystallize. The solids are combined yield 0.88 g (59%) m.p. 115° (dec.). 

Benzenesulfonimino Bis[2,2,3,3-tetrafluoropropoxy] Teliurium1 3.3 g(5 mmol)oftetrakis[2,2,3,3-tetrafluoro-propoxy] tellurium are mixed with 0.79 g (5 mmol) of benzenesulfonamide, and the mixture is heated at 110o/0.04 torr until the fluoroalkatiol ceases to condense in a trap cooled at — 25". The mixture is triturated with petroleum ether/diethyl ether (4/1, v/v), filtered, the solid is washed with diethyl ether cooled to — 10, and dried under anhydrous conditions yield 1.8 g (66%) m.p. 198° (dec.). 

Refluxing of equimolar amounts of bis[2,2,3,3-tetrafluoropropoxy] tellurium difluoride and Af,Af-bis[trimethylsilyl]benzenesulfonamide in benzene yielded benzenesulfonimino bis[tetrafluoropropoxy] tellurium1. 

Benzenesulfonimino 2,2,3,3-Tetrafluoropropoxy Tellurium Fluoride1 A solution of 9.0 g (30 mmol) of N,N-bis[trimethylsilyl]benzenesulfonamidc in 25 ml of benzene is added dropwise to a stirred solution of 9.5 g (30 mmol) of 2,2,3,3-tetrafluoropropoxy tellurium trifluoride in 15 ml of benzene. The mixture is heated under reflux until evolution of fluorotrimethylsilane ceases, the mixture is cooled, the precipitate collected, and recrystallized from benzene yield 9.1 g (70%) m.p. 201° (dec.)... 

When heated with W-trimethylsilylmorpholine in benzene at 60°, Benzenesulfonimino 2,2,3,3-tetrafluoropropoxy tellurium fluoride yielded benzenesulfonimino morpholino tetra-fluoropropoxy tellurium. ... 

Benzenesulfonimino Tellurium Difluoride2 A mixture of 12.8 g (30 mmol) of bis[2,2,3,3-tetrafluoropropoxy] tellurium difluoride and 4.7 g (30 mmol) of benzenesulfonamide is heated at 63°/0.035 torr for 40 min and at 95o/0.035 torr for 1 h. After all the alcohol has distilled off, benzene is added to the mixture, the deposited solid is filtered off, washed several times with small portions of hot benzene, and dried. The product should be stored with protection from moisture yield 9.4 g (98%) m.p. 237-240°. 

Bis[2,2,3,3-tetrafluoropropoxy] tellurium oxide was also obtained when the acetyl tellurium tris[fluoroalkoxide] was kept at 80° under 0.01 torr1. 

Tetrafluoropropoxy Tellurium Trifluoride2 6.1 g (30 mmol) of tellurium tetrafluoride are suspended in 50 ml of anhydrous benzene, the suspension is stirred, and 6.1 g (30 mmol) of 2,2,3,3-tetrafluoro-l-trimethylsiloxypropane are added dropwise. The mixture is heated at 60° for 1 h, filtered, fiuorotrimeth-... 

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