Fluoroalkoxides

Poly(Fluoroalkoxyphosphazene) Elastomers. When I is substituted with a mixture of trifluoroethoxide and telomer fluoroalkoxides, an elastomer II is obtained having a fluorine content of approximately 55 percent. A small amount of an unsaturated cure site may also be Incorporated into the polymer to promote vulcanization. 

These alkoxo complexes are also capable of cleavage of the C—Si bond of TMSCF3. The gold(III) fluoroalkoxides m-[AuMe2(OR)(PPh3)] (R = CH2CF3, CF1(CF3)2) can act as catalysts for the Knoevenagel condensation reaction.1775... 

An example of a much faster catalyst, equally well characterised is depicted in Figure 16.11. This catalyst gives thousands of turnovers of cis-2-pentene in a few minutes at 25 °C. The electron withdrawing fluoroalkoxides make the metal centre nucleophilic and the steric bulk prevents dimer formation or other degradation reactions. 

Among the derivatives of halide-substituted alcohols the fluoroalkoxides are of special interest. The presence of peripheral fluorine atoms enables the secondary M...F interaction and filling of the coordination sphere of the metal, which leads to an unusually high volatility. These compounds are described in the review by Willis [1749]. 

Solutions of sodium fluoroalkoxides in diethyl ether reacted with suspensions of tellurium tetrachloride or tellurium tetrabromide in ethanol at room temperature to produce the... 

Heating of tellurium tetrakis[fluoroalkoxides] with arenesulfonamides produced tellurium arenesulfonimide bis[fluoroalkoxides]2. 

Tellurium tetrakis[fluoroalkoxides] reacted with tellurium tetrahalides in benzene or tetrahydrofuran to yield fluoroalkoxy tellurium halides with one, two, or three flu-oroalkoxy groups in the molecule depending on the molar ratio of the reagents2. 

Depending on the nature of the anhydride, the ratio of the reagents, and the reaction temperature, tellurium tetrakis[fluoroalkoxides] and carboxylic acid anhydrides reacted to yield fluoroalkyl carboxylates, tellurium dioxide, acyloxy tellurium tris[fluoroalkoxide], bis[acyloxy] tellurium bis[fluoroalkoxides], tetrakis[acyloxy] tellurium compounds, or bis[fluoroalkoxy] tellurium oxides4. 

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. 

When 12 mmol of a carboxylic acid anhydride were gradually added to 6 mmol of tellurium tetrakis[2,2,3,3-tetrafluoropropoxide], bis[acyloxy tellurium bis[fluoroalkoxides] were formed as moisture-sensitive, colorless crystals or oils1. 

Tellurium tetralcis[fluoroalkoxides] mixed with an equimolar amount of a carboxylic anhydride at 0, and the mixture kept at 20° for two hours, produced moisture-sensitive acyloxy tellurium tns fluoroalkoxides The trifluoroalkyl carboxylates were removed under vacuum, the products washed several times with hexane-benzene (5 1), and the washed material dried in vacuo1. 

When the acyloxy tellurium tris[fluoroalkoxides] were heated at 80° under a vacuum of 0.01 torr, fluoroalkoxy carboxylates were eliminated with formation of bis[fluoroalkoxy] tellurium oxides (see p. 93). 

The same compounds were obtained when tellurium tetrafluoride and three molar equivalents of tellurium tetrakis[fluoroalkoxides] were refluxed in benzene3. 

The same compounds were obtained by refluxing equimolar amounts of tellurium tetrafluoride and tellurium tetrakis[fluoroalkoxides] in benzene1. 

V-Trimethylsilylmorpholine (2 mol) reacted with bis[2,2,3,3-tetrafluoropropoxide] tellurium difluoride (1 mol) in diethyl ether at 5° to yield dimorpholino tellurium bis(fluoroalkoxide)2. 

Tellurium tetrakis[fluoroalkoxides] and three molar equivalents of tellurium tetrafluoride in refluxing benzene produced fluoroalkoxy tellurium trifluorides1. 

Tellurium tetrakis[fluoroalkoxides] and tellurium tetrachloride reacted in refluxing benzene or tetrahydrofuran to produce fluoroalkoxy tellurium chlorides. The number of alkoxy groups in the product molecules is determined by the molar ratio of the reagents2. 

Under similar conditions but with three moles of tellurium tetrakis[fluoroalkoxide] per mole of tellurium tetrachloride, tris fluoroalkoxy] tellurium chlorides were obtained2. 

Tris fluoroalkoxy tellurium bromides were synthesized by refluxing a mixture of three moles of tellurium tetrakis[fluoroalkoxides] and one mole of tellurium tetrabromide in benzene. The oily products were isolated by removal of the solvent in vacuo1. 

Polydichlorophosphazene is a highly reactive polymer. The chlorine atoms can be replaced by a great variety of side groups leading to different polyorganophosphazenes aryloxy, fluoroalkoxide, etc. symmetrically or unsymmetrically substituted. The physical properties strongly depend on the nature of various substituents. 

Figure 14 Plot of vapor pressure as a function of molecular weight for a series of barium bis(alkoxides) and bis(fluoroalkoxides) ...

Dichloropyridazine was transformed with sodium 2,2,2-trifluoroethoxide into mono- or di-alkoxy derivatives, but with other sodium fluoroalkoxides, polysubstitution occurred (85CJC3037). 4,5-Dichloro-2-methyl-3(2// )-pyridazinone was used to prepare herbicidal py-ridazino-l,2,4-triazines (87MI16). 

Tellurium Tetrakis[fluoroalkoxide] 30 mmol of tellurium tetrafluoride are mixed with 150 mmol of fluoroalkoxytrimethylsilane and the mixture is heated at 100-120° until evolution of fluorotrimethylsilane has stopped. The mixture is filtered and the filtrate is distilled under reduced pressure. 

Tellurium tetrakis[fluoroalkoxides] with icc.-aminotrimethylsilanes in diethyl ether produced di-sec.-amino tellurium bis[fluoroalkoxides]. ... 

Acyloxy(2,2,3,3-tetrafluoropropoxy) tellurium oxides were formed upon heating bis[acyloxy] tellurium bis[fluoroalkoxides] under a vacuum of 0.01 torr. ... 

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