Setting reaction fluoride, effect

With Freon 112 or 113 as a solvent, fluonnation of pnmary butyl halides with bromine trifluonde can give mixtures of primary and secondary fluorides When 1,4 dibromobutane is the substrate, 93% l-bromo-4-fluorobutane and 1% 1-bro-mo-3-fluorobutane is obtained, with 1,4 dichlorobutane, the product contains 65% l-chloro-3-fluorobutane and 35% 1-chloro 4 fluorobutane When 4-bromo- or 4-chlorobutyl trifluoroacetate is used, the ratio of 4-fluorobutyl tnfluoroacetate to 3 fluorobutyl trifluoroacetate is 1 4 The effect of solvent is measured in another set of experiments When the reaction of bromine trifluonde and l,3-dichloro-2-fluoropropane in either Freon 113 or hydrogen fluoride is allowed to proceed to 40% conversion, the product mixture has the composition shown m Table 1 [/O] When 1 chloro 2,3-dibromopropane is combined with one-third of a mole of bromine trifluonde, both 1 bromo 3 chloro-2-fluoropropane and l-chloro-2,3-di-fluoropropane are formed [//] (equation 10)... 

Kinetic studies also provide other evidence for the SnI mechanism. One technique used F NMR to follow the solvolysis of trifluoroacetyl esters. If this mechanism operates essentially as shown on page 393, the rate should be the same for a given substrate under a given set of conditions, regardless of the identity of the nucleophile or its concentration. In one experiment that demonstrates this, benzhy-dryl chloride (Ph2CHCl) was treated in SO2 with the nucleophiles fluoride ion, pyridine, and triethylamine at several concentrations of each nucleophile. In each case, the initial rate of the reaction was approximately the same when corrections were made for the salt effect. The same type of behavior has been shown in a number of other cases, even when the reagents are as different in their nucleophilicities (see p. 438) as H2O and OH . 

Not surprisingly, the use of acidified water increased the level of fluoride release from the glass, and this effectively models what happens in a setting cement. The acid-base reaction between the glass and the water-soluble polymeric acid liberates fluoride from the glass, causing it to move to the matrix, from where it is gradually leached as the cement releases fluoride [227,228]. 

The acids are chosen so as to illustrate the main effects on the values of k3 j. Values of k13 are, in general, set by the strength of the AH bond, and can be interpreted in thermodynamic rather than kinetic terms. The simplest possible acid recombination reaction is that between the proton and the fluoride ion, which is simply a charged sphere. As expected, this reaction has the extremely high rate coefficient of 1 x 1011 1 mole-1 sec-1. Variations of rate coefficients from this value may be explained in terms of steric effects, ionic charge effects, and anion electronic and solvent rearrangement effects, the latter two usually being connected. 

The chemically inert character of sulfur hexafluoride is responsible for the almost complete lack of exchange of fluorine atoms between SFe and HF (249). It does react with hot alkali metals, however, and a study has been made of the rate of reaction of Na atoms with SF6 gas using the sodium diffusion flame technique. The rate constant at 247° is 2.23 X 10-1 cm mole-1 sec-1 and the energy of activation for the reaction SF6 + Na — SF6 + NaF, is about 37 keal. A film of sodium on a glass wall does not react with SF at room temperature. The reaction sets in at about 200° (57). The fluorides, SF , SF4, and S2F2, have no effect upon the viscosity of liquid sulfur in the range 180-195° (93). Sulfur hexafluoride forms a solid hydrate which has a crystal constant of 17.21 A. It decomposes just above 0° (285). 

Studies on the alkaline hydrolysis of various phosphonic and phosphinic esters have provided information on the electronic or steric effects of substituents and the effects of changes in reaction conditions amongst the substrates so extensively examined are the O-aryl esters of dimethylphosphinothioic acid (552) esters of diphenylphosphinic acid and O-aryfand S -aryf esters of diphenylphosphinothioic acid (553 Z, Y = O or S). Other studies have concentrated on aryl esters of diaryIphosphinic acids (554) , and the effects of the stepwise replacement of P-Me by P-Ph in esters of dimethyl-, methylphenyl- and diphenyl-phosphinic acids The esters 555 (R = EtO, R = Me or Ph, R = R = Ph X = SEt or hydrolyse under alkaline conditions faster than do the comparable 5 -(4-substituted-butyl) esters. Comparable steric and electronic influences on the hydrolyses of phosphonic and phosphinic fluorides phosphinic chlo-rides the phosphonothioic chlorides 556 and other phosphonic and phosphinic esters have been noted. Phosphonic and phosphinic halides are prone to undergo halo-gen-exchange reactions, a process which, in general, is faster for derivatives of phosphonic than for those of phosphonothioic and phosphonoselenoic acids, and to be particularly important for acid fluorides . ... 

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