Methyl bromide, hydrolysis

The predicted kinetic behavior is first order. Second order kinetic behavior is actually observed for methyl bromide hydrolysis, so the proposed mechanism cannot be correct. 

A new approach we found is based on the initial bromination of methane to methyl bromide, which can be effected with good selectivity, although still in relatively low yields. Methyl bromide is easily separated from exeess methane, whieh is readily recyeled. Hydrolysis of methyl bromide to methyl alcohol and its dehydration to dimethyl ether are readily achieved. Importantly, HBr formed as by produet ean be oxidatively reeycled into bromine, making the overall proeess cat-alytie in bromine. 

Is the two step sequence depicted in the following equations con sistent with the second order kinetic behavior observed for the hydrolysis of methyl bromide ... 

P.M. Jeffers and N.L. Wolfe, Hydrolysis of methyl bromide, ethyl bromide, chloropicrin, 1,4-dichloro-2-butene, and other halogenated hydrocarbons, in Fumigants Environmental Fate, Exposure, and Analysis, ed. J.N. Seiber, J.A. Knuteson, J.E. Woodrow, N.L. Wolfe, M.V. Yates, and S.R. Yates, ACS Symposium Series No. 652, American Chemical Society, Washington, DC, pp. 32-41 (1997). 

Hydrolysis of the primary halide bromomethane (methyl bromide) in aqueous base has been shown to proceed according to equation [1]... 

As a result of the inductive and hyperconjugative effects it is to be expected that tertiary carbonium ions will be more stable than secondary carbonium ions, which in turn will be more stable than primary ions. The stabilization of the corresponding transition states for ionization should be in the same order, since the transition state will somewhat resemble the ion. Thus the first order rate constant for the solvolysis of tert-buty bromide in alkaline 80% aqueous ethanol at 55° is about 4000 times that of isopropyl bromide, while for ethyl and methyl bromides the first order contribution to the hydrolysis rate is imperceptible against the contribution from the bimolecular hydrolysis.217 Formic acid is such a good ionizing solvent that even primary alkyl bromides hydrolyze at a rate nearly independent of water concentration. The relative rates at 100° are tertiary butyl, 108 isopropyl, 44.7 ethyl, 1.71 and methyl, 1.00.218>212 One a-phenyl substituent is about as effective in accelerating the ionization as two a-alkyl groups.212 Thus the reactions of benzyl compounds, like those of secondary alkyl compounds, are of borderline mechanism, while benzhydryl compounds react by the unimolecular ionization mechanism. 

The hydrolysis of methyl bromide (CffiBr) in dilute aqueous solution may be followed by titrating samples with AgNCfy The volumes of AgNC>3 solution (V) required for 10 cm3 samples at 330 K in a particular experiment in a constant-volume batch reactor were as follows... 

Due to its gaseous nature it may have an effect on the stratospheric ozone layer [281, 402, 404]. After injection into soil for fumigation, methyl bromide rapidly diffuses through the soil pore space to the soil surface and then into the atmosphere [159,162,163,405,406]. Since a plastic sheet typically covers the soil surface, the rate of emission into the atmosphere depends upon the thickness and density of the plastic, if other conditions are the same [159, 406]. Other routes of disappearance from soil include chemical hydrolysis, methylation to soil organic matter through free radical reactions, and microbial degradation [ 136,159,405,407]. Several reports appeared on the study of the microbial transformations of methyl bromide, summarized as follows ... 

These data also demonstrate the impact of bromine chemistry on the stratosphere (see Chapter 12.D). The initial ODP for methyl bromide is 15, due primarily to the large a factor associated with bromine chemistry. However, since it is removed by reaction with OH in the troposphere as well as by other processes such as hydrolysis in the oceans and uptake by soils and foliage (see Chapter 12.D), it has a short atmospheric lifetime of 1.3 years and hence the ODP decreases rapidly with time, toward a long-term steady-state value. 

When comparing the hydrolysis of methyl bromide with its reaction with Cl under the same conditions (i.e., [Cl-] = 100 mM, see Illustrative Example 13.2), we see that from a thermodynamic point of view, the hydrolysis reaction is heavily favored (compare ArG° values). This does not mean that the methyl bromide present is primarily transformed into methanol instead of methyl chloride (which it would be, if the reaction were to be thermodynamically controlled). In fact, in this and all other cases discussed in this chapter, we will assume that the reactions considered will be kinetically controlled that is, the relative importance of the various transformation pathways of a given compound will be determined by the relative reaction rates and not by the respective ArG° values. Thus, in our example, because CE is about a 103 times better nucleophile as compared to water (see Section 13.2) and because its concentration is about 103 times smaller than that of water (0.05 M versus 55.3 M), the two reactions would be of about equal importance under the conditions prevailing in this groundwater. Note that the product methyl chloride would subsequently also hydrolyze to yield methanol, though at a much slower rate. We will come back to this problem in Section 13.2 (Illustrative Example 13.2). 

No, the two-step sequence is not consistent with the observed behavior for the hydrolysis of methyl bromide. The rate-determining step in the two-step sequence shown is the first step, ionization of methyl bromide to give methyl cation. 

Hydrolysis can explain the attenuation of contaminant plumes in aquifers where the ratio of rate constant to flow rate is sufficiently high. Thus 1,1,1-trichloroethane (TCA) has been observed to disappear from a mixed halocarbon plume over time, while trichlo-roethene and its biodegradation product 1,2-dichloroethene persist. The hydrolytic loss of organophosphate pesticides in sea water, as determined from both laboratory and field studies, suggests that these compounds will not be long-term contaminants despite runoff into streams and, eventually, the sea (Cotham and Bidleman, 1989). The oceans also can provide a major sink for atmospheric species ranging from carbon tetrachloride to methyl bromide. Loss of methyl bromide in the oceans by a combination of hydrolysis... 

Jeffers, P.M. and N.L. Wolfe. 1996a. Hydrolysis and chloride ion exchange rate of methyl bromide in sea water. Geophys. Res. Lett. 23 1773-1776. 

Fig. 18 Possible transition state structures for the hydrolysis of methyl bromide. The case with 4>Sn2 = 1 >s calculated using equation (95) and the case with 0SNl = 0.75 is calculated using equation (96). The Marcus analysis shows that a 0.5...

Returning to the hydrolysis of methyl halides, we recognize that the deduction of structure from the deuterium isotope effect is sensitive to the choice at r = 1. If instead of (109) we write (128), then for the hydrolysis of methyl bromide we can calculate the values of r for different values of A. The... 

Z75. (a) Dieckmann of dimethyl adipate, alkylation by allyl bromide, hydrolysis and decarboxylation (c) Robinson with CH3CH = CHCOCH3 then reduction (d) form enamine or enolate, acylate with CICOOEt, methylate with CH3I, do aldol with benzaldehyde. 

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