The loss of CO from the ortho, meta and para forms of deprotonated methyl benzoate in the gas phase

The ortho, meta and para anions of methyl benzoate may be made in the sourc e of a mass spectrometer by the S(N)2(Si) reactions between HO- and methyl (o-, m-, and p-trimethylsilyl)benzoate respectively. All three anions lose CO upon collisional activation to form the ortho anion of anisole in the ra tio ortho>>meta > para. The rearrangement process is charge directed throug h the ortho anion. Theoretical calculations at the B3LYP/6-311++G(d,p)//HF/ 6-31+G(d) level of theory indicate that the conversion of the meta and para anions to the ortho anion prior to loss of CO involve 1,2-H transfer(s), r ather than carbon scrambling of the methoxycarbonylphenyl anion. There are two mechanisms which can account for this rearrangement, viz. (A) cyclisati on of the ortho anion centre to the carbonyl group of the ester to give a c yclic carbonyl system in which the incipient methoxide anion substitutes at one of the two equivalent ring carbons of the three membered ring to yield an intermediate which loses CO to give the ortho anion of anisole, and (B) an elimination reaction to give an intermediate benzyne-methoxycarbonyl an ion complex in which the MeOCO- species acts as a MeO- donor, which then ad ds to benzyne to yield the ortho anion of anisole. Calculations at the B3LY P/6-311++G(d,p)//HF/6-31+G(d) level of theory indicate that (i) the barrier in the first step (the rate determining step) of process A is 87 kJ mol(-1 ) less than that for the synchronous benzyne process B, and (ii) there are more low frequency vibrations in the transition state for benzyne process B than for the corresponding transition state for process A. Stepwise proces s A has the lower barrier for the rate determining step, and the lower Arrh enius factor: we cannot differentiate between these two mechanisms on avail able evidence.