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

McAnoy, A.M., Dua, S., Blanksby, S.J., & Bowie, J.H. (2000) The loss of CO from the ortho, meta and para forms of deprotonated methyl benzoate in the gas phase. Journal of the Chemical Society, Perkin Transactions 2, pp. 1665-1673.

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The ortho, meta and para anions of methyl benzoate may be made in the source 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 ratio ortho>>meta > para. The rearrangement process is charge directed through 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), rather than carbon scrambling of the methoxycarbonylphenyl anion. There are two mechanisms which can account for this rearrangement, viz. (A) cyclisation of the ortho anion centre to the carbonyl group of the ester to give a cyclic 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 anion complex in which the MeOCO- species acts as a MeO- donor, which then adds to benzyne to yield the ortho anion of anisole. Calculations at the B3LYP/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 process A has the lower barrier for the rate determining step, and the lower Arrhenius factor: we cannot differentiate between these two mechanisms on available evidence.

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ID Code: 71641
Item Type: Journal Article
Refereed: Yes
Additional URLs:
Keywords: collision-induced dissociations, charge-remote fragmentations, density-functional theory, organic negative-ions, anions, rearrangements, exchange, benzene, isomers
DOI: 10.1039/b002813o
ISSN: 1364-5471
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2000 The Royal Society of Chemistry
Deposited On: 21 May 2014 03:47
Last Modified: 18 Jun 2014 05:06

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