Wednesday, December 10, 2014

Gas-Phase Preparation of Carbonic Acid and Its Monomethyl Ester

Reisenauer, H. P.; Wagner, J. P.; Schreiner, P. R.  Angew. Chem. Int. Ed. 2014, 53, 11766-11771
Contributed by Steven Bachrach.
Reposted from Computational Organic Chemistry with permission

I remain amazed at how regularly I read reports of structure determinations of what seem to be simple molecules, yet these structures have eluded determination for decades if not centuries. An example is the recently determined x-ray crystal structure of L-phenylalanine;1 who knew that growing these crystals would be so difficult?

The paper I want to discuss here is on the gas-phase structure of carbonic acid 1.2 Who would have thought that preparing a pure gas-phase sample would be so difficult? Schreiner and co-workers prepared carbonic acid by high-vacuum flash pyrolysis (HVFP) of di-tert-butyl carbonate, as shown in Scheme 1.
Scheme 1
Carbonic acid can appear in three difference conformations, shown in Figure 1. The two lowest energy conformations are separated by a barrier of 9.5 kcal mol-1 (estimated by focal point energy analysis). These conformations can be interconverted using near IR light. The third conformation is energetically inaccessible.

1cc
(0.0)

1ct
(1.6)

1tt
(10.1)

2cc

2cc
Figure 1. CCSD(T)/cc-pVQZ optimized structures of 1 (and the focal point relative energies in kcal mol-1) and the CCSD(T)/cc-pVTZ optimized structures of 2.

The structures of these two lowest energy conformations were confirmed by comparing their experimental IR spectra with the computed spectra (CCSD(T)/cc-pVTZ) and their experimental and computed rotational constants.

An interesting added component of this paper is that sublimation of the α- and β-polymorphs of carbonic acid do not produce the same compound. Sublimation of the β-isomorph does produce 1, but sublimation of the α-isomorph produces the methylester of 1, compound (see Figure 1). The structure of 2 is again confirmed by comparison of the experimental and computed IR spectra.


References

(1) Ihlefeldt, F. S.; Pettersen, F. B.; von Bonin, A.; Zawadzka, M.; Görbitz, C. H. "The Polymorphs of L-Phenylalanine," Angew. Chem. Int. Ed. 201453, 13600–13604, DOI: 10.1002/anie.201406886.
(2) Reisenauer, H. P.; Wagner, J. P.; Schreiner, P. R. "Gas-Phase Preparation of Carbonic Acid and Its Monomethyl Ester," Angew. Chem. Int. Ed. 201453, 11766-11771, DOI: 10.1002/anie.201406969.


InChIs

1: InChI=1S/CH2O3/c2-1(3)4/h(H2,2,3,4)
InChIKey=BVKZGUZCCUSVTD-UHFFFAOYSA-N
2: InChI=1S/C2H4O3/c1-5-2(3)4/h1H3,(H,3,4)
InChIKey=CXHHBNMLPJOKQD-UHFFFAOYSA-N




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