Past exam of the chemistry course of the year 1 of the natural sciences course of the University of Cambridge / 2022 / Paper 1 / 1 / c

C is 2-Chloroethyl vinyl ether, $\mathrm{C}{\mathrm{H}}_2=\mathrm{CH}-\mathrm{O}-\mathrm{C}{\mathrm{H}}_2-\mathrm{C}{\mathrm{H}}_2\mathrm{Cl}$. There is one alkene and no carbonyl. Assign the carbon-13 NMR resonances asThe strongly differentiated pair of alkene shifts is characteristic of a vinyl ether; interpreting $151.1$ ppm as a carbonyl would leave the unusually shielded unsaturated $87.4$ ppm carbon and the three distinct vinylic protons unexplained.

The $1621\mathrm{c}{\mathrm{m}}^{-1}$ absorption is predominantly the carbon–carbon double-bond stretching vibration of the electron-rich vinyl ether. resonance donation from an oxygen lone pair changes both its frequency and its electric dipole moment variation during stretching. There is no carbonyl in the assigned structure, consistent with the absence of a carbon-13 NMR signal in the usual ketone or acyl chloride region.

Let $a$ be the internal vinylic proton, $b$ the terminal proton trans to $a$, $c$ the terminal proton cis to $a$, $d$ the oxygen-bound methylene and $e$ the chlorine-bound methylene. The assignments areFor the $a$ doublet of doublets, pairing corresponding lines gives $J_{ab}\simeq 300[(6.516-6.468)+(6.492-6.445)]/2=14.25$ Hz and $J_{ac}\simeq 300[(6.516-6.492)+(6.468-6.445)]/2=7.05$ Hz. The larger value identifies trans vinylic coupling; the smaller identifies cis vinylic coupling. The $b$ resonance confirms the large splitting, approximately $14.25$ Hz, and has a small geminal coupling to $c$.

The small spacings are not perfectly reciprocal if treated as exact First-order NMR multiplets: the $b$ lines imply $|J_{bc}|\simeq 2.55$ Hz, whereas the $c$ lines imply $|J_{bc}|\simeq 2.10$ Hz and $J_{ac}\simeq 6.60$ Hz. Thus report $J_{ab}\simeq 14.3$ Hz, $J_{ac}\simeq 7$ Hz and $|J_{bc}|\simeq 2$–$3$ Hz, rather than asserting incompatible exact constants. Printed precision and departures from a simple first-order pattern limit this line-picking estimate; a full spin-system fit would be needed for refined values. Splittings alone do not establish the signs of these couplings.

The two methylene groups split one another into approximate NMR triplets, with $J_{de}\simeq 300(3.727-3.708)=5.7$ Hz; the oxygen-bound triplet gives approximately the same value from its rounded line labels. The three vinylic protons plus two methylenes give the required seven-proton integral. The terminal vinylic protons are diastereotopic, because replacing one or the other creates different alkene geometries.

The vinyl ether has an important resonance contributorDonation from oxygen into the conjugated system increases electron density at the terminal unsaturated carbon, helping explain its unusually shielded ${\delta }_C=87.4$ ppm and its terminal protons near 4.1–4.2 ppm. The directly oxygen-bound unsaturated carbon is strongly deshielded at $151.1$ ppm; its proton at $6.480$ ppm also experiences the oxygen substituent and alkene magnetic anisotropy. These trends are consistent with the whole delocalized electronic structure; a chemical shift is not simply a meter for an atom's partial atomic charge.

For the saturated part, the stronger local deshielding by oxygen places $\mathrm{OC}{\mathrm{H}}_2$ at ${\delta }_C=67.8$, ${\delta }_H\simeq 3.948$, while $\mathrm{C}{\mathrm{H}}_2\mathrm{Cl}$ lies at $41.9$ and $3.708$ ppm. The two terminal vinylic protons have different geometrical relationships to the oxygen substituent and therefore different chemical shifts as well as different vicinal couplings.