The rearrangement of 2-ethoxyethylidene, generated photochemically from a nonnitrogenous precursor, leads to ethyl vinyl ether. Although this product could result, in principle, from a 1, 2-hydrogen shift and/or a 1, 2-ethoxy shift in the carbene, a deuterium labeling study indicates an essentially exclusive preference for hydrogen migration. The experimental results are in agreement with CCSD and W1BD calculations for the simpler ...