Biology:1,3-Butadienal
1,3-Butadienal, also called vinylketene, is an organic compound and the simplest vinylketene. Like other vinylketenes, it occurs primarily as a reactive intermediate in cycloaddition reactions.
Preparation
As a vinylketene not protected by steric effects, 1,3-butadienal is typically prepared in situ. Dehydrohalogenation of vinyl acyl chlorides produces vinylketene:[1]
- H
2C=CH–CH
2–COCl → H
2C=CH–CH=C=O + HCl
The molecule was first properly observed in pyrolysis of the ynol ether ethoxybutenyne, a retro-ene reaction:
- H
2C=CH–C≡C–O–C
2H
5 → H
2C=CH–CH=C=O + C
2H
4
An analogous decomposition of ethoxyethyne ({{{2}}}) yields ethenone.[2] The compound also occurs from the radical addition of the allyl and COCl radicals, a potential side reaction in the production of allyl radicals from propene and oxalyl chloride.[3] As a reaction intermediate, it is produced from electrocyclic ring-opening of cyclobutenone.[4]
Sources
- ↑ Holder, Richard W.; Freiman, Howard S.; Stefanchik, Michael F. (1976). "Preparation of vinylketene by 1,4-elimination. Cycloaddition and isomerization to form α-ethylidenecyclobutanones". The Journal of Organic Chemistry 41 (20): 3303–3307. doi:10.1021/jo00882a021.
- ↑ Terlouw, Johan K.; Burgers, Peter C.; Holmes, John L. (1979). "Thermochemistry and generation of vinylketene". Journal of the American Chemical Society 101: 225–226. doi:10.1021/ja00495a041.
- ↑ Schleier, D.; Constantinidis, P.; Faßheber, N.; Fischer, I.; Friedrichs, G.; Hemberger, P.; Reusch, E.; Sztáray, B. et al. (2018). "Kinetics of the a-C3H5 + O2 reaction, investigated by photoionization using synchrotron radiation". Physical Chemistry Chemical Physics 20 (16): 10721–10731. doi:10.1039/C7CP07893E. PMID 29340384.
- ↑ Chen, Peng-hao; Dong, Guangbin (2016). "Cyclobutenones and Benzocyclobutenones: Versatile Synthons in Organic Synthesis". Chemistry – A European Journal 22 (51): 18290–18315. doi:10.1002/chem.201603382. PMID 27620805.
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