Summary
TheDarzens reaction of dichloroacetophenone (DCAP) with substituted benzaldehydes has been studied. The structure of the products was shown to depend on the phenyl group substituents. Reaction of benzaldehyde, 4-bromo-, and 2,4-dichlorobenzaldehydes results in 1-phenyl-3-aryl-3-chloropropane-1,2-diones (2a–c), reaction ofpara- ormeta-nitrobenzaldehydes yields 1-phenyl-2-chloro-3-aryl-2,3-epoxypropane-1-ones (3a, b). Upon the introduction of an alkoxy group into the phenyl ring of benzaldexyde and/or dichloroacetophenone, symmetrically substituted dioxines were obtained (6a–c). The structure of the reaction products has been established by single crystal X-ray investigations.
Zusammenfassung
DieDarzens-Reaction von Dichloracetophenon (DCAP) mit substituierten Benzaldehyden wurde untersucht. Die Struktur der Produkte ist von den Substituenten an der Phenylgruppe abhängig. Die Umsetzung mit Benzaldehyd, 4-Brom- und 2,4-Dichlorbenzaldehyd liefert 1-Phenyl-3-aryl-3-chloropropan-1,2-dione (2a–c), die Reaktion vonpara- odermeta-Nitrobenzaldehyd 1-Phenyl-2-chloro-3-aryl-2,3-epoxipropan-1-one (3a,b). Durch Einführung einer Alkoxygruppe in den Phenylring des Benzaldehyds und/oder des Dichloracetophenons erhält man symmetrisch substituierte Dioxine (6a–c). Die Struktur der Reaktionsprodukte wurde mittels Röntgenstrukturanalyse bestätigt.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Darzens G. (1904) Compt. Rend.139: 1214; Newman M. S., Magerlein B. J. (1949) Org. React.5: 414; Elderfield R. C. (1950) Heterocyclic compounds, vol. 1. Wiley, New York, p 14
Mamedov V. A., Nuretdinov I. A., Sibgatullina F. G. (1988) Izv. Acad. Nauk SSSR, Ser. Khim.: N9, 2172
Mamedov V. A., Nuretdinov I. A. (1992) Izv. Acad. Nauk, Ser. Khim.: N9, 2159
Mamedov V. A., Malaev V. G., Sibgatullina F. G., Nuretdinov I. A., Kitaev Yu. P. (1992) Izv. Acad. Nauk, Ser. Khim.: N2, 438
Tsuboi S., Furutani H., Takeda A. (1987) Synthesis: 292
Takeda A., Wada S., Fuji M., Tanaka H. (1970) Bull. Chem. Soc., Jpn.43: 2997; Mamedov V. A., Nuretdinov I. A., Sadkova D. N. (1970) Izv. Acad. Nauk SSSR, Ser Khim.: N12, 2854; Mamedov V. A., Valeeva V. N., Antokhina L. A., Nuretdinov I. A. (1991) Izv. Acad. Nauk. SSSR, Ser. Khim.: N6, 1422
Credner H. H., Meier E., Lassig W. (1979) Chem. Ber.112: 3098
Mamedov V. A., Nuretdinov I. A. (1988) Izv. Acad. Nauk SSSR, Ser. Khim.: N7, 1670
Mamedov V. A., Nuretdinov I. A., Sibgatullina F. G. (1990) Izv. Acad. Nauk SSSR, Ser. Khim.: N11, 2627
Mamedov V. A., Nuretdinov I. A., Sibgatullina F. G. (1989) Izv. Acad. Nauk SSSR, Ser. Khim.: N6. 1412; Mamedov V. A., Polushina V. L., Mertsalova F. F., Nuretdinov I. A., Plyamovatyi A. H. (1991) Izv. Acad. Nauk SSSR., Ser. Khim.: N7, 1660
Allen F. H., Kennard O., Watson D. G. et al. (1987) J. Chem. Soc. Perkin Trans. II.: N12, S1–S19
Summenbell R. C., Umhoefer R. R. (1961) J. Am. Chem. Soc.61: 3020; Connett, J. E., Creighton, I. A., Green, J. H. S., Kynaston W. (1966) Spectrochim. Acta22: 1853
Beilstein V. 6 (1923) 1026
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Mamedov, V.A., Litvinov, I.A., Kataeva, O.N. et al. Darzens reaction as a convenient method for the synthesis of α-chloroketones, α-chloroepoxides, and symmetrically substituted dioxines. Monatsh Chem 125, 1427–1435 (1994). https://doi.org/10.1007/BF00811092
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00811092