Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter May 6, 2010

Synthesis of 1-phenylbut-3-ene-1,2-dione and its attempted radical polymerization

Branislav Husár EMAIL logo , Ivan Lukáč , Štefan Chmela , Jean-Louis Canet and Yves Troin
From the journal Chemical Papers


1,2-Diketone moiety-bearing monomer 1-phenylbut-3-ene-1,2-dione, an analogue of phenyl vinyl ketone, was synthesized from 4-chlorobutyryl chloride in a 29 % overall yield in five steps. Following acylation of benzene with 4-chlorobutyryl chloride, the resulting α-methylene group was oxidized to 1,2-diketone in three steps: successive bromination, substitution with lithium hydroxide, and oxidation of α-hydroxyketone with potassium dichromate. The final step was dehydrochlorination of 4-chloro-1-phenyl-butane-1,2-dione. The attempted copolymerization of this monomer with styrene, using AIBN as the initiator, was unsuccessful.

[1] Bevington, J. C. (1989). Overall mechanisms. In G. Allen, & J. C. Bevington (Eds.), Comprehensive polymer science (Vol. 3, Chap. 6, pp. 65–84). Oxford, UK: Pergamon Press. Search in Google Scholar

[2] Close, W. J. (1957) An improved synthesis of cyclopropyl phenyl ketone and related substances. Journal of the American Chemical Society, 79, 1455–1458. DOI: 10.1021/ja01563a049. in Google Scholar

[3] Habel, L.W., De Keersmaecker, S., Wahlen, J., Jacobs, P.A., & De Vos, D. E. (2004) Synthesis of vinyl 1,2-diketones. Tetrahedron Letters, 45, 4057–4059. DOI: 10.1016/j.tetlet.2004.03.157. in Google Scholar

[4] Hrdlovič, P., & Lukáč, I. (1982). Photolysis of poly(1-(4-substituted phenyl)-2-propen-1-ones): The Norrish type II reaction in polymers. In N. Grassie (Ed.), Developments in polymer degradation (Vol. 4, pp. 101). London, UK: Applied Science Publishers. Search in Google Scholar

[5] Hrdlovič, P., Lukáč, I., & Maňásek, Z. (1972) Effect of triplet quenchers on the photolysis of poly(vinyl phenyl ketone) in film. Chemical Papers-Chemické Zvesti, 26, 433–440. Search in Google Scholar

[6] Hrdlovič, P., Scaiano, J. C., Lukáč, I., & Guillet, J. (1986) Transient spectroscopy and kinetics of poly(1-(4-substituted-phenyl)-2-propen-1-ones). Macromolecules, 19, 1637–1643. DOI: 10.1021/ma00160a026. in Google Scholar

[7] Husár, B. (2004) Preparation of monomers and polymers containing 1,2-dicarbonyl group and photoperoxidation of 1,2-dicarbonyl group in polymer matrix. MSc. thesis, Comenius University, Bratislava, Slovak Republic. Search in Google Scholar

[8] Husár, B., & Lukáč, I. (2008) Synthesis, photoperoxidation and crosslinking of styrene copolymer with pendant benzil moieties. Journal of Photochemistry and Photobiology A: Chemistry, 195, 191–197. DOI: 10.1016/j.jphotochem.2007.10.001. in Google Scholar

[9] Kashiwabara, T., & Tanaka, M. (2009) Synthesis of 1,2-diketones by the transition metal-catalyst-free reaction of α-oxo acid chlorides or oxalyl chloride with organostannanes. Journal of Organic Chemistry, 74, 3958–3961. DOI: 10.1021/jo802814r. in Google Scholar

[10] Lukáč, I., Hrdlovič, P., Maňásek, Z., & Belluš, D. (1971) Influence of free and copolymerized triplet quenchers on the photolysis of poly(vinyl phenyl ketone) in solution. Journal of Polymer Science Part A: Polymer Chemistry, 9, 69–80. DOI: 10.1002/pol.1971.150090106. in Google Scholar

[11] Mosnáček, J., Lukáč, I., Chromik, Š., Kostič, I., & Hrdlovič, P. (2004) Network formation of a phenyl vinyl ketone copolymer with 4-vinylbenzil and its photodecrosslinking in films. Journal of Polymer Science Part A: Polymer Chemistry, 42, 765–771. DOI: 10.1002/pola.10860. in Google Scholar

[12] Oka, K., & Hara, S. (1977) Conversion of α-chlorosulfenyl chlorides to ketones via α-chlorosulfen-amides. Use of thionyl chloride for oxidation of active methylene compounds. Tetrahedron Letters, 18, 695–698. DOI: 10.1016/S0040-4039(01)92729-7. in Google Scholar

[13] Rabek, J. F. (1987) Mechanisms of photophysical processes and photochemical reactions in polymers. Chichester, UK: Wiley. Search in Google Scholar

[14] Wagner, P. J., & Lindstrom, M. J. (1987) Radical cleavage and competing photoreactions of phenacyl sulfides. Journal of the American Chemical Society, 109, 3062–3067. DOI: 10.1021/ja00244a032. in Google Scholar

[15] Wagner, P. J., Zepp, R. G., Liu, K. C., Thomas, M., Lee, T. J., & Turro, N. J. (1976) Competing photocyclization and photoenolization of phenyl α-diketones. Journal of the American Chemical Society, 98, 8125–8134. DOI: 10.1021/ja00441a042. in Google Scholar

Published Online: 2010-5-6
Published in Print: 2010-8-1

© 2010 Institute of Chemistry, Slovak Academy of Sciences

Downloaded on 4.12.2022 from
Scroll Up Arrow