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Light induced controlled release of fragrances by Norrish type II photofragmentation of alkyl phenyl ketones

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Abstract

The use of alkyl phenyl ketones as delivery systems for the controlled release of fragrances was investigated by photoirradiation of undegassed solutions with a xenon lamp as well as natural sunlight. A large variety of precursor compounds was prepared efficiently in a few reaction steps from commercially available starting materials. The Norrish type II photofragmentation was found to be the predominant reaction pathway to yield the desired perfumery alkenes and acetophenones in polar and apolar solution. Systematic GC-MS analysis of the irradiated solutions allowed identification of a series of side products that are due to the presence of oxygen. A detailed analysis of the product distribution after irradiation was carried out for a series of 4-alkoxy-1-phenylbutanone derivatives. Besides the expected acetophenones, vinyl ethers and phenylcyclobutanols, the formation of alkyl formates, alcohols and 4-oxo-4-phenylbutanoates was observed. The product distribution as influenced by solvent polarity, precursor concentration and substituent effects was investigated. The utility of alkyl phenyl ketones as precursors for the light induced controlled release of fragrances under natural daylight conditions was also demonstrated.

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References and notes

  1. (a) L. Brannon-Peppas, Controlled release in the food and cosmetics industries, ACS Symp. Ser., 1993, 520, 42

    Article  CAS  Google Scholar 

  2. (b) K. Rogers, Controlled release technology and delivery systems, Cosmet. Toiletries, 1999, 114, 53.

    Google Scholar 

  3. M. Gautschi, J. A. Bajgrowicz and P. Kraft, Fragrance chemistry — milestones and perspectives, Chimia, 2001, 55, 379.

    Article  CAS  Google Scholar 

  4. S. Rochat, C. Minardi, J.-Y. de Saint Laumer and A. Herrmann, Controlled release of perfumery aldehydes and ketones by Norrish type-II photofragmentation of α-keto esters in undegassed solution, Helv. Chim. Acta, 2000, 83, 1645.

    Article  CAS  Google Scholar 

  5. C. Plessis and S. Derrer, Novel photolactonisation from xanthenoic esters, Tetrahedron Lett., 2001, 42, 6519.

    Article  CAS  Google Scholar 

  6. 5 (a) H. Kamogawa, S. Okabe and M. Nanasawa, Syntheses of polymerizable Acetals. I. Vinylbenzaldehyde acetals with perfume alcohols, Bull. Chem. Soc. Jpn., 1976, 49, 1917

    Article  CAS  Google Scholar 

  7. (b) H. Kamogawa, H. Mukai, Y. Nakajima and M. Nanasawa, Chemical release control — Schiff bases of perfume aldehydes and aminostyrenes, J. Polym. Sci., Polym. Chem. Ed., 1982, 20, 3121.

    Article  CAS  Google Scholar 

  8. P. Enggist, S. Rochat and A. Herrmann, Controlled release of perfumery alcohols by alkaline hydrolysis of 2-formyl and 2-acetylbenzoates and their corresponding phthalides, J. Chem. Soc., Perkin Trans. 2, 2001, 438.

  9. A. Herrmann, C. Debonneville, V. Laubscher and L. Aymard, Dynamic headspace analysis of the light-induced controlled release of perfumery aldehydes and ketones from α-keto esters in bodycare and household applications, Flavour Fragrance J., 2000, 15, 415.

    Article  CAS  Google Scholar 

  10. Parts of this publication are the subject of a patent application: A. Herrmann, Utilisation of ketones as precursors of active compounds, to Firmenich SA, PCT Int. Pat. Appl., WO 01/96272, 2001; (Chem. Abstr., 2002, 136, 53577).

  11. C. H. Bamford and R. G. W. Norrish, Primary photochemical reactions. Part VII. Photochemical decomposition of isovaleraldehyde and di-n-propyl ketone, J. Chem. Soc., 1935, 1504.

    Google Scholar 

  12. D. C. Neckers, R. M. Kellogg, W. L. Prins and B. Schoustra, Developmental Photochemistry. The Norrish type II reaction, J. Org. Chem., 1971, 36, 1838.

    Article  CAS  Google Scholar 

  13. W. W. Epstein, D. S. Jones, E. Bruenger and H. C. Rilling, The synthesis of a photolabile detergent and its use in the isolation and characterization of protein, Anal. Biochem., 1982, 119, 304.

    Article  CAS  Google Scholar 

  14. For reviews see for example: (a) P. J. Wagner, Type II photoelimination and photocyclization of ketones, Acc. Chem. Res., 1971, 4, 168

    Article  CAS  Google Scholar 

  15. (b) P. J. Wagner, Chemistry of excited triplet organic carbonyl compounds, Top. Curr. Chem., 1976, 66, 1.

    Article  CAS  Google Scholar 

  16. 13 (a) E. S. Huyser and D. C. Neckers, The photochemical reactions of alkyl phenylglyoxylates in alcohols, J. Org. Chem., 1964, 29, 276

    Article  CAS  Google Scholar 

  17. (b) R. S. Davidson and D. Goodwin, The mechanism of photoinduced fragmentation of alkyl pyruvates, J. Chem. Soc., Perkin Trans. 2, 1982, 993

  18. (c) M. V. Encinas, E. A. Lissi, A. Zanocco, L. C. Stewart and J. C. Scaiano, Photochemistry of alkyl esters of benzoylformic acid, Can. J. Chem., 1984, 62, 386

    Article  CAS  Google Scholar 

  19. (d) J. C. Scaiano, M. V. Encinas, E. A. Lissi, A. Zanocco and P. K. Das, Photochemistry of alkyl pyruvates, J. Photochem., 1986, 33, 229

    Article  CAS  Google Scholar 

  20. (e) S. Hu and D. C. Neckers, Photochemical Reactions of alkyl phenylglyoxylates, J. Org. Chem., 1996, 61, 6407.

    Article  CAS  Google Scholar 

  21. S. Arctander, Perfume and flavor chemicals, published by the author, Montclair 1969.

  22. (a) A. A. Lamola, Lowest π,π* triplet state of acetophenone, J. Chem. Phys., 1967, 47, 4810

    Article  CAS  Google Scholar 

  23. (b) R. D. Rauh and P. A. Leermakers, Solvent effects upon the phosphorescence lifetimes and photoreactivity of butyrophenone, J. Am. Chem. Soc., 1968, 90, 2246

    Article  CAS  Google Scholar 

  24. (c) J. A. Barltrop and J. D. Coyle, Organic photochemistry. IX. Intramolecular photoreactions of simple γ- and para-substituted butyrophenones, J. Am. Chem. Soc., 1968, 90, 6584

    Article  CAS  Google Scholar 

  25. (d) P. J. Wagner, M. J. May, A. Haug and D. R. Graber, Concerning the phosphorescence of phenyl alkyl ketones, J. Am. Chem. Soc., 1970, 92, 5269.

    Article  CAS  Google Scholar 

  26. P. J. Wagner, A. E. Kemppainen and H. N. Schott, Effects of ring substituents on the type II photoreactions of phenyl ketones. How interactions between nearby excited triplets affect chemical reactivity, J. Am. Chem. Soc., 1973, 95, 5604.

    Article  CAS  Google Scholar 

  27. (a) N. C. Yang, D. S. McClure, S. L. Murov, J. J. Houser and R. Dusenbery, Photoreduction of acetophenone and substituted acetophenone, J. Am. Chem. Soc., 1967, 89, 5466

    Article  CAS  Google Scholar 

  28. (b) N. C. Yang and R. L. Dusenbery, Correlation between the photochemical reactivity and the nature of excited states of acetophenone and substituted acetophenones, J. Am. Chem. Soc., 1968, 90, 5899.

    Article  CAS  Google Scholar 

  29. E. J. Baum, J. K. S. Wan and J. N. Pitts Jr., Reactivity of excited states. Intramolecular hydrogen atom abstraction in substituted butyrophenones, J. Am. Chem. Soc., 1966, 88, 2652.

    Article  CAS  Google Scholar 

  30. J. N. Pitts Jr., D. R. Burley, J. C. Mani and A. D. Broadbent, Molecular structure and photochemical reactivity. IX. Photolytic and radiolytic type II elimination reaction of n-butyrophenones. Effects of meta-substituents, J. Am. Chem. Soc., 1968, 90, 5902.

    Article  CAS  Google Scholar 

  31. 20 (a) P. J. Wagner and H. N. Schott, Polar substituent effects in the reactions of 1,4 biradicals, J. Am. Chem. Soc., 1969, 91, 5383

    Article  CAS  Google Scholar 

  32. (b) P. J. Wagner and A. E. Kemppainen, Deactivation of the triplet states of phenyl ketones by electron-donating ring substituents, J. Am. Chem. Soc., 1968, 90, 5898.

    Article  CAS  Google Scholar 

  33. R. D. Small Jr. and J. C. Scaiano, Differentiation of excited-state and biradical processes. Photochemistry of phenyl alkyl ketones in the presence of oxygen, J. Am. Chem. Soc., 1978, 100, 4512.

    Article  CAS  Google Scholar 

  34. 22 (a) J. Grotewold, C. M. Previtali, D. Soria and J. C. Scaiano, Effect of oxygen on the photochemistry of 4-methyl-1-phenylpentan-1-one, J. Chem. Soc., Chem. Commun., 1973, 207

  35. (b) R. D. Small Jr. and J. C. Scaiano, Interaction of oxygen with transient biradicals photogenerated from γ-methyl valerophenone, Chem. Phys. Lett., 1977, 48, 354.

    Article  CAS  Google Scholar 

  36. 23 (a) D. J. Pasto and M. P. Serve, Neighboring group participation by carbonyl oxygen, J. Am. Chem. Soc., 1965, 87, 1515

    Article  CAS  Google Scholar 

  37. (b) H. R. Ward and P. D. Sherman Jr., Carbonyl participation in the solvolysis of ketone derivatives. The observation and isolation of intermediates, J. Am. Chem. Soc., 1968, 90, 3812.

    Article  CAS  Google Scholar 

  38. S. A. Hassarajani, B. Dhotare, A. Chattopadhyay and V. R. Mamdapur, A convenient synthesis of 1-phenylheptane-1,5-dione, Indian J. Chem., Sect. B, 1998, 37, 80.

    Google Scholar 

  39. B. Neises and W. Steglich, Esterification of carboxylic acids with dicyclohexylcarbodiimide/4-dimethylaminopyridine: tert-butyl ethyl fumarate, Org. Synth., 1990, Coll. Vol. VII, 93.

    Google Scholar 

  40. P. R. Jones, M. D. Saltzman and R. J. Panicci, Models for the study of macrocyclic ring-chain tautomerism, J. Org. Chem., 1970, 35, 1200.

    Article  CAS  Google Scholar 

  41. W. Biernacki and A. Gdula, Modification of the method of Julia for the preparation of homoallylic bromides and iodides, Synthesis, 1979, 37.

    Google Scholar 

  42. R. M. Sayre, C. Cole, W. Billhimer, J. Stanfield and R. D. Ley, Spectral comparison of solar simulators and sunlight, Photodermatol. Photoimmunol. Photomed., 1990, 7, 159.

    CAS  Google Scholar 

  43. 29 (a) M. C. Pirrung and R. J. Tepper, Photochemistry of substituted benzoylformate esters. A convenient method for the photochemical oxidation of alcohols, J. Org. Chem., 1995, 60, 2461

    Article  CAS  Google Scholar 

  44. (b) S. Hu and D. C. Neckers, Mechanism of alkyl phenylglyoxylates photoreaction in the presence of oxygen, J. Photochem. Photobiol. A, Chem., 1998, 118, 75.

  45. R. Rothermel and M. Hanack, Synthese von cis-konfigurierten Bis(trifluormethyl)pyrethroiden, Liebigs Ann. Chem., 1991, 1013.

    Google Scholar 

  46. C. D. J. Boden, J. Chambers and I. D. R. Stevens, A concise, efficient and flexible strategy for the synthesis of the pheromones of Oryzaephilus and Cryptolestes grain beetles, Synthesis, 1993, 411.

    Google Scholar 

  47. For a recent account of developments in photochemical research see for example: C. G. Bochet, Photolabile protecting groups and linkers, J. Chem. Soc., Perkin Trans. 1, 2002, 125.

    Google Scholar 

  48. L. J. Durham, D. J. McLeod and J. Cason, Methyl hydrogen hendecanedioate, Org. Synth., 1963, Coll. Vol. IV, 635.

    Google Scholar 

  49. A. Orjales, M. Bordell and V. Rubio, Synthesis and structure-activity relationship of new piperidinyl and piperazinyl derivatives as antiallergics, J. Heterocycl. Chem., 1995, 32, 707.

    CAS  Google Scholar 

  50. K. Steliou and M.-A. Poupart, Tin-mediated esterification in macrolide synthesis, J. Am. Chem. Soc., 1983, 105, 7130.

    Article  CAS  Google Scholar 

  51. Z. G. Hajos and D. R. Parrish, Stereo-controlled total synthesis of 19-nor steroids, J. Org. Chem., 1973, 38, 3244.

    Article  CAS  Google Scholar 

  52. C. J. Kok, F. Kasten, C. G. Justus, Solar Spectral Irradiance, Publ. No. CIE 85, International Commission on Illumination (CIE), 1989.

    Google Scholar 

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Acknowledgements

We are grateful to Dr. Esther Oliveros for fruitful discussions and Dr. Alvin Williams for proof-reading the manuscript. We thank Walter Thommen for NMR measurements and Laurence Frascotti for her assistance in the synthesis of some of the compounds.

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  1. Firmenich SA, Division Recherche et Développement, B.P. 239, CH-1211, Genève 8, Switzerland

    Barbara Levrand & Andreas Herrmann

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  1. Barbara Levrand
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  2. Andreas Herrmann
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Correspondence to Andreas Herrmann.

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Levrand, B., Herrmann, A. Light induced controlled release of fragrances by Norrish type II photofragmentation of alkyl phenyl ketones. Photochem Photobiol Sci 1, 907–919 (2002). https://doi.org/10.1039/b207918f

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