Synthesis of ortho-hydroxyacetophenone derivatives from Baylis-Hillman acetates

Tetrahedron Letters

Volumn 43, Issue 37, 2002, Pages 6597-6600

  Kim, Jae Nyoung ^a   Im, Yang Jin ^a   Kim, Jeong Mi ^a  

^a Chonnam National University   (South Korea)

Author keywords

Baylis Hillman acetates; Deacetylation; N,N dimethylformamide; Ortho hydroxyacetophenones

Indexed keywords

1 BENZOYLACETONE; ACETIC ACID DERIVATIVE; ACETOPHENONE DERIVATIVE; ACETYLACETONE; CARBENOID; ETHYLACETOACETATE; METHANESULFONYLACETONE; N,N DIMETHYLFORMAMIDE; POTASSIUM CARBONATE; UNCLASSIFIED DRUG;

ALDOL REACTION; ARTICLE; DEACETYLATION; DECOMPOSITION; PROTON TRANSPORT; SYNTHESIS;

EID: 0037048508     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(02)01441-7     Document Type: Article

References (22)

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14. 3. As expected, however, 3-benzyl-2,4-pentanedione was remained intact after 3-4 h in DMF at 70-80°C. For more general references regarding deacetylation and decarboalkoxylation, see: (a) Krapcho, A. P. Synthesis 1982, 805; (b) Bauchat, P.; Le Rouille, E.; Foucaud, A. Bull. Soc. Chim. Fr. 1991, 128, 267; (c) Beltaief, I.; Amri, H. Synth. Commun. 1995, 25, 2981; (d) Kroutil, W.; Osprian, I.; Mischitz, M.; Faber, K. Synthesis 1997, 156; (e) Celli, A. M.; Lampariello, L. R.; Chimichi, S.; Nesi, R.; Scotton, M. Can. J. Chem. 1982, 60, 1327; (f) Hamed, A. A.; Salem, M. A. I.; Hataba, A. M.; Attia, I. A. Pol. J. Chem. 1985, 59, 1161.
15. 3. As expected, however, 3-benzyl-2,4-pentanedione was remained intact after 3-4 h in DMF at 70-80°C. For more general references regarding deacetylation and decarboalkoxylation, see: (a) Krapcho, A. P. Synthesis 1982, 805; (b) Bauchat, P.; Le Rouille, E.; Foucaud, A. Bull. Soc. Chim. Fr. 1991, 128, 267; (c) Beltaief, I.; Amri, H. Synth. Commun. 1995, 25, 2981; (d) Kroutil, W.; Osprian, I.; Mischitz, M.; Faber, K. Synthesis 1997, 156; (e) Celli, A. M.; Lampariello, L. R.; Chimichi, S.; Nesi, R.; Scotton, M. Can. J. Chem. 1982, 60, 1327; (f) Hamed, A. A.; Salem, M. A. I.; Hataba, A. M.; Attia, I. A. Pol. J. Chem. 1985, 59, 1161.
16. 3. As expected, however, 3-benzyl-2,4-pentanedione was remained intact after 3-4 h in DMF at 70-80°C. For more general references regarding deacetylation and decarboalkoxylation, see: (a) Krapcho, A. P. Synthesis 1982, 805; (b) Bauchat, P.; Le Rouille, E.; Foucaud, A. Bull. Soc. Chim. Fr. 1991, 128, 267; (c) Beltaief, I.; Amri, H. Synth. Commun. 1995, 25, 2981; (d) Kroutil, W.; Osprian, I.; Mischitz, M.; Faber, K. Synthesis 1997, 156; (e) Celli, A. M.; Lampariello, L. R.; Chimichi, S.; Nesi, R.; Scotton, M. Can. J. Chem. 1982, 60, 1327; (f) Hamed, A. A.; Salem, M. A. I.; Hataba, A. M.; Attia, I. A. Pol. J. Chem. 1985, 59, 1161.
17. 3. As expected, however, 3-benzyl-2,4-pentanedione was remained intact after 3-4 h in DMF at 70-80°C. For more general references regarding deacetylation and decarboalkoxylation, see: (a) Krapcho, A. P. Synthesis 1982, 805; (b) Bauchat, P.; Le Rouille, E.; Foucaud, A. Bull. Soc. Chim. Fr. 1991, 128, 267; (c) Beltaief, I.; Amri, H. Synth. Commun. 1995, 25, 2981; (d) Kroutil, W.; Osprian, I.; Mischitz, M.; Faber, K. Synthesis 1997, 156; (e) Celli, A. M.; Lampariello, L. R.; Chimichi, S.; Nesi, R.; Scotton, M. Can. J. Chem. 1982, 60, 1327; (f) Hamed, A. A.; Salem, M. A. I.; Hataba, A. M.; Attia, I. A. Pol. J. Chem. 1985, 59, 1161.
18. 3. As expected, however, 3-benzyl-2,4-pentanedione was remained intact after 3-4 h in DMF at 70-80°C. For more general references regarding deacetylation and decarboalkoxylation, see: (a) Krapcho, A. P. Synthesis 1982, 805; (b) Bauchat, P.; Le Rouille, E.; Foucaud, A. Bull. Soc. Chim. Fr. 1991, 128, 267; (c) Beltaief, I.; Amri, H. Synth. Commun. 1995, 25, 2981; (d) Kroutil, W.; Osprian, I.; Mischitz, M.; Faber, K. Synthesis 1997, 156; (e) Celli, A. M.; Lampariello, L. R.; Chimichi, S.; Nesi, R.; Scotton, M. Can. J. Chem. 1982, 60, 1327; (f) Hamed, A. A.; Salem, M. A. I.; Hataba, A. M.; Attia, I. A. Pol. J. Chem. 1985, 59, 1161.
19. 3. As expected, however, 3-benzyl-2,4-pentanedione was remained intact after 3-4 h in DMF at 70-80°C. For more general references regarding deacetylation and decarboalkoxylation, see: (a) Krapcho, A. P. Synthesis 1982, 805; (b) Bauchat, P.; Le Rouille, E.; Foucaud, A. Bull. Soc. Chim. Fr. 1991, 128, 267; (c) Beltaief, I.; Amri, H. Synth. Commun. 1995, 25, 2981; (d) Kroutil, W.; Osprian, I.; Mischitz, M.; Faber, K. Synthesis 1997, 156; (e) Celli, A. M.; Lampariello, L. R.; Chimichi, S.; Nesi, R.; Scotton, M. Can. J. Chem. 1982, 60, 1327; (f) Hamed, A. A.; Salem, M. A. I.; Hataba, A. M.; Attia, I. A. Pol. J. Chem. 1985, 59, 1161.
20. +, 90).
21. The structure of 5a was confirmed further by NOE experiment. Irradiation of the benzylic proton (δ=3.95 ppm) showed NOE increment (0.9%) of methyl proton at 4-position (δ=2.21 ppm) and two aromatic protons (0.9 and 0.7%, respectively). From the NOE experiment we can exclude the regioisomeric structure, 2-methyl-4-hydroxy-5-benzylacetophenone.
22. . We examined the reaction of Baylis-Hillman acetate derived from hexanal as an example of aliphatic aldehydes. However, intractable mixtures were formed due to many side reactions. Elimination of acetic acid and subsequent Diels-Alder reaction was one of the side reactions as reported in our previous paper, see: Kim J.N., Lee H.J., Lee K.Y., Gong J.H. Synlett. 2002;173.