1
226
M. Kueny-Stotz et al.
LETTER
(8) For a review on the synthesis of anthocyanidins, see:
Iacobucci, G. A.; Sweeny, J. G. Tetrahedron 1983, 39, 3005.
(9) (a) Pratt, D. D.; Robinson, R. J. Chem. Soc. 1922, 1577.
(b) Pratt, D. D.; Robinson, R. J. Chem. Soc. 1923, 745.
(c) Pratt, D. D.; Robinson, R. J. Chem. Soc. 1924, 188.
(d) Pratt, D. D.; Robinson, R. J. Chem. Soc. 1924, 199.
(e) Pratt, D. D.; Robinson, R. J. Chem. Soc. 1925, 1128.
(10) Kuhnert, N.; Clifford, M. N.; Radenac, A.-G. Tetrahedron
Lett. 2001, 42, 9261.
Typical Procedure for the Acid-Mediated Condensation of
Phloroglucinol Derivatives with Arylethynylketones
To a solution of arylethynylketone 6 (5 mmol, 1.0 equiv) and phlo-
roglucinol derivative 7 or 8 (5 mmol, 1.0 equiv) in 10 mL of AcOH
were added 2 mL of HPF (50% in H O). The solution, becoming
immediately dark red, was stirred during 48 h at r.t. The resulting
mixture is then plunged in 100 mL of Et O where the flavylium salt
precipitated. The orange to red solid is recovered by filtration,
washed with Et O and finally dried under vacuum to give the ex-
6
2
2
2
pected 3-deoxyanthocyanidin. Recrystallization from AcOH was
performed when necessary.
(11) Mas, T. Synthesis 2003, 1878.
(12) A similar approach, using sulfuric acid, has been mentioned
in the early fifties and surprisingly reported only once
thereafter: (a) Johnson, A. W.; Melhuish, R. R. J. Chem. Soc.
Acknowledgment
1947, 346. (b) Gramshaw, J. W.; Johnson, A. W.; King, T. J.
J. Chem. Soc. 1958, 4040. (c) Costantino, L.; Rastelli, G.;
Rossi, M. C.; Albasini, A. J. Chem. Soc., Perkin Trans. 2
The authors thank the CNRS and the MNERT for funding. Three of
us (S.C., M.K. and G.I.) thank the MNERT for PhD fellowships.
1995, 227.
(
(
13) Marcus, Y.; Hefter, G. Chem. Rev. 2006, 106, 4585.
14) (a) Katritzky, A. R.; Czerney, P.; Level, J. R.; Du, W. Eur. J.
Org. Chem. 1998, 2623. (b) Fichtner, C.; Remennikov, G.;
Mayr, H. Eur. J. Org. Chem. 2001, 4451.
References and Notes
(
1) (a) Timberlake, C. F.; Bridle, P. The Flavonoids; Academic
Press: New York, 1975, 214–266. (b) Hrazdina, G. The
Flavonoids Advances in Research; Chapman and Hall:
London, 1982, 135–188. (c) Harborne, J. B.; Grayer, R. J.
The Flavonoids: Advances in Research since 1980;
Chapman and Hall: London, 1988, 1–20. (d) Strack, D.;
Wray, V. The Flavonoids: Advances in Research since 1986;
Chapman and Hall: London, 1994, 1–22. (e) Harborne, J.
B.; Williams, C. A. Nat. Prod. Rep. 1998, 15, 631.
(15) Doxsee, K. M.; Feigel, M.; Kent, D. S.; Canary, J. W.;
Knobler, C. B.; Cram, D. J. Am. Chem. Soc. 1987, 109, 3098.
(16) Apigeninidin Trimethylether Hexafluorophosphate (10)
Purple powder; yield 93%; mp 201 °C. IR (KBr): 1652, 1640
(s, C=O), 1600, 1569, 1506, 1456, 1436, 1378, 1339, 1241,
–
1
1124, 1052, 834 (m, P–F) cm . UV/Vis [MeOH–HCl (5%,
1 N)]: l (e) = 266 (24900), 394 (18000), 460 nm (13600
max
–
1
–1
1
M ·cm ). H NMR [300 MHz, CD CN–TFA-d (1%)]:
3
1
(
f) Harborne, J. B.; Williams, C. A. Nat. Prod. Rep. 2001,
d = 3.96 (3 H, s, OCH ), 4.07 (3 H, s, OCH ), 4.09 (3 H, s,
3
3
18, 310. (g) Williams, C. A.; Grayer, R. J. Nat. Prod. Rep.
OCH ), 6.80 (1 H, d, J = 2.2 Hz), 7.19 (2 H, m), 7.23 (1 H,
3
2004, 21, 539. (h) Andersen, O. M.; Jordheim, M.
dd, J = 2.2, 0.7 Hz), 8.05 (1 H, d, J = 8.5 Hz), 8.32 (2 H, m),
5
13
Flavonoids: Chemistry, Biochemistry and Applications;
CRC Press: Boca Raton, 2006, 471–551.
9.07 (1 H, dd, J = 8.5 Hz, J = 0.7 Hz). C NMR [75 MHz,
CD CN–TFA-d (1%)]: d = 55.9/57.0/57.2 (OCH ), 93.4,
3
1
3
(
2) (a) Coggon, P.; Moss, G. A.; Graham, H. N.; Sanderson, G.
W. J. Agric. Food Chem. 1973, 21, 727. (b) Mazza, G.;
Miniati, E. Anthocyanins in Fruits, Vegetables and Grains;
CRC Press: Boca Raton, 1993, 225.
99.8, 111.3, 113.4, 115.8, 120.8, 131.9, 148.7, 158.8, 159.0,
167.0, 171.4, 171.7. MS (ESI, positive mode): 297 (100)
+
[M ]. HRMS (ESI): m/z calcd: 297.1121; found: 297.1109.
(17) Chrysinidin Hexafluorophosphate (13)
(
(
3) Dangles, O.; Elhajji, H. Helv. Chim. Acta 1994, 77, 1595.
4) (a) Darmenton, P.; Philippe, M. FR 2757383, 1996; Chem.
Abstr. 1998, 129, 140458n. (b) Sauter, G.; Braun, H.-J.;
Brouillard, R.; Fougerousse, A.; Roehri-Stoeckel, C. WO
Orange powder; yield 91%. IR (KBr): 3412 (s, br, OH), 1642
(s, C=O), 1580, 1563, 1541, 1381, 1340, 1269, 1239, 1203,
–
1
1193, 835 (m, P–F) cm . UV/Vis [MeOH–HCl (5%, 1 N)]:
–
1
–1
1
lmax (e) = 274 (35400), 474 nm (36200 M ·cm ). H NMR
03000214 A1, 2003.
[300 MHz, CD CN–TFA-d (1%)]: d = 6.81 (1 H, d, J = 2.2
3
1
(
(
5) Czerney, P.; Graness, G.; Birckner, E.; Vollmer, F.; Rettig,
W. J. Photochem. Photobiol. A 1995, 89, 31.
6) (a) Pina, F.; Melo, M. J.; Maestri, M.; Passaniti, P.;
Comaioni, N.; Balzani, V. Eur. J. Org. Chem. 1999, 3199.
Hz), 7.11 (1 H, dd, J = 2.2, 0.7 Hz), 7.72 (2 H, m), 7.84 (1 H,
m), 8.13 (1 H, d, J = 8.4 Hz), 8.35 (2 H, m), 9.25 (1 H, dd,
1
3
J = 8.4, 0.7 Hz). C NMR [75 MHz, CD CN–TFA-d
3 1
(1%)]: d = 95.7, 102.9, 111.2, 114.4, 128.9, 129.1, 130.0,
(
b) Roque, A.; Lodeiro, C.; Pina, F.; Maestri, M.; Ballardini,
135.8, 150.5, 158.4, 159.4, 171.1, 171.4. MS (ESI, positive
+
R.; Balzani, V. Eur. J. Org. Chem. 2002, 2699.
mode): 239 (100) [M ]. HRMS (ESI): m/z calcd: 239.0703;
(7) (a) Mas, T.; Susperregui, J.; Berké, B.; Chèze, C.; Moreau,
found: 239.0696.
S.; Nuhrich, A.; Vercauteren, J. Phytochemistry 2000, 53,
(18) All synthesized compounds exhibit NMR spectroscopic data
1
0–12
679. (b) Clifford, M. N. J. Sci. Food Agric. 2000, 80, 1063.
identical to previously reported ones in the literature.
(
c) Kong, J. M.; Chia, L. S.; Goh, N. K.; Chia, T. F.;
Brouillard, R. Phytochemistry 2003, 64, 923. (d) Hou, D. X.
Curr. Mol. Med. 2003, 3, 149.
Synlett 2007, No. 8, 1223–1226 © Thieme Stuttgart · New York