1748 J. Agric. Food Chem., Vol. 47, No. 4, 1999
Capasso et al.
Capasso, R.; Evidente, A.; Visca, C.; Gianfreda, L.; Maremonti,
M.; Greco, G., J r. Production of glucose and bioactive
aglycone by chemical and enzymatic hydrolysis of purified
oleuropein from Olea europea. Appl. Biochem. Biotechnol.
1996, 60, 365-377.
Chikamatsu, Y.; Ando, H.; Yamamoto, A.; Kyo, S.; Yamashita,
K.; Dojo, K. Hydroxytyrosol as melanin formation inhibitor
and lipid peroxide formation inhibitor and its application
to topical preparations and bath preparations. J pn. Patent
8119825, 1996; pp 1-10.
Chimi, H.; Sadik, B.; Le tutour, M.; Rahmani, M. Contribution
a` l’e´tude comparative des pouvoirs antioxidants dans l’huile
d’olive du tyrosol, de l’hydroxytyrosol, de l’acide cafe´ique,
de l’oleuropeine et du BHT. Rev. Fr. Corps Gras 1988, 8/ 9,
339-344.
Cortesi, N.; Fedeli, E. I composti polari di oli di oliva vergine
(Nota I). Riv. Ital. Sostanze Grasse 1983, 60, 341-351.
Forcadell, M. L.; Comas, M.; Miquel, X.; De la Torre, M. C.
Tyrosol and hydroxytyrosol determination in virgin olive
oils. Rev. Fr. Corps Gras 1987, 34, 547-549.
Galli, C.; Petroni, A.; Visioli, F. Natural antioxidants, with
special reference to those in olive oil, and cell protection.
Eur. J . Pharm. Sci. 1994, 2, 67-68.
J aner del Valle, C.; Vazquez Roncero, A. A study of the poplar
compounds in olive oil by gas chromatography. Grasas
Aceites 1980, 31, 309-316.
Mannino, S.; Cosio, M.; Bertuccioli, M. High performance
liquid chromatography of phenolic compounds in virgin olive
oils using amperometric detection. Ital. J . Food Sci. 1993,
4, 363-370.
could allow a natural and nontoxic antioxidant to be
obtained and (2) recovery of 2 could be a useful process
for recycling omww, thus resolving its disposal prob-
lems, albeit partially. However, despite that at present
this kind of production is more convenient than the
other methods (Ragazzi and Veronesi, 1967; Capasso et
al., 1992, 1994a), it gives scarce yields, because 2
undergoes both retention and chemical modification
processes on the stationary phase during the chromato-
graphic purification.
Complete chromatographic purification of 2 is achieved
by a third step using preparative TLC (scheme shown
in Figure 2), and consequently at this level it could be
only used for laboratory uses.
The synthetic method we propose thus appears to be
the most convenient for three reasons with respect to
the other methods reported in the literature: it consists
of only one step, the reaction is completed in 2 h, and it
gives a yield of 82.8%, starting from 1, which is a
commercially available product. It is also more conve-
nient than the chromatographic purification methods
from omww reported in this paper and previously
(Ragazzi and Veronesi, 1967; Capasso et al., 1992,
1994a) because they produce 2 in small yield and are
more expensive than the synthesis method.
ACKNOWLEDGMENT
We are grateful to Prof. G. Palumbo for the helpful
discussion. The MS data were provided by “Servizio di
spettrometria di massa” of the CNR and the Universita`
di Napoli “Federico II”: assistance of the staff is
gratefully acknowledged. We thank the “Centro di
Metodologie chimico fisiche” of the Universita` degli
Studi di Napoli “Federico II" for NMR spectroscopy.
DISCA Contribution 177.
Montedoro, G.; Servili, M.; Badioli, M.; Miniati, E. Simple and
hydrolyzable phenolic compounds in virgin olive oil. Their
extraction, separation and quantitative and semiquantita-
tive evaluation by HPLC. J . Agric. Food Chem. 1992, 40,
1571-1576.
Papadoupulos, G.; Boskou, D. Antioxidant effect of natural
phenols on olive oil. J . Am. Oil Chem. Soc. 1991, 68, 669-
671.
Ragazzi, E.; Veronesi, G. Ricerche sui costituenti idrosolubili
delle olive. I. Zuccheri e fenoli. Ann. Chim. 1967, 57, 1476-
1486.
LITERATURE CITED
Aeschbach, R.; Loeliger, J .; Scott, B.; Murcia, A.; Butler, J .;
Halliwell, B.; Aruoma, O. L. Antioxidant actions of thymol,
carvacrol, 6-gingerol, zingerone and hydroxytyrosol. Food
Chem. Toxicol. 1994, 32, 31-36.
Amiot, M. J .; Fleuriet, A.; Macheix, J . J . Accumulation of
oleuropein derivatives during olivematuration. Phytochem-
istry 1989, 28, 67-69.
Angerosa, F.; d’Alessandro, N.; Konstantinou, P.; Giacinto, I.
GC-MS evaluation of phenolic compounds in virgin olive oil.
J . Agric. Food Chem. 1995, 43, 1802-1807.
Baraldi, P. G.; Simoni, D.; Manfredini, S.; Menziani E.
Preparation of 3,4-Dihydroxy-1-benzeneethanol: A Rein-
vestigation. Liebigs Ann. Chem. 1983, 83, 684-686.
Bianco, A.; Passacantilli, P.; Righi; G. Improved procedure for
the reduction of esters to alcohols by sodium borohydride.
Synth. Commun. 1988, 18, 1765-1771.
Camurati, F.; Fedeli, E. Attivita` antiossidante di estratti
fenolici delle acque di vegetazione delle olive. Riv. Ital.
Sostanze Grasse 1982, 49, 623-626.
Capasso, R.; Cristinzio, G.; Evidente, A.; Scognamiglio, F.
Isolation, spectroscopy and selective phytotoxic effects of
polyphenols from vegetable waste waters. Phytochemistry
1992, 12, 4125-4128.
Capasso, R.; Evidente, A.; Visca, C. Production of hydroxyty-
rosol from olive oil vegetation water. Agrochimica 1994a ,
38, 165-172.
Ragazzi, E.; Veronese, G. Indagini sui componenti fenolici degi
oli di oliva. Riv. Ital. Sostanze Grasse 1973, 50, 443-452.
Salami, M.; Galli, C.; De Angelis, L.; Visioli, F. Formation of
F2-isoprostanes in oxidized LDL: protective effect of hy-
droxytyrosol. Pharm. Res. 1995, 31, 225-279.
Scho¨pf, C.; Go¨ttmann, G.; Meisel, E. M.; Neuroth, L. U¨ ber
â-(3,4-Dioxyphenyl)-a¨thylalkohol. Liebigs Ann. Chem. 1949,
563, 86-93.
Vazquez Roncero, A.; Maestro Duran, R.; Graciani Costante,
E. Componentes fenolicos de la la aceituna II. Polifenoles
del alpecin. Grasas Aceites 1974, 25, 341-345.
Vazquez Roncero, A.; J aner del Valle, C.; J aner del Valle, L.
Componentes fenolicos de la la aceituna. III. Polifenoles del
aceite. Grasas Aceites 1976, 27, 185-191.
Verhe, R.; Papadopoulos, G.; Boskou, D. Preparation of hy-
droxytyrosol. Bull. Liason Groupe Polyphenols 1992, 15,
237-244.
Visioli, F.; Galli, C. Natural antioxidants and prevention of
coronary heart disease: the potential role of olive oil and
its minor constituents. Nutr. Metabol. Cardiovasc. Dis. 1995,
5, 306-314.
Visioli, F.; Vinceri, F.; Galli, C. Wastewaters from olive oil
production are rich in natural antioxidants. Experientia
1995a , 51, 32-34.
Visioli, F.; Bellomo, G.; Montedoro, G.; Galli, C. Low-density
lipoprotein oxidation is inhibited, in vitro, by olive oil
constituents. Atherosclerosis 1995b, 117, 25-32.
Capasso, R.; Evidente, A.; Tremblay, E.; Sala, A.; Santoro, C.;
Cristinzio, G.; Scognamiglio, F. Direct and mediated effects
on Bactrocera oleae (Gmelin) of natural polyphenols and
some related synthetic compounds: structure-activity re-
lationships. J . Chem. Ecol. 1994b, 20, 1189-1199.
Capasso, R.; Evidente, A.; Schivo, L.; Orru`, G.; Marcialis, M.
A.; Cristinzio, G. Antibacterial polyphenols from olive oil
mill wastewaters. J . Appl. Bacter. 1995, 79, 393-398.
Received for review August 12, 1998. Revised manuscript
received J anuary 22, 1999. Accepted J anuary 26, 1999. This
work was aided by grants from the Consiglio Nazionale delle
Ricerche.
J F9809030