SAR Studies of Benzoxazinones
J. Agric. Food Chem., Vol. 53, No. 3, 2005 547
(6) Wolf, R. B.; Spencer, G. F.; Plattner, R. D. Benzoxazolinone,
2,4-dihydroxy-1,4-benzoxazin-3-one, and its glucoside from
Acanthus mollis seeds inhibit velvetleaf germination and growth.
J. Nat. Prod. 1985, 48, 59-63.
(7) Cambier, V.; Hance, T.; De Hoffmann, E. Noninjured maize
contains several 1,4-benzoxazin-3-one related compounds but
only as glucoconjugates. Phytochem. Anal. 1999, 10, 119-126.
(8) Woodward, M. D.; Corcuera, L. J.; Helgeson, J. P.; Upper, C.
D. Decomposition of 2,4-dihydroxy-7-methoxy-2H-1,4-benzox-
azin-3(4H)-one in aqueous solutions. Plant Physiol. 1978, 61,
796-802.
(9) Mac´ıas, F. A.; Oliveros-Bastidas, A.; Mar´ın, D.; Castellano, D.;
Simonet, A. M.; Molinillo, J. M. G. Degradation Studies on
Benzoxazinoids. Soil Degradation Dynamics of 2,4-Dihydroxy-
7-methoxy-(2H)-1,4-benzoxazin-3(4H)-one (DIMBOA) and Its
Degradation Products, Phytotoxic Allelochemicals from Gramine-
ae. J. Agric. Food Chem. 2004, 52, 6402-6413.
(10) Mac´ıas, F. A.; Oliveros-Bastidas, A.; Mar´ın, D.; Castellano, D.;
Simonet, A. M.; Molinillo, J. M. G. Degradation studies on
benzoxazinoids. Soil degradation dynamics of (2R)-2-O-beta-
D-glucopyranosyl-2,4-dihydroxy-(2H)-1,4-Benzoxazin-3(4H)-
one (DIBOA-Glc) and its degradation products, phytotoxic
allelochemicals from Gramineae. J. Agric. Food Chem. 2005,
53, in press.
(11) Peng, S.; Chilton, W. S. Biosynthesis of DIMBOA in maize using
deuterium oxide as a tracer. Phytochemistry 1994, 37, 167-171.
(12) Kumar, P.; Moreland, D. E.; Chilton, W. S. 2H-1,4-benzoxazin-
3(4H)-one, an intermediate in the biosynthesis of cyclic hydrox-
amic acids in maize. Phytochemistry 1994, 36, 893-898.
(13) Bravo, R.; Lazo, W. Antialgal and antifungal activity of natural
hydroxamic acids and related compounds. J. Agric. Food Chem.
1996, 44, 1569-1571.
(14) Sahi, S. V.; Chilton, M.; Chilton, W. S. Corn metabolites affect
growth and virulence of Agrobacterium tumefaciens. Proc. Natl.
Acad. Sci. U.S.A. 1990, 87, 3879-3883.
(15) Zikmundova, M.; Drandarov, K.; Bigler, L.; Hesse, M.; Werner
C. Biotransformation of 2-benzoxazolinone and 2-hydroxy-1,4-
benzoxazin-3-one by endophytic fungi isolated from Aphelandra
tetragona. Appl. EnViron. Microb. 2002, 68, 4863-4870.
(16) Gagliardo, R. W.; Chilton, W. S. Soil transformation of 2(3H)-
benzoxazolone of rye into phytotoxic 2-amino-3H-phenoxazin-
3-one. J. Chem. Ecol. 1992, 18, 1683-1691.
with lipophilia expressed above. The high persistence of this
compound in wheat crop soil recorded by us (10) makes this
compound a weak candidate for new herbicide models develop-
ment at least at this research stage. Further research will be
needed to discover its utility in pest management. Taking into
consideration reports from the literature (31) describing deg-
radation for aminophenoxazines, which proceeds with detoxi-
fication, as phytotoxicity for AAPO and AAMPO data show,
further research is needed to determine the final fate of
aminophenoxazines in soil and other environments. Antifungal
activity shown by APO (31) could affect its own degradation
dynamics in soil, at least at the higher dosed employed in its
degradation experiments (10).
Nevertheless, APO showed high phytotoxicity and also higher
persistence in soil that its precursors BOA and DIBOA. These
facts allow us to conclude that some of the allelopathic behaviors
observed in plants that produce DIBOA could be due to its
degradation compound rather than the compound originally
released by plant. The low phytotoxicity of AMPO points to
the opposite direction regarding the DIMBOA series, so a more
accurate study about its interaction with soil biological popula-
tion and inorganic materials will be needed to discover its
ecological role. This fact, in addition to the higher persistence
in soil shown by DIBOA degradation series compounds (10),
allows us to conclude that DIBOA producing species take more
advantage of allelopathic defense strategies based on benzox-
azinones than DIMBOA producing ones.
The many different bioactivities shown by degradation
products of DIBOA and DIMBOA have to be taken into account
in the research of their biological activities and mode of action
since the effects observed could be related to the presence of
such derivatives in stock solutions and standards employed for
these evaluations, especially in the longer time experiments.
Our current efforts are directed toward the evaluation of these
compounds over common wheat weeds and other target organ-
isms.
ACKNOWLEDGMENT
(17) Kumar, P.; Gagliardo, R. W.; Chilton, W. S. Soil transformation
of wheat and corn metabolites MBOA and DIM2BOA into
aminophenoxazinones. J. Chem. Ecol. 1993, 19, 2453-2461.
(18) Friebe, A.; Vilich, V.; Hennig, L.; Kluge, M.; Sicker, D.
Detoxification of benzoxazolinone allelochemicals from wheat
by Gaeuannomyces graminis var. tritici, G. graminis var.
graminis, G. graminis var. avenae, and Fusarium culmorum.
Appl. EnViron. Microb. 1998, 64, 2386-2391.
(19) Yue, Q.; Bacon, C. W.; Richardson, M. D. Biotransformation
of 2-benzoxazolinone and 6-methoxy-benzoxazolinone by Fusar-
ium moniliforme. Phytochemistry 1998, 48, 451-454.
(20) Macias, F. A.; Castellano, D.; Molinillo, J. M. G. Search for a
standard phytotoxic bioassay for allelochemicals. Selection of
standard target species. J. Agric. Food. Chem. 2000, 48, 2512-
2521.
This work was financially supported by the program ‘Quality
of life and management of living resources (1998 to 2002)’ of
the European Union, FATEALLCHEM Contract No. QLRT-
2000-01967. Fellowships from Universidad de los Andes-
Venezuela (A. O. B.), European Comission (European Union),
and Junta de Andaluc´ıa-Spain (D. M.) are also gratefully
acknowledged.
LITERATURE CITED
(1) Virtanen, A. I.; Hietala, P. K. The structures of the precursors
of benzoxazolinone in rye plants. II. Suom. Kemistil. B 1959,
32B, 252.
(21) Larsen, E.; Christensen, L. P. Simple method for large scale
isolation of the cyclic arylhydroxamic acid DIMBOA from maize
(Zea mays L.). J. Agric. Food Chem. 2000, 48, 2556-2558.
(22) Barnes, J. P.; Putnam, A. R. Role of benzoxazinones in
allelopathy by rye (Secale cereale L.). J. Chem. Ecol. 1987, 13,
889-906.
(23) Hashimoto, Y.; Ishizaki, T.; Seudo, K.; Okamoto, T. Rearrange-
ment of 4-acetoxy-2H-1,4-benzoxazin-3(4H)-one. Chem. Pharm.
Bull. 1983, 31, 3891-3896.
(24) Atkinson, J.; Morand, P.; Arnason, J. T.; Niemeyer, H. M.; Bravo,
H. R. Analogues of the cyclic hydroxamic acid 2,4-dihydroxy-
7-methoxy-2H-1,4-benzoxazin-3-one (DIMBOA): decomposi-
tion to benzoxazolinones and reaction with â-mercaptoethanol.
J. Org. Chem. 1991, 56, 1788-1800.
(2) Hamilton, R. H.; Bandurski, R. S.; Reusch, W. H. Isolation and
characterization of a cyclic hydroxamate from Zea mays. Cereal
Chem. 1962, 39, 107-113.
(3) Honkanen, E.; Virtanen, A. I. Synthesis of some 1,4-benzoxazine
derivatives and their antimicrobial activity. Acta Chem. Scand.
1960, 14, 1214-1217.
(4) Escobar, C. A.; Sicker, D.; Niemeyer, H. M. Evaluation of
DIMBOA analogues as antifeedants and antibiotics towards the
aphid Sitobion aVenae in artificial diets. J. Chem. Ecol. 1999,
25, 1543-1554.
(5) Schulz, M.; Friebe, A.; Kueck, P.; Seipel, M.; Schnabl, H.
Allelopathic effects of living quack grass (Agropyron repens L.).
Identification of inhibitory allelochemicals exuded from rhizome
borne roots. Angew. Bot. 1994, 68, 195-200.