Investigating specialized plant metabolites, traditionally referred to as ‘secondary metabolites’ present in leaf extracts of cashew trees (Anacardium occidentale) resistant and susceptible to anthracnose disease was carried out using metabolomics combined with chemometric tools. We used clones of dwarf-cashew with the following variations of characteristics: resistant and healthy (CCP 76, BRS 226, BRS 189), susceptible and healthy (BRS 265), and another clone also susceptible but affected by the disease (BRS 265). The UPLC-QTOF-MSE (ultra performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry) analysis of the leaves of Anacardium clones allowed us to annotate a total of 39 metabolites. The multiple orthogonal partial discriminant analysis of the least-squares (OPLS-DA) allowed twelve metabolites to be potential biomarkers of differentiation among the clones studied. Namely, the triene-(17:3)-anacardic acid found on CCP 76 and BRS 189 clones, respectively, is the main candidate for biomarker of resistance. While catechin, B-type procyanidin isomers, and procyanidin dimer monogallate identified in BRS 265 are significant potential biomarkers of susceptibility.

Myracrodruon urundeuva (“aroeira-do-sertão”) is a species threatened with extinction due to anthropogenic exploitation. Phytochemical analysis of bark, branch and leaf extracts revealed the presence of several compounds such as flavonoids, phenols, tannins, quercetin derivatives and anacardic acids. Dereplication methodology was performed to tentatively identify 50 compounds analyzed by ultra-performance liquid chromatography coupled with an electrospray ionization quadrupole time-of-flight mass spectrometry operating in MSE mode (UPLC-QTOF-MSE). The extracts exhibited anti-tumor effect in cancer cells HCT-116 (colorectal), SF-295 (glioblastoma), HL-60 (leukemia), and RAJI (leukemia). Also, these results correlate with the principal component analysis (PCA) data that identified three distinct groups indicating, efficiently, metabolic differences between organs of M. urundeuva. Through discriminatory analysis of the orthogonal partial least squares (OPLS-DA), the variable of importance in the projection (VIP) and S-Plot, we were able to determine 30 potential biomarkers. The fingerprint of hydroethanolic extracts was correlated with the cytotoxicity assay and demonstrated a significant difference in the composition of plant extract.

Condensações de Knoevenagel de aldeídos aromáticos com 4-cloro-3-oxobutanoato de etila catalisadas por morfolina/ácido acético foram conduzidas em líquidos iônicos para fornecerem 2-cloroacetil-3-arilpropenoatos de etila em 44 a 84% de rendimentos após 0,5 a 2 h à temperatura ambiente (25-28 ºC). Estas condições representam um protocolo mais verde para a condensação de Knoevenagel do que aquelas realizadas com refluxo de benzeno e tolueno, utilizados como solventes. Aldeídos aromáticos contendo grupos arila, 4-clorofenila, 4-metoxifenila, 2-tiofuranila, 2-furanila, fenila e 3,4-metilenodioxifenila apresentaram razões diastereoméricas (E)/(Z) de 56/44 a 85/15. A estrutura do isômero-(E) do 2-cloroacetil-3-(3',4'-metilenodioxifenil)propenoato de etila foi determinada por difração de raio X, e uma metodologia inequívoca da análise estrutural-(E)/(Z) por RMN de 13C (ressonância magnética nuclear) é apresentada.

Knoevenagel condensations of aromatic aldehydes with ethyl 4-chloro-3-oxobutanoate catalyzed by morpholine/acetic acid were carried out in ionic liquids to give ethyl 2-chloroacetyl-3-arylpropenoates in 44-84% yield after 0.5 to 2 h at room temperature (25-28 ºC). These conditions represent a greener protocol for the Knoevenagel condensation than those using refluxing benzene or toluene as solvent. Aromatic aldehydes having aryl groups 4-chlorophenyl, 4-methoxyphenyl, 2-thiofuranyl, 2-furanyl, phenyl and 3,4-methylenedioxyphenyl gave (E)/(Z) diastereomeric ratios of products from 56/44 to 85/15. The two isomers of each compound were separately isolated and characterized. The structure of the (E)-isomer of ethyl 2-chloroacetyl-3-(3',4' methylenedioxyphenyl)propenoate was determined by X-ray crystallography and an unequivocal methodology of (E)/(Z)-structural analysis by 13C NMR (nuclear magnetic resonance) is presented.