2-Picolinic acid and benzoic acid from di-2-pyridyl ketone and acetophenone: A case of two copper catalysed Baeyer-Villiger rearrangements?

The synthesis and crystal structure elucidation of two novel polymeric copper(II) complexes has led us to propose a mechanism for the formation of 2-picolinic acid (pic) from di-2-pyridyl ketone (dpk) and benzoic acid from acetophenone. During studies into the interaction of copper ions with the dpk-acetophenone system, two complexes Na₂(NCS)₂(H₂O)[Cu(pic)₂] (1) and Na₂(H₂O)₂[Cu(pic)₂(NCS)₂] (2) which contain pic coordinated to copper were isolated. The occurrence of (1) and (2) has led us to consider the Baeyer-Villiger rearrangement as a possible mechanism for the formation of (1) and (2).     

Cholinergic and neuroprotective drugs for the treatment of Alzheimer and neuronal vascular diseases. II. Synthesis, biological assessment, and molecular modelling of new tacrine analogues from highly substituted 2-aminopyridine-3-carbonitriles

The synthesis, biological assessment, and molecular modelling of new tacrine analogues 11-22 is described. Compounds 11-22 have been obtained by Friedländer-type reaction of 2-aminopyridine-3-carbonitriles 1-10 with cyclohexanone or 1-benzyl-4-piperidone. The biological evaluation showed that some of these molecules were good AChE inhibitors, in the nanomolar range, and quite selective regarding the inhibition of BuChE, the most potent being 5-amino-2-(dimethylamino)-6,7,8,9-tetrahydrobenzo[1,8-b]-naphthyridine-3-carbonitrile (11) [IC₅₀ (EeAChE: 14 nM); IC₅₀ (eqBuChE: 5.2 ??M]. Kinetic studies on the easily available and potent anticholinesterasic compound 5-amino-2-(methoxy)-6,7,8,9-tetrahydrobenzo[1,8-b]-naphthyridine-3-carbonitrile (16) [IC₅₀ (EeAChE: 64 nM); IC₅₀ (eqBuChE: 9.6 ??M] showed that this compound is a mixed-type inhibitor (K_i = 69.2 nM) of EeAChE. Molecular modelling on inhibitor 16 confirms that this compound, as expected and similarly to tacrine, binds at the catalytic active site of EeAChE. The neuroprotective profile of molecules 11-22 has been investigated in SH-SY5Y neuroblastoma cells stressed with a mixture of oligomycin-A/rotenone. Compound 16 was also able to rescue by 50% cell death induced by okadaic acid in SH-SY5Y cells. From these results we conclude that the neuroprotective profile of these molecules is moderate, the most potent being compounds 12 and 17 which reduced cell death by 29%. Compound 16 does not affect ACh- nor K⁺-induced calcium signals in bovine chromaffin cells. Consequently, tacrine analogues 11-22 can be considered attractive therapeutic molecules on two key pharmacological targets playing key roles in the progression of Alzheimer, that is, cholinergic dysfunction and oxidative stress, as well as in neuronal cerebrovascular diseases.     

Synthesis of aryl pyrazole via Suzuki coupling reaction,in vitro mushroom tyrosinase enzyme inhibition assay and in silico comparative molecular docking analysis with Kojic acid

Aryl pyrazoles are well recognized class of heterocyclic compounds found in several commercially available drugs. Owing to their significance in medicinal chemistry, in this current account we have synthesized a series of suitably substituted aryl pyrazole by employing Suzuki cross-coupling reaction. All compounds were evaluated for inhibition of mushroom tyrosinase enzyme both in vitro and in silico. Compound 3f (IC₅₀ = 1.568 ± 0.01 µM) showed relatively better potential compared to reference kojic acid (IC₅₀ = 16.051 ± 1.27 µM). A comparative docking studies showed that compound 3f have maximum binding affinity against mushroom tyrosinase (PDBID: 2Y9X) with binding energy value (−6.90 kcal/mol) as compared to Kojic acid. The 4-methoxy group in compound 3f shows 100% interaction with Cu. Compound 3f displayed hydrogen binding interaction with His61 and His94 at distance of 1.71 and 1.74 Å which might be responsible for higher activity compared to Kojic acid.     

Tetra-acylated cyanidin 3-sophoroside-5-glucosides from the flowers of Iberis umbellata L. (Cruciferae)

The structures of 11 acylated cyanidin 3-sophoroside-5-glucosides (pigments 1-11), isolated from the flowers of Iberis umbellata cultivars (Cruciferae), were elucidated by chemical and spectroscopic methods. Pigments 1-11 were acylated with malonic acid, p-coumaric acid, ferulic acid, sinapic acid and/or glucosylhydroxycinnamic acids.Pigments 1-11 were classified into four groups by the substitution patterns of the linear acylated residues at the 3-position of the cyanidin. In the first group, pigments 1-3 were determined to be cyanidin 3-O-[2-O-(2-O-(acyl)-β-glucopyranosyl)-6-O-(trans-p-coumaroyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside], in which the acyl moiety varied with none for pigment 1, ferulic acid for pigment 2 and sinapic acid for pigment 3. In the second one, pigments 4-6 were cyanidin 3-O-[2-O-(2-O-(acyl)-β-glucopyranosyl)-6-O-(4-O-(β-glucopyranosyl)-trans-p-coumaroyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside], in which the acyl moiety varied with none for pigment 4, ferulic acid for pigment 5 and sinapic acid for pigment 6. In the third one, pigments 7-9 were cyanidin 3-O-[2-O-(2-O-(acyl)-β-glucopyranosyl)-6-O-(4-O-(6-O-(trans-feruloyl)-β-glucopyranosyl)-trans-p-coumaroyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside], in which the acyl moiety varied with none for pigment 7, ferulic acid for pigment 8, and sinapic acid for pigment 9. In the last one, pigments 10 and 11 were cyanidin 3-O-[2-O-(2-O-(acyl)-β-glucopyranosyl)-6-O-(4-O-(6-O-(4-O-(β-glucopyranosyl)-trans-feruloyl)-β-glucopyranosyl)-trans-p-coumaroyl)-β-glucopyranoside]-5-O-[6-O-(malonyl)-β-glucopyranoside], in which acyl moieties were none for pigment 10 and ferulic acid for pigment 11.The distribution of these pigments was examined in the flowers of four cultivars of I. umbellata by HPLC analysis. Pigment 1 acylated with one molecule of p-coumaric acid was dominantly observed in purple-violet cultivars. On the other hand, pigments (9 and 11) acylated with three molecules of hydroxycinnamic acids were observed in lilac (purple-violet) cultivars as major anthocyanins. The bluing effect and stability on these anthocyanin colors were discussed in relation to the molecular number of hydroxycinnamic acids in these anthocyanin molecules.     

Group 3 complexes incorporating (furyl)-substituted disilazide ligands

A series of mono- and bis-amide scandium and yttrium compounds incorporating the furyl-substituted disilazide ligand, [N{SiMe₂R}₂]⁻ {i} (where R = 2-methylfuryl) have been synthesized. The compounds Sc{i}Cl₂ (1), Sc{i}(CH₂SiMe₃)₂ (2) and Sc{i}(OAr)₂ (3) were made from suitable scandium starting materials employing either a salt metathesis protocol with Li{i} or via protonolysis of Sc-C bonds by the neutral amine H{i}. The thermally unstable bis-alkyl yttrium compound, ‘Y{i}(CH₂SiMe₃)₂^’ was isolated as the bis-THF adduct (4) and the bis-aryloxide Y{i}(OAr)₂ (5) was synthesized by elimination of LiOAr from Y(OAr)₃. The bis-amide complex Y{i}₂Cl (6) and conversion to a rare example of an yttrium benzyl compound Y{i}₂(CH₂Ph) (7) are described. The yttrium cation, [Y{i}₂]⁺, was synthesized by benzyl abstraction from 7 using B(C₆F₅)₃. Structural characterization of representative examples show variation in the coordination modes for amide ligand {i}, differing primarily in the number of furyl groups that coordinate to the metal, with examples in which zero, one or two M-O_furyl bonds are present. Preliminary investigation in two areas of catalysis are presented.     

Structural and thermal properties of three novel alkaline earth metal coordination polymers based on 5-hydroxyisophthalate ligand

Three novel coordination polymers [Ca(5-OH-BDC)(H₂O)₃] · H₂O (1), [Sr(5-OH-BDC)(H₂O)₄] · H₂O (2) and [Ba(5-OH-BDC)(H₂O)₃] (3) were obtained by self-assembly of the corresponding alkaline earth metal chlorate with a ligand, 5-hydroxyisophthalic acid (5-OH-H₂BDC), and their structures were determined by X-ray crystallography. The results revealed that complexes 1, 2 and 3 have two-dimensional network with (6, 3) topology observed in the bc plane. Moreover, the two-dimensional layers can be assembled into three-dimensional supramolecular architectures via intermolecular hydrogen bonds. The two carboxylate groups of 5-OH-BDC²⁻ ligand adopt the same coordination mode in complex 1 as that in 2: a μ3-η2:η1 mode and a chelated mode while in complex 3 they coordinate to Ba(II) ions in a μ3-η2:η1 mode and a monodentate mode, which is not observed in previous reports. The constant-volume combustion energies, Δ_cU, of these complexes were determined by a precise rotating-bomb calorimeter at 298.15 K, then their standard enthalpies of combustion, , and the standard enthalpies of formation, , have been calculated.     

Synthesis and characterisation of new molybdenum - oxo complexes containing diphenylphosphinylacetic acid and 2-(tert-butylsulphoxide)phenyldiphenylphosphine oxide as bidentate ligands

Reaction of the ligands diphenylphosphinylacetic acid Ph₂P(O)CH₂COOH (1) and 2-(tert-butylthio)phenyldiphenylphosphine oxide Ph₂P(O)C₆H₄^tBuS (2) with “MoO₂Cl₂”, resulted in two complexes MoO₂Cl₂Ph₂P(O)CH₂COOH (3) and MoO₂Cl₂Ph₂P(O)C₆H₄^tBuS(O) (4). Complexes 3 and 4 were isolated and analysed by ¹H NMR, ³¹P NMR and X-ray crystallography. Complex 3 crystallised with a molecule of the free ligand in a 1:1 ratio (3·1) and complex 4 crystallised with molecules of the solvent CH₂Cl₂ within the unit cell in a 2:1 ratio (4·0.5CH₂Cl₂). Tetrameric arrangements comprised of hydrogen bonds were observed in complexes 1 and 3. Complex 4 exhibited a seven-membered ring structure owing to the oxidation of the sulphide in 2 to sulphoxide and coordination of this ligand via the oxygen atoms to the molybdenum atom.     

Syntheses and structures of vinyl and aryl derivatives of carbonyl halide iron complexes

cis,trans-Fe(CO)₂(PMe₃)₂(p-Y-C₆H₄)X [X=Br, Y=H (4a), MeO (4b), Cl (4c), F (4d), Me (4e); X=I, Y=H (5); X=Cl, Y=H (6)] and cis,trans-Fe(CO)₂(PMe₃)₂(σ-CHCH₂)X [X=Br (7); X=I (8); X=Cl (9)] are prepared by reacting dihalide complexes cis,trans,cis- Fe(CO)₂(PMe₃)₂X₂ [X=Br (1), X=I (2), X=Cl (3)] with Grignard reagents p-Y-C₆H₄-MgBr (Y=H, OMe, Cl, F, Me) or CH₂CH-MgBr and with lithium reagents PhLi, CH₂CH-Li. With both reagents, the reaction proceeds following two parallel pathways: one is the metallation reaction which yields alkyl derivatives, the other affords 17 electron complexes [Fe(CO)₂(PMe₃)₂X] via monoelectron reductive elimination. The influence of the halides and organometallic reagents on the yield of the metallation reaction is discussed. The solution structure of the complexes is assigned on the basis of IR and ¹H, ¹³C, ¹⁹F, ³¹P NMR spectra. The solid state structure of complexes 4a, 5 and 6 is determined by single crystal X-ray diffractometric methods.     

Zinc complexes with 1,2,4-triazole functionalized amino acid derivatives: Synthesis, structure and β-lactamase assay

Coordinating abilities of 4R-1,2,4-triazole derivatives (R = glycine ethyl ester (L1), glycine (L2), diethylamino malonate (L3), methionine (L4) and diethyl aminomethylphosphonate (L5)) towards Zn^II ions have been studied in solution, in solid state and versus three zinc-β-lactamases. The crystal structure of [Zn₃(L4)₆(H₂O)₆] (6) is described; it is the first crystal structure involving a 1,2,4-triazole functionalized methionine. It forms a trinuclear complex with central zinc octahedrally coordinated by only L4, whereas terminal zinc ions coordination sphere is completed by three water molecules. L4 exhibits a dual functionality of a bridging bidentate ligand as well as an anion. A dense hydrogen bonding network connects these trinuclear entity into a 3D supramolecular network. The Zn^II ions in 6 are held at equidistance (3.848 Å) which coincidently matches with the corresponding Zn?Zn distance in the binuclear zinc enzyme from Bacillus cereus (3.848 and 4.365 Å). Among L1-L5 screened for β-lactamase assay, L4 shows modest inhibition for BcII enzyme.     

Assembly and upconversion luminescence of lanthanide-organic frameworks with mixed acid ligands

Three new lanthanide coordination polymers based on mixed acid ligands [Ln(oba)(ox)_0.5(H₂O)₂]_n (Ln = Y (1); Er (2); Yb (3). H₂oba = 4,4′-oxybis (benzoic acid); H₂ox = oxalic acid) were prepared by hydrothermal reactions and characterized by single-crystal X-ray diffraction. In these complexes, lanthanide ions are bridged by oba ligands to form 1D double-stranded chains, which are further connected by ox ligands, resulting in the formation of 2D (4,4) grids. The upconversion emission of the Y:Er-Yb co-doped coordination polymer was studied and the unusual blue emission for the Er(III) complexes was observed, which arises from the ²H_9/2 → ⁴I_15/2 transition and can be explained by three-photon excitation mechanism which is mostly phonon-dependent. The introduction of the oxalate anion without high-energy vibrational groups is beneficial to the increasing intensity of upconversion fluorescence. The magnetic properties of complexes 2 and 3 were investigated. The decrease of χ_MT over the temperature range of 300-2 K and the negative value of θ are due primarily to the splitting of the ligand field of the Er^III and Yb^III ions together with the possible weak antiferromagnetic coupling between the rare earth ions.     

Anti-inflammatory activity of constituents from Glechoma hederacea var. longituba

Rosmarinic acid, its analogues, and a phenolic compound were obtained from G. hederacea var. longituba. There were two new compounds, methyl isoferuloyl-7-(3,4-dihydroxyphenyl) lactate (1) and benzyl-4′-hydroxy-benzoyl-3′-O-β-d-glucopyranoside (4), and four known compounds (2, 3, 5 and 6). The structures of these compounds were determined on the basis of spectroscopic methods. Each compound was tested by NF-κB luciferase assay and three rosmarinic acid analogues inhibited NF-κB production and the induction of COX-2 and iNOS mRNA in HepG2 cells.     

Synthesis and structures of pyridinecarboxylate-containing zinc(II) complexes in dien and tren system

Four new zinc(II) complexes [Zn(dien)(μ-nic)]₂(BPh₄)₂·2CH₃OH (1), {[Zn(dien)(isonic)]BPh₄}_n (2), [Zn(tren)(nic)]BPh₄ (3) and [Zn(tren)(isonic)]BPh₄ (4) (dien/tren = diethylenetriamine/triethylenetriamine, nic/isonic = nicotinate/isonicotinate anion) were synthesized and structurally characterized by IR, ¹H NMR and single crystal X-ray diffraction. In the zinc(II) complexes of dien, both nicotinate and isonicotinate connect the zinc(II) ions via N,O-bis-monodentate mode. Complex 1 contains a centrosymmetric dinuclear unit bridged by two nicotinate anions in anti-parallel way. Complex 2 is characterized by an infinite one-dimensional zigzag chain bridged by isonicotinate anion in an end-to-end mode. The Zn···Zn distance is 6.782 for 1 and 8.805 Å for 2. While in the complexes of tren, both 3 and 4 are mononuclear complexes with nicotinate and isonicotinate coordinated to zinc(II) ion through only one oxygen atom of their carboxylate groups. The zinc(II) ions in all of the four complexes are in a distorted trigonal bipyramidal geometry. Complex 3 forms a dinuclear unit and complex 4 forms an infinite 2D sheet structure through intermolecular H-bonds. In all of the crystal lattices, the counterions act to balance the electronic charge at the same time to construct different 3D structures through noncovalent interactions such as C-H···π, N-H···π and van der Waals interactions.     

Lanthanide complexes with disulfide ligand generated in situ: Syntheses, crystal structures and fluorescent properties

Five new lanthanide complexes [Ln₂(DTDN)₄(phen)₄]·7H₂O·2H₃O⁺ (Ln = Nd (1), Sm (2), Eu (3), Tb (4), Dy (5), H₂DTDN = 2,2′-dithiodinicotinic acid, phen = 1,10-phenanthroline) have been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, and TG analyses. By in situ oxidation of 2-mercaptonanicotinic acid (2-H₂MN), the expected ligand H₂DTDN was generated. All crystals are isostructural and crystallize in monoclinic system with space group C2/c. The metal center is eight-coordinated completely by four carboxylic oxygen atoms from four different DTDN²⁻ ligands, and four nitrogen atoms from two phen molecules with a distorted square-antiprismatic geometry. The structures can be considered as two-dimensional (2D) structures and further linked by hydrogen bonds into the final trinodal 4-connected network. Photoluminescence studies revealed that complexes 2-5 exhibit strong fluorescent emission bands in the solid state at room temperature.     

The unexpected reactions of [RuCl3(2mqn)NO] (H2mqn=2-methyl-8-quinolinol) with 2-chloro-8-quinolinol (H2cqn) and of [RuCl(2cqn)(2mqn)NO] on photoirradiation

The reaction of [RuCl₃(2mqn)NO]⁻ (H2mqn=2-methyl-8-quinolinol) with 2-chloro-8-quinolinol (H2cqn) afforded cis-1 [RuCl(2cqn)(2mqn)NO] (the oxygen of 2cqn is trans to the NO) (complex 1), cis-1 [RuCl(2cqn)(2mqn)NO] (the oxygen of 2mqn is trans to the NO) (complex 2) and a 1:1 mixture of cis-2 [RuCl(2cqn)(2mqn)NO] (the oxygen of 2mqn is trans to the NO) and cis-2 [RuCl(2cqn)(2mqn)NO] (the oxygen of 2cqn is trans to the NO) (complex 3). The reaction was compared with that of [RuCl₃(2mqn)NO]⁻ with 8-quinolinol (Hqn) or 5-chloro-8-quinolinol (H5cqn). Photoirradiation reaction of complex 1 at room temperature in deaerated CH₂Cl₂ in the presence of NO gave trans-[RuCl(2cqn)(2mqn)NO] (the Cl is trans to the NO) and complex 2 with recovery of complex 1. The reaction was contrasted with that of cis-1 [RuCl(qn)(2mqn)NO] or cis-1 [RuCl(5cqn)(2mqn)NO]. The crystal structure of complex 1 was determined by X-ray diffraction. The reactions were examined under consideration of atomic charge of the phenolato oxygen in 8-quinolinol and its derivatives calculated at the restricted Hartree-Fock/6-311G** level.     

Four metal-organic networks based on benzene-1,4-dioxyacetic acid and dipyrido[3,2-a:2′,3′-c]phenazine ligand

Four structurally diverse complexes, [Cd(dppz)(bdoa)]_n (1), [Zn(dppz)(bdoa)(H₂O)]_n (2), [Fe(dppz)₂(bdoa)]_n·2nH₂O (3), and [Co₂(dppz)₂(bdoa)₂(H₂O)]_n·3nH₂O (4), where H₂bdoa = benzene-1,4-dioxyacetic acid and dppz = dipyrido[3,2-a:2′,3′-c]phenazine, have been hydrothermally synthesized. Compounds 1-4 feature chain structures. There exist π-π interactions in the structures of 1, 2 and 4. Two neighboring chains of 1 are linked through the π-π interactions into a double chain supramolecular structure. The chains of 2 and 4 are further extended by the π-π interactions to form 3D and 2D supramolecular structures, respectively. The structural differences among such complexes show that the transition metals have important influences on their structures. The photoluminescent property of complex 2 and the magnetic property of complex 4 have also been investigated.     

Synthesis and evaluation of chromenyl barbiturates and thiobarbiturates as potential antitubercular agents

A novel series of barbiturate and thiobarbiturate analogs of 2-benzoyl-3-methyl-5-oxo-5H-furo[3,2-g]chromene-6-carbaldehydes (3a-g and 4a-d, respectively) and 6-methyl-4,8-dioxo-4,8-dihydropyrano[3,2-g]chromenes (7a-c), were synthesized and evaluated for their antitubercular activities against Mycobacterium tuberculosis H37RV, and cytotoxicity (CC₅₀) in the VERO cell MABA assay. The results indicate that the furanochromene series of compounds (3a-g and 4a-d) showed only weak to moderate antitubercular activity. However, the pyranochromene analog 7b showed good antitubercular activity (IC₉₀: 5.9 μg/mL) and cytotoxicity (CC₅₀: 14.27 μg/mL). The antitubercular activity of 7b was superior to the antituberculosis drug, pyrazinamide (PZA; IC₉₀: >20 μg/mL). Analog 7b was considered to be a lead compound for subsequent structural optimization.     

Syntheses and structures of lanthanide complexes containing a bis(imidazolin-2-imino)pyridine pincer ligand

The Lewis acid-base reaction of 2,6-bis[1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine (TL^tBu) and LnCl₃ in THF leads to the corresponding neutral lanthanide complexes of type [(TL^tBu)LnCl₃], Ln = Y (1a), Er (1b), Lu (1c). The yttrium and lutetium complexes have been characterized by X-ray diffraction analysis. The solid state structures reveal that the bulky TL^tBu ligand causes steric crowding around the lanthanide atoms by coordinating to the metal center in a tridentate fashion. In addition, remote C-H?Ln interactions (H?Ln ca. 2.7 Å) involving one of the ^tBu methyl groups are observed in both cases. A DFT (density functional theory) calculation on 1a was able to reproduce this interaction, which was additionally characterized by means of an H?Y compliance constant and by employing the AIM (atoms in molecules) theory.     

Synthesis and characterization of ruthenium(II) complexes based on diphenyl-2-pyridylphosphine and their applications in transfer hydrogenation of ketones

Synthesis and characterization of the ruthenium complexes [RuH(CO)Cl(κ¹-P-PPh₂Py)₂(PPh₃)] (1) and [Ru(CO)Cl₂(κ¹-P-PPh₂Py)(κ²-P-N-PPh₂Py)] (2) containing diphenyl-2-pyridylphosphine (PPh₂Py) are described. Spectral and structural data suggested linkage of the PPh₂Py in κ¹-P bonding mode in 1 and both the κ¹-P and κ²-P-N bonding modes in 2. The complex 1 reacted with N,N-donor bases viz., ethylenediamine (en), N,N′-dimethyl-(ethylenediamine) (dimen), 1,3-diaminopropane (diap), 2,2′-bipyridine (bipy), 1,10-phenanthroline (phen) and di-2-pyridylaminomethylbenzene (dpa) to afford cationic complexes of formulation [RuH(CO)(κ¹-P-PPh₂Py)₂(N-N)]⁺ (3-8) [N-N = en, 3; dimen, 4; diap, 5; bipy, 6; phen, 7; and dpa, 8], which have been isolated as their tetrafluoroborate salts. The complexes under investigation have been characterized by elemental analyses, spectroscopic and electrochemical studies. Molecular structures of 2, 3, 6, and 8 have been determined by single crystal X-ray diffraction analyses. Further, the complexes 1-8 act as effective precursor catalyst in transfer hydrogenation of acetophenone/ketones in basic 2-propanol.     

Determination of the hydroxycinnamate profile of 12 members of the Asteraceae family

The hydroxycinnamates of the leaves of 12 plants of the Astreraceae family, Achillea millefolium, Arnica montana, Artemesia dracunculus, Cichorium intybus, Cnicus benedictus, Cynara scolymus, Echinops humilis, Inula helenium, Lactuca sativa, Petasites hybridus, Solidago virgaurea, and Tanacetum parthenium were investigated qualitatively by LC-MSⁿ. Thirty-nine chlorogenic acids were detected and all characterized to regioisomeric level on the basis of their fragmentation pattern in the tandem MS spectra, most of them for the first time from these sources with two of them previously not reported in nature. Both chlorogenic acids based on trans and cis-cinnamic acid substituents were identified. Assignment to the level of individual regioisomers was possible for seven caffeoylquinic acids (1-7), 11 dicaffeoylquinic acids (17-27), six feruloylquinic acids (9-14), two p-coumaroylquinic acids (15-16), two caffeoyl-feruloylquinic acids (28 and 29), four caffeoyl-p-coumaroylquinic acids (30-33), three dicaffeoyl-succinoylquinic acids (34-36), two dicaffeoyl-methoxyoxaloylquinic acids (37 and 38), and one tricaffeoylquinic acid (39). Furthermore, one caffeoylshikimic acid (40), one caffeoyltartaric acid (41), three dicaffeoyltartaric acids (42-44), and three caffeoyl-feruloyltartaric acids (45-47) were detected and shown to possess characteristic tandem MS spectra and were tentatively assigned on the basis of their retention time and previously developed hierarchical keys.