N-Formyllapatin A,a new N-formylspiroquinazoline derivative from the marine-derived fungus Penicillium adametzioides AS-53

N-Formyllapatin A (1), a new spiroquinazoline derivative, and four known quinazoline metabolites, lapatins A (2) and B (3), prelapatin B (4), and glyantrypine (5), along with two known indolediketopiperazine derivatives, fumitremorgin B (6) and verruculogen (7), were characterized from Penicillium adametzioides AS-53, a fungus obtained from the fresh tissue of an unidentified marine sponge. The structure of compound 1 was established by detailed interpretation of NMR and MS data, and its absolute configuration was established by a single-crystal X-ray diffraction analysis. N-Formyllapatin A (1) represents the first N-formylspiroquinazoline secondary metabolite. Compounds 3 and 5–7 showed moderate inhibitory activity against aqua-pathogenic bacterial Vibrio harveyi.     

Synthesis of asperphenamate,a novel fungal metabolite

The proposed structure of asperphenamate (1), a novel fungal metabolite, was confirmed by synthesis. Esterification of N-benzoyl-L-phenylalaninol with N-carbobenzoxy-L-phenylalanine, followed by deprotection of the carbobenzoxy group and benzoylation yielded a product which was identical to the natural fungal metabolite.     

Secondary metabolites from the seaweed Gracilaria lemaneiformis and their allelopathic effects on Skeletonema costatum

A new secondary metabolite, 8-hydroxy-4E,6E-octadien-3-one (1), was isolated from the seaweed Gracilaria lemaneiformis together with previously uncharacterized loliolide (2), 3β-hydroxy-5α,6α-epoxy-7-megastigmen-9-one (3), N-phenethylacetamide (4), squamolone (5), and 2-ethylidene-4-methylsuccinimide (6). Their structures were elucidated on the basis of spectroscopic data. Among them, compounds 1 and 3 were found to show moderate allelopahic effect on the growth of the red tide alga Skeletonema costatum with the IC₅₀ values of 165.6 and 147.6 μM, while the others were not particularly toxic to S. costatum. This is a preliminary study and the mechanism of species-specific allelopathic antialgal activity requires further investigation.     

Identification of urine metabolites of TFAP,a cyclooxygenase-1 inhibitor

Only a few COX-1-selective inhibitors are currently available, and the research on COX-1 selective inhibitors is not fully developed. The authors have produced several COX-1 selective inhibitors including N-(5-amino-2-pyridinyl)-4-trifluoromethylbenzamide: TFAP (3). Although 3 shows potent analgesic effect without gastric damage, the urine after administration of 3 becomes red–purple. Since the colored-urine should be avoided for clinical use, in this research we examined the cause of the colored-urine. UV–vis spectra and LC–MS/MS analyses of urine samples and metabolite candidates of 3 were performed to afford information that the main reason of the colored urine is a diaminopyridine (4), produced by metabolization of 3. This information is useful to design new COX-1 selective inhibitors without colored urine based on the chemical structure of 3.     

N-Substituted acetamide glycosides from the stems of Ephedra sinica

Five new N-mono-/bis-substituted acetamide glycosides, N-{4-O-[3-O-(4-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)-α-l-rhamnopyranosyl]-phenethyl}-acetamide (1), N-methyl-N-{4-O-[3-O-(4-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)-α-l-rhamnopyranosyl]-phenethyl}-acetamide (2), N-methyl-N-{4-O-[3-O-(6-O-benzoyl-4-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)-α-l-rhamnopyranosyl]-phenethyl}-acetamide (3), N-methyl-N-{4-O-[3-O-(6-O-benzoyl-β-d-glucopyranosyl)-α-l-rhamnopyranosyl]-phenethyl}-acetamide (4), and N-methyl-N-{4-O-[3-O-(6-O-trans-cinnamoyl-4-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)-α-l-rhamnopyranosyl]-phenethyl}-acetamide (5), along with one known acetamide derivative, N-methyl-N-(4-hydroxyphenethyl)-acetamide, the shared aglycone of 2–5, were isolated from the ethanol extract of the stems of Ephedra sinica. The structures of these new compounds were elucidated on the basis of extensive spectroscopic examination, mainly including multiple 1D and 2D NMR and HRESIMS examinations, and qualitative chemical tests. All N,N-bissubstituted acetamide glycosides were found to show the obvious rotamerism, as in the case of the isolated known N-methyl-N-(4-hydroxyphenethyl)-acetamide, under the experimental NMR conditions, with the ratios of integrated intensities between anti- and syn-rotamers always being found to be about 4 to 3.     

N6-Trimethyl-lysine metabolism. Structural identification of the metabolite 3-hydroxy-N6-trimethyl-lysine

¹H and ¹³C nuclear-magnetic-resonance spectroscopy and functional-group analysis were used to determine the molecular structure of an isolated metabolite (II_b) of trimethyl-lysine as 3-hydroxy-N⁶-trimethyl-lysine, an important intermediate in the conversion of trimethyl-lysine into trimethylammoniobutyrate and carnitine [Hoppel, Cox & Novak (1980) Biochem. J. 188, 509–519]. Functional-group analysis revealed the presence of a primary amine and reaction of metabolite (II_b) with periodate yielded 4-N-trimethylammoniobutyrate as a product, showing 2,3-substitution on the molecule and suggesting that the 3-substitution on the molecule may be an alcohol ([unk]CH–OH), amine ([unk]CH[unk]–NH₂) or carbonyl ([unk]C=O) functional group. ¹H integration ratios, ¹H and ¹³C chemical-shift data and ¹H and ¹³C signal multiplicities from the sample (II_b) were used to complete the identification of metabolite (II_b) as 3-hydroxy-N⁶-trimethyl-lysine. For example, the proton multiplet at δ 4.2p.p.m. and doublet at δ 4.1p.p.m., positions representative of amine or alcohol substitution on methylene carbon atoms, integration ratios of 1:1:2:9:4 and a positive ninhydrin test suggest 3-hydroxy-N⁶-trimethyl-lysine as the molecular structure for metabolite (II_b). ¹³C chemical-shift data obtained from the sample (II_b) and compared with several model compounds (trimethylammoniohexanoate, trimethyl-lysine and 3-hydroxylysine) resulted in generation of the spectrum of the metabolite and allowed independent identification of metabolite (II_b) as 3-hydroxy-N⁶-trimethyl-lysine. The ¹H spectrum of erythro- and threo-3-hydroxylysine are presented for comparison, and the ¹H and ¹³C n.m.r. spectra of the erythro-isomer support this analysis.     

Facile synthesis of SSR180575 and discovery of 7-chloro-N,N,5-trimethyl-4-oxo-3(6-[18F]fluoropyridin-2-yl)-3,5-dihydro-4H-pyridazino[4,5-b]indole-1-acetamide,a potent pyridazinoindole ligand for PET imaging of TSPO in cancer

A novel synthesis of the translocator protein (TSPO) ligand 7-chloro-N,N,5-trimethyl-4-oxo-3-phenyl-3,5-dihydro-4H-pyridazino[4,5-b]indole-1-acetamide (SSR180575, 3) was achieved in four steps from commercially available starting materials. Focused structure–activity relationship development about the pyridazinoindole ring at the N3 position led to the discovery of 7-chloro-N,N,5-trimethyl-4-oxo-3(6-fluoropyridin-2-yl)-3,5-dihydro-4H-pyridazino[4,5-b]indole-1-acetamide (14), a novel ligand of comparable affinity. Radiolabeling with fluorine-18 (¹⁸F) yielded 7-chloro-N,N,5-trimethyl-4-oxo-3(6-[¹⁸F]fluoropyridin-2-yl)-3,5-dihydro-4H-pyridazino[4,5-b]indole-1-acetamide ([¹⁸F]-14) in high radiochemical yield and specific activity. In vivo studies of [¹⁸F]-14 revealed this agent as a promising probe for molecular imaging of glioma.     

Synthesis and urease inhibitory potential of benzophenone sulfonamide hybrid in vitro and in silico

This study deals with the synthesis of benzophenone sulfonamides hybrids (1–31) and screening against urease enzyme in vitro. Studies showed that several synthetic compounds were found to have good urease enzyme inhibitory activity. Compounds 1 (N′-((4′-hydroxyphenyl)(phenyl)methylene)-4′′-nitrobenzenesulfonohydrazide), 2 (N′-((4′-hydroxyphenyl)(phenyl)methylene)-3′′-nitrobenzenesulfonohydrazide), 3 (N′-((4′-hydroxyphenyl)(phenyl)methylene)-4′′-methoxybenzenesulfonohydrazide), 4 (3′′,5′′-dichloro-2′′-hydroxy-N′-((4′-hydroxyphenyl)(phenyl)methylene)benzenesulfonohydrazide), 6 (2′′,4′′-dichloro-N′-((4′-hydroxyphenyl)(phenyl)methylene)benzenesulfonohydrazide), 8 (5-(dimethylamino)-N′-((4-hydroxyphenyl)(phenyl)methylene)naphthalene-1-sulfono hydrazide), 10 (2′′-chloro-N′-((4′-hydroxyphenyl)(phenyl)methylene)benzenesulfonohydrazide), 12 (N′-((4′-hydroxyphenyl)(phenyl)methylene)benzenesulfonohydrazide) have found to be potently active having an IC₅₀ value in the range of 3.90–17.99?µM. These compounds showed superior activity than standard acetohydroxamic acid (IC₅₀?=?29.20?±?1.01?µM). Moreover, in silico studies on most active compounds were also performed to understand the binding interaction of most active compounds with active sites of urease enzyme. Structures of all the synthetic compounds were elucidated by ¹H NMR, ¹³C NMR, EI-MS and FAB-MS spectroscopic techniques.     

Synthesis and biological evaluation of substituted imidazoquinoline derivatives as mPGES-1 inhibitors

We have previously reported 7-bromo-2-(2-chrolophenyl)-imidazoquinolin-4(5H)-one (1) as a novel potent mPGES-1 inhibitor. To clarify the essential functional groups of 1 for inhibition of mPGES-1, we investigated this compound structure–activity relationship following substitution at the C(4)-position and N-alkylation at the N(1)-, the N(3)-, and the N(5)-positions of 1. To prepare the target compounds, we established a good methodology for selective N-alkylation of the imidazoquinolin-4-one, that is, selective alkylation of 1 at the N(3)- and N(5)-positions was achieved by use of an appropriate base and introduction of a protecting group at the nitrogen atom in the imidazole part, respectively. Replacement of the C(4)-oxo group with nitrogen- or sulfur- linked substituents gave decreased inhibitory activity for mPGES-1, and introduction of alkyl groups on the nitrogen atom at the N(1)-, the N(3)-, and the N(5)-positions resulted in even larger loss of inhibitory activity. These results revealed that the C(4)-oxo group, and the hydrogen atoms at the N(5)-position and the imidazole part were the best substituents.     

Synthesis of some glycodipeptides containing hydroxyamino acids, and their stabilities to acids and bases

The following new compounds were prepared and characterized: N-benzyl-oxycarbonyl-O-(tetra-O-acetyl-β-D-glucopyranosyl)-N-glycyl-L-serine methyl ester (1) and L-threonine methyl ester (2), N-benzyloxycarbonyl-O-(β-D-glucopyranosyl)-N-glycyl-L-serine amide (3), N-benzyloxycarbonyl-O-(β-D-glucopyranosyl)-N-glycyl-L-threonine methyl ester (4) and L-threonine amide (5), N-benzyloxycarbonyl-O-(tri-O-acetyl-2-deoxy-2-trifluoroacetamido-β-D-glucopyranosyl)-N-glycyl-L-serine methyl ester (6), and N-benzyloxycarbonyl-O-(2-deoxy-2-trifluoroacetamido-β-D-glucopyranosyl)-N-glycyl-L-serine amide (7). Although various modifications of the Koenigs-Knorr synthesis were used, the best, over-all yields of the deacetylated dipeptide derivatives were only 5–10%. Although the products are alkali-labile, deacetylation was accomplished with methanolic ammonia. Of the deacetylated products, the threonine derivatives (4 and 5) were more rapidly hydrolyzed by acids than phenyl β-D-glucopyranoside, which in turn was more rapidly cleaved than the serine derivatives (3 and 7). The stabilities of 3, 4, 5, and 7 to sodium hydroxide and sodium borohydride were similar, and essentially complete β-elimination of the glycosyl residue occurred for the amide derivatives (3, 5, and 7). For the ester derivative 4, pH 9 was optimal; above this pH, ester hydrolysis was more rapid than β-elimination, and the resulting carboxyl derivatives did not undergo β-elimination. Under optimal conditions with sodium borohydride, the β-elimination reaction was complete, but the corresponding alanine and α-aminobutyric acid residues were not formed; presumably reductions to the amino alcohols occurred. A mechanism for the β-elimination is proposed.     

Microbial C-hydroxylation and β-4-O-methylglucosidation of methyl-benzamide 7-azanorbornane ethers with Beauveria bassiana

N-Substituted 7-azanorbornanes were prepared by acylation of easily accessible 7-azanorbornane hydrochloride. Derivatives possessing an electron-withdrawing docking/protecting group and bearing an aryl methylether were subjected to biotransformation with the fungus Beauveria bassiana ATCC 7159. O-Demethylation and β-4-O-methylglucosidation reactions were observed for the major metabolite in this biotransformation (isolation yields: 6, 30%; 11a, 44%; 11b, 47%; 11c, 14%). C-Hydroxylation on an unfunctionalized carbon was also observed in most of the cases.     

Synthesis and anti-proliferative activity of aromatic substituted 5-((1-benzyl-1H-indol-3-yl)methylene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione analogs against human tumor cell lines

Based on previous SAR studies on N-benzylindole and barbituric acid hybrid molecules, we have synthesized a series of aromatic substituted 5-((1-benzyl-1H-indol-3-yl)methylene)-1,3-dimethylpyrimidine-2,4,6(1H,3H,5H)-trione analogs (3a–i) and evaluated them for their in vitro growth inhibition and cytotoxicity against a panel of 60 human tumor cell lines. Compounds 3c, 3d, 3f and 3g were identified as highly potent anti-proliferative compounds against ovarian, renal and breast cancer cell lines with GI₅₀ values in low the nanomolar range. The 4-methoxy-N-benzyl analog (3d) was the most active compound with GI₅₀ values of 20 nM and 40 nM against OVCAR-5 ovarian cancer cells and MDA-MB-468 breast cancer cells, respectively. Two other analogs, 3c (the 4-methyl-N-benzyl analog) and 3g (the 4-fluoro-N-benzyl analog) exhibited equimolar potency against MDA-MB-468 cells GI₅₀ = 30 nM). Analog 3f (the 4-chloro-N-benzyl analog) exhibited a GI₅₀ value of 40 nM against renal cancer cell line A498. These results suggest that aromatic substituted N-benzylindole dimethylbarbituric acid hybrids may have potential for development as clinical candidates to treat a variety of solid tumors.     

Biotransformation of capsaicin by Penicillium janthinellum AS 3.510

Biocatalysis of capsaicin (1) was performed by Penicillium janthinellum AS 3.510. Nine metabolites including four new compounds were afforded, and their structures were elucidated as (8S)-trans-8-hydroxy-8-hydroxymethyl-N-vanillyl-6-nonenamide (2), 6-hydroxy-8-methyl-N-vanillyl-7-nonenamide (3), trans-8-methoxy-8-methyl-N-vanillyl-6-nonenamide (4), 6-methoxy-8-methyl-N-vanillyl-7-nonenamide (5), dihydrocapsaicin (6), ω-1-hydroxydihydrocapsaicin (7), ω-1-hydroxycapsaicin (8), ω-hydroxycapsaicin (9), N-(4-hydroxy-3-methoxybenzyl)-5-[3-(propan-2-yl)oxiran-2-yl]pentanamide (10) by 1D and 2D NMR and HRESIMS spectra. The biotransformation processes include hydroxylation, methylation, reduction, and epoxylation.     

Copper(II) and zinc(II) complexes with Schiff-base ligands derived from salicylaldehyde and 3-methoxysalicylaldehyde: Synthesis,crystal structures,magnetic and luminescence properties

The following Schiff bases were employed as ligands in synthesizing copper(II) and zinc(II) complexes: N-[(2-pyridyl)-methyl]-salicylimine (Hsalampy), N-[2-(N,N-dimethyl-amino)-ethyl]-salicylimine (Hsaldmen), and N-[(2-pyridyl)-methyl]-3-methoxy-salicylimine (Hvalampy). The first two ligands were obtained by reacting salicylaldehyde with 2-aminomethyl-pyridyne and N,N-dimethylethylene diamine, respectively, while the third one results from the condensation of 3-methoxysalicylaldehyde with 2-aminomethyl-pyridine. Four new coordination compounds were synthesized and structurally characterized: [Cu(salampy)(H₂O)(ClO₄)] 1, [Cu₂(salampy)₂(H₂trim)₂] 2 (H₂trim^? = the monoanion of the trimescic acid), [Cu₄(valampy)₄](ClO₄)₄ · 2CH₃CN 3, and [Zn₃(saldmen)₃(OH)](ClO₄)₂ · 0.25H₂O 4. The crystal structure of 1 consists of supramolecular dimers resulted from hydrogen bond interactions established between mononuclear [Cu(salampy)(H₂O)(ClO₄)] complexes. Compound 2 is a binuclear complex with the copper ions connected by two monoatomic carboxylato bridges arising from two molecules of monodeprotonated trimesic acid. The crystal structure of 3 consists of tetranuclear cations with a heterocubane {Cu₄O₄} core, and perchlorate ions. Compound 4 is a trinuclear complex with a defective heterocubane structure. The magnetic properties of complexes 1–3 have been investigated. Compound 4 exhibits solid-state photoluminescence at room temperature.     

Preparations of 2-epi-fortimicins A from 2-epi-fortimicin B by intramolecular base-catalyzed 2-O-acylation of 1,2′,6′-tri-N-benzyloxycarbonyl-2-epi-fortimicin B

Preparations of 2-epi-fortimicin A (4) from 2-epi-fortimicin B (3) are described. In contrast to the previously reported, selective 4-N-acylation of 1,2′,6′-tri-N-benzyloxycarbonylfortimicin B (8) with N-(N-benzyloxycarbonylglycyloxy)succinimide, 1,2′,6′-tri-N-benzyloxycarbonyl-2-epi-fortimicin B (5) underwent predominant 2-O,4-N-diacylation under similar conditions. Proof of the structure of the diacylated product is presented, with evidence that the diacylated product is formed by initial intramolecular, base-catalyzed 2-O-acylation. The in vitro antibacterial activities of 2-epi-fortimicin A (4), 2-O-glycyl-2-epi-fortimicin A (11), 1-N-glycyl-2-epi-fortimicin A (12), and 5-deoxy-2-epi-fortimicin A (13) are reported.     

Synthesis and antiproliferative evaluation of N,N-disubstituted-N′-[1-aryl-1H-pyrazol-5-yl]-methnimidamides

A series of N,N-disubstituted-N′-[1-aryl-1H-pyrazol-5-yl]-methnimidamides was synthesized by a newly developed microwave reaction and their antiproliferative activities were evaluated. Microwave irradiation of 5-amino-1,3-disubstituted pyrazoles with various amide solvents in the presence of POCl₃ provided the corresponding 2a–2k, 3a–3c, and 4a–4f in good to excellent yields. The obtained methnimidamides were tested against NCI-H661, NPC-TW01, and Jurkat cancer cell lines and the results indicated that compounds 2d and 2e were the most potent with IC₅₀ values in low micromolar range.     

Synthesis of new 1-(4-methane(amino)sulfonylphenyl)-5-(4-substituted-aminomethylphenyl)-3-trifluoromethyl-1H-pyrazoles: A search for novel nitric oxide donor anti-inflammatory agents

A group of 1-(4-methane(amino)sulfonylphenyl)-5-(4-substituted-aminomethylphenyl)-3-trifluoromethyl-1H-pyrazoles (12a–f) was synthesized and evaluated as anti-inflammatory agents. While all the compounds (20 mg/kg) showed significant anti-inflammatory activity after 3 h of inflammation induction (69–89%) as compared to celecoxib (80%), 1-(4-methanesulfonylphenyl)-5-(4-methylaminomethylphenyl)-3-trifluoromethyl-1H-pyrazole (12a) was found to be the most effective one (89%). The synthesis of model hybrid nitric oxide donor N-diazen-1-ium-1,2-diolate derivatives of 1-(4-methanesulfonylphenyl)-5-(4-substituted-aminomethylphenyl)-3-trifluoromethyl-1H-pyrazoles (10a–f) requires further investigation since the reaction of N-(4-(1-(4-(methylsulfonyl)phenyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl)benzyl)ethanamine (12b) or 1-(4-(1-(4-(methylsulfonyl)phenyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl)benzyl)piperazine (12c) with nitric oxide furnished N-nitroso derivatives (13 and 14), respectively, rather than the desired N-diazen-1-ium-1,2-diolate derivatives (10b and 10c).     

An application of the palladium-catalyzed,allylic amination of unsaturated sugars: a new synthesis of d-forosamine

Methyl 4-O-benzoyl-6-bromo-6-deoxy-α-d-glucopyranoside, obtainable from methyl 4,6-O-benzylidene-α-d-glucopyranoside (1), was converted into the 2,3-unsaturated 4-benzoate (3) by application of the triiodoimidazole method. Debenzoylation of 3, followed by acetylation, afforded crystalline methyl 4-O-acetyl-6-bromo-2,3,6-trideoxy-α-d-erythro-hex-2-enopyranoside (5). Treatment of 5 with benzylmethylamine under conditions of palladium-catalyzed, allylic substitution gave a separable mixture of the corresponding 4-(N-benzyl)methylamino-6-bromo-2-enoside (37%) and the 4,6-di-[(N-benzyl)methylamino]-2-enoside (55%). Debromination of 5 with lithium triethylborohydride, proceeding with simultaneous deacetylation, readily yielded methyl 2,3,6-trideoxy-α-d-erythro-hex-2-enopyranoside (8). The 4-acetate of 8 (obtained by reacetylation), and also its 4-benzoate (prepared by a different synthetic route), furnished high yields (～80%) of methyl 4-[(N-benzyl)-methylamino]-2,3,4,6-tetradeoxy-α-d-erythro-hex-2-enopyranoside (13) upon palladium-catalyzed animation with benzylmethylamine. Catalytic hydrogenation of 13 effected saturation of the alkenic double bond and removal of the N-benzyl group, to afford methyl 2,3,4,6-tetradeoxy-4-methylamino-α-d-erythro-hexopyranoside, which was subsequently N-methylated with formaldehyde and sodium borohydride, to give its N,N-dimethyl analog, methyl α-d-forosaminide (15). The overall yield of 15 from 1 was 24%. Hydrolysis of 15 to the free sugar has been described previously.     

The synthesis of 3-amino-2,3,6-trideoxy-l-xylo-hexopyranose derivatives

Derivatives (the 3-acetamido-4-benzoate 12, the 3-acetamido-4-acetate 13, and the N-acetyl derivative 14) of the methyl glycoside of the title sugar were prepared in a sequence of high-yielding steps from methyl 3-azido-4,6-O-benzylidene-2,3-di-deoxy-α-d-arabino-hexopyranoside (4). N-Bromosuccinimide converted 4 into the crystalline 4-O-benzoyl-6-bromide 5, which was treated with silver fluoride to afford the 5,6-unsaturated glycoside 6. Catalytic hydrogenation of 6 led, essentially, to a 7:1 mixture of 12 and its 5-epimeric d-arabino isomer 7. Alternatively, 6 was debenzoylated to 10, and the latter treated with lithium aluminum hydride to give crystalline methyl 3-amino-2,3,6-trideoxy-α-d-threo-hex-5-enopyranoside (11). Reduction of 11 (as its salt) by hydrogen, with subsequent N-acetylation, furnished the methyl β-l-xylo-glycoside 13 almost exclusively, with net inversion at C-5. Compound 13 was readily converted into the crystalline target compound 14. When dehydrobromination by silver fluoride was attempted with the 3-acetamido analog (2) of 5, a 3,6-anhydro product (1) was obtained, instead of the expected 5,6-alkene 3.     

Amino acids and low-molecular-weight carbohydrates of some marine red algae

Amino acids and low-MW carbohydrates of 18 red algae have been analyzed. Several non-protein amino acids have been identified, including pyrrolidine-2,5-dicarboxylic acid (3c) and N-methylmethionine sulfoxide (5), new natural products, and 13 known compounds, citrulline, β-alanine, γ-aminobutyric acid, baikiain (1), pipecolic acid (2), domoic acid (3a), kainic acid (3b), azetidine-2-carboxylic acid (4), methionine sulfoxide taurine, N-methyltaurine, N,N-dimethyltaurine and N,N,N-trimethyltaurine. Sugars present were mainly floridoside, isofloridoside and mannoglyceric acid. Details of the structural elucidation of new compounds are also given.