New sesquiterpenes and calebin derivatives from Curcuma longa

One novel sesquiterpene with new skeleton, (6S)-2-methyl-6-(4-hydroxyphenyl-3-methyl)-2-hepten-4-one (1), two new bisabolane sesquiterpenes, (6S)-2-methyl-6-(4-hydroxyphenyl)-2-hepten-4-one (2), (6S)-2-methyl-6-(4-formylphenyl)-2-hepten-4-one (3), and two calebin derivatives, 4'-(4'-hydroxyphenyl-3'-methoxy)-2'-oxo-3'-butenyl-3-(4'-hydroxyphenyl)-propenoate (4) and 4'-(4'-hydroxyphenyl)-2'-oxo-3'-butenyl-3-(4'-hydroxyphenyl-3'-methoxy)-propenoate (5) were isolated along with five known bisabolane sesquiterpenes from Curcuma longa. 1-4 were new compounds and 5 was a new natural product. Their structures were established by spectral methods.     

Two new homoisoflavonoids from Caesalpinia pulcherrima

Two new homoisoflavonoids, (E)-7-methoxy-3-(4'-methoxybenzylidene)chroman-4-one (1) and (E)-7-hydroxy-3-(3',4',5'-trimethoxybenzylidene)chroman-4-one (5), along with three known homoisoflavonoids (Z)-7-hydroxy-3-(4'-methoxybenzylidene)chroman-4-one (isobon ducellin) (2), (E)-7-hydroxy-3-(4'-methoxybenzylidene)chroman-4-one (bonducellin) (3) and (E)-7-hydroxy-3-(2',4'-dimethoxybenzylidene)chroman-4-one (4) were isolated from the whole plant of Caesalpinia pulcherrima. The structures of these new compounds were elucidated by electron impact mass spectrometry (EI-MS) and 1D and 2D-NMR spectral studies. Antimicrobial activity of the new compounds was evaluated.     

Structures of new ceramides from the fruit bodies of Grifola frondosa

Four new phytosphingosine-type ceramides, (2S,3S,4R)-2-[(2'R)-2'-hydroxydocosanoylamino]-1,3,4-octadecane triol (1), (2S,3S,4R)-2-[(2'R)-2'-hydroxytricosanoylamino]-1,3,4-octadecan etriol (2), (2S,3S,4R)-2-[(2'R)-2'-hydroxypentacosanoylamino]-1,3,4-octadec anetriol (3) and (2S,3S,4R)-2-[(2'R)-2'-hydroxyhexacosanoylamino]-1,3,4-octadeca netriol (4), have been isolated from the fruit bodies of Grifola frondosa. The structures of the new compounds were elucidated on the basis of their spectral data.     

Synthesis, characterization and some properties of mononuclear Ni and trinuclear NiFe2 complexes related to the active site of [NiFe]-hydrogenases

The [N(2)S(2)]-type ligand 1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4) (L) is prepared in 84% yield by a new method and its structure has been confirmed by X-ray crystallography. The new synthetic method involves sequential reaction of 1,2-phenylenedithiol with EtONa followed by treatment of the resulting disodium salt of 1,2-phenylenedithiol with in situ generated 2-(chloromethyl)pyridine from its HCl salt. Further treatment of ligand L with NiCl(2)·6H(2)O or NiI(2) affords the expected new mononuclear Ni complexes Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Cl(2) (1) and Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]I(2) (3) in 87-88% yields, whereas reaction of L with NiBr(2) under similar conditions results in formation of the expected new mononuclear complex Ni[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)]Br(2) (2) and one unexpected new mononuclear complex Ni[1-(2-C(5)H(4)NCH(2)S)-2-(2-C(5)H(4)NCH(2)SC(6)H(4)S)C(6)H(4)]Br(2) (2*) in 82% and 5% yields, respectively. More interestingly, the ligand L-containing novel trinuclear NiFe(2) complex Ni{[1,2-(2-C(5)H(4)NCH(2)S)(2)C(6)H(4)}Fe(2)(CO)(6)(μ(3)-S)(2) (4) is found to be prepared by sequential reaction of (μ-S(2))Fe(2)(CO)(6) with Et(3)BHLi, followed by treatment of the resulting (μ-LiS)(2)Fe(2)(CO)(6) with mononuclear complex 1, 2, or 3 in 12-20% yields. The new complexes 1-4 and 2* are fully characterized by elemental analysis and various spectroscopies, and the crystal structures of 1, 2* and 3 as well as some electrochemical properties of 1-4 are also reported.     

Synthesis and Characterization of new Monomers and Polymers Containing Hindered Piperidine Groups

Abstract

Two new methacryloyl ureas, 1-(2-methylacryloyl)-3-(2,2,6,6-tetra-methylpiperidin-4-yl)-urea and 1-butyl-3-(2-methylacryloyl)-1-(2,2,6,6-tetramethylpiperidin-4-yl)-urea (monomer I and monomer II), were prepared by the addition reaction of 2-methylacryloyl iso-cyanate with 2,2,6,6-tetramethylpiperidin-4-yl-amine or butyl-(2,2,6,6-tetramethylpiperidin-4-yl)-amine in a molar ratio of 1:1 at low or room temperature. In a similar way, the syntheses of two new methacryloyl carbamates, 1-(2,2,6,6-tetra-methylpiperidin-4-yl)-3-(2-methylacryloyl)-carbamate and l-(1,2,2,6,6-pentamethyl-piperidin-4-yl)-3-(2-methylacryloyl)-carbamate (monomer III and monomer IV), were completed by the reaction of 2,2,6,6-tetra-methylpiperidin-4-ol or 1,2,2,6,6-pentamethylpiperidin-4-ol with 2-methylacryloyl isocyanate in the presence of dibutyltin dilaurate as catalyst at 60°C. The four new monomers were homopolymerized, and copolymerized with styrene by AIBN as initiator at 70°C. The structures of the new monomers and their polymers were characterized by FT-IR and NMR spectroscopy and by GPC.     

Five new nortropane alkaloids and six new amino acids from the fruit of Morus alba LINNE growing in Turkey

Investigation of the constituents of the fruits of Morus alba LINNE (Moraceae) afforded five new nortropane alkaloids (1-5) along with nor-psi-tropine (6) and six new amino acids, morusimic acids A-F (7-12). The structures of the new compounds were determined to be 2alpha,3beta-dihydroxynortropane (1), 2beta,3beta-dihydroxynortropane (2), 2alpha,3beta,6exo-trihydroxynortropane (3), 2alpha,3beta,4alpha-rihydroxynortropane (4), 3beta,6exo-dihydroxynortropane (5), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (7), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid (8), (3R)-3-hydroxy-12-1(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (9), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid (10), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-hydroxymethyl-piperidin-1-yl]-dodecanoic acid-3-O-beta-D-glucopyranoside (11), and (3R)-3-hydroxy-12-[(1R,4S,5S)-4-hydroxy-5-methyl-piperidin-1-yl]-dodecanoic acid (12) on the basis of spectral and chemical data.     

Isolation and structure of four new ceramides from the starfish Luidia maculata

A new sphingosine-type ceramide LMCer-1-1 (1) and three new phytosphingosine-type ceramides, LMCer-2-1 (2), LMCer-2-6 (3), and LMCer-2-7 (4), were isolated from the anti-hyperglycemic active ceramide molecular species LMCer-1 and LMCer-2, obtained from the less polar fraction of the chloroform-methanol extract of the whole bodies of Luidia maculata. The structures of these ceramides were determined on the basis of chemical and spectroscopic evidence as: (2S,3R,4E,2'R)-2-(2-hydroxyhexadecanoylamino)-16-methyl-4-octadecene-1,3-diol (1), (2S,3S,4R,2'R)-2-(2-hydroxyhexadecanoylamino)-16-methyl-octadecane-1,3,4-triol (2), (2S,3S,4R,2'R)-2-(2-hydroxydocosanoylamino)-hexadecane-1,3,4-triol (3), and (2S,3S,4R,2'R)-2-(2-hydroxydocosanoylamino)-14-methyl-hexadecane-1,3,4-triol (4).     

Synthesis and Characterization of Poly(ether amide)s Containing Phthalazinone Moieties

Soluble aromatic polyamides containing phthalazinone moieties were prepared. Those polymers were obtained from the solution polymerization of a new diacid containing phthalazinone moieties with various diamines. The new monomer, 2-(4-carboxyphenyl)-4-(4-carboxyphenoxy)phenyl-1(2H)phthalazinone(Ⅳ) was synthesized in a two-step reaction sequence. 2-(4-Cyanophenyl)-4-(4-cyanophenoxy)phenyl-1(2H)phthalazinone (Ⅲ) was prepared via the condensation reaction of 4-(4-hydroxyphenyl)-1(2H)phthalazinone (Ⅰ) with p-chlorobenzonitrile (Ⅱ). After (Ⅲ) was hydrolyzed, (Ⅳ) was acquired. The synthesized polyamides were characterized by means of viscosimetry, DSC, FT-IR, 1H NMR and EA. The polyamides have a high glass transition temperature which can be as high as 316 ℃. The polyamides also have good solubilities in some organic solvents.     

Synthesis of acyclic nucleoside analogs of 6-substituted 2-aminopurines and 2-amino-8-azapurines

Several new acyclonucleoside purine and 8-azapurine analogs have been prepared from 2-amino-4,6-dichloropyrimidine ( 1 ) and 3-amino-1,2-propanediol ( 2a ) and 4-amino-1-butanol ( 2b ), respectively, as the starting materials. The new target compounds are: 2-amino-6-chloro-9-(2,3-dihydroxypropyl)purine ( 6a ), 2-amino-6-chloro-9-(4-hydroxybutyl)purine ( 6b ), 2-amino-6-chloro-9-(2,3-dihydroxypropyl)-8-azapurine ( 7a ), 2-amino-6-chloro-9-(4-hydroxybutyl)-8-azapurine ( 7b ), 9-(2,3-dihydroxypropyl)-8-azaguanine ( 8a ), 9-(4-hydroxybutyl)-8-azaguanine ( 8b ), 9-(2,3-dihydroxypropyl)-8-azathioguanine ( 9a ), and 9-(4-hydroxybutyl)-8-azathioguanine ( 9b ). Also, the requisite intermediate pyrimidine derivatives, 2,5-diamino-4-(2,3-dihydroxypropylamino)-6-chloropyrimidine ( 5a ) and 2,5-diamino-4-(4-hydroxybutylamino)-6-chloropyrimidine ( 5b ) are novel.     

Five new phenylethanoid glycosides from the whole plants of Lamium purpureum L

Five new phenylethanoid glycosides, lamiusides A (1), B (2), C (3), D (4) and E (5), were isolated from the whole plants of Lamium purpureum L. (Labiatae) together with seven known compounds (6-12). On the basis of chemical and spectral analyses, the structures of the new compounds were elucidated to be 2-(3,4-dihydroxyphenyl)ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(4-O-trans-caffeoyl)-beta-D-glucopyranoside (1), 2-(3,4-dihydroxyphenyl)ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(4-O-trans-feruloyl)-beta-D-glucopyranoside (2), 2-(3,4-dihydroxyphenyl)ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(6-O-trans-caffeoyl)-beta-D-glucopyranoside (3), 2-(3,4-dihydroxyphenyl)-R,S-methoxy-ethyl-O-beta-D-galactopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->3)-(4-O-trans-caffeoyl)-beta-D-glucopyranoside (4) and 2-(3-hydroxy-4-methoxyphenyl)ethyl-O-alpha-L-rhamnopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->6)-(4-O-cis-feruloyl)-beta-D-glucopyranoside (5). In addition, the radical-scavenging activities of compounds 1-4 on 1,1-diphenyl-2-picrylhydrazyl radical were examined.     

Three new diarylheptanoids and their antioxidant property

Three new diarylheptanoids,i.e.,sodium(5S,2E)-1,7-bis(4-hydroxyphenyl)-1-hydroxy-2-hepten-5-sulfonate(1), sodium(5R,2E)-1,7-bis(4-hydroxyphenyl)-1-hydroxy-2-hepten-5-sulfonate (2) and 3,5-diacetoxy-1-(3-methoxy-4,5-dihydroxy- phenyl)-7-(4-hydroxy-3-methoxyphenyl)heptane (3) were isolated from the rhizomes of Zingiber officinale.The structures of the new compounds were elucidated on the basis of spectroscopic methods.The antioxidant activities of 3 were assayed by in vitro models involving DPPH free radicals and superoxide anion radicals.     

微波辐射下2-[4-二-(4-氟苯)甲基]哌嗪乙酰腙化合物的合成

微波辐射条件下, 以丙酮作溶剂, 1-[二-(4-氟苯)甲基]哌嗪与氯乙酸乙酯反应得到2-[二-(4-氟苯)甲基]哌嗪乙酸乙酯(1), 1与水合肼在微波辐射条件下反应得到2-[二-(4-氟苯)甲基]哌嗪乙酰肼(2), 进一步在微波辐射条件下由2-[二- (4-氟苯)甲基]哌嗪乙酰肼(2)与取代芳香醛反应制得目标化合物3a～3f. 合成的6个目标化合物通过熔点测定和质谱、红外光谱、核磁共振氢谱分析、元素分析对其结构进行确证.     

苯甲酸(苯并三唑基)苯酯类紫外光稳定剂的合成及表征

以邻硝基苯胺和间苯二酚为原料,经重氮化-偶合、环化、酯化合成了6个新型苯甲酸(苯并三唑基)苯酯类化合物:3-羟基-4-苯并三唑基-4′-硝基苯甲酸苯酯(58.6%)、3-羟基-4-苯并三唑基-2′-硝基苯甲酸苯酯(60.7%)、3-羟基-4-苯并三唑基-3′-硝基苯甲酸苯酯(55.7%)、3-羟基-4-苯并三唑基-3′,5′-二硝基苯甲酸苯酯(62.1%)、3-羟基-4-苯并三唑基-2′-羟基苯甲酸苯酯(48.6%)和3-羟基-4-苯并三唑基-2′-羟基-3′,5′-二硝基苯甲酸苯酯(52.2%)。通过1H-NMR、FT-IR和MS确定了这些化合物的分子结构,紫外光谱测试表明它们均具有较好的紫外吸收性能。     

A new homostilbene and two new homoisoflavones from the bulbs of Scilla scilloides

A new homostilbene, named scillabene A (2), and two new homoisoflavones, named scillavones A (3) and B (4), were isolated from the bulbs of Scilla scilloides DRUCE (Liliaceae) along with 13 known compounds comprising a homostilbene, seven homoisoflavones, a xanthone, a lignan, and three nortriterpenes. The structures of 2-4 were characterized as 3,5,4'-trihydroxy-3'-methoxy-4-methyl-trans-stilbene, (3R)-5,7,2'-trihydroxy-3',4'-dimethoxyspiro{2H-1-benzopyran-7'-bicyclo[4,2,0]octa[1,3,5]-trien}-4-one and (3S)-3-(3,4-dihydroxybenzyl)-5-hydroxy-6,7-dimethoxychroman-4-one, respectively, on the basis of spectroscopic data and X-ray crystallographic analysis.     

Studies on the constituents of Broussonetia species VIII. Four new pyrrolidine alkaloids, broussonetines R, S, T, and V and a new pyrroline alkaloid, broussonetine U, from Broussonetia kazinoki Sieb

Four new pyrrolidine alkaloids, broussonetines R, S, T, and V and a new pyrroline alkaloid, broussonetine U were isolated from the branches of Broussonetia kazinoki SIEB. (Moraceae) in low yield. Broussonetines R, S and T were formulated as (2R,3R,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(1R)-1-hydroxy-3-[6-(4-hydroxybutyl)-cyclohexy-2-on-1(6)-enyllpropyl] pyrrolidine (1), (2R,3R,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(1R,10S)-1,10,13-trihydroxytridecyl] pyrrolidine (2), (2R,3R,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(1R,5S)-1,5, 13-trihydroxy-10-oxo-tridecyl] pyrrolidine (3). And broussonetines U and V were proposed to be (2S,3S,4S)-2-hydroxymethyl-3, 4-dihydroxy-5-(9-oxo-13-hydroxytridecyl)-5-pyrroline (4), (2R,3S,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(E)-9-oxo-13-hydroxy-3-tridecenyl] pyrrolidine (5), respectively, by spectroscopic and chemical methods.     

New stilbenoids from Pholidota yunnanensis and their inhibitory effects on nitric oxide production

Six new stilbenoids, a (bibenzyldihydrophenanthrene) ether designated phoyunnanin D (1), a bis(dihydrophenanthrene) ether designated phoyunnanin E (2), and four stilbenes designated phoyunbene A-D (3-6), were isolated from the air-dried whole plant of Pholidota yunnanensis ROLFE. The new compounds were identified as 7-[2-(3-hydroxyphenethyl)-4-hydroxy-6-methoxyphenoxy]-4-hydroxy-2-methoxy-9,10-dihydrophenanthrene (1), 1-[(9,10-dihydro-4-hydroxy-2-methoxy-7-phenanthrenyl)oxy]-4,7-dihydroxy-2-methoxy-9,10-dihydrophenanthrene (2), trans-3,3'-dihydroxy-2',4',5-trimethoxystilbene (3), trans-3,4'-dihydroxy-2',3',5-trimethoxystilbene (4), trans-3,3'-dihydroxy-2',5-dimethoxystilbene (5), and trans-3-hydroxy-2',3',5-trimethoxystilbene (6) based on spectroscopic evidence. Furthermore, the inhibitory effects of compounds 1-6 on nitric oxide production in a murine macrophage-like cell line (RAW 264.7) activated by lipopolysaccharide and interferon-gamma were examined.     

New phenolic principles from Hypericum sampsonii

Using the anti-hepatitis B virus (HBV)-producing cell line MS-G2 in vitro cultural system-guided screening was performed, and two new benzophenones, 2,6-dihydroxy-4-[(E)-5-hydroxy-3,7-dimethylocta-2,7-dienyloxy]benzophenone (1) and 2,6-dihydroxy-4-[(E)-7-hydroxy-3,7-dimethylocta-2-enyloxy]benzophenone (2), a new xanthone, hyperxanthone (3), a new bisanthraquinone glycoside, R-(-)-skyrin-6-O-beta-D-xylopyranoside (4), and 2-caffeoyloxy-3-hydroxy-3-(3,4-dihydroxyphenyl)propyl alcohol (5), and 16 known compounds were isolated from the anti-HBV active fraction of the whole herbs of Hypericum sampsonii. Their structures were elucidated using spectroscopic methods, mainly 2D NMR and MS spectrometry. Circular dichroism was used to determine the stereochemistry of bisanthraquinone glycosides.     

Substituted 3-and 5-formylpyridin-2-ones in the synthesis of 1-aryl-1, 6-naphthyridinone derivatives

New 1-aryl-6-[2-(dimethylamino)vinyl]4-oxo-1,4-dihydropyrimidine-5-carbonitriles and 4-arylamino-2-oxo-1,2-dihydropyridine-3-carbonitriles containing electron-withdrawing substituents in the benzene ring were synthesized from enamino amides and dimethylformamide dialkylacetals. The influence of various dimethylformamide acetals on the yield of 3-(4-chloro-anilino)-2-cyano-5-(dimethylamino)penta-2,4-dienoic acid N-(dimethylamino)methyl-ideneamide was investigated in the reaction of these acetals with 3-(4-chloroanilino)-2-cyanocrotonamide. New 4-arylamino-5-formyl-2-oxo-1,2-dihydropyridine-3-carbonitriles and 4-arylamino-2-oxo-1,2-dihydropyridine-3-carbaldehydes containing electron-withdrawing substituents in the benzene ring were synthesized. The latter compounds were converted into new substituted l,6-naphthyridinones by the action of various CH acids. A new approach to the synthesis of 4-(4-fluoroanilino)-5-formyl-2-oxo-1,2-dihydropyridine-3-carbonitrile using dimethylformamide diisopropylacetal under mild conditions was developed. The comparative reactivity of the formyl group in the reactions of 4-arylamino-5-formyl-2-oxo-1,2-dihydropyridine-3-carbonitriles and in 4-arylamino-2-oxo-1,2-dihydropyridine-3-carb-aldehydes with malononitrile was determined using HPLC.     

Synthesis of new 1-substituted 4-(2-phenylquinazolin-4-yl)-and 4-(2-phenylquinazolin-4-ylidene) thiosemicarbazides

Two new 1-substituted 4-(2-phenylquinazolin-4-yl)-and 4-(2-phenylquinazolin-4-ylidene) thio-semicarbazides were formed by a multistep domino reaction of imidoyl isothiocyanate derivative with 1,1-di-R-hydrazine in acetone solution. Application of hydrazine hydrate under the same reaction conditions afforded 4-(2-phenylquinazolin-4(3H)-ylidene)-2-(propen-2-yl)-1-(propan-2-ylidene) thio-semicarbazide via a six-step triple-component domino reaction. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1688–1693, November, 2008.     

Four superhard carbon allotropes: a first-principles study

Using a generalized genetic algorithm, we propose four new sp(3) carbon allotropes with 5-6-7 (5-6-7-type Z-ACA and Z-CACB) or 4-6-8 (4-6-8-type Z4-A(3)B(1) and A4-A(2)B(2)) carbon rings. Their stability, mechanical and electronic properties are systematically studied using a first-principles method. We find that the four new carbon allotropes show amazing stability in comparison with the carbon phases proposed recently. Both 5-6-7-type Z-ACA and Z-CACB are direct band-gap semiconductors with band gaps of 2.261 eV and 4.196 eV, respectively. However, the 4-6-8-type Z4-A(3)B(1) and A4-A(2)B(2) are indirect band-gap semiconductors with band gaps of 3.105 eV and 3.271 eV, respectively. Their mechanical properties reveal that all the four carbon allotropes proposed in present work are superhard materials, which are comparable to diamond.