A New Synthesis of 4, 4-Diaryl/Diheteroaryl-3-butenyl Derivatives of Nipecotic Acids as GABA Transporter Inhibitors

A new method for the synthesis of 4, 4-diaryl/diheteroaryl-3-butenyl derivatives of nipecotic acid as GABA transporter inhibitors is described. The key intermediates 4-tosyl-1, 1-diaryl/diheteroaryl-1-butene 10a-d were synthesized by Wittig reaction, and followed by alkylation with （R）-3-piperidinecarboxylate. The resulting N-cycloalkylated amino acid esters 11a-d were saponified and then acidified to get the target compounds 1a-d. The preliminary bioassays showed that la-d exhibited excellent inhibition of [3H]-GABA uptake in vitro of culture cells.     

Synthesis and Microbial Studies of New Pyridine Derivatives-Ill

2-Amino substituted benzothiazole 4a--4I and p-acetamidobenzenesulfonyl chloride 2 were used to prepare 2-（p-aminophenylsulfonamido） substituted benzothiazole 6a--6I using mixture of pyridine and acetic anhydride which formed an electrophilic complex （N-acetyl pyridinium） to facilitate condensation to give desired product by removal of HC1. 2-{p-[（3-Carboxypyrid-2-y1）amino]phenylsulfonamido}benzothiazoles 8a--81 were synthesized from 2-chloropyridine-3-carboxylic acid 7 and 6a--6I in 2-ethoxy ethanol using Cu-powder and K2CO3. Acid chlorides 9a--91 were condensed with 2-hydroxyethyl piperazine 10 and 2,3-dichloropiperazine 11 for amide deriva- tives 2-（p-（（3-（4-（2-hydroxyethy1）piperazin-1-ylcarbonyl）pyrid-2-y1）amino）phenylsulfonamido）benzothiazoes 12a -121 and 2-{p-[3-（2,3-dichloropiperazin-l-ylcarbonyl）pyrid-2-ylamino]phenylsulfonamido}benzothiazoles 13a- 131 respectively. The structures of the new compounds have been established on the basis of their chemical analysis and spectral data （IR, 1↑H NMR and mass）. All the compounds have been screened for their antibacterial and antifungal activities.     

New Aliphatic Alcohol and Ester Constituents from Rice Hulls of Oryza sativa

Six new aliphatic alcohol and ester compounds of n-octacos-9-enyl propionate （1）, 4-（3-formylheptyl）cyclohexyl 4-（cyclohexylcarbonyloxymethyl）cyclohexyl-carboxylate （2）, n-hentriacont-25-en-5α-ol （3）, n-hexetriacont-9,26-dien-8α,11β,23α-triol （4）, n-tetracontan-15α-ol （5） and n-tritetracontan-5α-ol （6） were isolated from the hulls of Oryza sativa. The structures were established on the basis of spectroscopic analysis.     

Two New C-21 Steroidal Glycosides from the Stems of Stephanotis mucronata

Two new C-21 steroidal glycosides, mucronatosides M（1） and N（2）, were isolated from the stems of Stephanotis mucronata, together with one known compound stephanoside M（3）. On the basis of chemical evidence and extensive spectroscopic methods, including one-dimensional and two-dimensional NMR, the structures of the two new compounds were identified as 12-O-tigloyl-20-O-N-methylanthraniloyl sarcoslin 3-O-β-D-glucopyranosyl-（1→4）-6- deoxy-3-O-methyl-β-D-allopyranosyl-（→4）-β-D-cymaropyranosyl-（1→4）-β-D-cymaropyranoside （1）, and 12-O- cinnamoyl-20-O-nicotinoyl（ 2OS）-pregn-6-ene-3 β,5α,8βm12 β,14β,17β,20-heptanol 3-O-β-D-glucopyranosyl-（1→4）-6- deoxy-3-O-methyl-β-D-allopyranosyl-（1→4）-β-D-cymaropyranosyl-（1→4）-β-D-cymaropyranoside （2）.     

Constituents from the Roots of Semiaquilegia adoxoides

In present literature search, some cyano-containing compounds, which are very rare in plants, from the traditional anticancer herb Tiankuizi were reported. To find more cyano-containing compounds in the important plant Semiaquilegia adoxoides （DC） Makino （Chinese name Tiankuizi）, the isolation of the chemical constituents was investigated for advancing the research. Two new compounds, a new alkaloid, 1,2,3,4-tetrahydro-6-hydroxy-1[（3,4-dihydroxyphenyl）methyl]-7-methoxy-2,2-dimethyl-isoquinolinium, named Semiaquilegine A （1）, and a new ester, 3-（4＇-hydroxyphenyl）-2-propenoic acid （4＂-carboxyl）-phenyl ester （2）, and four cyano-containing compounds, （Z）-6a-（β-D-glucosyloxy）-4a,5a-dihydroxy-2-cyclohexene-△^1,a-acetonitrile （3）, （L0-6α-（β-D-glucosyloxy）-4α-hydroxy-2-cyclohexene-△^1,α-acetonitrile （4）, lithospermoside （5）, ehretioside B （6）, as well as eleven known compounds, were isolated from the roots of Semiaquilegia adoxoides. The structures of new compounds 1 and 2 were elucidated mainly by 1D/2D-NMR techniques. Very unusual cyano-containing compounds 3 and 4 were first isolated from Ranunculaceae family. Hitherto, there were six cyano-containing compounds found in the herb.     

中药枸骨叶中三萜皂苷和黄酮苷类成分研究

A new triterpene glycoside, pomolic acid 3-O-6″-methyl-β-D-glucuronopyranosyl-（1→3）-α-L-arabino- pyranoside, and a new flavonol glycoside, quercetin 3-O-β-D-glucopyranosyl-（1→2）-α-L-arabinopyranoside together with three known triterpene saponins and two flavonol glycosides, were isolated from the leaves of Ilex cornuta. Their structures were established on the basis of spectroscopic analysis.     

Two New Compounds from Hemsleya penxianensis var.gulinensis

Two new compounds,oleanolic acid 28-O- β-D-glucopyranosyl-3-O-α-L-arabinopyranosyl-(1→3)-(6′-butyl ester)-β-D-glucuropyranoside 1,oleanolic acid 28-O-β-D-glucopyranosyl(1→6)-β-D-glucopyranoside 2 have been isolated from the roots of Hemsleya penxianensis var.gulinensis.Their structures were determined on the bases of the spectral and chemical evidences.     

A New Diels-Alder Type Adduct and a New Flavone from the Stem and Root Bark of Morus mongolica

A new Diels-Alder type adduct mongolicin G （1） and a new flavone 5＇-（1＂, 1＂-dimethylallyl）-5,7,2＇,4＇-tetrahydroxyflavone （2） were isolated from the stem and root bark of Morus mongolica. Their structures were determined by spectroscopic analysis and chiroptical methods.     

A New Flavanone and a New Flavanone Glycoside from ScuteUaria baicalensis

A new flavanone （2S）-5, 7, 2＇, 5＇-tetrahydroxy-flavanone 1 together with a new flavanone glycoside （2S）-5, 7, 2＇, 5＇-tetrahydroxy-flavanone 7-O-13-D-glucopyranoside 2, were isolated from the dry roots of Scutellaria baicalensis. Their structures were elucidated on the basis of spectroscopic data.     

Two new lanostane triterpenoids from Abies sachalinensis

The continuous chemical investigation on the ethyl acetate （EtOAc） soluble fraction of the MeOH extract afforded two new lanostane triterpenoid derivatives including one with a rearranged lanostane skeleton. They were identified as 3,4-seco-8-（14→13R）abeo-17,13-friedo-9β-lanosta-4（28）, 7,14（30）,24-tetraen-26,23-olide-23-hydroxy-3-oic acid （1） and 7,14-mariesa- dien-3oL-hydroxy-25-methoxy-26-oic acid （2）. Structural determination of these compounds were carried out by the spectral studies especially by the two digital （2D）-NMR and high-resolution MS experiences.     

Anticancer Drugs ( Ⅳ )——New Derivatives of Podophyllotoxin

Four new derivatives of podophyllotoxin, N'-podophyllic acid-N-[3-(2, 2, 5, 5-te-tramethyl-pyrrolinenyloxy)] semicarbazide(GP-11, 6), podophyllic acid [3-(2,2,5,5-te-tramethyl-pyrrolinenyloxy)]hydrazone (GP-12, 7), podophyllic acid-[4-(2, 2, 6, 6-tetramethyl-1-hydroxy piperidine)]hydrazone(GP-1-OH, 8) and podophyllic acid[4-(2,2, 6, 6-tetramethyl piperidine)]hydrazone(GP-1-H, 9) were synthesized. The inhibition effect of the four new compounds on L-1210 cells were determined. The antitumor activity and toxicity of GP-1(2), GP-1-OH(8), GP-1-H(9) and VP-16-213(1) were discussed.     

New flavan and unusual chalcone glycosides from Drypetes parvifolia

Two new compounds 7-hydroxy-5-O-（β-D-glucopyranoside） flavan （1） and （Z）-4＇,6＇-dihydroxy-2＇-O-（β-D-glucopyranoside） chalcone （2）, along with eight known compounds, were isolated from the stem bark of Drypetes parvifolia （Euphorbiaceae）. Their structures were established on the basis of spectroscopic analysis and chemical evidence.     

Antitumor triterpene saponins from Anemone flaccida

A new triterpenoid saponin, 3-O-[（6′-butyryl）-β-D-glucopyranosyl]-28-O-[α-L-rhamnopyranosyl-（1→4）-β-D-glucopyranosyl-（1→6）-β-D-glucopyranosyl] oleanolic acid, as well as three known triterpenoid saponins were isolated from the rhizomes of Anemone flaccida. Their structures were elucidated by spectroscopic methods. These compounds showed significant antitumor activities.     

Studies on the esterifications of 9-（hydroxyimino）-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one with acid chlorides under different conditions

The esterifications of 9-（hydroxyimino）-4-methyl-8,9-dihydrofuro[2,3-h]chromen-2-one （4） with acid chlorides afforded normal oxime-esters 3a-e in 35-78% yields in presence of excessive 4-dimethylaminopyridine as the acid scavenger, whereas the reactions gave unexpected 8-substituted products N-（8-chloro-4-methyl-2-oxo-2H-furo-[2,3-h]chromen-9-yl）amides （5a-c） and 4-methyl-2,9-dioxo-8,9-dihydro-2H-furo[2,3-h]chromen-8-ylcarboxyloates （6d-e） by using excessive acid chlorides. The structures of 10 new compounds were determined by 1H NMR, 13C NMR, MS and HRMS, and the possible mechanism for the formation of unexpected products 5a--c and 6d-e was also proposed.     

New Diarylheptanoid from the Barks of Alnus japonica Steudel

A new diarylheptanoid glycoside, 1,7-bis-（3,4-dihydroxyphenyl）-5-hydroxyheptane- 3-O-β-D-xylopyranoside （1）, together with nine known diarylheptanoids （2-10） were isolated from the fresh bark of Alnus japonica which is a species of the genus Alnus species, growing throughout Korea.     

New Myrsinol Diterpenes from Euphorbia prolifera

Four new myrsinol diterpenes, euphorprolitherins A-D (1-3, 5), were isolated from the ethanolic extract of the root of Euphorbia prolifera, along with a known one, SPr5 (4). The structures were elucidated on the basis of their spectroscopic evidences. The structure and relative stereochemistry of 1 were confirmed by X-ray crystallography.     

A New Stigmasterol and a New Eremophilenolide from Ligularia dolichobotrys

A new stigmasterol 3β, 7α, 22-trihydoxystigmast-5-ene (1) and a new eremophilenolide 8α-methoxy-6β-angeloyloxyeremophil-7(1 l)-en-8β, 12-olide-14-oic acid (2) were isolated from Ligularia dolichobotrys Diels. Their structures were deduced on the basis of spectral data.     

Surface-relief-grating formation behavior of two hyperbranched azo polymers

In this work,surface-relief-grating formation behavior was studied by using two hyperbranched azo polymers.The hyperbranched polymers containing pseudo-stilbene type azo chromophores throughout the hyperbranched structure were synthesized by step-growth polycondensation of AB₂ type monomers.The AB₂ monomer,4-（4’-（bis（2-chloroethyl）amino）-phenylazo） benzoic acid（BAA）,was prepared through azo-coupling reaction between N,N’-bis（2-chloroethyl）aniline and 4- aminobenzenic acid.The another AB₂ monomer,4-（4’-（bis（2-chloroethyl）amino）phenylazo）-3-nitro-benzoic acid（BANA）, was prepared through azo-coupling reaction between N,N-bis（2-chloroethyl）aniline and 3-nitro-4-aminobenzcnic acid.The hyperbranched polymers（PBAA and PBANA） were prepared through nucleophilic substitution reaction of BAA and BANA, respectively.The polymers synthesized were characterized by using spectroscopic methods and thermal analysis.The photoinduced dichroism and photo-induced surface-relief-grating（SRG） formation of the hyperbranched polymers were investigated upon irradiation with Ar⁺ laser at 488 nm.PBAA shows typical photoinduced dichroism SRG formation behavior.On the contrary,PBANA does not show the photoresponsive properties.The results indicate that the nitro at the ortho position of azo group of PBANA shows the effect of inhibiting the photoinduced variations.The effect can be attributed to the blockage of the trans-cis isomerization of the azobenzene moieties by the steric hindrance.     

Two New Triterpene Esters from Daphniphyllum oldhami

Two new triterpene esters,2-O-eaffeoylalphitolic acid(1)and methyl 2-O-eaffeoyl-alphitolate(2),together with two known triterpenes were isolated from the shrub Daphniphyllum oldnami.The structures of new compounds were elucidated on the basis of detailed spectroscopic analysis and compared with related compound.     

Two New Pentacyclic Triterpenes from Sabia parviflora

Two new pentacyclic triterpene acids,1α,3β-dihydroxyl-olean-12-en-28-oic acid and 1α，2α,3β-trihydroxyl-olean-12-en-28-oic acid, were isolated from the arial parts of Sabia parviflora.