薯蓣属植物化学成分的研究——Ⅱ.叉蕊薯蓣中甾体皂甙的分离和鉴定

从叉蕊薯蓣(D.collettii HooK.f.)根茎的乙醇提取物分离到四个甾体皂甙,根据理化性质、光谱数据,推定化学结构为3-O-(β-D-葡萄吡喃糖)-约莫皂甙元(3-O-(β-D-glucopyranosyl)-yamogenin)[Ⅰ];3-O-[α-L-鼠李吡喃糖(1→4)-β-D-葡萄吡喃糖]-约莫皂甙元(3-O-[α-L-rahmnopyranosyl(1→4)-β-D-glucopyranosyl]-yamogenin)[Ⅱ];3-O-{α-L-鼠李吡喃糖(1→4)-[α-L-鼠李吡喃糖(1→2)]-β-D-葡萄吡喃糖}-约莫皂甙元(3-O-{α-L-rhamnopyranosyl(1→4)-[α-L-rhamnopyranosyl(1→2)]-β-D-glucopranosyl}-yamogenin)[Ⅲ];3-O-{β-D-葡萄吡喃糖(1→3)-[α-L-鼠李吡喃糖(1→2)3-β-D-葡萄吡喃糖}-约莫皂甙元(3-O-{β-D-glucopyranosyl(1→3)-[α-L-rhamnopyranosyl(1→2)]-β-D-glucopyranosyl}-yamogenin)[Ⅳ]。其中Ⅰ为已知物,Ⅱ、Ⅲ、Ⅳ为首次从植物界得到的新甾体皂甙。     

水蔓菁中黄酮类化合物的研究

从民间草药玄参科植物水蔓菁[Veronica linariifolia Pall. ex Link. sub dilatata(Nakai et Litagawa)Hong.]的干燥全草的乙醇提取物中分离得到三个黄酮甙和两个黄酮甙元,其中甙Ⅰ是新化合物,命名为水蔓菁甙(linariifolioside)。根据光谱数据和水解产物分析确定甙Ⅰ的结构为木犀草素-7-O-6″′-O-乙酰基-β-D-葡萄糖基-(1→2)-β-D-葡萄糖甙[luteolin-7-O-6″′-O-acetyl-β-D-glucosyl-(1→2)-β-D-glucoside]。另外甙Ⅱ,甙Ⅲ以及两个甙元为已知物,分别为木犀草素-7-O-β-D-葡萄糖基(1→2)-β-D-葡萄糖甙[luteolin-7-O-β-D-glucosyl(1→2)-β-D-glucoside,Ⅱ]和芹黄素-7-O-x-L-鼠李糖甙(apigenin-7-O-α-L-rhamnoside,Ⅲ)、以及木犀草素(luteolin,Ⅳ)和芹黄素(apigenin,Ⅴ)。这些化合物在水蔓菁中均是首次得到。     

商陆中三种新皂甙的分离与鉴定

从商陆科植物商陆(Phytolacca esculenta Van Houtte)中分离得三种新的三萜皂甙,根据化学性质和光谱分析(UV,IR,¹HNMR,¹³CNMR,MS),确定甙Ⅰ为3-O-β-D-吡喃木糖基商陆酸,甙Ⅱ为3-O-β-D-吡喃葡萄糖基-羟基商陆酸,甙Ⅲ为3-O-[β-D-吡喃葡萄糖基(1→4)-β-D-吡喃木糖基(1→4)-β-D-吡喃葡萄糖基]-2-羟基商陆酸,分别命名为商陆皂甙O,P,Q。     

异叶梁王茶化学成分的研究

从异叶梁王茶[Nothopanax davidii(Franch)Harms]树皮中分离得到两种五环三萜皂甙,经化学和光谱(IR,¹HNMR,¹³CNMR,¹H-¹H COSY,¹H-¹³C COSY,NOESY,MS)分析,分别鉴定为3-O-α-(3′,4′-O-二乙酰基)-L-吡喃阿拉伯糖-β-羟齐墩果-12-烯-28,29-双羧酸-28-O-[α-L-吡喃鼠李糖(1→6)-β-D-吡喃葡萄糖(1→4)-β-D-吡喃葡萄糖]酯甙(Ⅱ)和3-O-α-(3′-O-乙酰基)-L-吡喃阿拉伯糖-3β-羟齐墩果-12-烯-28,29-双羧酸甙(Ⅱ),前者命名为异叶梁王茶甙Ⅰ,后者命名为异叶梁王茶甙Ⅱ。这两个皂甙均系新化合物。     

川续断的化学成分研究

从川续断(Dosacus asper Wall)的根中分得六个化合物(Ⅰ～Ⅵ)。Ⅰ,Ⅱ,Ⅲ和Ⅵ分别鉴定为蔗糖、胡萝卜甙、β-谷甾醇和akebia saponin D.Ⅵ和Ⅴ为新化合物,根据光谱分析和化学方法证明其结构分别为3-O-(4-O-乙酰基)-α-L-吡喃阿拉伯糖常春藤皂甙元28-O-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖酯甙和3-O-α-L-吡喃阿拉伯糖齐墩果酸28-O-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖酯甙。     

薯蓣属植物化学成分的研究——Ⅱ.叉蕊薯蓣中甾体皂甙的分离和鉴定

从叉蕊薯蓣(D.collettii HooK.f.)根茎的乙醇提取物分离到四个甾体皂甙,根据理化性质、光谱数据,推定化学结构为3-O-(β-D-葡萄吡喃糖)-约莫皂甙元(3-O-(β-D-glucopyranosyl)-yamogenin)[Ⅰ];3-O-[α-L-鼠李吡喃糖(1→4)-β-D-葡萄吡喃糖]-约莫皂甙元(3-O-[α-L-rahmnopyranosyl(1→4)-β-D-glucopyranosyl]-yamogenin)[Ⅱ];3-O-{α-L-鼠李吡喃糖(1→4)-[α-L-鼠李吡喃糖(1→2)]-β-D-葡萄吡喃糖}-约莫皂甙元(3-O-{α-L-rhamnopyranosyl(1→4)-[α-L-rhamnopyranosyl(1→2)]-β-D-glucopranosyl}-yamogenin)[Ⅲ];3-O-{β-D-葡萄吡喃糖(1→3)-[α-L-鼠李吡喃糖(1→2)3-β-D-葡萄吡喃糖}-约莫皂甙元(3-O-{β-D-glucopyranosyl(1→3)-[α-L-rhamnopyranosyl(1→2)]-β-D-glucopyranosyl}-yamogenin)[Ⅳ]。其中Ⅰ为已知物,Ⅱ、Ⅲ、Ⅳ为首次从植物界得到的新甾体皂甙。     

牡丹根中的新成分——丹皮酚新甙的鉴定

从牡丹Paeonia suffruticosa(本所药物栽培场的栽培品)根中分到一新的甙类成分,根据理化性质,光谱数据及衍生物制备推定其结构为丹皮酚-[D-β-D-呋喃芹糖(1→6)]-β-D-葡萄吡喃糖甙(Paeonol-[D-apio-β-D-furanosy1(1→6)]-β-D-glucopyranoside),并命名为丹皮酚新甙(apiopaeonoside)。     

川续断中的新三萜皂甙

从川续断(Dispsacus asper Wall.)根的乙醇提取物中得到二个新三萜皂甙(Ⅶ和Ⅷ)。根据光谱分析、化学反应及双向高效薄层层析结果,证明其结构分别为:3-O-β-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖常春藤皂甙元28-O-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙和3-O-α-L-吡喃鼠李糖(1→3)-β-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖-常春藤皂甙元28-O-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙。     

川续断中皂甙Ⅺ,Ⅻ和ⅩⅢ的结构研究

从川续断(Dipsacus asper Wall.)根的醇提物中得到三个微量新三萜皂甙(Ⅺ～ⅫⅠ),根据光谱分析和化学反应,其结构分别鉴定为3-O-[β-D-吡喃葡萄糖(1→4)][α-L-吡喃鼠李糖(1→3)]-β-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖-常春藤皂甙元(Ⅺ)、Ⅺ的28-O-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙( Ⅻ)和3-O-[β-D-吡喃木糖(1→4)-B-O-吡喃葡萄糖(1→4)][α-L-吡喃鼠李糖(1→3)]-B-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖-齐墩果酸-28-O-β-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙(ⅫⅠ)。     

乌拉尔甘草中皂甙的研究

自乌拉尔甘草(Glycyrrhiza uralensis Fisch)的根茎中共分离出三个皂甙类化合物,经化学方法和光谱解析,鉴定1为3β-羟基-11-氧化-齐墩果-12-烯-30-羧酸-3-O-β-D-葡萄吡喃糖醛酸基(1—2)-β-D-葡萄吡喃糖醛酸甙,命名为乌拉尔甘草皂甙甲(ura1saponin A)。Ⅱ为3β-羟基-11-氧化-齐墩果-12-烯-30-羧酸-3-O-β-D-葡萄吡喃糖醛酸基(1-3)-β-D-葡萄吡喃糖醛酸甙,命名为乌拉尔甘草皂甙乙(uralsaponin B)。Ⅰ,Ⅱ均未见文献报道。Ⅲ为已知甘草酸。本文报道两个新甙的结构鉴定。     

Zur Kenntnis der 2-Amino-1,3,4-oxdiazole 31. Mitt.: Darstellung von 1-Acyl-5-alkoxy(aroxy)carbonyl-diaminoguanidinen durch Ringöffnung von 2-Amino-1,3,4-oxdiazolen mit Carbazinsäureestern

2-Amino-1,3,4-oxdiazoles. Part 31 2-Amino-5-aryl(alkyl)-1,3,4-oxdiazoles (I) react with carbazinate esters by ring opening and formation of 1-acyl-5-alkoxy(aroxy)diaminoguanidines (II, III). The hydrolysis of IIa with HCl (20%) gives ethoxycarbonyl-diaminoguanidine (IV), isolated as benzylidene compound (V). The structure is proved by the IR-spectrum.     

柔红酮和阿霉酮二肽衍生物的合成

本文报道柔红酮和阿霉酮二肽衍生物的合成。二肽与柔红酮在DCC/DMAP或苯磺酰氯/吡啶存在下反应,得到柔红酮衍生物,继之溴化、水解得到阿霉酮衍生物或直接由二肽与保护阿霉酮酯化,脱保护后得到阿霉酮衍生物。合成的18个化合物对L₁₂₁₀白血病细胞增殖均有抑制作用,并存在一定的构效关系,游离氨基的位置与抗肿瘤活性相关。     

Solid-phase synthesis of a cyclic decapeptide, analog of the antibiotic polymyxin M

Pelargonoyl-cyclo[Dab-Thr-Dab-Dab(Pel)-Dab-D-Leu-Thr-Dab-Dab-Thr]. 5 HCl (5), analog of the polymyxin M, has been synthesized by the solid phase method. The intermediate linear Boc-protected decapeptide-resin (1) was assembled on the solid support by the stepwise addition of Boc-amino acids in the presence of DCC. For side-chain protection of diaminobutyric acid, Z-group was used. The peptide was cleaved from the resin in the form of methyl ester by triethylamine-catalyzed transesterification with methanol. Alkaline hydrolysis of the peptide ester with aqueous KOH (1 mol/l) afforded the Bocpenta-benzyloxycarbonyl-decapeptide acid (2) in 60% yield (based on Thr/resin). After removal of the Boc-group, the linear peptide 3 was cyclized with DCC in high dilution in DMF (10(-3) mol/l) to give 4 in 51% yield. Hydrogenolysis of 4 in 80% formic acid afforded the pelargonyl cyclic decapeptide 5 in 74% yield. The synthetic peptide 5 retained the same activity of the natural polymyxin M against Bacillus subtilis and Staphylococcus aureus, whereas it showed only 3% of the activity of Escherichia coli.     

左旋沙丁胺醇盐酸盐的合成

目的研究左旋沙丁胺醇盐酸盐的合成方法。方法以水杨醛和溴乙酰氯为原料经Friedel-Crafts酰基化反应、取代反应合成5-[[(1,1-二甲基乙基)胺基]乙酰基]-2-羟基苯甲醛盐酸盐(4),再经手性铑配合物催化的不对称氢转移反应协同还原得到左旋沙丁胺醇(5),最后与盐酸成盐制得左旋沙丁胺醇盐酸盐(1)。结果与结论以水杨醛计,4步反应总收率为35.6%,对映体过量值达92%,该合成路线易行。目标产物的结构经质谱、红外光谱和核磁共振氢谱确证。     

硝基精氨酸—赖氨酸三肽合成及其对一氧化氮合酶的抑制作用

液相合成法合成了由左旋精氨酸、左旋赖氨酸组成的硝基精氨酸-赖氨酸三肽HCl．Arg(NO     

Potential inhibitors of L-asparagine biosynthesis. 2. Chemistry and biological activity of beta-hydroxyaspartic acid and its derivatives.

Several derivatives of erythro-beta-hydroxy-DL-aspartic acid (1) were prepared as a potential inhibitors of L-asparagine synthetase (ASase) from rat Novikoff hepatoma. Benzylation of 1 gave the dibenzyl ester 2 which upon coupling with carbobenzoxyglycine afforded the blocked dipeptide 3. Deblocking of 3 gave glycl-erythro-beta-hydroxyl-DL-aspartic acid (4) which could not be diazotized. The dimethyl ester of 1 was coupled with carbobenzoxyglycine to give the blocked dipeptide 7a which was deblocked to give dimethyl glycel-erythro-beta-hydroxy-DL-aspartate hydrochloride (8). Diazotization of 8 gave impure diazo compound 9 which on reaction with HCl gave the chloro compound 10. The methods of isolation, assay, and inhibition of ASase are discribed. At 10 mM concentrations 10, 1, and its D and L enantiomers inhibit ASase by 45, 47, 36 and 66 percent, respectively.     

新的高强度高选择性阿片μ受体激动剂[11C]-羟甲芬太尼的合成

羟甲芬太尼(I)是一个新的高强度高选择性阿片μ受体激动剂。本文用cis-A-N-[1-(2-羟基-2-苯乙基)-3-甲基-4-哌啶基]-苯胺(II)或cis-N-[1-(苯甲酰甲基)-3-甲基-4-哌啶基]-苯胺(III)作为前体合成了[¹¹C]-羟甲芬太尼,以便用正电子发射断层扫描(PET)来观察μ受体。通过水解cis-A-羟甲芬太尼(I)和cis-N-[1-(苯甲酰甲基)-3-甲基-4-哌啶]-N-苯基丙酰胺(cis-IV)的4-N-丙酰基分别获得II和III。溴乙烷的格氏试剂与回旋加速器产生的[¹¹C]-二氧化碳反应后继而直接加入邻苯二甲酸二酰氯和2,6-二叔丁基吡啶生成同位素标记中间体[¹¹C]-丙酰氯。[¹¹C]-丙酰氯与OH-前体(II)反应后再经HPLC分离纯化直接得[¹¹C]-羟甲芬太尼;[¹¹C]-丙酰氯与酮-前体(III)反应后,再用硼氢化钠甲醇溶液处理,然后进行HPLC分离纯化得[¹¹C]-羟甲芬太尼。两种方法均可获得ll.1～14.8GBq/μmol的特异性放射化学纯[¹¹C]-羟甲芬太尼。总共耗时为40～50min(EOB)。     

Metabolism of an anxiolytic imidazobenzodiazepine by the dog

14C-labeled 8-chloro-6-(2-chlorophenyl)-4H-imidazo [1,5a][1,4]-benzodiazepine-3-carboxamide hydrochloride, 1 X HCl, was administered iv to two dogs. 14C-1 X HCl was extensively metabolized; in one dog, only 2% of the administered radioactivity was excreted as unchanged 1. The 4-hydroxy derivative of 1, compound 2, accounted for an additional 5% of the dose. Three urinary metabolites were identified by enzyme hydrolysis and NMR spectroscopy as conjugates of the phenolic 3'-, 4'-, and 5'-hydroxy derivatives of 1. In both dogs, the 4'-hydroxy derivative was the major identified metabolite (21 and 15% of the dose). Oral administration of 100 mg/kg/day of unlabeled 1 to dogs for 11 weeks resulted in the excretion of four urinary metabolites, the conjugated 3'-hydroxy and 4'-hydroxy derivatives of both 1 and 2. This prominent excretion of conjugated phenolic metabolites does not fit the usual pattern of 1,4-benzodiazepine metabolism in the dog.     

倍半氧化羧乙锗及其口服制剂的含量测定

倍半氧化羧乙锗及其制剂经ＨＮＯ＿３－Ｈ＿２ＳＯ＿４消化后，以苯基荧光酮为显色剂，用比色法进行测定，在６ｍｏｌ／Ｌ盐酸中无机锗化合物可转变为低沸点的ＧｅＣｌ＿４，藉与有机锗分离。     

滇产苦绳甾体成分的研究

从滇产苦绳(Dregea sinensis var.corrrugata)的根茎中分得两个新的C₂₁-甾体甙元,命名为苦绳甙元Ⅰ及Ⅱ(drevogenin Ⅰ,Ⅱ),经光谱分析和化学反应证明,甙元Ⅰ的结构为C/D顺式5α-H,3β,8β,14β,17β四羟基-12β-O-异戊酰基-20-O-异戊酰基娠烷(C/D cis 5α-H,3β,8β,14β,17βtetrahydroxy一12β-O-isovaleryl-20-O-isovaleryl-pregnane)。甙元Ⅱ的结构为C/D顺式5α-H,3β-14β,17β三羟基-12-β-O-乙酰基-20-O-苯甲酰基娠烷(C/Dcis 5α-H,3β,14β,17βtrihydroxy-12β-O-acetyl-20-0-benzoyl-pregnane)。