中国乌头的研究——ⅩⅦ.伏毛铁棒锤Aconitum flavum Hand-Mazz中生物碱

From a Chinese herb Fu Mao Tie Bang Ghui, the root of Aconitum flavum Hand-Mazz, collected from Ning Xia Autonomous Region, two alkaloids Ⅰ and Ⅱ have been isolated. On the basis of spectroscopic analyses and chemical methods, Ⅰ and Ⅱ were identified as 3-acetylaconitine and aconitine respectively.3-acetylaconitine, C₃₆ H₄₉ O₁₂ N, mp. 196-197℃, [α]_D²⁴+18.6° (C. 1.0, CHCl₃) was discovered in nature for the first time.     

鲜卑花酯的分离和结构

A new ferulic acid ester, C₁₆H₂₂O₉, mp 141～143℃ (EtOAc), named sibirate (Ⅰ), was isolated from the aerial part of Sibiraea angustata (Rchd.) Hand.-Mazz. in addition to a known compound ferulic acid. By means of IR, EI-MS, FAB-MS, ¹H NMR, ¹³C NMR and chemical evidences the structure of sibirate was established as glucityl ferulate.     

雷公藤化学成分的研究 Ⅲ.两种新二萜内酯——雷酚内酯甲醚和雷酚新内酯的分离及结构

从福建产雷公藤(Tripterygium wilfordii Hook.f.)的根皮中分离到三种二萜内酯。(1)雷酚内酯(triptophenolide),C₂₀H₂₄O₃,熔点232～233℃。(2)雷酚内酯甲醚(triptophenolide methyl ether),C₂₁H₂₆O₃,熔点152～154℃。(3)雷酚新内酯(neotriptophenolide),C₂₁H₂₆O₄,熔点189～191℃。根据理化性质及UV、IR、¹HNMR、¹³CNMR、MS等光谱数据,推测化学结构分别为Ⅴ、Ⅵ及Ⅶ。Ⅵ与Ⅶ是二种新的二萜内酯化合物。     

薯蓣属植物化学成分的研究——Ⅹ.蜀葵叶薯蓣中甾体皂甙和皂甙元的分离和鉴定

Four components were isolated from acid-treated rhizome of Dioscorea althaeoides Kunth. Their structures were identified as diosgenin (Ⅰ), β-sitosterol (Ⅱ), diosgenin palmitate (Ⅲ) and △^3,5-deoxytigogenin (Ⅳ) on the basis of physical constants and spectral data.Two sparingly soluble steroid saponins were also isolated from this plant Their physicochemical constants showed that one of them is dioscin (Ⅴ) and the other graeillin (Ⅵ).     

湖北贝母化学成分的研究 Ⅴ、湖贝新的分离和鉴定

A new C-nor-D-homosteroid alkaloid of 22,27-imino-17, 23-oxidojervane skeleton was isolated from the bulb of Fritillaria hupehensis Hsiao et K. C. Hsia by column chromatographic techniques, C₂₇H₄₁NO₃, mp257～259℃, named hupehenisine.On the basis of study of the UV. IR. ¹H-NMR and EI-mass spectra of hupehenisine and its diacetyl derivative, the structure of hupehenisine has been established as 22,27-imino-17,23-ozido-5α, 6-dihydrojerv-12-en-11-oxo-3β-ol (Ⅶ).     

秦艽化学成份的研究(Ⅰ)

From the root of Chinese drug "Chin-Chiu" (秦艽)—Gentiana macrophylla we have isolated alkaloid A C₁₀H₉O₂N, alkaloid B C₉H₉O₂N and alkaloid C (m. p. 79-81℃, 128-130℃ and 206-208℃ respectively). Alkaloid A has been identified as gentianine, whose structure is     

Different tachykinin receptors mediate chloride secretion in the distal colon through activation of submucosal neurones

We investigated the role of tachykinin receptor subtypes on secretory responses in the guinea-pig distal colon using Ussing chamber experiments and intracellular recordings from submucosal neurones. Choline acetyltransferase (ChAT) and vasoactive intestinal polypeptide (VIP) were demonstrated in submucosal neurones by immunohistochemistry. In Ussing chamber experiments substance P (SP), the NK-1-receptor agonist [SAR⁹,Met(O₂)¹¹]-SP and the NK-3-receptor agonist (MePhe⁷)-NKB increased dose-dependently short-circuit currents. The NK-2-receptor agonist (βAla⁸)-NKA(4–10) had no effect. Responses to 1–100 nM SP, [(SAR⁹,Met(O₂)¹¹]-SP and (MePhe⁷)-NKB were tetrodotoxin-sensitive but hexamethonium-insensitive. While (MePhe⁷)-NKB-responses were atropine-sensitive at all concentrations, the atropine sensitivity of the secretory responses to SP and [SAR⁹,Met(O₂)¹¹]-SP dramatically decreased with increasing concentrations. [SAR⁹,Met(O₂)¹¹]-SP and (MePhe⁷)-NKB effects were blocked by the selective NK-1 and NK-3 antagonists CP-99,994–1 (1 μM) and SR 142801 (1 μM), respectively. Combination of both antagonists blocked the SP-response. SR 142801 also suppressed the response to [SAR⁹,Met(O₂)¹¹]-SP. Desensitization with [SAR⁹,Met(O₂)¹¹]-SP significantly decreased (MePhe⁷)-NKB-responses but not vice versa. In intracellular recordings 90% of submucosal neurones were activated by both [SAR⁹,Met(O₂)¹¹]-SP and (MePhe⁷)-NKB as indicated by membrane depolarisation and enhanced spike discharge. These effects were tetrodotoxin-resistant and potentiated by atropine. NK-1- and NK-3-mediated responses occurred equally in ChAT-positive and in VIP-positive neurones. The results suggest the importance of NK-1- and NK-3-receptors on cholinergic and non-cholinergic submucosal neurones for secretory processes in the guinea-pig distal colon. Received: 16 June 1998 / Accepted: 22 September 1998     

鲜罗汉果中黄酮甙的分离及结构测定

A new flavonol glycoside named grosvenorine and a known compoundwere isolated from the fresh fruits of Siraitia grosvenori( swingle)C. By means of UV,FAB-MS,¹H-¹H COSY,¹³C-1H COSY and NOE difference ,spectra,the structure of grosvenorinewas established as kaempferol-3-O-α-L-rhafmnopyranoside-7-O[β-D-glucopyranosyl-(1-2)-α-L-rhamnopyranoside].The known compound was identified as kaempferol-3,7-α-L-dirhamnopyra-noside.     

宁国贝母中宁贝新甙的分离和结构鉴定

A new steroidal alkaloidal glucoside, C₃₄H₅₇NO₇, mp 284～286℃, named ningpeisinoside, was isolated from the bulb of Fritillaria ningguoensis S.C. Chen et S F. Yin. Based on preparation of derivatives and IR, MS, ¹HNMR, ¹³CNMR spectral studies, the structure of ningpeisinoside has been established as N- methyl- 5α- veratranine-6-oxo-3β-O-β-D-glucoside (Ⅰ).     

中药槐花米的化学成分研究[Ⅰ]槐花米甲素(1)

Hwai-Hua-Me has long been used as insecticide,dye-stuff,nutriment,heamosta- tic agent as well as remedies for haemorrhoids and brain hyperemia (apoplexy). Hitherto six substances have been isolated by the author from a sample ob- tainable in Shanghai. The presant paper deals with the study of Sorphorine-A,a yellowish crystal- line subtance.The yield is about 14%.The sample was first extracted with dilute alcohol,then washed with ether,acetone and petroleum ether,and the Product was recrystallized from alcohol and hot water,and then reated with methyl alcohol and ether mixture in order to remove Sorphorn-B,Sorphorin-C & etc.The substance thus obtained gives the following: m.p.180-182°(bulbing),185-188°(Changing forom),199-203°(Sintering with plastic appearance) and decomposing at 245-250°). [a]_D²⁴=+12°(0.5% C₂H₅OH);+5°(% CH₃OH). Mol.formula:C₂₉H₃₆O₁₇. Crystallization of water:7.16;7.33%;CH₂₉H-(36)O₁₇·3H₂O. Crystallizion of methyl alcohol:4.86%,C₂₉H₃₆O₁₇·CH₃OH. Crystallization of ethyl alcohol:6.57%,C₂₉H₃₆O₁₇·C₂H₅OH. Solubility:cold water(1:60,000);boiling water (1:167). cold methyl alcohol(1:1,080);boiling methyl alcohol(111:100). cold ethyl alcohol(1:600);boiling ethyl alcohol(3:5). cold acetone(1:600);boiling acetone(1:350). Pyridine(1:12). cold dioxan(1:12);boiling dioxan(1:15). cold ethyl acetate(trace);boiling ethyl acetate(small). cold amyl alcohol(slightly);hot amyl alcohol(slightly). Reactions:1.Tollen's reagent:black ppt. 2.Fehling's solution:no reaction. 3.HCl+Mg+C₂H₅OH:reddish purple coloration. 4.HAC+Mg+C₂H₅OH:greenish fluorescence. 5.Hydrolysis(1:100 HCl): a.yellowish brown crystals(yield 59%),306-308°(blackens),310-311° (melts),C₁₇H₁₃₍₁₄₎O₉₍₁₀₎. b.acetone Insoluble osazone:m.p.215-217°(D). c.acetone soluble osazone:m.p.188-189. 6.FeCl₃ solution:dark green solution. 7.Lead acetate solution:Lemon-yellow ppt. 8.Basic lead acetate solution:yellowish Orange ppt. 9.Hydrolyzed product:yellowish brown crystal. a.FeCl₃ solotion:bark green solution. b.Lead acetate:yellowish orange ppt. c.Tollen's reagent:black ppt. d.Fehling's solution:no reaction. e.Acetate,C₂₇₍₂₈₎ H₂₃₍₂₄₎O₁₄:m.p.198-203°,CH₃CO%=44.4%;hydro- lyzed with KOH,give greenish yellow crystals,yield about 98% with m.p.310-312°(D). f.Methyated:(1)m.p.300-302° greenish yellow. (2)m.p.151-152° slight yellowish white. The spectrophotometric determination: As show in Fig.Vl (1) Hwai-hua-menine-A exhibits absorption at E_1cm^1% 258 mμ =353;E_1cm^1% 364 mμ=277.8(95% ethyl alcohol+1% 0.2N HAC),(Conc.1.551 mg/100CC.)(Beckman DU). (2) aglucone of Hwai-Hua-Menine-A exhibits absorpotion at: E_1cm^1% 258 mμ=660;E_1c%^1% 375 mμ=550. The paper chromatography determination: Solvent:n-butanol:acetic acid:water=4:1:5 for 10 hours. R_f.=0.68 (0.71-0.72) Aglucone:R_f=0.75.(0.73) Acetic acid:water(6:4 V/V), R_f.=0.71,0.72;Aglucone:R_f=0 The active Oh-groug of aglucone(Tschugajiff Zerrmettinoff's method 26.8%.) The mixed m.p.of rutin(obtained from leaf and stem of Fagoyprum esculentuni, Moench 蕎麦茎叶) and Hwai-Hua-Menine-A:154°(contract),180-190°(syrup), 240-250°(D). It may be concluded from the above results,that the compound is neither rutin, nor its homologues.     

刺梨酸的分离与结构研究

从刺梨中分离出一种新的五环三萜酸,命名为刺梨酸。通过光谱分析和衍生物的制备,确定其化学结构为2β,3α,7β,19α-四羟基乌苏-12-烯-28-羧酸。     

西南獐牙菜化学成分的研究

从西南獐牙菜的全植物中分离出五个化合物,其中四个分别被鉴定为β-谷甾醇(Ⅶ),齐墩果酸(Ⅵ),1,3,7,8-四羟基咄酮(Ⅴ)和山楂酸(Ⅱ)。另一化合物系新的三萜酸糖酯甙,命名为獐牙菜皂甙(swericinctoside,Ⅰ),其结构为2α,3β-二羟基齐墩果-12-烯-28-羧酸-28-O-β-D-葡萄吡喃糖基-(1-6)-β-D-葡萄吡喃糖基-(1-2)-β-D-葡萄吡喃糖甙。     

国产沉香化学成分的研究 Ⅱ.白木香醇和去氢白木香醇的分离和结构

自国产沉香[系瑞香料(Thymelaceae)植物白木香(Aquilaria slnensuis(Lour.)Gilg.)的含有黑色树脂的木质部]的挥发油中经硅胶柱层析和制备性薄层层析分离得到两个新的沉香呋喃类倍半萜,分别命名为白木香醇(baimuxinol)和去氢白木香醇(dehydrobaimuxinol)。经光谱IR,¹H NMR,MS分析和化学方法,确定它们的结构分别为式(Ⅰ)和(Ⅱ)。     

走马芹中香豆素成分的研究

自走马芹根中分离出八种香豆素化合物(Ⅰ～Ⅷ),经鉴定为异佛手柑内酯(Ⅰ)、茴芹内酯(Ⅱ)、甲氧基欧芹素(Ⅲ)、佛手柑内酯(Ⅳ)、异茴芹内酯(Ⅴ)和牛防风素(Ⅵ)。4′-羟基-二氢欧山芹醇(Ⅶ)和香豆素化合物(Ⅷ)是新化合物,后者命名为走马芹内酯(moellendorffiline)。从走马芹叶和种子中均分离到六种香豆素化合物(Ⅰ～Ⅵ)。     

乌棒子甙丙的分离鉴定

本文报道乌棒子(Polygala caudata Rehd et Wils)中另一个新的(口山)酮甙,乌棒子甙丙(wubangziside C,I)的分离鉴定,根据理化性质和光谱分析,证明其化学结构为1,3,7-三羟基(口山)酮-2,4-C-双-β-D-葡萄吡喃糖甙。它是(口山)酮类化合物中第一个从植物界分离到的双碳甙。     

独角莲化学成分的研究

从天南星科植物独角莲块茎中分得三种成分:(1)β一谷甾醇,C₂9H₅₀O,熔点137—138℃,[α]_D²³=-36.4°(CHCl3).(2)β-谷甾醇-D-葡萄糖甙,C₃₅H₆₀O₆,熔点277—279℃(分解),[α]_D²²=-44.5°(吡啶).(3)不活性肌醇,C₆H₁₂O₆,熔点223—225℃. 尚未肯定部分有:(1)酸性部分:由醚浸出液经碳酸氢钠提得部分,进行纸上层析,溶剂系梳为正丁醇:5M甲酸水溶液(90:55),在紫外线下有二个蓝色萤光点.R_f1值=0.78,R_f2值=0.90.如以正戊醇:5M甲酸水溶液作溶剂,则R(f1)值=0.73,R_f2)值=0.90.(2)溶血成分:由醇浸出液经铅盐法处理,由盐基性沉淀部分,分得具溶血及吸湿性的淡棕色粉末,未能测得熔点,可能为皂甙。     

变色马兜铃中银袋内酯乙、丙的结构测定

从变色马兜铃(Aristolochia versicolar S M Hwang)的块根中分离到两个新倍半萜内酯,分别命名为银袋内酯乙(versicolactone B)和银袋内酯丙(versicolactone C)。前者分子式C₁₅H₂₀O₃,熔点135～136℃;后者分子式C₁₅H₂₂O₄,熔点181～182℃,[α]_D³⁶—11.4°(C,2.6,EtOH)。经光谱(UV,IR,¹H NMR,¹³SCNMR,MS)分析和化学方法证明,并经x-衍射证实,两者的结构分别为(Ⅰ)和(Ⅲ)。银袋内酯丙系一新型骨架的奠类倍半萜内酯。     

中国乌头的研究——Ⅸ.川乌、附子中的生物碱

作者对中药川乌的生物碱进行研究,从其中共分得六种结晶性的生物碱,并证明四种是已知物,卽次乌头碱(hypaconitine)、乌头碱(aconitine)、新乌头碱(mesaconitine)和塔拉地萨敏(talatisamine).另二种为新生物碱,暂称为川乌碱甲和川乌碱乙.川岛碱甲,熔点111℃,实验式为C₂₃H₃₇NO₆;川乌碱乙,熔点185℃,实验式为C₂₂H₃₅NO₄。另在附子中亦分得新马头碱及次乌头碱.     

野蔷薇根化学成分的研究

野蔷薇根系蔷薇科植物多花蔷薇(Rosa multiflora Thunb.)的干燥根,民间用其除风湿、活气血和治疗乳糜尿。Takahashi等从野蔷薇根中分离出2α,19α-二羟基熊果酸(tomentic acid)。我们从野蔷薇根中分离出三个化合物,通过光谱和化学反应分别鉴定为β-谷甾醇,2α,19α-二羟基熊果酸,和2α,19α-二羟基熊果酸-(28-1)-β-D-