华东蓝刺头根的化学成分

目的对中药华东蓝刺头根的化学成分进行分离鉴定。方法采用硅胶柱色谱、制备型反相HPLC等方法分离纯化,1H-NMR1、3C-NMR等方法进行结构鉴定。结果从华东蓝刺头根中分离并鉴定了8个化合物,分别鉴定为:5-(3,4-二羟基丁炔-1)-2,2′-联噻吩[5-(3,4-dihydroxy-but-1-ynyl)-2,2-′bithiophene,1]、2-(戊二炔-1,3)-5-(3,4-二羟基-丁炔-1)噻吩[2-(penta-1,3-diynyl)-5-(3,4-dihydroxybut-1-ynyl)thiophene,2]2、-(丙炔-1)-5-(5,6-二羟基-己二炔-1,3)噻吩[2-(pro-1-ynyl)-5-(5,6-dihydroxyhexa-1,3-diynyl)thiophene,3]、木犀草素(luteolin,4)、筋骨草甾酮C(ajugasterone C,5)、丁香苷(syringin,6)、绿原酸(chlorogenic acid,7)、菜蓟素(cynarin,8)。结论化合物5、7、8为首次从该属植物中分离得到。     

禹州漏芦中噻吩类的化学成分

目的研究禹州漏芦(Echinops latifoliusTausch)噻吩类化学成分。方法采用反复硅胶柱层析分离纯化,通过理化常数测定和光谱分析鉴定其化学结构。结果从禹州漏芦中分离得到6个噻吩类化合物,即5-(丁烯-3--炔1)-2,2′-联噻吩[5-(but3-en-1-ynyl)-2,2-′bithiophene,1]、α-三联噻吩(-αterthienyl,2)、卡多帕亭(cardopatine,3)、5-乙酰-基2,2′-联噻吩(5-acetyl-2,2-′bithiophene,4)、5-(3-乙酰氧基-4-异戊酰氧基丁炔-1)-2,2′-联噻吩[5-(3-acetoxy-4-isovaleroyloxybut-1-ynyl)-2,2-′bithio-phene,5]、5-(4-羟基丁炔-1)-2,2′-联噻吩[5-(4-hydroxybut-1-ynyl)-2,2-′bithiophene,6]。结论化合物4-6为首次从该植物中分离得到。     

（＋）-生物素的合成

(3aS,4S,6aR)-1,3-二苄基-6-(3-甲氧基丙基)四氢噻吩并[3,4-d]咪唑-2-酮在甲酸中和浓盐酸反应制得(3aR,8aS,8bS)-1,3-二苄基-2-氧代十氢咪唑并[4,5-c]噻吩并[1,2-α]氯化锍鎓盐,再经缩合开环、水解后脱羧得剑(+)-生物素,总收率73%.     

克立硼罗的合成工艺优化

以2-溴-5-羟基苯甲醛(2)为原料,在对甲苯磺酸和吡啶的催化下与乙二醇进行缩合反应,得4-溴-3-(1,3-二氧杂环戊-2-基)苯酚(3);此步骤中吡啶的加入缓冲了对甲苯磺酸的酸性,解决了反应不完全和聚合物生成的问题。化合物3与4-氟苯甲腈在无水碳酸钾和四丁基溴化铵作用下缩合,得4-[4-溴-3-(1,3-二氧杂环戊-2-基)苯氧基]-苯甲腈(4);相转移催化剂可缩短反应时间至8 h。化合物4脱保护得4-(4-溴-3-甲酰基苯氧基)苯甲腈(5)。化合物5与联硼酸频哪醇酯在[1,1’-双(二苯基膦基)二茂铁]二氯化钯[Pd(dppf)Cl₂]催化下,发生Miyaura硼化反应得4-[4-(4,4,5,5-四甲基-1,3,2-二氧硼杂环戊-2-基)-3-甲酰基苯氧基]苯甲腈(6),避免使用易燃易爆试剂、不产生易爆中间体,且无严苛操作要求。化合物6在碱性条件下经硼氢化钠还原后成环,得克立硼罗(1);硼氢化钠以水溶液(含5%氢氧化钠)形式滴加,操作简便安全。本工艺总收率51.7%(以2计),1纯度99.9%。     

碘帕醇的合成

5-氨基-2,4,6-三碘-1,3-苯二甲酰氯经N-酰化、酰胺化得到N,N'-双[2-羟基-(1-羟甲基)乙基]-5-[(2(S)-(2-乙酰氧基)丙酰胺基]-2,4,6-三碘-1,3-苯二甲酰胺,再经酸性脱乙酰基制得非离子型X射线造影剂碘帕醇,总收率约78%.     

沃塞洛托的合成工艺研究

目的 改进沃塞洛托的合成工艺。方法 以2,6-二羟基苯甲酸(2)为起始原料,与丙酮反应得到5-羟基-2,2-二甲基-4H-苯并[d][1,3]二氧六环-4-酮,其与3-溴丙烯反应得到5-(烯丙氧基)-2,2-二甲基-4H-苯并[d][1,3]二氧六环-4-酮,经DIBAL-H还原得到2-(烯丙氧基)-6-羟基苯甲醛,再经羟烷基化反应得到2-(烯丙氧基)-6-{[2-(1-异丙基-1H-吡唑-5-基)吡啶-3-基]甲氧基}苯甲醛,最后脱除烯丙基保护基得到沃塞洛托。结果与结论目标化合物及其中间体的结构经¹H-NMR和ESI-MS谱确证,总收率为64.3%(以化合物2计),纯度为98.3%(HPLC法)。本工艺操作简便,原料价廉易得,适合工业化生产。     

4-甲基-香豆素及4-甲基喹啉-2(1H)-酮的7位羟基、巯基与炔丙基卤代物的不同反应性

目的合成具有抗HIV活性的三环杂环化合物的关键中间体.方法 7-羟基-4-甲基-香豆素、7-羟基-4-甲基喹啉-2(1H)-酮、7-巯基-4-甲基-香豆素分别与3-氯-3-甲基-1-丁炔、3-溴丙炔反应得到相应产物,其结构经波谱确证.结果 4-甲基-香豆素的7位羟基发生正常的双分子亲核取代反应(SN2),得到炔丙基醚产物4、7和10,进一步热环合得到三环杂环化合物5、8和11;7-巯基-4-甲基-香豆素、7-巯基-4-甲基喹啉-2(1H)-酮与3-氯-3-甲基-1-丁炔反应分别得丙二烯醚双分子亲核取代反应(SN2′)产物聚集双键硫醚化合物12和14,且不能进一步热环合成三环杂环.结论 4-甲基-香豆素及4-甲基喹啉-2(1H)-酮的7位羟基、巯基与炔丙基卤代物表现出不同的反应性.     

大蓝刺头化学成分研究

从大蓝刺头（Echinops talassicus Golosk.）的根中分离出5种化合物，根据理化常数及波谱分析鉴定为5－（3－丁烯－炔－1）联噻吩（Ⅰ），α－三联噻吩（Ⅱ），5－（3，4－二 －丁炔－1）联噻吩（Ⅲ），棕榈酸（Ⅳ）及β－谷甾醇（Ⅴ），这些化合物均为首次从该植物中分得。     

α—（氨甲基）—4—羟基—1，3—苯二甲醇的合成

a-(氨甲基)-4-羟基-1,3-苯二甲醇(1)是合成β2-肾上腺素能激动剂沙美特罗(salmetero1)的重要中间体[1～5]。     

神经肌肉阻滞剂罗库溴铵有关物质D的制备

目的合成1-[3α-乙酰氧基-17β-羟基-2β-(吗啡啉-4-基)-5α-雄甾烷-16β-基]-1-(丙烯-2-基)四氢吡咯鎓溴化物(有关物质D)。方法以2α,3α,16α,17α-二环氧-17-乙酰氧基-5-雄甾烷为起始原料,经吡咯烷开环、硼氢化钠还原、开环反应、酰化反应等反应,经柱层析分离纯化拆分了三种光学异构体,合成(2β,3α,5α,16α,17β)-2-(4-吗啉)-16-(1-吡咯基)-雄甾-3,17-二醇3-乙酸酯,然后经催化和烯丙基溴反应合成了有关物质1-[3α-乙酰氧基-17β-羟基-2β-(吗啡啉-4-基)-5α-雄甾烷-16β-基]-1-(丙烯-2-基)四氢吡咯鎓溴化物(有关物质D)。结果其结构经1H-NMR和LC-MS证实。结论该合成方法能够合成罗库溴铵有关物质D,为控制产品质量提供有关物质对照品。     

杜仲叶中倍半萜及降碳倍半萜的分离与鉴定

目的 研究植物杜仲(Eucommia ulmoides Oliver)叶中的化学成分.方法 综合运用硅胶柱色谱、反相硅胶柱色谱和Sephadex LH-20凝胶柱色谱以及制备型高效液相色谱等方法进行系统分离,根据化合物的理化性质及其波谱数据确定化合物的结构.结果 从杜仲叶80％(体积分数)乙醇提取物中分离得到了12个倍...     

Two new thiophenes from Echinops latifolius and their phototoxic activities

Two new thiophenes, 5-{4-[4-(5-pent-1,3-diynylthiophen-2-yl)-but-3-ynyloxy]-but-1-ynyl}-2,2'-bithiophene (1) and 5-(4-hydroxybut-1-one)-2,2'-bithiophene (2), together with two known thiophenes 5-(4-hydroxybut-1-ynyl)-2,2'-bithiophene (3) and 5-(3,4-dihydroxybut-1-ynyl)-2,2'-bithiophene (4), were isolated from the roots of Echinops latifolius Tausch. Their structures were elucidated based on the detailed NMR spectroscopic analysis and comparison with literature values. Compounds 1 and 2 showed significant inhibition activities against human cancer cell lines A375-S2 and HeLa with IC(50) values from 3.1 to 13.5 micromol/L, depending on their exposure to long wavelength ultraviolet light.     

了哥王石油醚部位化学成分的分离与鉴定

目的 对苗药了哥王[Wikstroemia indica(L.)C.A.Mey]石油醚部位中的化学成分进行研究.方法 采用硅胶柱色谱、Sephadex LH-20凝胶柱色谱、中压ODS柱色谱、制备HPLC等多种分离纯化手段,对了哥王乙醇提取后石油醚萃取部位的化学成分进行分离、纯化,通过各化合物的理化性质和波谱数据确定化...     

Chemical constituents from Teucrium viscidum

A new monoterpenoid, 4,​5,​8-​trihydroxy-​6(7)-en-​decenoic acid γ-​lactone (1) and six known compounds, 3,7-dimethyloct-1-ene-3,6,7-triol (2), 2,8-bornanediol (3), 1-(4-hydroxyphenyl)ethane-1,2-diol (4),2-(3-methoxy-4-hydroxyphenyl)-propane-1,3-diol(5), indole-3-carboxylic acid (6), and 3-hydroxy-benzenemethanol (7) were isolated from the whole parts of Teucrium viscidum. Their structures were established by a combination of spectroscopic data analysis, besides comparison with literature data. Compounds 2–7 described above were isolated from this genus for the first time.     

Sesquiterpene lactones from Inula hookeri

Four new sesquiterpene lactones, (1 S,5 R,6 S,7 S,8 R,9 R,10 S,11 S)-6-acetoxy-9-hydroxy-4-oxo-pseudoguai-2(3)-en-12,8-olide, (1 S,2 R,5 R,6 S,7 R,8 S,10 R)-6-acetoxy-2-ethoxy-4-oxo-pseudoguai-11(13)-en-12,8-olide, (1 S,2 R,5 R,6 S,7 R,8 S,10 R)-6-acetoxy-2-hydroxy-4-oxo-pseudoguai-11(13)-en-12,8-olide, and 14-acetoxy-1 β,5 α,7 αH-4 β-hydroxy-guai-9(10),11(13)-dien-12,8 α-olide, along with 26 known sesquiterpene lactones, were isolated from the whole plants of Inula hookeri C. B. Clarke. Their structures were established based on spectroscopic methods including HRESIMS, 1D and 2D NMR, and CD techniques. All compounds were evaluated for their cytotoxic activities against HepG2, HeLa, PC-3, and MGC-803 cell lines by CCK-8 assay. Some of the isolates, especiallly pseudoguaianolides and guaianolides, exhibited significant cytotoxicities against these four examined cell lines.     

紫花前胡化学成分的研究

目的研究中药紫花前胡［Peucedanum decursivum(Miq.)Maxim］根的化学成分。方法用硅胶柱色谱和制备型高效液相色谱进行分离纯化,用光谱分析和化学方法鉴定其结构。结果从紫花前胡根中分得7个线型吡喃香豆素类化合物,其结构分别鉴定为3′(S)-hydroxy-4′(R)-angeloyloxy-3′,4′-dihydroxanthyletin(1);3′(S)-acetoxy-4′(R)-hydroxy-3′,4′-dihydroxanthyletin(2);3′(S)-acetoxy-4′(R)-angeloyloxy-3′,4′-dihydroxanthyletin(3);Pd-C-IV(4);Pd-C-II(5);(+)-3′S-Decursinol(6);(+)-trans-Decursidinol(7)。结论化合物1和2为新化合物,分别命名为紫花前胡素D和紫花前胡素F;6和7为首次从该植物中分得。     

Antimicrobial constituents from fruits ofAilanthus altissima SWINGLE

A new naturally occurring sterol, compound 5, and six known stigmasterols were isolated from fruits of Ailanthus altissima Swingle by repeated column chromatography and RP-HPLC. Their structures were identified as, 5alpha-stigmastane-3,6-dione (1), 3beta-hydroxystigmast-5-en-7-one (2), stigmast-5-ene-3beta, 7alpha-diol (3), 6alpha-hydroxystigmast-4-en-3-one (4), 5alpha-stigmastane-3beta, 6beta-diol (5), stigmast-4-ene-3beta, 6alpha-diol (6), stigmast-5-ene-3beta, 7alpha, 20xi-triol (7) by spectral analysis and comparison with the published data. These compounds have not been reported from genus Ailanthus, whereas compound 7 was identified by NMR for the first time. In addition, the 95% ethanol extract and compounds from the fruits of Ailanthus altissima SWINGLE were assayed for in vitro antimicrobial activity. The extract was potent active against the assayed bacteria while compounds 3 and 7 exhibited moderate activity.     

Sesquiterpenes from Dysoxylum oliganthum and Dysoxylum excelsum

Three new sesquiterpenes (1-3), (6R,7S,11R,10S)-15-hydroxy-sesquisabinene hydrate (1), (6R,7R,11S,10S)-15-hydroxy-sesquisabinene hydrate (2), and (6R,7R,10S)-15-hydroxy-zingiberenol (3), along with three known compounds, were isolated from the stems of Dysoxylum oliganthum; and three new isodaucane (salvionane) sesquiterpenes, namely isodauc-6-ene-10β,14-diol (4), 4-epi-isodauc-6-ene-10β,14-diol (5), and 4-epi-6α,10β-dihydroxy-artabotrol (6) together with 15 known compounds were isolated from the twigs and leaves of D. excelsum. Their structures were established on the basis of extensive spectroscopic analysis and chemical shifts. The absolute configuration of C-10 in compounds 1-3 of a rare class was determined by using Snatzke's method.