含取代嘧啶环的戊菊酰基硫脲及其稠环化合物的合成和除草活性测定

合成了5种未见文献报道的N'-(4,6-二取代嘧啶-2-基)-N-3-甲基-2对氯苯基丁酰硫脲(3),并以Br2为氧化剂,进行氧化环化反应,得到5种新的2H-1,2,4-噻二唑并[2,3-a]嘧啶的碳酰亚胺衍生物4.化合物3和4的结构均经IR,1H NMR及元素分析得到确证.初步生物活性测定结果表明,化合物3a有较好的除草活性.     

一种D-π-A型咔唑类衍生物的合成

从咔唑,N,N-二甲基甲酰氨,溴己烷和丙二腈为原料,高效合成了双氰基功能性化合物--3-(2,2'-二氰基乙烯基)-N-己基咔唑(4),其结构经UV-Vis,荧光光谱,1H NMR,IR,MS及元素分析表征.考察了4的光学性质.     

N-(2,2,5,5-四甲基-3-吡咯啉-1-氧自由基)-N-(酰胺基)脲化合物的合成及抗癌活性

本文合成19个新的N-(2,2,5,5-四甲基-3-吡咯啉-1-氧自由基)-N-(酰胺基)脲化合物.研究了此类化合物的ESR,MS及IR波谱性质.初步观察了此类化台物对白血病L7712癌细胞以及腹水型肝癌细胞的抑制作用.发现有的化合物抑制效果显著.     

1-杂环芳酰氧基-2,8,9-三氧杂-5-氮杂-1-硅杂三环[3.3.3.O[1.5]]十一碳烷的研究

本文合成了六个1-杂环芳酰氧基杂氨硅三环和三个1-杂环芳酰氧甲基杂氮硅三环,这些化合物均未见文献报道.通过1H NMR,IR和X射线衍射的方法,确证上述化合物为五配位络构,分子内的N→Si配键强度较大.这是一类低毒或中毒化合物.     

南鹤虱中两个新的倍半萜类化合物（英文）

从中药南鹤虱(Fructus carotae)中分离纯化得到7个倍半萜类化合物,分别鉴定为7-ethoxy-4(15)-oppositen-1β-ol(1),11-乙酰氧基-8β-当归酰氧基-15-甲氧基-4α,5α-环氧愈创木烷-3-酮(2),11-乙酰氧基-8β-丙酰氧基-4-愈创木烯-3-酮(3),1-oxo-5α,7αH-eudesma-3-en-15-al(4),1β-hydroxy-4(15),7-eudesmadiene(5),1β-hydroxy-4(15),5E,10(14)-germacratriene(6),1β-hydroxy-4(15),5-eudesmadiene(7).其中化合物1和2为新的化合物,新化合物的结构进一步通过HR-ESIMS,1D NMR和2D NMR等光谱技术确定.     

三光气法合成盐酸罗哌卡因

以三光气为酰氯化剂,2-哌啶甲酸经酰氯化,酰胺化制得1-N-(2,6-二甲基苯基)-2-哌啶甲酰胺(2),收率50.1%(以2-哌啶甲酸计)。以DMF为溶剂,2经丙基化反应合成了盐酸罗哌卡因(1),收率54%。1和2的结构经1H NMR表征。     

新型5-甲基-1,2,4-三唑-3-硫酮类化合物的合成及抗菌活性研究

利用生物活性叠加原理,以4-氨基-5-甲基-1,2,4-三唑-3-硫酮为原料,设计合成了15个未见报道的化合物2-N-2′,3′,4′,6′-四-O-乙酰基-β-D-吡喃葡萄糖基-4-N-取代苯基亚胺基-5-甲基-1,2,4-三唑(2a～2e),4-N-取代苄基氨基-5-甲基-1,2,4-三唑(3a～3e)和2-N-2′,3′,4′,6′-四-O-乙酰基-β-D-吡喃葡萄糖基-4-N-取代苄基氨基-5-甲基-1,2,4-三唑(4a～4e).其结构经IR,1H NMR,13C NMR和元素分析确认.生物活性测试表明,所有化合物均表现出一定的抑菌活性,尤其是化合物4b对大肠杆菌和金黄色葡萄球菌的最小抑菌浓度为8μg/mL,明显优于市售抗菌药物氟康唑,表现出较强的抗细菌活性;同时,与三氯生相比,所有化合物对白色念珠菌的最小抑菌浓度(MIC)均小于或等于32μg/mL,亦表现出较好的抗真菌活性.     

川西獐牙菜中两个新的链状单萜类化合物

利用多种色谱分离方法对川西獐牙菜的化学成分进行研究,从其全草的乙醇提取物中分离得到四个化合物,应用HR-ESIMS,1D和2D NMR,IR,UV等多种现代波谱技术确定了这些化合物的化学结构,经鉴定分别为(S,2E,6E)-2,6-二甲基-4,8-二羟基辛烷-2,6-二烯酸(1),(S,2E,6E)-2,6-二甲基-4-羟基-8-甲酰氧基辛烷-2,6-二烯酸(2),swerimilegenins B和C(3和4).化合物1和2为两个新的链状单萜类化合物,分别命名为川西獐牙菜酸C和D,化合物3和4是两个不常见的C_9骨架的环烯醚萜,为首次从该植物中分离得到.     

两种新的多羟基甾醇化合物分离与结构鉴定

采用现代分离手段,从采自中国南海硇洲岛的软珊瑚Chromonephthea sp.中分离纯化得到两种甾醇化合物,经过MS,IR,1H NMR,13C NMR(DEPT),HSQC,HMBC和NOE等光谱技术鉴定它们的结构为:24-甲基胆甾-5-烯-3β,12β,16β,20-四醇(1)和24-乙基胆甾-5-烯-3β,12β,16β,20-四醇(2),这两个化合物均为新化合物.肿瘤活性实验表明两种甾醇化合物显示微弱的细胞毒性.     

3-N-乙酰基-2-取代芳基-5-[5′-甲基-异(口恶)唑-3′]-Δ3-1,3,4-(口恶)唑啉类化合物的合成

由相应的酯(1)肼解制得5-甲基-异(口恶)唑-3-甲酰肼(2),后者与醛缩合得到酰腙(3a～3h),3a～3h再进一步与乙酸酐环合,以良好的收率合成出了3-N-乙酰基-2-取代芳基-5-[5′-甲基-异(口恶)唑-3′]-Δ3-1,3,4-(口恶)唑啉衍生物(4a～4h). 以上化合物的结构均经过1H NMR、MS和元素分析的确证.     

新型肟基取代豆甾类化合物的合成及其抗肿瘤活性

以豆甾醇为原料,通过臭氧化将豆甾醇的C20—C22键断裂,再经过官能团转换,合成了22-肟基取代的单肟基化合物(3和9),6,22-二肟基取代的双肟基化合物(13和14)及3,6,22-三肟基化合物(17),其中涉及4个中间体(5~8)及目标化合物9,13,14和17共8个新化合物,其结构经~1H NMR,~(13)C NMR,IR和HR-MS(ESI)表征。采用MTT法测试了化合物对人胃癌细胞(SGC-7901)、人肝癌细胞(Bel-7404)和人体乳腺癌细胞株(He La)的体外抗肿瘤活性。结果表明,具有22-肟基取代的3-羟基-5-烯结构的豆甾化合物3对受试细胞均有一定活性,IC50分别为34±2μmol·L~(-1),32±1μmol·L~(-1)和38±3μmol·L~(-1)。但是进一步在甾核上引入肟基或羟基的其他几种类型化合物的抗肿瘤活性没有提高。     

Structural assignment of regioisomeric 3-[2- or 5-anilino-2-(alkylamino)phenyl]propanoic acids, 2H-1,4-benzothiazin-3(4H)-ones and 2,3-dihydro-1,5-benzothiazepin-4(5H)-ones by 1D NOE and gHMBC NMR techniques

The 1H and 13C NMR spectra of compounds 1-11 and 16-22 in CDCl3 and DMSO-d6 solutions allowed structural assignment to regioisomers 1/5 and 2/6 and their regioselective cyclization products 16-18 utilizing one- and two-dimensional NMR techniques (APT, DEPT, NOE difference, COSY, NOESY, HETCOR and gHMQC, gHMBC). Temperature-dependent 1H NMR spectra of 8-anilino-5-(4-methyl-2-pentyl)-2,3-dihydro-1,5-benzothiazepin-4(5H)-one (18) indicated a free energy of activation (deltaG++) of ca 17 kcal mol(-1) for interconversion between rotamers. The 1H and 13C NMR spectra of 20 and 22 containing two chiral centers exhibit duplication of several signals, indicating the existence of two diastereomeric forms. The structure of 4 was unambiguously confirmed by x-ray crystallography.     

新型二硫杂环戊烯硫酮化合物的合成及其对谷氨酸诱导损伤HT22细胞的保护作用

在保留ADT-OH的3H-1,2-二硫杂环戊烯-3-硫酮结构的基础上,用芳乙烯基替换4-羟基苯环,设计并合成了6个二硫杂环戊烯硫酮化合物（L₁~L₆,其中L₂, L₃, L₅和L₆为新化合物）,其结构经¹H NMR, ¹³C NMR和HR-MS(ESI)表征。采用MTT法研究了L₁~L₆对谷氨酸诱导损伤的海马神经元HT22细胞的影响。药理初筛结果表明:给药浓度为10~100 μmol·L^-1时,L₁, L₂, L₄和L₆均能提高受损HT22细胞的存活率(P<0.01);给药浓度为1 μmol·L^-1时,L₃和L₅均可提高损伤HT22细胞的存活率(P<0.01)。     

Structure and stereochemistry of novel ecdysteroids from the roots of Serratula wolffii

Three new natural ecdysteroids viz. 22‐dehydro‐20‐deoxy‐ajugasterone C (1), 1‐hydroxy‐22‐deoxy‐20,21‐didehydro‐ecdysone (2) and 22‐deoxy‐20,21‐didehydro‐ecdysone (3) were isolated from the methanol extract of the roots of Serratula wolffii. The structures of compounds 1–3 were established by various spectroscopic techniques, including one‐ and two‐dimensional NMR, circular dichroism and mass spectroscopic methods. Copyright © 2010 John Wiley & Sons, Ltd.     

[N,N-二-(2-氯乙基)]-O-[O′,O′-二烷基膦酰甲基]-N′,N′-二烷基磷酰二胺的合成及性质研究

合成了6种含有氮芥结构及膦酰甲基取代基的磷酰二胺。其结构经~1H NMR、MS和元素分析确定,讨论了它们的性质,并对部分化合物的抗癌活性进行了初步试验。     

NMR spectral assignments of two sterols from a soft coral Sinularia brassica

Two new steroids, named 4α,22-dimethyl-Cholest-22-en-3β-ol (1) and 4α-methyl-Cholest-7,22-dien-3β-ol (2), along with two known steroids, were isolated from the soft coral Sinularia brassica. The structures of the new compounds were determined on the basis of extensive spectroscopic data (MS, (1)H and (13)C NMR, (1)H-(1)H COSY, (13)C-(1)H COSY, HMBC and NOESY) analysis.     

1H, 13C NMR, X-ray and conformational studies of new 1-alkyl-3-benzoyl-pyrazole and 1-alkyl-3-benzoyl-pyrazoline derivatives

The (1)H and (13)C NMR resonances of 22 1-alkyl-pyrazole and 25 1-alkyl-pyrazoline derivatives were assigned completely using the concerted application of one- and two-dimensional experiments (DEPT, gs-HMQC and gs-HMBC). Nuclear Overhauser enhancement (NOE) effects, conformational analysis and X-ray crystallography confirm the preferred conformation of those compounds.     

New Macrocyclic Diamide from Rauvolfia Yunnanensis Tsiang

A new macrocyclic diamide, 22-membered macrocyclic diamide, named cyclodicaprylamide（2）, and five known compounds, bis（2-ethylhexyl） phthalate（1）, ethyl 3,4,5-trimethoxybenzoate（3）, ethyl 3,4,5-trimethoxycinnamate （4）, （＋）-syringaresinol（5）, loliolide（6）, were isolated from the roots of Rauvolfia yunnanensis Tsiang. Their structures were elucidated based on NMR, 2D NMR, and MS spectrum, respectively. They were obtained from it for the first time.     

Antibacterial sphingolipid and steroids from the black coral Antipathes dichotoma

From the black coral Antipathies dichotoma, a sphingolipid (2S*,3S*,4E,8E)-2N-[tetradecanoyl]-4(E),8(E)-icosadiene-1,3-diol (1) and a steroid (22E)-methylcholesta-5,22-diene-1α,3β,7α-triol (2) were isolated. Other known compounds, 3β,7α-dihydroxy-cholest-5-ene (3), (22E,24S),5α,8α-epidioxy-24-methylcholesta-6,22-dien-3β-ol (4) and (22E,24S),5α,8α-epidioxy-24-methylcholesta-6,9(11),22-trien-3β-ol (5). The structures were established on the basis of NMR spectroscopic analysis and comparison with literature. The antibacterial activity of five compounds was evaluated.     

Phosphorus-nitrogen compounds. Part 13. Syntheses, crystal structures, spectroscopic, stereogenic, and anisochronic properties of novel spiro-ansa-spiro-, spiro-bino-spiro-, and spiro-crypta phosphazene derivatives

The condensation reactions of N2Ox (x = 2, 3) donor-type aminopodand (4) and dibenzo-diaza-crown ethers (5, 6, and 9) with hexachlorocyclotriphosphazatriene, N3P3Cl6, produce two kinds of partially substituted novel phosphazene derivatives, namely, spiro-bino-spiro- (19) and spiro-crypta (21, 22, and 25) phosphazenes. The partially substituted spiro-ansa-spiro-phosphazene (11) reacted with pyrrolidine and 1,4-dioxa-8-azaspiro[4,5]decane (DASD) give the corresponding new fully substituted phosphazenes (14 and 16). Unexpectedly, the reactions of 23 and 24 with pyrrolidine result in only geminal crypta phosphazenes (26 and 27). The solid-state structures of 16 and 22 have been determined by X-ray diffraction techniques. The relative inner hole-size of the macrocycle in the radii of 22 is 1.27 A. The relationship between the exocyclic NPN (alpha') and endocyclic (alpha) bond angles for spiro-crypta phosphazenes and exocyclic OPN (alpha') bond angles for spiro-ansa-spiro- and spiro-bino-spiro-phosphazenes with 31P NMR chemical shifts of NPN and OPN phosphorus atoms, respectively, have been investigated. The structures of 10, 14, 16, 19, 21, 22, and 25-27 have also been examined by FTIR, 1H, 13C, and 31P NMR, HETCOR, MS, and elemental analyses. The 31P NMR spectra of 10, 21, 22, and 25 indicate that the compounds have anisochrony. In compounds 16 and 22, the spirocyclic nitrogen atoms have pyramidal geometries resulting in stereogenic properties.