N-芳基-二茂铁甲酰烯胺的合成

含二茂铁基的烯胺及其过渡金属络合物前人做过一些工作^[1-4]。但二茂铁甲酰烯胺类衍生物未见文献报道。我们考虑二茂铁甲酰烯胺及其络合物的应用前景,研究了二茂铁甲酰烯胺类化合物的合成方法及其络合性质。由二茂铁甲酰丙酮^[5]与取代苯胺缩合,得到了十种不同N-芳基-二茂铁甲酰烯胺:FcCOCH=C(CH₃)-NHC₆H₄X 其中:X=H; O-, m-, p-OH; m-, p-OCH₃; O-, p-Cl; m-, p-NO₂着重研究了取代基的种类与位置对缩合反应的影响。     

有机镓、铟芳酰腙配合物的制备与结构表征

通过芳酰腙与三甲基镓或三甲基铟的反应,制备得到了七个有机镓或铟的镓芳酰腙配合物,在配合物中金属直接与芳酰腙的氧和烯胺氮成键,形成五元环状分子内配合物。对得到的化合物通过元素分析、红外光谱、质子核磁共振和质谱进行了结构表征。     

新型手性固定相的合成及其应用

本文采用了一种新的简便方法合成了四个新型手性固定相; N-十一碳-10-烯酰-L-缬氨酸-S-α-苯乙胺(手性-S-1)N-十一碳-10烯酰-L-缬氨酰-R-α-苯乙胺(手性-R-1)及生-S-α, 手性-S-3, 并对外消旋的α-β-氨基酸, 外消旋的α-β-羟基酸和含手性烃基的外消旋胺的进行了折分, 在四丁固定相中手性-S-1对上述对映体的折分选择性最好。     

铜试剂介导下烯胺酮的氧化环化/迁移合成取代的2H-氮杂丙烯啶的方法

报道了铜试剂介导下烯胺酮化合物通过氧化环化/迁移反应合成2-苯酰氧基-2H-氮杂丙烯啶的新方法.该方法具有反应条件温和、反应时间短和操作简单等优点.     

含可聚合基团的萘酰亚胺衍生物的合成

以4-溴-1,8-萘酐和4-硝基-1,78-萘酐为起始原料,与各种芳胺经亚胺化,再与脂肪胺经取代反应,最后与丙烯酰氯经酯化得到一系列具有强烈荧光的含丙烯酰氧乙基氨基的1,8-萘酰亚胺衍生物,它们可作为一种聚合荧光色素的单体。     

烷基步长对聚丙烯酸修饰咔唑电聚合的影响

合成了含有不同烷基链取代的N-丙烯酰氧癸基咔唑(MACZ10)和N-丙烯酰氧十二烷基咔唑(MACZ12), 通过自由基聚合得到聚N-丙烯酰氧烷基咔唑(PMACZ). 分子量分析表明, 随着烷基链长度的增加, 聚合物分子量减小, 分布变宽. 荧光光谱表明, 随着烷基链长度的增加, 聚合物在353 nm处的发射峰逐渐减弱. 在四氢呋喃和体积分数为10%三氟化硼乙醚与四氟化硼四丁基胺的混合电解质溶液中, 直接阳极氧化PMACZ获得自支撑交联网状的聚(聚N-丙烯酰氧烷基咔唑)(PPMACZ)薄膜. PPMACZ薄膜具有良好的氧化还原活性、热稳定性和蓝色发光性能, 聚合物氧化还原可逆性随着烷基链长的增加而增加, 且发射峰变宽.     

1, 3-二烷氧基丙酮的C-酰基化

1,3-二烷氧基丙酮(1)证实是很活泼的化合物,它们在Claisen缩合反应条件下发生自缩合,但是可以通过Stork烯胺程序成功地酰化为1,3-二烷氧基-乙酰丙酮(2)和1,3,5-三烷氧基-乙酰丙酮(3)。甲氧基丙酮(4)在与吗啉加热时发生自缩合而不形成烯胺。     

固定化酶新载体-N′-ε-甲基丙烯酰胺基己酸酯的研究

合成了一种新的反应性聚合物聚N-ε-甲基丙烯酰胺基己酰氧-5-降冰片烯-2,3-双甲酰亚胺[P(MACONB)],其相应的新单体N-ε-甲基丙烯酰胺基己酰氧-5-降冰片烯-2,3-双甲酰亚胺(MACONB),是由N-ε-甲基丙烯酰胺基己酸(MACOH)与N-羟基-5-降冰片烯-2,3-双甲酰亚胺(HONB)在环己基羰二亚胺存在下经偶联成酯反应而得。反应性聚合物P(MACONB)是一个较好的固定化胰蛋白酶的载体,它极易与胰蛋白酶在温和反应条件下进行胺解反应,形成一个具有较高酶活力的固定化胰蛋白酶。     

聚丙烯酸修饰咔唑的电化学聚合及表征

合成了侧链带有咔唑的N-丙烯酰氧己基咔唑(MACZ),通过自由基聚合得到聚N-丙烯酰氧己基咔唑(PMACZ),在四氢呋喃含10%三氟化硼乙醚与四氟化硼四丁基胺的混合电解质溶液中,直接阳极氧化PMACZ获得自支撑交联网状的聚(聚N-丙烯酰氧己基咔唑)(PPMACZ)薄膜.PPMACZ薄膜具有良好的氧化还原性和热稳定性,电导率为1.34×10-5S·cm-1.1HNMR和红外光谱表明PMACZ二次聚合反应发生在咔唑单元的3,6位上,荧光光谱表明PPMACZ薄膜是一种良好的蓝色发光材料.     

基于缺电子烯胺交叉氨化过程的多组分反应研究进展

缺电子烯胺结构上含有多个不同活性的亲核和亲电反应位点,同时双键本身可以作为烯键给予体参与反应,因此可以通过各种亲核、亲电以及环加成等转化广泛应用于有机合成反应.综述结合我们自己小组的研究工作和兴趣,对基于缺电子烯胺如烯胺酮、烯胺酯等和含胺基试剂包括铵、胺、烯胺、脲和硫脲等之间的交叉氨化为关键转化,并和其它底物发生串联转化的多组分反应研究进展进行了总结.     

Complete assignments 1H and 13C NMR spectral data of four anabaseine derivatives

The anabaseine derivatives 6-methoxy-7-hydroxy-1-(pyridin-3-yl)-3,4-dihydroisoquinoline, 6,7-dimethoxy-1-(pyridin-3-yl)-1,2,3,4-tetrahydroisoquinoline and 6,7-dimethoxy-1-(piperidin-3-yl)-1,2,3,4-tetrahydroisoquino- line were prepared either by demethylation with HBr or by reduction with different reagents, NaBH4 and H2/PtO2 from 6,7-dimethoxy-1-(pyridin-3-yl)-3,4-dihydroisoquinoline, as starting material. The structures have been fully assigned by the combination of one- and two-dimensional experiments.     

Cyclization of 2-methoxy-6-(substituted benzyloxy)acetophenone hydrazones in the presence of polyphosphoric acid(PPA)

Cyclization of 2-methoxy-6-benzyloxy acetophenone hydrazone gave 3-methyl-4-meth-oxy indazole and 3-methyl-4-methoxy-7-benzyl indazole in the presence of polyphosphoric acid(PPA).The hydrazone was probably converted to 2-hydroxy-6-methoxy acetophenone hydra-zone and 2-hydroxy-3-benzyl-6-methoxy acetophenone hydrazone followed by cyclization to thecorresponding indazoles in acidic conditions.Cyelization of 2-methoxy-6-(halo or alkyl or arylbenzyloxy)acetophenone hydrazones gave similar products.Cyclization of 2-methoxy-6-(p-nitrobenzyloxy)acetophenone hydrazone gave 2-(p-nitrophenyl)-3-methyl-4-methoxy benzo-furan and 3-methyl-4-methoxy indazole while 2-methoxy-6-(m-nitrobenzyloxy)acetophenonehydrazone gave 3-methyl-4-methoxy indazole,3-methyl-4-methoxy-7-(m-nitrophenyl)indazole and3-methyl-4-(m-nitrobenzyloxy)indazole.     

Total synthesis of (±)-fangchinoline

(±)-Fangchinoline was synthesized by condensation of (±)-1-(3-bromo-4-methoxy-benzyl)-2-methyl-6-methoxy-7-hydroxy-8-bromo-1,2,3,4-tetrahydroisoquinoline ( 2 ) and (±)-1-(4-hydroxy-benzyl)-2-methyl-6-methoxy-7-hydroxy-1,2,3,4-tetrahydroisoquinoline ( 3 ) in the presence of copper, pyridine and potassium carbonate.     

Reactions of 5-(6-Methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-1,3,4-oxadiazole-2-thione with Electrophiles

 Treatment of 5-(6-methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-1,3,4-oxadiazole-2-thione with haloalkanes yielded oxadiazole S-alkyl derivatives, whereas its reaction with formaldehyde and amines resulted in formation of oxadiazole N(3)-aminomethyl derivatives. The alkylation of 2-alkylsulfanyl-5-(6-methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-1,3,4-oxadiazoles with methyl bromoacetate proceeded at the N(1)-position of pyrimidine to give 2-alkylsulfanyl-5-(1-methoxycarbonylmethyl-6-methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-1,3,4-oxadiazoles, whereas aminomethylation, bromination, or nitration took place at position 5 of pyrimidine ring and afforded the corresponding 5-pyrimidine substituted derivatives.     

3-acyl-1,2,3,4-tetrahydropyridine-2,4-diones: Synthesis and chemical properties

N-Substituted 6-methyl-1,2,3,4-tetrahydropyridine-2,4-diones reacted with aliphatic carboxylic acid chlorides in the presence of pyridine or triethylamine to give the corresponding 4-O-acyl derivatives which underwent O,C-migration of the acyl group by the action of 2 equiv of triethylamine and a catalytic amount of 2-hydroxy-2-methylpropanenitrile. Reactions of 3-acyl-6-methyl-1,2,3,4-tetrahydropyridine-2,4-diones thus formed with aliphatic and aromatic amines gave the corresponding enamino derivatives at the side acyl group. Enamino derivatives at the C⁴ =O group were obtained by transformation of 3-acyl-1,2,3,4-tetrahydropyridine-2,4-diones into 3-acyl-4-methoxy-6-methyl-1,2-dihydropyridin-2-ones via alkylation with dimethyl sulfate and subsequent treatment with amines.     

Synthesis and pharmacological evaluation of 2-(3-piperidyl)-1,2,3,4-tetrahydroisoquinoline derivatives as specific bradycardic agents

Novel 1,2,3,4-tetrahydroisoquinoline derivatives bearing directly a cyclic amine at the 2-position were prepared and examined for their bradycardic activities in isolated right atria and in anesthetized rats. The structure-activity relationships (SAR) study revealed that the 2-(3-piperidyl)-1,2,3,4-tetrahydroisoquinoline skeleton is essential for the appearance of potent in vitro activity, and that the presence of at least one methoxy group at the 6- or 7-position of the 1,2,3,4-tetrahydroisoquinoline ring is important to exert potent in vitro activity. In vivo tests of selected compounds demonstrated that 2-(1-benzyl-3-piperidyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline (6c) exhibited potent bradycardic activity with negligible influence on mean blood pressure in rats, although its potency is a half of that of Zatebradine.     

Reactions of 5-(6-Methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-1,3,4-oxadiazole-2-thione with Electrophiles

Summary.  Treatment of 5-(6-methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-1,3,4-oxadiazole-2-thione with haloalkanes yielded oxadiazole S-alkyl derivatives, whereas its reaction with formaldehyde and amines resulted in formation of oxadiazole N(3)-aminomethyl derivatives. The alkylation of 2-alkylsulfanyl-5-(6-methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-1,3,4-oxadiazoles with methyl bromoacetate proceeded at the N(1)-position of pyrimidine to give 2-alkylsulfanyl-5-(1-methoxycarbonylmethyl-6-methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinyl)-methyl-1,3,4-oxadiazoles, whereas aminomethylation, bromination, or nitration took place at position 5 of pyrimidine ring and afforded the corresponding 5-pyrimidine substituted derivatives. Received May 9, 2001. Accepted (revised) August 17, 2001     

Nucleophilic Substitution in the Allylic System of Codeine and Pseudocodeine: Reactions with lithium cyano(methyl)-and (aryl)cyanocuprates. Crystal and molecular structure of 8α-phenyl-6,7-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan and 6α-phenyl-7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan

Nucleophilic substitution of 6β-chloro-7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan ( 1 ) and 8α-bromo-6,7-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan ( 2 ) with lithium cyano(methyl)- and (aryl)cyanocuprates(I) ( 5a–c ) was accompanied by allylic rearrangement with both change and retention of orientation of the substituting group (Scheme 1, Table 1). Nucleophilic substitution in 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan-6α-yl methanesulfonate ( 3 ) and 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methylmorphinan-6β-yl methanesulfonate ( 4 ) proceeded without allylic rearrangement with both change and retention of the orientation of the substituting group (Scheme 2, Table 1). X-Ray diffraction studies of the products 6,7-didehydro-4,5α-epoxy-3-methoxy-17-methyl-8α-phenylmorphinan ( 6b ) and 7,8-didehydro-4,5α-epoxy-3-methoxy-17-methyl-6β-phenylmorphinan ( 7b ) were carried out (Figs. 1 and 2).     

二醇及氨基醇类鬼臼毒素衍生物的合成

以天然产物鬼臼毒素(1)为原料，合成了四种二醇及氨基醇类鬼臼毒素衍生物：4-O-乙基表鬼臼苦醇(4)，(1R,2S,3R,4S)-1-3',4',5'-三甲氧基苯基-2-氨甲基-3-羟甲基-4-乙氧基-6,7-亚甲二氧基-1,2,3,4-四氢萘(5)，(1R,2S,3R,4S)-1-3',4',5'-三甲氧基苯基-3-羟甲基-2-氨基-4-乙氧基-6,7-亚甲二氧基-1,2,3,4-四氢萘(6)和4-O-异丙基表鬼臼苦醇(7)。4～7及中间产物8～11都是新化合物。     

Alkynylation of Cotarnine Hydrochloride by Ag(I) Acetylenides

1-Organoacetylene derivatives were prepared by reaction of cotarnine hydrochloride with silver organoacetylenides with brief heating in acetonitrile. The structure of one of these, 1-(3-hydroxypropyn-1-yl)-2-methyl-6,7-methylenedioxy-8-methoxy-1,2,3,4-tetrahydroisoquinoline, wasproved by an X-ray structure analysis.