分子筛催化萜烯烷氧基化反应的研究 Ⅰ.异菠基烷基醚的合成

本文报导沸石分子筛催化蔌烯(1)、三环烯(2)与C_1～C_4醇发生烷氧基化反应,生成异菠基烷基醚(3a-3g)和副产物6,7,7-三甲基-2-烷氧基双环(2,2,1)庚烷(4a-4g)的结果。产物的结构经红外、质谱、核磁和元素分析测定,此法被认为是一种合成异菠基烷基醚的新方法。文中还讨论了可能的反应机理。     

1,7,7-三甲基双环[2.2.1]庚基环烷基(或环取代的烷基)醚的合成

近年来,我们曾报道了莰烯-三环烯在氢型丝光沸石催化下与开链醇及二醇等进行烷氧基化反应的结果。最近,Scheidll,Fran报道用浓硫酸催化莰烯与环戊醇反应,合成exo-1,7,7-三甲基双环[2.2.1]庚基环戊醚。     

分子筛催化萜烯烷氧基化反应的研究 I: 异菠基烷基醚的合成

报导了以氢型丝光沸石 为催化剂催化茨烯和(或)三环烯与C1-C4醇发生烷氧基化的反应, 得到一系列7,7-二甲基-2-烷氧基双环[2,2,1]庚烷及相应付产物6,7,7-三甲基-2-烷氧基双环[2,2,1]庚烷衍生物. 这些付产物均为新化合物. 所有产物的结构均由元素分析, 红外, 质子核磁共振及质谱确认这些化合物具有清凉香气和木质龙涎香气.     

分子筛催化萜烯烷氧基化反应的研究 Ⅰ.异菠基烷基醚的合成

文献报道合成异菠基烷基醚(3)的路线有两条.一条是莰烯(1)和(或)三环烯(2)在酸性催化剂作用下与醇发生反应生成3;另一条是以异龙脑为原料,与氢化钠、硫酸二烷基酯反应生成3.前者生成3的选择性不高,且产率较低;而后者选择性虽然比较高,但产率仍不理想,且所用原料较多.本文首次报道以氢型丝光沸石为催化剂催化1和(或)2与 C_1—C_4醇发生烷氧基化反应,以比较高的选择性和较好的产率得到一系列相应的烷基化合物(3a—3g),     

6,6-二烷基富烯同α-吡啶甲基锂和α-吡啶基锂的反应——吡啶基取代环戊二烯及其铁衍生物的合成和结构

6,6-二烷基富烯和6,6-多亚甲基富烯同α-吡啶甲基锂发生环外双键的加成反应。形成的取代环戊二烯基锂经水解或与二氯化铁反应,分别制得α-吡啶烷基环戊二烯和α-吡啶烷基二茂铁。α-吡啶基锂与6,6-四亚甲基富烯进行α-摄氢反应,与6,6-五亚甲基富烯则发生环外双键的加成反应。 测定了双(η~5-1-(α-吡啶甲基)环戊基环戊二烯基)铁的分子结构。晶胞中含有三个分子,每个分子处在各自独立的位置。根据分子中两个环戊二烯基环上取代基的相对指向,分子Ⅰ与Ⅱ可以认为具有相同的构象,而分子Ⅲ则是它们的镜像。     

2′-羟基-1′,3′-苯撑二亚甲基冠醚的合成

2,6-二羟甲基-4-氯苯甲醚(3)和2,6-二羟甲基-4-苯基苯甲醇(4)与三缩四乙二醇和四缩五乙二醇的二对甲苯磺酸酯在含有叔丁醇钾的无水四氢呋喃中反应生成甲氧基冠醚5—7。后者与过量无水碘化锂在无水吡啶中廻流有选择性地除去甲基而不影响大环苄醚基的破裂生成三种2’-羟基-1’,3’-亚苯基二甲基冠醚8—10,产率为85—89％。     

取代苯基烷基酮与叔丁基氯化镁反应的机理研究

通过EPR技术观察到一系列典型的烷基或甲氧基取代的苯基烷基酮ArCOR(Ar=2,5-二甲基苯基(1);2,5-二甲氧基苯基(2);4-叔丁基-2,5-二甲氧基苯基(3))与t-BuMgCl反应中形成的自由基阴离子中间体[ArC(R)OMgCl]。产物分析表明,反应主要生成还原产物[ArCH(R)OH]和1,2-加成产物[ArC(R)(t-Bu)OH]。降低溶剂极性及反应温度都有利于还原产物的生成。对上述反应的可能历程作了简单讨论。     

几种β-烷基萘的催化脱氢环化的研究

在铬铝催化剂上,温度400—500℃和空速0.1—0.87时~(-1)的反应条件下,研究了β-正庚萘、β-(2-甲基丁基)萘、β-(1-丙基丁基)萘和β-(1-丁基丁基)萘的脱氢环化。β-烷基萘的烷基侧链结构对脱氢环化反应有明显的影响。β-(2-甲基丁基)萘的脱氢环化同β-(3-甲基丁基)萘比较类似,生成30％的2-甲基蒽;但同β-(1-甲基丁基)萘较少类似,仅生成约5％的菲。当β-烷基萘的烷基侧链碳原子多于6个时,不仅在烷基侧链与萘环碳原子之间可以脱氢环化,生戍菲、蒽及其同系物,而且在烷基侧链碳原子之间也可以脱氢环化生成苯井芴和(?)等稠环芳烃,在β-烷基萘脱氢环化的同时,还伴随有裂解反应;烷基侧链愈长,裂解现象就越严重。     

取代环戊二烯的合成和^1HNMR谱

本文研究了苯基锂和对、间、邻甲苯基锂及对、邻甲氧苯基锂与6,6-二烷基富烯环外双键加成反应的立体效应。在室温下于乙醚溶剂中,6,6-二烷基富烯同上述芳基锂反应,形成取代环戊二烯基锂,经水解给出含或不含手性碳的叔烷基环戊二烯。     

长链烷基锂与6,6-二烷基富烯的反应研究——取代茂钛、锆化合物的合成

研究了正庚基锂、正辛基锂同 6,6-二烷基富烯反应的立体和溶剂效应对反应类型的影响。在弱极性溶剂中 (方法 A,B) ,正庚基锂、正辛基锂同 6,6-二烷基富烯主要发生加成反应 ;在极性溶剂中 (方法 C) ,则倾向于加成和还原两种反应。利用上述反应形成的环戊二烯基阴离子同Ti Cl4、Zr Cl4反应 ,合成了一系列新的取代茂钛、锆化合物。     

Facile Syntheses of New Pyrazolo[1,5-a] pyrimidines Derivatives via Reactions of Enaminones with Aminopyrazole

Ethyl 7-aryl-2-benzyhhiopyrazolo [ 1,5-a ] pyrimidine-3-carboxylates （3a-3f） were conveniently synthesized through the reactions of enaminones with 5-amino-3-benzyhhio4-ethoxycarbonyl-1 H-pyrazole in good yields and high regioselectivity. The structures of the new compounds were fully characterized by spectroscopic measurmehts, elemental analysis and X-ray diffraction analysis. A plausible reaction mechanism for the formation of the title compounds was also presented.     

3-取代卓酚酮5位偶联产物的溴氧化成环反应

报道了采用溴氧化3-异丙烯基卓酚酮和3-肉桂酰基卓酚酮合成杂环并卓酮化合物的新方法。3-异丙烯基卓酚酮5位偶联产物1a-1f和3-肉桂酰基卓酚酮5位偶联产物3a-3d分别在吡啶介质中与过量溴作用生成5-取代苯偶氮基-7-溴-3-甲基-8-氢环庚并呋喃-8-酮2a-2f和6-取代苯偶氮基-2-苯基-8-溴-4,9-二氢环庚并吡喃-4,9-二酮4a-4d。     

Cyclization of aromatic propargyl alcohol with a thiophene group yielding naphthothiophene aldehyde induced by a ruthenium complex

The reactions of [Cp(PPh(3))(2) RuCl] (Cp=cyclopentadienyl) with phenyl propargylic alcohol 1a, with a 3-thiophene group, are explored. The carbene complex 2a, obtained exclusively from this reaction at low temperature, contains the naphthothiophene group, which is formed through a new cyclization process between the thiophene group and the inner carbon of the triple bond. Details of this process have been revealed by conducting the reaction at room temperature, affording the allenylidene complex 3a as a side product. Complex 3a is not converted into 2a, indicating that the cyclization takes place while the triple bond is π coordinated to the metal center. Complex 2a reacts with oxygen in the presence of NEt(3) at room temperature to afford, in high yield, naphthothiophene aldehyde 4a, ONEt(3), OPPh(3), and [Cp(PPh(3))(2)RuCl]. Molecular O(2) is likely activated by coordination to the metal center when one of the phosphane ligands dissociates. Then, NEt(3) promotes the oxygenation process by reacting with the coordinated O(2) to afford ONEt(3) and possibly an unobserved oxo-carbene complex. Coupling of the oxo and carbene ligands then yields 4a and [Cp(PPh(3))(2) RuCl] in CHCl(3). In a solvent system containing MeOH, the oxygenation reaction affords a mixture of 4a and naphthothiophene ester 5a-1. The reactions of [Cp(dppf)RuCl] (dppf=1,1'-bis(diphenylphosphino)ferrocene) with 1a, also afford the carbene complex 2a', 4a, and 5a, which have been characterized by X-ray diffraction analyses. For the phenyl propargylic alcohol 1b, with a 2-thiophene substituent, different naphthothiophene aldehyde and ester compounds are also obtained in high yields through a similar cyclization process followed by oxygenation under mild conditions.     

Studies on the Synthesis of New 3-(3,5-Diamino-1-substituted-pyrazol-4-yl)azo-thieno[2,3-b]pyridines and 3-(2-Amino-5,7-disubstituted-pyrazolo[1,5-a]pyrimidine-3-yl)azothieno[2,3-b]pyridines

Coupling the diazonium salt of 3-amino-2-cyano-4,6-dimethylthieno[2,3-b]pyridine 1 with malononitrile 2 gave 2-cyano-3-(hydrazonomalononitrile)-4,6-dimethylthieno[2,3-b]pyridine 3 which then reacted with hydrazine compounds 4a-4h to yield corresponding 2-cyano-3-(3,5-diamino-1-substituted-pyrazol-4-yl)azo-4,6-dimethylthieno[2,3-b]pyridines 5a-5h. The 2-cyano-3-(2-amino-5,7-disubstituted-pyrazolo-[1,5-a]pyrimidine-3-yl)azo-4,6-dimethylthieno[2,3-b]pyridines 7a-7f were obtained in good yield by the cyclocondensation reaction of 2-cyano-3-(3,5-diamino-pyrazol-4-yl)azo-4,6-dimethylthieno[2,3-b]pyridine 5a with the appropriate 1,3-diketones 6a-6f under acidic condition.     

反式-2,5-二芳基四氢呋喃合成的新方法

以(±)4,10-二氧杂三环[5,2,1,0_2,6]-癸-8-烯-3-醇为原料,经过芳基化、氧化、芳基化、环化、热分解和加氢反应,得到PAF新的拮抗物反式-2,5-二芳基四氢呋喃,并合成了化合物8.     

Transition Metal Complexes with Bidentate Ligands Spanning trans-Positions. XII. Steric effects in the kinetics and mechanism of substitutions at hydride and methyl bisphosphine platinum (II) complexes

Ligand substitution reactions on square-planar platinum (II) complexes of the types trans-[PtRXL₂], trans-[PtR(4-PADA)L₂][BF₄], trans-[PtRX( ) and trans-[PtR(4-PADA)( )][BF₄] R=H, Me; X=Cl^?, I^?; L=PEt₃, bis(3-trifluoromethyl-phenyl)benzylphosphine ( 4 ), =the trans-spanning 2,11-bis[bis(3-trifluoro-methylphenyl)phosphinomethyl]benzo [c]phenanthrene ( 3 ); 4-PADA (=pyridine-4-azo-4′-(N, N-dimethyl)aniline have been studied at 30° using stopped-flow and conventional spectrophotometry, methanol as solvent, and 2.5 × 10^?2 M ionic strength (LiClO₄ as supporting electrolyte). 4-PADA was used as indicator ligand, as its absorption spectrum differs from those spectra where it is complexed. The expected steric effects of the bulky ligands, especially of 3 , on the rates and mechanisms of all the reactions studied are small. All reactions take place by the usual two-term rate law. Noteworthy, for the complexes with the bulky ligands 3 and 4 , the direct reaction path with the entering nucleophile is predominant. There is no preference for a solvent or dissociative path. The reactivity order for the hydride complexes is trans-[PtHX (PEt₃)₂]<trans-[PtHX( 4 )₂]<trans-[PtHX ( 3 )]. However, for the corresponding methyl complexes, there is some retardation by ligand 3 , probably due to an interaction between the methyl group and the hydrocarbon moiety of 3 , which inhibits the fluxional behavior of this ligand. The results have some relevance for the understanding of olefin-insertion reactions of hydride complexes containing these phosphine ligands.     

Electron ionization mass spectra of 8‐aryl‐3,4‐dioxo‐2H,8H‐6,7‐dihydroimidazo[2,1‐c][1,2,4]triazines. Do they exhibit tautomerism in the gas phase?

The electron ionization mass spectra of the title compounds (1: a R = H, b 2-CH(3), c 4-CH(3), d 2,3-diMe, e 2-OCH(3), f 4-OCH(3), g 2-Cl, h 3-Cl, i 4-Cl, j 3,4-diCl) were recorded at 70 eV to determine the effects of substituents and the possible keto-enol tautomerism. The compounds showed several common fragment ions but also fragment ions which divided them into three classes, namely 1a-1d (parent compound and Me-substituted derivatives), 1e and 1f (MeO-substituted derivatives), and 1g-1j (Cl-substituted derivatives). The presence of the HOCN(+.) ion as well as the exponential dependence of its total ion current in the case of p- and also 3-Cl-substituted compounds (1a, c, f, h-j) on the Hammett sigma constants and the loss of CHO or one or two HOCN moieties can be somewhat easier explained by the presence of the enol form but as a whole the results support the predominance of the keto form, in parallel to the situation in solution.     

α-羰基一硫代半缩醛与脂肪族脲反应合成2, 4-咪唑啉二酮衍生物

利用α-羰基一硫代半缩醛与脂肪基取代脲反应合成了六个新的咪唑啉二酮类衍生物。并用IR,NMR,MS和元素分析进行测定,最后用X四圆衍射仪确定了它们的结构。     

烯胺酮与氨基吡唑的反应：7-芳基-3-氰基-2-取代吡唑并[1,5-a]嘧啶的合成、结构及生物活性

利用3-取代-4-氰基-5-氨基-1H-吡唑分别与取代烯胺酮反应，合成了共12种新的2-取代-3-氰基-7-芳基吡唑并[1,5-a]嘧啶化合物。所有化合物的结构均经红外、核磁、元素分析进行表征。另外，利用X-单晶衍射对化合物4a的结构进一步加以确认。同时提出了反应可能的机理，并对部分化合物的除草活性进行了测试。     

Preparation of twelve 1-methyl-2-formyl-5-substituted pyrroles and their hydrazones

Preparation of twelve 1-methyl-2-formyl-5-substituted pyrroles (2a-1), with five of them as new compounds, is described. Their derivatives, i.e., 1-methyl-2-formyl-5-substituted pyrrole phenyl hydrazones (3a-1) and 1-methyl-2-formyl-5-substituted pyrrole (4-nitrophenyl) hydrazones (4a-1) are all new compounds. They have also been prepared and further identified.