Synthesis of anti-9-Bromo- and anti-9-Chlorobicyclo[4.2.1]nonatriene via Bicyclo[4.2.1]nonatriene→Bicyclo[4.2.1]nonatriene Rearrangement

The first syntheses of 9-bromo- and 9-chlorobicyclo[4.2.1]nona-2,4,6-trienes were each achieved in three stereoselective steps from the 9,9-bis(selenophenyl) derivative 9 in 79% overall yield for the bromide and 64% for the chloride. A deuterium-labeling experiment reveals the first rearrangement of a bicyclo[4.2.1]nonatriene which leaves the ring system intact.     

9-Phospha-bicylco [6.1.0] nona-2,4,6-triene 9-Phospha-bicylco [4.2.1.] nona-2,4,7-triene

The synthesis of the title compounds with substituents R=Alkyl, Cl, H by reaction of COT^2? with RPCl₂ at ?70°C is described.     

The Synthesis and Chemistry of 8-Substituted Bicyclo[5.1.0]oct-1(8)-ene

8-Bromobicyclo[5.1.0]oct-1(8)-cne (7), an intermediate for the preparation of 8-substituted bicyclo[5.1.0]oct-1(8)-enes, was synthesized by denomination of 1,8,8-tribromobicyclo[5.1.0]octane (6). Compound 7 underwent bromo-lithium exchange followed by nucleophilic substitution reactions to generate bicyclo[5.1.0]oct-1(8)-ene (5), 8-methylbicyclo[5.1.0]oct-1(8)-ene (10), and 8-trimethylsilylbicyclo[5.1.0]oct-1(8)-ene (11). The bicyclic cyclopropenes 7, 5, 10, and 11 reacted with cyclopentadiene to form adducts 12, 13, 14, and 15, respectively. All of these Diels-Alder adducts are endo-exo isomers (endo-addition from the view of the cyclopropene and exo-addition from the view of the cyclooctene).     

Sequential thermal rearrangements of syn-9-vinyl-bicyclo[6.1.0]-nona-2,4,6-triene

The title compound 1-syn at 65°C undergoes a cascade of thermal rearrangements to yield tetracyclo[5.4.0.0.^2,11O^4,10]undeca-5, 8-diene (5). The kinetics for the isomerization of the intermediate bicyclo(4.3.2]-undeca-2,4,7,10-tetraene (3) have been measured.     

Synthesis of (perfluoroalkyl)aryliodonium sulfonates [1]

(Perfluoroalkyl)aryliodonium halides [2] and -tetra- fluoroborates [3] were previously synthesized. We now wish to report the synthesis of several kinds of (perfluoroalkyl)aryliodonium sulfonates which are important as electrophilic perfluoroalkylating agents [4].     

[Z]-2-(芳基锡基)-1-(9-芴醇)乙烯的合成、结构与性质

用三苯基氢化锡,三对甲苯基氢化锡作为锡氢化试剂与9-乙炔基-9-芴醇进行反应,合成了2个有机锡化合物:[Z]-2-(三苯基锡基)-1-(9-芴醇)乙烯(1)和[Z]-2-(三对甲苯基锡基)-1-(9-芴醇)乙烯(2)。化合物1和2分别与ICl,Br~2,I~2反应,得到6个有机锡一卤化物,6个有机锡二卤化物和2个有机锡混合卤化物(3-16)。有机锡一碘化物7,13和有机锡二碘化物8,14与KOH乙醇溶液反应,分别得到相应的有机锡氢氧化物17,18和有机锡氧化物19,20。有机锡二碘化物8,14分别与含氮双齿配体1,10-邻菲罗啉(Phen),2,2'-联吡啶(Bipy),8-羟基喹啉(Oxin)反应,得到6个相应的配合物21-26。26个新化合物通过元素分析,锡含量测定,IR,^1HNMR测定对其结构进行了表征。同时测定了化合物2的晶体结构,晶体属单斜晶系,空间群P2~1/c。化合物2是以Sn原子为中心扭曲的四面体构型。     

9-phenylbicyclo[6.1.0]nonatetraenyl anion: A new diatropic 10 π-electron system

Treatment of 9-chloro-9-phenylbicyclo[6.1.0]nona-2,4,6-triene with excess bases gives, by the intermediacy of 9-phenylbicyclo[6.1.0]-1-(9),2,4,6-tetraene, 9-phenylbicyclo[6.1.0]tetraenyl anion of which ¹H-NMR spectrum suggests some diatropic character of the molecule.     

制备2-O-[1(R)-(9-次夹氧蒽基)-2-羟基乙基]丙三醇的新方法

以肌苷为底物,用两种性质相反的聚合物支载的高碘酸根离子和硼氢要离子一锅法合成了２－Ｏ－「１（Ｒ）－（９－次夹氧蒽基）－２－羟基乙基」丙三醇。该法具有操作简便,反应条件温和,缩短合成中线,无须分离中间体、产率较高等特点。     

1,4-双正丙氧基柱[7]芳烃的合成及主客体化学

我们以1,4-二正丙氧基-2,5-双甲氧甲基苯为原料用对甲苯磺酸为催化剂在二氯甲烷中制备了1,4-双正丙氧基柱[5]芳烃, 1,4-双正丙氧基柱[6]芳烃和1,4-双正丙氧基柱[7]芳烃. 我们用氢谱, 碳谱和质谱对它们进行了表征. 它们有不同的氢谱却有相似的碳谱. 对比它们的空腔尺寸, 柱[5]的内径大约是4.6 Å, 与葫芦脲[6]及α-环糊精类似. 柱[6]的内径大约是6.7 Å, 与葫芦脲[7]及β-环糊精类似. 柱[7]的内径大约是8.7 Å, 与葫芦脲[8]及γ-环糊精类似. 我们用正辛基三乙基六氟磷酸铵盐作为模型客体研究了它们之间的主客体络合. 柱[5]与之有微弱的络合, 柱[6]显示了良好的络合, 而柱[7]与之没有络合.     

Synthesis of 8-methoxy-1-methyl-1H-benzo[de][1,6]naphthyridin-9-ol (Isoaaptamine) and analogues

8-Methoxy-1-methyl-1H-benzo[de][1,6]naphthyridin-9-ol, isoaaptamine, a PKC inhibitor isolated from sponge was synthesized. The synthesis parallels a synthesis of 8,9-dimethoxybenzo[de][1,6]naphthyridine, aaptamine, but uses a nitromethyl substituent as a precursor of the key 5-(2-aminoethyl)-1H-quinolin-4-one intermediate. The quinolone intermediates were prepared by thermolysis (220-240 degrees C) of anilinomethylene derivatives of Meldrum's acid. The quinolone intermediates were N-methylated prior to cyclization to the benzo[de][1,6]naphthyridine derivatives. Aaptamine and several analogues of aaptamine and isoaaptamine were prepared including 9-demethylaaptamine, 1-methyl-8-demethylaaptamine, 1-methylaaptamine, and the 8,9-methylenedioxy analogues of aaptamine and 1-methylaaptamine.     

Chemistry of pyrido[c]coumarins (review)

Summary Information on methods of synthesis and the chemical conversions of pyrido[c]coumarins has been correlated and arranged systematically.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1011-1033, August, 1994.     

Intramolecular C-Alkylation Using a Vinyl Thioether. The Regiospecific Synthesis of Methyl 3-Methyl-9-Oxobicyclo [3, 3, 1] Non-2-ene 1-Carboxylate

As a model for the total synthesis of the unusual Lycopodium alkaloid selagine (I) ^1,2 we required a convenient and regiospecific route to methyl 3-methyl-9-oxobicyclo [3, 3, 1] non-2-ene 1-carboxylate (II). Whereas the corresponding 3-ene (III) is readily accessible by conventional Michael addition of 2-carbomethoxycyclohexanone enolate to methacrolein followed by aldol cyclization and dehydration,³ construction of the desired 2-ene would require the inverse regiochemistry in the Michaelaldol sequence.