氮杂二烯光化学反应合成喹啉衍生物

综述了以氮杂二烯为原料,光化学反应合成喹啉衍生物的最新进展.参考文献18篇.     

硅杂苯与亲二烯体的Diels-Alder反应

采用密度泛函理论(DFT)在B3LYP/6-311G(d,p)水平上研究了硅杂苯与一些亲二烯体的两类可能的Diels-Alder反应的微观机理、势能剖面、取代基效应和溶剂化效应. 计算结果表明, 所研究反应均以协同的方式进行. 亲二烯体分子碳原子上的苯基取代基对两个新键形成的非同步性和反应的活化能垒的影响取决于苯基在产物中的相对位置, 而硅杂苯分子中硅原子上的CCl3取代基有利于杂Diels-Alder反应的进行. 形成一个C—Si键的杂Diels-Alder反应在热力学和动力学上均远比相应的全碳Diels-Alder反应容易进行, 实验观察到的杂Diels-Alder反应中的区域选择性由动力学因素所控制. 硅杂苯与烯烃的反应比与相应炔烃的反应在动力学上容易进行一些, 但在热力学上后者远比前者容易进行. 苯溶剂对所研究反应的势能剖面影响较小.     

杂原子烯反应研究进展

烯反应是有机合成中简单而用途广泛的反应之一。杂原子烯反应是该反应的重要组成部分。本文主要综述了含氮、氧、硫、磷、硅等杂原子烯组分参与的杂原子烯反应的研究现状。     

二苯并四氮杂轮烯金属配合物及其亲电取代反应性能

本文用量子化学半经验方法和从头算研究二苯并四氮杂[14]轮烯离子及其金属配合物，讨论了轮烯配合物的活性位置。^1HNMR谱表明Lunxi-Ni配合物中金属离子对位C7、C16上的H原子被取代，与理论计算结果一致。     

过渡金属催化氮杂二环烯烃不对称开环反应的研究进展

综述了近年来过渡金属催化氮杂二环烯烃的开环反应的研究进展,重点讨论了过渡金属催化剂的种类、亲核试剂的类型、配体、底物氮杂二环烯烃及其衍生物的结构、溶剂和添加剂等因素对开环反应的影响,并对开环反应的可能的机理进行了讨论.     

制备二氮杂冠醚和三氮杂冠醚的新方法

以糖精为原料合成二氮杂冠醚和三氮杂冠醚。使糖精与二甘醇或三甘醇二氯化物和N,N-二(β-氯乙基)丁胺的DMF溶液在少量碘化钾存在下烃化、氨解,再用二甘醇或三甘醇的二对甲苯磺酸酯烃化生成保护的冠醚环。后者与20％盐酸作用除去保护基生成游离的环体。此法合成路线短原料价廉易得。二氮杂18-冠-6总产率37％左右。     

氮杂Wittig反应的最近进展

综述了最近几年氮杂Wittig反应的研究进展,包括分子间氮杂Wittig反应、分子内氮杂wittig反应及串联的氮杂Wittig反应。讨论了氮杂Wittig反应在一些含氮杂环、稠杂环及天然产物合成中的应用。     

三蝶烯衍生的双氮杂双氧杂杯芳烃的合成与结构

2,7-二氨基三蝶烯、2,7-二羟基三蝶烯与杂环化合物如三聚氰氯、1,5-二氟-2,4-二硝基苯和2,6-二氯-3,5-二氰基吡啶等通过两步芳香亲核取代反应得到系列双氮杂双氧杂杯芳烃大环分子. 通过核磁谱以及X射线单晶衍射研究其在溶液中及固态下的结构以及组装行为.     

含四氮杂十四轮烯的Li／SOCl2电池的研究

含四氮杂十四轮烯的Ｌｉ／ＳＯＣｌ２电池的研究章福平胡祝庆纪佩珍吴俭俭（浙江丝绸工学院纤维分院杭州３１００３３）关键词锂电池亚硫酰氯四氮杂十四轮烯过渡金属离子的有机大环络合物如Ｍ－ＰＣ［１，２］，Ｍ－ｐｏｒｐｈ［２］，Ｃｏ－ＴＡＡ［３］等掺入炭阴极后，...     

Highly diastereoselective intramolecular Diels-Alder reaction of chiral silatrienes

New Si-chiral 2-silahexa-3,5-dienyl acrylates were prepared in six steps from dichloro(chloromethyl)methylsilane. The EtAlCl₂ catalysed intramolecular Diels-Alder reaction of these compounds gave chiral 4-sila-4a,7,8,8a-tetrahydroisochroman-1-ones in good yield. Very good diastereoselectivity was observed for a silatriene bearing a methyl and a 2-methoxyphenyl substituent on the chiral silicon atom.     

Asymmetric intramolecular Diels-Alder reaction of a sulphoximine-substituted triene

The synthesis and thermally-induced intramolecular Diels-Alder (IMDA) reaction of (S)_s-(+)-S-[(1E,7E)-1,7,9-decatrienyl]-S-phenyl-N-(p-tolylsulphonyl)sulphoximine 4 is described. A model is proposed for the cis-selectivity of the cycloaddition based on previous results from the reactions of sulphonyl-substituted trienes. The stereochemistry of the major cis-fused cycloadduct is determined by single-crystal X-ray analysis of that obtained from reaction of racemic 4.     

Synthesis and Diels-Alder reaction of a sapphyrin derivative

Sapphyrins participate in Diels-Alder reactions with pentacene affording novel barrelene-fused sapphyrins. The new compounds were synthesized using traditional heating and microwave irradiation conditions. The experiments carried out under microwave irradiation proved cleaner, affording only the monoadduct and in higher yields.     

The reaction of selenoaldehydes with 2-methoxyfuran using their generation by retro Diels-Alder reaction

Selenoaldehydes, regenerated by thermal retro Diels-Alder reaction of anthracene cycloadducts under neutral conditions, reacted with 2-methoxyfuran to give methyl penta-2,4-dienoates along with the deposition of elemental selenium. In a similar reaction with 2-methoxyfuran using thioaldehyde, thiirane compound was isolated. This suggests the formation of selenirane intermediates in the above reaction.     

Intramolecular hetero Diels-Alder reactions of vinyl allenes and aldehydes

Compounds containing a vinyl allene moiety linked to an aldehyde by a tether have been synthesised and shown to undergo the intramolecular hetero Diels-Alder reaction. Only one compound with stereochemistry consistent with an exo approach of the dienophile to the dienic portion of the vinyl allene was obtained in each case. Depending on the length of the tether and on the substitution pattern on the allene the reactions were spontaneous at room temperature or required heating or the presence of a Lewis acid to proceed.     

Novel porphyrin-quinazoline conjugates via the Diels-Alder reaction

Novel derivatives of meso-tetraphenylporphyrin with appended quinazoline moieties were synthesized, via the Diels-Alder reaction, between a 4-(porphyrinyl)pyrimidine ortho-quinodimethane and 1,4-benzoquinone, 1,4-naphthoquinone and N-(p-nitrophenyl)maleimide. The structure of one bis adduct was established by X-ray crystallography and mass spectrometry. We have unequivocally confirmed that the 2:1 adducts obtained from the reaction of pyrimidine-fused 3-sulfolenes with N-arylmaleimides have an open-chain structure and not a cyclooctapyrimidine structure, as previously published.     

Intramolecular Diels-Alder reaction of 1-aminoisobenzofurans: Application to the synthesis of benzo[c]phenanthridines

Intramolecular Diels-Alder reactions of 1-aminoisobenzofurans give benzo[c]phenanthridines. The reactive intermediates are generated from o-(diazomethyl)benzamides.     

Total synthesis of suaveoline and norsuaveoline via intramolecular oxazole-olefin Diels-Alder reaction

Total synthesis of two Rauwolfia alkaloids, suaveoline (1) and norsuaveoline (2), has been achieved through a highly stereoselective route starting from l-tryptophan methyl ester (9) and exploiting the intramolecular Diels-Alder reaction of the oxazole-olefin 16.     

Intramolecular Diels-Alder reaction leading to tricyclic derivatives as intermediates of natural products synthesis

Tricyclic compounds 4a and 4b possessing a bicyclo[4.3.0] moiety, were successfully synthesized by using the intramolecular Diels-Alder reaction. The siloxy- rather than acyloxy-substituents increased the ratio of the endo-cylcoadducts 10 and 12. The oxygen substitution of 9 influenced conformation of the transition state, which was stereochemically restricted by the butenolide moiety. In addition, 9b carrying a hydroxyl group also produced 10b in a similar ratio to 9a. Compound 11 was the only exo-adduct produced in all of the entries.     

Fluoropropenoates as dienophiles in the Diels-Alder reaction

Several fluorinated alkenes were prepared from known ethyl (R)-2-fluoro-4,5-dihydroxyisopropylidine-2-pentenoate (1). The fluoroalkenoates were tested as dienophiles with several dienes and showed cycloaddition only with the very reactive diene, 1,3-diphenylisobenzofuran (5). Fluorobutenolide 2 reacted with 5 to produce the endo-syn adduct 9 in a highly stereoselective manner.