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Starting from 3-benzoyl-5-formyl-indolizine, 3-benzoyl-5-(2'2'-diacetylethenyl)-indolizines and analogs were obtained by the 〓mediated aldol condensation or Wittig reaction. These compounds,promoted by low-valent titanium, gave highly functionlizedcycl[3,2,2]azine derivatives. The coupling reaction proceeded betweenthe carbonyl group and the carbon-carbon double bond, a rare example inMcMurry reaction.
我们以3-苯甲酰基-5-甲酰基中氮茚为原料,通过三碘化钐促进的aldol反应和Wittig反应制备了3-羰基-5-羰基乙烯基中氮茚,随后经低价钛还原偶联,没有生成正常的分子内羰基-羰基偶联产物,而是得到反常的羰基与α,β-不饱羰基的双键偶联产物,较高收率地得到了含多官能团的CycI[3,2,2]azine衍生物。
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The degradation and removal of nitrogenous heterocyclic compound-pyridine under aeration stripping, aerobic, anoxia, anaerobic conditions and co-metabolism with quinoline, 2-methylpyridine, aniline, indene, naphthalene in A2/O process were conducted by flask-shaking tests.
通过摇瓶试验研究了氮杂环化合物吡啶在曝气吹脱、好氧、缺氧和厌氧条件下的降解规律以及吡啶与喹啉、2-甲基吡啶、苯胺、茚和萘共代谢条件下在A2/O工艺中的去除规律。
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In this thesis,the AM1,MNDO,MINDO/3(mainly AM1)and INDO/S-CI semiempirical MO methods were used toinvestigate the excited-state intramolecular protontransfer reactions of salicylic acid derivatives—salicylic acid,methyl salicylate,salicylaldehyde,o-hydroxyaceto-phenone,salicylamide and 3-hydroxy-picolinamide (6 conformers and 2-3 anion species);2-(2'-hydroxy-5' methylphenyl) benzotriazole(4 conformers),2-(2' hydroxyphenyl) benzimidazole (3 conformers and 3anion species),Bis-2,5-(2-benzoxazolyl)hydroquinone(3 conformers),2-(2'-hydroxyphenyl)benzothiazole(2conformers) and 7-azaindole dimer (2 conformers).Theinvestigations were described as follows.Geometry optimization,relative stability andhydrogen bonding energy First,for sylicylic acid derivative molecules,the AM1,MNDO and MINDO/3 methods were used toinvestigate ground-state geometry optimization,energies,relative stabilities and hydrogen-bondingenergies on the five kinds of the molecules(designing 6 conformers and 2-3 anion species).Comparing with experimental data,the optimizedgeometry,the order of stability,the hydrogen-bonding energies and the distances between O-O in O-H..O hydrogen bonds by AM1 method were in agreementwith the experimental data,however,the C-C bondlengths optimized by MNDO and MINDO/3 were longer,C-O and O-H bond lengths were shorter;for C-N bondlengths,the results opitimized by MNDO method werethe same as those by AM1 method,nevertheless the C-Nbond lengths given by MINDO/3 method were muchshorter.For some sylicylic acid derivatives(e.g.methyl salicylate,salicylamide),the order ofstabilities on the conformers given by MNDO andMINDO/3 methods were not in agreement with theexisting conformers deduced by experimental methods,and the hydrogen bonding energies calculated by MNDO.and MINDO/3 methods were smaller.Second,the studyon the other systems found that the optimizedgeometry of the proton-transfered product with INDOmethod could not be obtained,only could theoptimized geometry of reactant be obtained,and thecalculated hydrogen bonding energies were greater.Many results of calculation indicated that the studyon the excited-state intramolecular proton transferreaction system using AM1 method was suitable andreliable.
本论文用AM1、MNDO、MINDO/3(主要是AM1)和INDO/S-CI半经验分子轨道方法对水杨酸衍生物系列——水杨酸、水杨酸甲酯、水杨醛、O-羟基乙酰苯酮、水杨酰胺和3-羟基吡啶酰胺(6种异构体和2-3种阴离子);2-(2'-羟基-5'-甲基苯基)苯并三〓唑(4种异构体);2-(2'-羟基苯基)苯并咪唑(3种异构体和3种阴离子);2,5-二间氮杂氧茚氢醌(3种异构体);2-(2'-羟基苯基)间〓杂硫茚(2种异构体)和7-〓吲哚二体(2种异构体)的激发态分子内质子转移反应在以下几个方面进行了较系统的理论研究:几何构型优化和相对稳定性及氢键能首先以水杨酸衍生物系列分子为例,用AM1、MNDO和MINDO/3方法考察了5种分子(每种分子设计6种异构体和2-3种阴离子)的基态几何构型优化,能量、相对稳定性和氢键能计算,通过和实验数据进行比较,AM1方法给出的优化几何构型、稳定性次序、氢键能和O—H。。。O氢键的0—0距离与实验数据吻合最好,MNDO和MINDO/3方法优化的C-C键长偏长,C-O键和O-H键长偏短;对于C-N键长,MNDO和AM1优化结果差别不大,而MINDO/3给出了过短的C-N键长,MNDO和MINDO/3方法给出的有些水杨酸衍生物分子(如水杨酸甲酯和水杨酰胺)异构体的稳定性次序和实验上推测的可存在异构体结果不一致,MNDO和MINDO/3方法给出的氢键能偏低,对其他体系的研究发现INDO方法常常不能得到质子转移产物的优化几何构型,只能得到反应物的优化构型,并且估算的氢键能偏高,大量的计算结果表明AM1方法对本论文研究的激发态分子内质子转移反应体系是适宜和可靠的。
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The 6- cyano-1, 1 (1, 3- dioxypropylidene)-7-(carbomethoxyl group- methyl - 5- oxo-Delt6 (8)- tetrahydrochysene indolizine and haloethane reacts with each other for ethylization with existence of alkali and organic solution with or without phase transversion catalyst, and produces mentioned product.
本发明在相转移催化剂或无相转移催化剂存在下,6-氰基-1,1-(1,3-亚丙二氧基)-7-(甲氧羰基-甲基-5-氧代-Δ6(8)-四氢中氮茚类化合物与卤代乙烷在碱和有机溶剂的存在下进行乙基化反应即得6-氰基-1,1-(1,3-亚丙二氧基)-7-1′-(烷氧羰基-丙基-5-氧代-Δ6(8)-四氢中氮茚类化合物。
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The preparation method comprises removing benzyl of the compound IV0 in alkali condition to obtain the compound (V, reacting the compound with benzyl chloroformate to obtain the compound, wherein the compounds can be used to prepare 5-substituted-hydride indolizine natural alkaloids.
本发明所提供的制备方法是将化合物在碱性条件下去苄基得到的化合物,将化合物与氯甲酸苄酯反应,生成的化合物。和化合物可以用于制备5-取代-氢化中氮茚天然生物碱。
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A general method for preparing multi-cyclic indolizine compounds(1a—1c, 2a—2b and 3) in moderate yields(45%—71%) by a 1,3-dipolar cycloaddition reaction of pyridinium N-ylides, isoquinolinium N-ylides or quinolinium N-ylides to 1,4,4a ,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione, followed by an aromatization, in the presence of tetrakispyridine cobalt dichromate is described.
在 [ 4Co( HCr O4 ) 2 ]存在下,吡啶叶立德、喹啉叶立德或异喹啉叶立德分别和 1 ,4,4a,8a-四氢-1 ,4-桥亚甲基萘-5 ,8-二酮反应,一步法合成了中氮茚类多环化合物( 1 a~ 1 c,2 a~ 2 b,3 )。该方法原料易得,反应条件容易控制,为合成这类化合物提供了新方
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A one-step method for the synthesis of aromatic indolizine derivatives byintramolecular 1,5-dipolar cyclization reaction of 2-(2-arylethenyl)pyridinium N-ylidesin the presence of an oxidant has been studied for the first time. In the presence ofelectron-deficient olefins, however, 2-(2-phenylethenyl)pyridinium N-ylides underwent1,3-dipolar cycloadditions and then aromatized in situ by TPCD to produce indolizinederivatives, indicating 1,3-dipolar cycloaddition proceed more readily than 1 ,5-dipolarcyclization in these conditions. Pyridinium disubstituted N-ylides, readily obtainedfrom corresponding pridinium and β-chlorovinyl ketone, underwent thermalintramolecular 1,5-dipolar cyclization to give indolizine derivatives easily.Indolizinecarbaldehyde derivatives were synthesized starting from 2-pyridinecarbaldehyde in four-steps involving 1,3-dipolar cycloaddition reaction.
本文首次研究了2-(2-芳基乙烯基)吡啶N-叶立德在氧化剂存在下的分子内1,5-偶极环化反应,采用一锅法合成了中氮茚衍生物;研究了这些N-叶立德的1,5-偶极环化和1,3-偶极环加成反应的选择性,发现当有缺电子烯烃存在时,优先进行1,3-偶极环加成反应,而不再发生分子内1,5-偶极环化反应;由β-氯乙烯酮方便地得到了烯丙基N-叶立德,他们在加热时进行分子内1,5-偶极环化反应而得到中氮茚衍生物;由2-吡啶甲醛为起始原料,通过1,3-偶极环加成反应等四步反应,得到了重要的中氮茚甲醛衍生物,这些反应都具有条件温和和操作简便的特点,是合成中氮茚衍生物的新方法。
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Finally, we found that cycl[3.2.2]azines can be synthesized by carbonyl-couplinreactions using low valent titanium compounds from indolizinecarbaldehydderivatives.
最后,本文由中氮茚甲醛衍生物通过低价钛偶联反应,合成得到了cycl[3.2.2]azines,这是一条全新的合成cycl[3.2.2]azines的方法。
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We developed a new method for the synthesis of cycl[3,2,2]azines.Using oxidant promoted 1,3-dipolar cycloaddition reaction, 3,5-dicarbonyl-indolizines were prepared. By treating with low-valenttitanium, cycl[3,2,2]azines were obtained in high yields.
我们通过l,3—偶极加成反应合成了多种3,5-二羰基中氮茚,然后在低价钛试剂作用下还原偶联,以较高收率得到各种取代Cycl[3,2,2]azine,开发了一种全新的Cycl[3,2,2]azine合成法。
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When 3-benzoyl-5-formyl-indolizine or ethyl 5-benzoyl-indolizine-3-carboxylatewere used as substrates, a novel coupling reaction occurred, givinghydroxy-cycl[3,2,2]azines. A mechanism of the reaction was proposed.
其中3-苯甲酰基-5-甲酰基中氮茚和5-苯甲酰基-3-中氮茚甲酸乙酯在低价钛试剂的作用下,发生了新奇的偶联反应,得到了用其它方法难以制备的Hydroxy-cycl[3,2,2]azine,并对此现象作了解释。
- 更多网络解释与氮茚相关的网络解释 [注:此内容来源于网络,仅供参考]
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benzimidazole:苯并咪唑,间(二)氮茚
benziloyl | 二苯乙醇酰基 | benzimidazole | 苯并咪唑,间(二)氮茚 | benzimide | 苯甲亚胺
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indenoestrol diacetate:二醋酸茚雌酚
二醋水杨酸 Diacesalyl | 二醋酸茚雌酚 Indenoestrol Diacetate | 二氮嗪 Diazoxide