1,5-二氮杂双环[4,3,0]壬碳-5-烯与全氟炔酸酯的反应及其产物的核磁共振研究

1，5—二氮杂双环[4，3，0]壬碳—5—烯(DBN)与全氟炔酸酯反应生成成环化合物。通过对成环产物的^1HNMR、^13C NMR及相关的2D NMR谱的分析，确证了该类化合物的结构，并讨论了其化学位移及J-偶合特征。同时提出了整个反应可能的历程和机理。     

无催化剂条件下的全氟烷基取代的1H-苯并[b][1,4]二氮-2(3H)-酮的简易合成

1,5-苯并二氮-2-酮作为一个独特的骨架广泛存在于很多具有生理活性的化合物中,而全氟烷基的引入影响到有机化合物的理化性质以及生理活性的改变.因此将全氟代烷基引入1,5-苯并二氮-2-酮的方法的研究正变得日趋重要.发展了一个制备全氟代烷基取代的1,5-苯并二氮-2-酮的简易方法.采用全氟代炔酸甲酯为含氟砌块,与邻芳基二胺,以无水甲苯为溶剂,在无催化剂存在条件下,80℃反应24 h,以较好的收率顺利得到4-全氟烷基-1,3-二氢-1,5-苯并二氮-2-酮类化合物.     

由全氟烷基联烯砜和硝酮偶极加成反应生成的一类特殊环加成产物

研究了全氟烷基联烯砜和硝酮的偶极加成反应。与不含氟的联烯砜不同，由于氟烷基的强吸电子性，使得全氟烷基联烯砜和硝酮在室温下即可发生反应，以很高的收率得到一类新颖的内盐环状产物。产物结构通过谱学数据和X-射线单晶衍射分析确定。     

BnNH2·TFA/1,4-二氮杂二环[2.2.2]催化Michael加成反应合成季碳-叔碳化合物

在BnNH2.TFA/1,4-二氮杂二环[2.2.2]辛烷催化下,α-取代的苄叉丙酮与α-取代β-酮酸酯发生Mi-chael加成反应,合成了季碳-叔碳化合物——α,α-双取代β-酮酸酯,其结构经1H NMR和13C NMR表征。     

全氟烷基膦酸锂电解液的制备与性能研究

选取氯代二异丙基膦(C6H14PCl)为原料, 利用电化学氟化方法, 得到全氟烷基膦酸[(C3F7)2PF3], (C3F7)2PF3与氟化锂(LiF)反应得到全氟烷基膦酸锂(Li[(C3F7)2PF4]), 将其溶于碳酸乙烯酯(EC)和碳酸二甲酯(DMC)质量比为1∶1的混合溶剂中得到电解液, 考察电解液的电导率、抗水性及氧化分解电位. 以LiCoO2为正极, 锂片为负极组装两电极模拟电池体系, 测试得到电池的放电平台为3.7 V; 电池的首次放电比容量为107 mA•h•g－1; 当循环放电40次后, 容量衰减较快, 电池循环50周后, 效率仍保持102%. 交流阻抗图谱表明电解液放电时的阻抗约为140 Ω. 研究结果表明, 全氟烷基膦酸锂有望成为新型锂离子二次电池的电解质盐.     

手性二环[3.3.0]辛-3-烯类化合物的合成

研究了5-(1-孟氧基)-3-溴-2(5H)-呋喃酮新手性源(1)与某些碳亲核试剂发生的串联不对称Michael加成/分子内亲核取代反应,反应中生成2个新的手性中心得到一般方法难以合成的光学纳二环[3.3.0]辛-3-烯类化合物.通过[α]、IR、UV、¹HNMR、¹³CNMR、MS、元素分析以及X射线四圆衍射等方法确定了手性二环[3.3.0]辛-3-稀类化合物化学结构和绝对构型.     

膦、胂叶立德的化学与应用 XII. 对硝基苯基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及(Z)3-全氟烷基 4-对硝基苯基-3-丁烯酸甲酯的立体专一性合成

溴化对硝基苄基三苯基 (1a)、 (1b)在碳酸钾存在下与2-全氟炔酸甲酯(2)在常温下反应, 生成加合物3(当M=As时)或3和4的混合物(当M=P时), 其中3的含量随反应温度升高而增加, 当反应温度为90℃时, 产物全部为3。4c加热时转化为3c。膦加合物3或4在甲醇-水中于封管内150℃加热, 发生P-C键断裂。两者都立体专一性地生成(Z)3-全氟烷基-4-对硝基苯基-3-丁烯酸甲酯(5)。胂加合物3在甲醇-水中回流, 发生As-C键断裂, 生成(Z)-5。对水解机理进行了研究。     

钌催化二环烯烃与炔烃的[2＋2]环加成反应的研究进展

综述了近年来钌催化二环烯烃与炔烃发生[2＋2]环加成反应的研究进展, 重点讨论了钌催化二环烯烃和炔烃的 [2＋2]环加成反应中反应物结构、反应物比例、溶剂及温度等因素对反应的影响.     

碳酸铯催化吡唑与α,β-不饱和酮的氮杂Michael反应

发展了一种碳酸铯催化吡唑与α,β-不饱和酮的氮杂Michael反应新方法.在5 mol%Cs2CO3存在下,于1,4-二氧六环中回流反应7~12 h,以86%~95%的产率得到21种β-(N1-吡唑基)酮.此法对芳香类和脂肪类α,β-不饱和酮均适用良好,易实现克级放大.产物可容易地转化为相应的γ-氨基醇.发展的方法同样适用于吡唑与丙烯酸甲酯和硝基苯乙烯的氮杂Michael反应.     

N-Acyl 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) tetraphenylborate salts as O-acylating agents

Air-stable and crystalline N-acyl DBN tetraphenylborate salts have been shown to be effective O-acylating agents, reacting with both primary and secondary alcohols to give the corresponding esters in good yields. In the case of diols, the N-acyl DBN·BPh₄ salts have been shown to acylate regioselectively the primary alcohol functionality in the presence of a secondary alcohol. The DBN hydrotetraphenylborate side product can be readily removed by filtration, providing the ester products without the need for further purification.     

Synthesis of cis-bicyclo[4.3.0]non-2-ene derivatives. The potent homoisocarbacyclin analogs

Synthesis of homoisocarbacyclin has been achieved efficiently by a general strategy with stereo- and regiochemical control. One of homoisocarbacyclin derivatives, 3-oxa homoisocarbacyclin analog (4), was shown to be potently active in inhibiting gastric ulcer. Another analog, conjugated diene derivative (5), was found to have a biological profile similar to prostacyclin.     

Friedel-Crafts acylation of pyrroles and indoles using 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) as a nucleophilic catalyst

1,5-Diazabicyclo[4.3.0]non-5-ene (DBN) has been shown to be an effective catalyst for the regioselective Friedel-Crafts C-acylation of pyrroles and indoles in high yields. A detailed mechanistic study implies that DBN is acting as a nucleophilic organocatalyst, with the X-ray crystal structure of a key N-acyl-amidine intermediate having been determined for the first time.     

Reaction and sensing of octafluorocyclopentene with 1,5-diazabicyclo[4,3,0]non-5-ene

Reactions of octafluorocyclopentene (C₅F₈) with 1,5-diazabicyclo[4,3,0]non-5-ene (DBN) are studied by analyses of an isolated product and optical spectra from the viewpoint of applications to gas-sensors. Obtained results suggest that nucleophilic reactions of DBN proceed toward the double bond of C₅F₈ molecule accompanied with hydroxide anion attack on carbon-fluoride bonds of C₅F₈ moiety under ambients, forming unique C₅F₈-modified adducts. The present reaction is conducive to a new type of technologies for quick and selective sensing that can be used to develop alarm systems in the field of the environment and etching processing factories.     

Trifluoromethanesulfonate,trifluromethylsulfonylimide, and bis(trifluoromethylsulfonyl)imide salts and ionic liquids based on 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-diazabicyclo[ 4.3.0]non-5-ene

Trifluoromethanesulfonate, trifluoromethylsulfonylimide, and bis(trifluoromethylsulfonyl)imide salts and ionic liquids were synthesized from 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine (1,8-diazabicyclo[5.4.0]undec-7-ene) and 2,3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidine (1,5-diazabicyclo[4.3.0]non-5-ene). Their physicochemical properties, spectral parameters, and some chemical transformations were studied.     

Iodine-Catalyzed Addition of Methyl Thioglycolate to Chalcones

Abstract

A series of novel β-mercapto carbonyl compounds (3a–z), methyl 2-(3-oxo-1,3-diarylpropylthio)acetate, were synthesized and characterized via iodine-catalyzed addition of methyl thioglycolate to chalcones (1a–z).

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Addition of bromine to 2-methyl-2-azabicyclo[2.2.1]hept-5-ene

Addition of bromine to 2-methyl-2-azabicyclo[2.2.1]hept-5-ene was studied. Unexpectedly, 3-bromo-1-methyl-1-azoniatricyclo[2.2.1.0^2,6]heptane tribromide was isolated rather than the product of bromine addition to the double bond. The former reacted with the starting alkene in a polar solvent to form the corresponding monobromide.