多氟芳烃的亲核反应 Ⅱ.一氯五氟苯的亲核环化

本文报道一氯五氟苯与双官能团亲核试剂反应制备环化产物的研究结果,发现应用 NaH-DMF 体系制备醇钠,有利于亲核反应的顺利进行,环化产物产率有较大幅度提高.     

α-和β-三氟萘乙烯的热二聚 阻旋异构体的生成

α-和β-三氟萘乙烯在120℃下热二聚,产物用HPLC分离。对β-三氟萘乙烯,可分离到三个纯的二聚体。而对α-三氟萘乙烯,虽然分离到的热二聚产物也是三个组分,但其中一个仍然是混合物。由~(19)F,~1HNMR,MS分析表明是环化二聚产物,即1,2-二萘六氟环丁烷的反式及顺式阻旋异构体。     

5-(2,4-二氯苯氧亚甲基)-2-芳酰胺基-1,3,4-噻二唑的合成

研究了对1-(2,4-二氯苯氧乙酰基)-4-芳酰基氨基硫脲的酸催化环化, 它在酸催化下的环化是定向进行的, 环化途径是生成中间体后脱水而得到5-(2,4-二氯苯氧亚甲基)-2-芳酰胺基-1,3,4-噻二唑, 产物的结构经元素分析, 红外, 核磁以及质谱方法确证。     

丁基苯的三氟化钴气相氟化

以元素氟、高价金属氟化物和电化氟化链状有机化合物往往得到许多副产物,而主要产物产率较低,通常认为氟化时伴随有链的降解,重排和聚合等副反应.以三氟化钴进行氟化只有少量环化产物生成.近年来由于分离技术的提高,对复杂的氟化产物进行分离鉴定、探讨氟化机理从而提高反应得率,使氟化反应进一步得到开发利用.我们将丁基苯以三氟化钻进     

通过碳-碳键形成杂环的合成方法及应用

综述了包括五种带电荷中间体通过碳-碳键形成杂环的反应:(1)亚胺翁离子-乙烯基硅烷的环化反应,(2)亲核试剂引发的亚胺翁离子-炔的环化反应,(3)缩醛-烯烃的环化反应,(4)aza-Cope-Mannich反应,(5)通过Prins-pinacol重排合成环醚的反应;以及这些反应在有机合成特别是在天然产物全合成研究的进展。     

三氟苯乙烯及其二聚体的化学 3.溶剂对α;β;β,-三氟苯乙烯热环化二聚反应动力学参数的影响

在393K下,测定了三氟苯乙烯在六种溶液中的热环化二聚反应的速率常数,并在其中的三种溶液中测定了速率常数的温度依赖性。反应产物为顺式与反式1,2-二苯基全氟环丁烷。反应速率常数根据Arrhenius方程计算,在n-C_6H_(14)溶液中,其logA为6.02±0.18,E_a为19.5±0.3(kcaal·mol~(-1));在乙二醇二甲醚溶液中,logA为5.31±0.19,E_a为18.0±0.3(kcal·mol~(-1));在甲醇溶液中,logA为4.93±0.13,E_a为17.1±0.3(kcal·mol~(-1))。三氟苯乙烯的热环化二聚反应按双自由基机理进行。     

多氟烯烃和炔烃的钯催化氢化

本文报道Pd/Al_2O_3(1%)催化剂催化氢化CF_3CCl=CClCF_3,CF_3CCI==CHCF_3和CF_3C=CCF_3等多氟烯烃和炔烃的结果。经1~H和(19)~F核磁共振、质谱、红外等分析,证明了用制备色谱分离后的氢化产物主要成份的结构。前二者的氢化产物中主要是CF_3CH_2CH_2CF_3和CF_3CH_2CHClCF_3的混合物,而CF_3C=CCF_3氢化后只生成CF_3CH_2CH_2CF_3。     

1,1-二氯-4,8-二甲基-1,3,7-壬二烯的酸催化环化反应

在多烯的酸催化环化反应中,类似于Ⅰ的结构的单萜类衍生物的酸催化环化产物通常均为α-和β-异构体的混合物,如由柠檬酸制备环柠檬醛^[1],由伪紫罗兰酮制备紫罗兰酮^[2],…….虽然依具体反应条件的不同,两种异构体的比例可以有所改变,但欲得到无双键异构的单一产物往往比较困难.     

苯乙烯内酯类天然产物的全合成进展

结合本研究小组的相关课题工作，综述了苯乙烯内酯类天然产物全合成方法的 研究进展。主要包括以呋喃甲醇类化合物的氧化重排反应、烯烃复分解环化反应（ RCM）和酸催化的酯化关环等作为关键反应的方法。     

4-甲基和4-三氟甲基烟酸的合成工艺研究

以乙酰乙酸乙酯和三氟乙酰乙酸乙酯与氰基乙酰胺为原料,经环化、氯化、水解、催化氢解脱卤得目标产物4-甲基烟酸和4-三氟甲基烟酸,中间体及目标产物结构由IR,MS和1H-NMR表征。     

碳苷研究XXVI:异黑豆素类似物的合成

本文首次报道了异黑豆素类似物, 6-非环糖基-4',7一二羟基黄酮的合成, 以2,4-二羟基苯甲酸为原料, 溴化和脱羧后以苄基作为羟基保护基, 通过Grignarcl反应获得具有各种不同侧链的中间体7,7氢解脱除苄基再用Fries重排或Frieclel-Crafts反应得到了C-Z酰化产物, 接着用碱缩合生成查尔酮, 经I2/H2SO4/DM SO氧化环合得到目标产物。     

冠醚菁染料的研究V.苯并咪唑冠醚衍生物的合成

Crown ether cyanine dye precursors I (R = Et, CH2CH2OH; X = I, Cl, (CH2)3SO3) were prepared and characterized by elemental anal., NMR, and IR spectroscopy. The unquaternized I was prepared by cyclization of 4,5-dinitrobenzo-15-crown-5 in the presence of AcOH followed by ethylation in the presence of KOH.     

二氧化碳: 一种同时提供亲核中心保护和亲电中心活化的试剂 XI:2-取代四氢噻唑的新合成方法

四氢噻唑和正丁基锂反应生成的N-锂代四氢噻唑(2)与二氧化碳作用生成N-羟酸锂盐3; 3然后在叔丁基锂作用下失去2-位质子形成相应的2-位碳阴离子4; 该碳阴离子和一系列亲电试剂反应, 并在酸性条件下除去保护基团得产物-2-取代四氢噻唑7. 在此过程中, 二氧化碳既是氨基的保护基团, 同时又活化了2-位亲电中心.此方法不需分离各步中间体, 产率中等.     

吲哚并喹嗪衍生物的立体选择性合成

用锂铝氢四还原卟啉得到卟啉醇,它与甲乙酮反应得相应的羟甲基氨基酮,在相转移条件下,它能被转化成光学纯吲哚并喹嗪衍生物.列出了环化机理的反应流程.     

The nucleophilic reaction of polyfluoroaromatic compounds: II. The nucleophilic cyclization of chloropentafluorobenzene

The results of cyclization reaction between chloropentafluorobenzene and bifunctional nucleophiles such as XCH₂CH₂OH(X=OH, NHMe, NHEt) and HN (CH₂CH₂OH)₂, NH₂CH₂CH₂NH₂ were reported. It was found that the NaH/DMF system was a better reagent for the preparation of sodium alcoholates and the yields of cyclic products ranged from 50–80% which were much higher than that reported by previous workers.³     

The behavior of oxygen as a collision-induced dissociation target gas

The unusual and unique ability of O2 as target gas in kV collision-induced dissociations, to enhance a specific fragmentation of a mass selected ion, has been examined in detail. The affected dissociations studied were the loss of CH3* from CH3CH+X (X = OH, CH3, NH2, SH); CH3* and C1* loss from CH3C+(C1)CH3; C2H5* loss from CH3CH2CH+X (X = OH and NH2); H* loss from +CH2OH and +CH2NH2; O loss from 1,2-, 1,3-, and 1,4-C6H4(NO2)2+*; CH3NO+*; C6HsNO2+*; C5H5NO+* (pyridine N-oxide); 3- and 4-CH3C5H4NO+*. A general explanation of the phenomena, which was semiquantitatively tested in the present work, can be summarized as follows: the ion - O2 encounter excites the target molecules to their 3sigma(g)- state which resonantly return this energy to electronic state(s) in the ion. The excited ion now contains a sharp excess of a narrow range of internal energies, thus significantly and only enhancing fragmentations whose activation energies lie within this small energy manifold.     

氨和甲醇团簇中的质子转移反应

应用激光多光子电离质谱和分子束技术研究了氨和甲醇二元团簇,实验观测到两个系列质子化的团簇离子: (CH3OH)nH+和(CH3OH)nNH4+(1≤n≤14 ),其产生是经过二元团簇内的质子转移反应。同时也研究了氘代甲醇CH3OD和氨混合团簇,结果表明OD原子团中的D转移概率比CH3原子团中的质子转移概率大几倍。在HF/STO-3G和MP2/6-31G*　*水平上对氨和甲醇二元团簇进行了计算,结果表明与CH3相比OH中的质子转移更加容易,因为CH3中的质子转移过程要克服高度约120 kJ/mol的能垒。     

二取双恶唑啉衍生物的合成及其在不对称环丙烷化反应中的应用

通过双亚氨酸盐酸盐与手性胺醇反应简便地合成了二取代双恶唑啉衍生物, 并将其与铜配位运用于重氮醋酸酯对烯烃的不对称环丙化反应, 不对称诱导反应光学产物收率最高达95%d.e.     

Synthesis and characterization of ionic liquids containing copper, manganese, or zinc coordination cations

Copper-, manganese-, and zinc-based ionic liquids (Cu{NH(2)CH(2)CH(2)OH}(6)[CH(3)(CH(2))(3)CH(C(2)H(5))CO(2)](2) (2), Cu{NH(CH(2)CH(2)OH)(2)}(6)[CH(3)(CH(2))(3)CH(C(2)H(5))CO(2)](2) (3A), Cu{NH(CH(2)CH(2)OH)(2)}(6)[CF(3)SO(3)](2) (3B), Cu{NH(CH(2)CH(2)OH)(2)}(6)[(CF(3)SO(2))(2)N](2) (3C), Mn{NH(CH(2)CH(2)OH)(2)}(6)[CF(3)SO(3)](2) (4), and Zn{NH(2)CH(2)CH(2)OH}(6)[CF(3)SO(3)](2) (5)) are synthesized in a single-step reaction. Infrared data suggest that ethanolamine preferentially coordinates to the metal center through the amine group in 2 and the hydroxyl group in 5. In addition, diethanolamine coordinates through the amine group in 3A, 3C, and 4 and the hydroxyl group in 3B. The compounds are viscous (>1000 cP) at room temperature, but two (3C and 4) display specific conductivities that are reasonably high for ionic liquids (>20 mS cm(-1)). All of the compounds display a glass transition (T(g)) below -50 °C. The cyclic voltammograms (CVs) of 2, 3A, 3B, and 3C display a single quasi-reversible wave associated with Cu(II)/Cu(I) reduction and re-oxidation while 5 shows a wave attributed to Zn(II)/Zn(0) reduction and stripping (re-oxidation). Compound 4 is the first in this new family of transition metal-based ionic liquids (MetILs) to display reversible Mn(II)/Mn(III) oxidation and re-reduction at 50 mV s(-1) using a glassy carbon working electrode.     

Amidines derived from Pt(IV)-mediated nitrile-amino alcohol coupling and their Zn(II)-catalyzed conversion into oxazolines

The reaction between the platinum(IV) complex trans-[PtCl(4)(EtCN)(2)] and the amino alcohols NH(2)CH(2)CH(2)OH, NH(2)CH(2)CH(Me)OH-(R)-(-), NH(2)CH(Ph)CH(2)OH-(R)-(-), NH(2)CH(Et)CH(2)OH-(R)-(-), NH(2)CH(Et)CH(2)OH-(S)-(+), and NH(2)CH(Pr(n)())CH(2)OH proceeds rapidly at room temperature in CH(2)Cl(2) to furnish the amidine complexes [PtCl(4)(HN=C(Et)NH(arcraise;)OH)(2)] (1-6) in good yield (70-80%). The related reaction between the platinum(II) complex trans-[PtCl(2)(EtCN)(2)] and monoethanolamine in a molar ratio of 1:2 in CH(2)Cl(2) results in the addition of 4 equiv of NH(2)CH(2)CH(2)OH per mole of complex to give [Pt(HN=C(Et)NHCH(2)CH(2)OH)(2)(NH(2)CH(2)CH(2)OH)(2)](2+) (7). Formulation of 1-6 is based upon satisfactory C, H, N elemental analyses, electrospray mass spectrometry, IR spectroscopy, and (1)H, (13)C((1)H), (15)N, and (195)Pt NMR spectroscopies, while the structures of trans-[PtCl(4)((Z)-NH=C(Et)NHCH(2)CH(2)OH)(2)] (1), trans-[PtCl(4)((Z)-NH=C(Et)NHCH(2)CH(Me)OH-(R)-(-))(2)] (2), and trans-[PtCl(4)((Z)-NH=C(Et)NHCH(Et)CH(2)OH-(R)-(-))(2)] (4) were determined by X-ray single-crystal diffraction. The Z-amidine configuration of the ligands is preserved in CDCl(3) solutions as confirmed by gradient-enhanced (15)N,(1)H-HMQC spectroscopy and NOE experiments. The amidines, formed upon Pt(IV)-mediated nitrile-amino alcohol coupling, were liberated from their platinum(IV) complexes 1, 3, and 4 by reaction with Ph(2)PCH(2)CH(2)PPh(2) (dppe) giving free NH=C(Et)NHCHRCH(2)OH (R = H 8, Et 9, Ph 10), with the substituents R of different types, and dppe oxides; the P-containing species were identified by (31)P((1)H) NMR spectroscopy. NOESY spectroscopy indicates that the liberated amidines retained the same configuration relative to the C=N double bond, i.e., syn-(H,Et)-NH=C(Et)NHCHRCH(2)OH. The liberated hydroxo-functionalized amidines 8-10 were converted into oxazolines (11-13) in the presence of a catalytic amount of ZnCl(2). A similar catalytic effect has also been reached using anhydrous MSO(4) (M = Cu, Co, Cd), CdCl(2), and AlCl(3).