2,4-二氧代-1,3,2-苯并二氮磷杂环己烷与■C=C■及CS_2加成反应的研究

本文研究了2,4-二氧代-1,3,2-苯并二氮磷杂环己烷的磷氢键对β-硝基苯乙烯、丙烯酸酯、丙烯腈及二硫化碳的加成反应,共合成了18个新的加成产物.发现通过选用不同的碱或控制碱的用量.可选择性的进行加成或开环反应.由X衍射证实:在加成产物的结构中,环外P-C键构象因受磷杂环船式构象影响,以邻位交叉式(A)为主.     

2-Polyfluoroalkyl thiopyrylium salts: synthesis and reactions with nucleophiles

2-Polyfluoroalkylthiopyrylium salts have been synthesized by oxidative aromatization of 2-polyfluoroalkyl-2H-thiopyrans with triphenylmethane tetrafluoroborate. Nucleophilic addition of methanol, sodium azide, or urea to 2-trifluoromethylthiopyrylium tetrafluoroborate in a basic medium proceeds at the α-position to give the corresponding 2-substituted 6-trifluoromethyl-2H-thiopyrans whereas imidazoles, fluorine-containing 1,2,3-triazole, potassium thiolacetate, and sodium nitromethane afford mixtures of 2H- and 4H-thiopyrans. cis-Dihydroxylation of 6-trifluoromethyl-2-methoxy-2H-thiopyran affords the fluorine-containing thiohexenopyranoside derivative 8.     

具有共轭体系的酮类烯醇硅醚与全氟碘代烷的反应

最近,我们报道了应用连二亚硫酸钠的引发,通过全氟碘代烷与醛类,酮类烯醇硅醚的反应,合成α-全氟烷基羰基类化合物的方法。利用该方法,还可以用“一锅法”合成含     

Palladium-Catalyzed Addition Reaction of 1-Octene,Carbon Tetrachloride and Carbon Monooxide in Alcohols

In the presence of pyridine, the Pd-catalyzed addition reaction of CO and CCI₄ to 1-octene could be carried out smoothly under mild conditions. In this reaction, the satisfactory results were afforded when different alcohols and palladium catalysts were used.     

N-芳亚甲基-2-丙烯-1-胺与甲醇钠的反应

研究了N-芳亚甲基-2-丙烯-1-胺（1）与甲醇钠的反应，当甲醇钠过量，反应 时间足够长时，生成的主要产物是N-芳亚甲基-1-甲氧基-丙胺（2）。     

N-芳亚甲基-1-丙烯-1-胺与醇钠的反应

研究了N-芳亚甲基-1-丙烯-1-胺与醇钠(甲醇钠,乙醇钠)的加成反应,该反应具有高度的区域选择性,提出了可能的反应机理。     

钯催化一氧化碳、四氯化碳和1-辛烯的加成反应

在吡啶的存在下和不同的醇溶剂中 ,一氧化碳、四氯化碳和 1 -辛烯在钯催化下的加成反应能在较温和的条件下进行 ,反应生成共加成产物 2 - ( 2 ,2 ,2 -三氯乙基 )辛酸酯和简单加成产物 1 ,1 ,1 ,3-四氯壬烷     

Microwave-assisted, solvent-free synthesis of 1-(α- or β-hydroxynaphthyl)-1,2,3,4-tetrahydroisoquinolines by the Mannich reaction

As a new extension of the Mannich reaction of naphthols, 1-(hydroxynaphthyl)-substituted 1,2,3,4-tetrahydroisoquinolines were synthesized by the nucleophilic addition of 1- or 2-naphthol to 3,4-dihydroisoquinolines under solvent-free conditions, using microwave irradiation. The additions to 3-methyl-6,7-dimethoxy-3,4-dihydroisoquinoline proved to be a highly diastereoselective processes, resulting in the cis isomers as the main or the only products.     

碘化1-甲基-2-异丙基(或丙基)-3-苯磺酰基咪唑啉的合成及基团转移反应

合成了新的四氢叶酸辅酶(THF)模型化合物碘化1-甲基-2-异丙基-3-苯磺酰基咪唑啉(5a)和碘化1-甲基-2-丙基-3-苯磺酰基咪唑啉(5b),研究了其反应性能.结果表明,化合物5与双官能团亲核体邻苯二胺或邻氨基苯酚反应,完全转移了4个碳的异丁基和正丁基单元,基于此探索了合成2-取代苯并咪唑及2-取代苯并唑的新方法;化合物5a与单官能团亲核体胺类反应部分转移了4个碳的异丁基单元,生成不同基团取代的N,N,N'-三取代乙二胺盐;化合物5a在Na BH4作用下可发生还原反应,在Na OH水溶液中可发生水解反应,也可与碳负离子基团(硝基甲基负离子或二腈基甲基负离子)发生亲核加成反应,生成了3类不同基团取代的N,N,N'-三取代乙二胺衍生物,探索了此类化合物的简易合成方法.这些反应模拟了四氢叶酸辅酶在生物体内转移一碳单元的功能,并将其扩展到4个碳原子单元,获得了可应用于有机合成的新方法和新试剂.     

4-羰基-2-戊烯醛与硫代乙酸加成的研究

以2-甲基-2,5-二甲氧基-2,5-二氢呋喃水解产物与硫代乙酸加成并在不同条件下关环,制得了β-乙酰硫基呋喃、噻吩和毗咯的各种异构产物,提供了按需要制备不同α-甲基-β-巯基呋喃、噻吩和吡咯衍生物的途径。     

Reaction of methyl 1-(2-bromo-4-methoxy-1,4-dioxobutyl)- cyclohexanecarboxylate with zinc and aromatic aldehydes

1. Download : Download full-size image

     

Photopolymerization of styrene,p-chlorostyrene,methyl methacrylate,and butyl methacrylate with polymethylphenylsilane as photoinitiator

The rates of photochemical polymerization of styrene (St), p-chlorostyrene (Cl-St), methyl methacrylate (MMA), and butyl methacrylate (BMA) with polymethylphenylsilane (PMPS) as an initiator were measured. Polymethylphenylsilane is photodegrated to form silyl radicals that may initiate polymerization of vinyl monomers. Rate constants k_p and k_t have been determined for these systems. A good correlation (log P = α + βμ) of the resonance stabilization (P) of the chain radicals and the dipole moment (μ) of the monomers is observed for these polymerization systems. This equation may be used to estimate the resonance stabilization (P) of a monomer and the polymerization rate constant (k_p). © 1996 John Wiley & Sons, Inc.     

Synthesis of Alkyl (5-Oxo-2-thioxo-[1,3,4]thiadiazinan-6-ylidene)acetates by the Reaction of N-Aminorhodanine,Dialkyl Acetylenedicarboxylates,and Triphenylphosphine

Protonation of the reactive zwitterionic intermediate produced from the reaction between triphenylphosphine and dialkyl acetylenedicarboxylates by N-aminorhodanine followed by the addition of the conjugate anion of N-aminorhodanine on the produced vinylphosphonium cation leads to alkyl (5-oxo-2-thioxo-[1,3,4]thiadiazinan-6-ylidene)acetates in good yields.     

Reaction of 1-bromovinyl and 1-bromo-2-phenylvinyl sulfones with some CH acids

Benzyl, methyl, and phenyl α-bromovinyl sulfones reacted with malononitrile and dimethyl malonate sodium enolates in THF to give sulfonyl-substituted cyclopropanes. Reactions of the same sulfones with methyl acetoacetate sodium enolate afforded the corresponding sulfonyl-substituted cyclopropanes as mixtures of cis and trans isomers with a small impurity of 5-sulfonyl-4,5-dihydrofuran derivative. Phenyl and p-tolyl 1-bromo-2-phenylvinyl sulfones reacted with methyl acetoacetate sodium salt to produce a mixture of trans-isomeric 5-sulfonyl-4,5-dihydrofuran and Michael adduct of the CH acid with activated acetylene generated by concurrent 1,2-dehydrobromination of the initial α-bromovinyl sulfone.     

Criegee中间体CH3CHOO与H2O反应机理及酸催化效应

采用CCSD（T）//B3LYP/6-311+G（d,p）方法研究了H₂O及甲酸等6种有机酸对CH₃CHOO与H₂O加成反应的催化作用。结果表明,非催化反应存在双质子迁移和加成反应2条通道,其中加成反应为优势通道。其加成机理为H₂O中OH加到CH₃CHOO的α-C上,同时H₂O中另一个H迁移到CH₃CHOO的端O上。催化剂H₂O及有机酸以氢键复合物的形式参与反应促进了H质子转移,可降低基元反应能垒和表观活化能,且催化效应与有机酸的强度成正比。例如,当分别用H₂O（pK_a=15.7）、甲酸（pK_a=3.75）和草酸（pK_a=1.23）催化时,生成syn-HAHP的基元反应能垒由非催化的69.12 kJ·mol^-1分别降至40.78、18.88和10.61 kJ·mol^-1。非催化反应具有正的表观活化能,而所有催化反应则均具有负的表观活化能。     

金属催化二氯化物RCCl_2CH_2CH_2R~1合成反应的研究

在醇溶剂中，用金属或金属合金作为反应的催化剂，多氯化物RCCl_3和含吸电 子基的末端烯烃CH_2=CHR~1反应一步生成RCCl_2CH_2CH_2R~1。在此反应中，加成 反应和脱氯反应一步完成。     

3,3-二甲基-1-(1H-1,2,4-三唑-1-基)-2-丁酮及1-(1H-1,2,4-三唑-1-基)取代苯乙酮与二溴化物的关环反应及产物的生物活性

通过二溴化物与唑酮1[R=(CH₃)₃C]或α-三唑基苯乙酮1(R=Ar)的亲核取代反应,合成了新型的环状三唑类化合物3和4,经元素分析,¹HNMR,IR,EI-MS和X射线衍射等方法确证其结构,讨论了反应过程.生物活性测试发现大部分化合物具有很好的杀菌活性,尤其对小麦锈病具有较强的抑制作用.