π-烯丙基氯化铁三吡啶配合物与丁烯醛反应的研究

丁烯醛在π-烯丙基氯化铁三吡啶配合物作用下,会生成自缩合产物,经色谱-质谱、红外光谱、核磁等手段表征,确认产物为6-甲基-1,3环已二烯基甲醛。推测反应机理是丁烯醛与π-烯丙基氯化铁三吡啶配合物进行配位体交换,然后与另一丁烯醛分子加成环化而成。由于配合物中配位体的定位作用,大大提高了反应的选择性而未见其它副反应发生。     

甲基丙烯酸3-三甲氧基硅丙酯/苯乙烯细乳液共聚合过程中的水解及缩合反应

研究了甲基丙烯酸3-三甲氧基硅丙酯(MPS)和苯乙烯(St)细乳液聚合过程中的水解及缩合反应.用气相色谱仪测定聚合过程中水解产物——甲醇的含量来研究MPS的水解度.MPS分子主要在细乳液液滴与水的界面以及乳胶粒与水的界面上发生水解反应.MPS和St比例、介质pH值、乳化剂用量、引发剂类型和用量都会影响MPS的水解程度.缩合产物用29Si固态核磁共振表征,中性条件下,缩合反应受到抑制,在高MPS/St比例的体系中也只生成少量缩合产物.酸性和碱性条件下,缩合产物量均增加,但碱性条件下,体系中仍有一定数量未缩合的硅氧烷存在,这与细乳液聚合独特的液滴成核机理及聚合过程中较少液滴间物质交换有关.     

2,6-二(5-烷基水杨基)-4-烷基苯酚的合成

以自制的正构长链烷基酚为原料与多聚甲醛在碱性催化剂下进行羟甲基化反应,生成2,6-二羟甲基-4-烷基苯酚,再与另两分子烷基酚在固体超强酸催化下进行缩合反应生成2,6-二(5-烷基水杨基)-4-烷基苯酚,用核磁共振氢谱和碳谱、红外光谱和元素分析对产物进行了结构鉴定,探讨了催化剂、反应物料配比、反应时间等条件对产物产率的影响.另外根据上述反应路线,以工业品壬基酚和多聚甲醛为原料,经羟甲基化反应、缩合反应合成了2,6-二(5-壬基水杨基)-4-壬基苯酚.上述两种结果表明,选用SO24-/SnO2固体超强酸作催化剂,2,6-二羟甲基-4-烷基苯酚和烷基酚的配比为1:2,140℃反应2h,产率达到95%.     

倍半木脂素threo-(±)-3,4-二香草基四氢呋喃阿魏酸酯的全合成

报道了一条合成天然产物3,4-二香草基四氢呋喃阿魏酸酯的方法.以香草醛为原料,经过两步Stobbe反应构建木脂素骨架,然后再加氢、LiAlH4还原,产物经柱层析分离后得到两个异构体meso-和threo-(±)-开环落叶松脂素;它们分别与TsCl作用,发生分子内反应得到关键的四氢呋喃木脂素中间体meso-和threo-(±)-shonanin;最后,分别与MOM保护的阿魏酸缩合得到倍半木脂素threo-(±)-3,4-二香草基四氢呋喃阿魏酸酯和衍生物erythro-(±)-3,4-二香草基四氢呋喃阿魏酸酯.合成采用汇聚法,经13步,以约8%～9%的总产率得到了目标产物.     

2-甲基-4-甲氧基苯基苯胺的合成

邻硝基甲苯在甲醇、乙酸和硫酸混合溶液中, 在Pt/C的催化下发生氢化和Bamberger重排生成2-甲基-4-甲氧基苯胺. 后者在Pd/C的存在下以苯酚为反应介质与环已酮缩合生成2-甲基-4-甲氧基苯基苯胺, 反应总产率63.0%. 文中给出了产物与中间产物的核磁共振氢谱和质谱, 同时讨论了影响反应的因素.     

α,α-二乙酰基二硫缩烯酮和芳醛的缩合反应研究

在碱性条件下,α,α-二乙酰基二硫缩烯酮和芳醛的缩合反应受烷硫基的影响.α,α-二乙酰基二苄硫缩烯酮1和芳醛3缩合生成单面缩合脱乙酰基产物α-肉桂酰基二苄硫缩烯酮4;α,α-二乙酰基环二硫缩烯酮2和芳醛3缩合生成双面缩合产物α,α-二肉桂酰基环二硫缩烯酮5.     

2-苯氧(硫)甲基-6,7-亚甲二氧-3-喹啉酸乙酯及其衍生物的合成

6-氨基胡椒醛与乙酰乙酸乙酯在碱的催化下, 缩合产物与NBS发生溴代反应, 生成2-溴甲基-6,7-亚甲二氧基-3-喹啉酸乙酯,产物与苯酚,取代苯酚, 苯硫酚, 取代苯硫酚发生Williamson取代反应, 高分辨地得到一系列喹啉吩醚衍生物, 苯酚和硫酚上的吸电子基团有利于增强亲核能力,有利于Williamson反应.     

2, 3-二氢蒽并(1, 2-b)(1, 4)恶嗪-7, 12-二酮的合成

2-溴-1, 4-二羟基蒽醌与氨基醇, 缩合可以生成2-取代氨基-1, 4-二羟基蒽醌, 但在较高温度下并延长反应时间, 部分产物可以进行分子内脱水而进一步环化为2, 3-二氢蒽并(1, 2-b)(1, 4)恶嗪-7, 12-二酮的衍生物。用MS和NMR确定其结构。     

水介质中芳醛与1-苯基-3-甲基-5-吡唑啉酮的缩合反应研究

水介质中芳醛与3-甲基-1-苯基-5-吡唑啉酮发生缩合, 生成相应的4,4'-芳亚甲基双(1-苯基-3-甲基-5-吡唑啉酮), 与其他的方法相比该方法具有产率高、价廉、环境友好等优点. 产物结构经¹H NMR和IR进行了表征.     

脯氨酸催化新型3-α,β-不饱和酮取代-4-羟基喹啉-2-酮简便合成及其荧光性质研究

3-乙酰-4-羟基喹啉-2-酮和芳香醛在L-脯氨酸有效催化下发生Aldol反应,生成一系列缩合产物3-α,β-不饱和酮取代-4-羟基喹啉-2-酮.该反应在甲醇溶液中进行,并且产物作为沉淀直接从溶液中析出,简单洗涤可得纯产物.研究表明芳香醛上的取代基性质对产物的产率有显著影响,其结果证实了该缩合反应经历了一个脱水中间体的反应历程.此外,对产物的荧光性质研究表明该类化合物可作为潜在应用价值的有机光学材料.     

Some reactions of 3-halogenocinnolines catalysed by palladium compounds

3-Bromo- or 3-iodo-cinnoline (and 4-substituted analogues) are condensed with terminal alkynes in the presence of Pd and Cu compounds as catalysts to give the 3-alkynyl-derivatives. When 4-chloro- or 4-phenoxy-compounds are used, the products react with amines, in the presence of copper(I) iodide, to form pyrrolo[3,2-c]cinnolines and with hydrazines to give either the same ring system or a pyrazolo[4,3-c]cinnoline. Hydrolysis of 3-alkynyl-4-phenoxycinnoline to 3-alkynyl-4(1H)-cinnoline, followed by cyclisation, yields the furo[3,2-c]cinnoline. Attempts to condense 3-halogenocinnolines with alkenes gave variable results: 3-phenyl ethenyl- and 3(2-pyridylethenyl)-4-(1H)-cinnolinones were obtained but 3-bromocinnoline gave the 3,3′-bicinnolinyl. Action of palladium acetate in the presence of ethyl acrylate converted 3-bromo-4-phenoxycinnoline into benzofuro[3,2-c]cinnoline and 3-bromo-4-phenylaminocinnoline into indolo[3,2-c]cinnoline.     

Synthesis and properties of substituted 2-methylene-hydrazono-2,3-dihydro-3-benzo[<Emphasis Type="Italic">b</Emphasis>]furanones

The reaction of 2,3-dihydro-2,3-benzo[b]furandione with the triphenylphosphazines of diazo compounds leads to substituted 2-methylenehydrazono-2,3-dihydro-3-benzo[b]furanones, which are hydrolyzed in an acidic medium to the substituted methylenehydrazides of o-hydroxyphenylglyoxalic acid and react with amines to form the products of addition at the activated CH=N bond of the side chain or 2-hydrazono-2,3-dihydro-3-benzo[b]furanone respectively. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 817–822, June, 2007.     

Part 1: Synthesis of Polyfused Heterocyclic Systems Derived From 3-Phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4- b ][1,3,4]thiadiazepine-6,8-dione

3-Phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4- b ][1,3,4]thiadiazepine-6,8-dione ( 1 ) was condensed with o -aminothiophenol, 2-amino-ethanol or cystamine to afford compounds 2-4 respectively. Treatment of compound 1 with dimethylthiomethylenemalononitrile yielded the corresponding pyrano[3,2- f ][1,2,4]triazolo[3,4- b ]-[1,3,4]thiadiazepine derivative 5 . 7-[5-Amino-1,3-dithiolan-2-ylidene]-3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4- b ][1,3,4]thiadiazepine-6,8-dione ( 6 ) was obtained by treating compound 1 with CS 2 and chloroacetonitrile. Thiation of compound 1 gave the corresponding thioanalog 7 , which in turn was condensed with malononitrile to give 3-phenyl-5,6,7,8-tetrahydro[1,2,4]triazolo[3,4- b ][1,3,4]thiadiazepine-6-one-8-ylidenemalononitrile ( 8 ). On treating compound 8 with benzaldehyde or p -nitrobenzaldehyde, pyrano[1,2,4]triazolo[1,3,4]thiadiazepin derivatives 9a , b , respectively, were obtained. Compound 8 was treated with CS 2 and methyl iodid to give the corresponding dithiomethylmethylene derivative 10 which was subjected to react with aniline to give pyrido[1,2,4]triazolo[1,3,4]thiadiazepine derivative 11 . Compound 8 was treated with 3-aminopyridine, o -aminothiophenol, or o -phenylenediamene to yield compounds 12 and 13a , b respectively. Finally, tertiary amines or activated phenols were condensed with compound 8 to yield compounds 14 and 15a , b respectively.     

The Condensation of Cyclic Aminoketones,Cyclohexanone and Cyclohexane-1,4-dione with some Phenolic Ethers in Polyphosphoric Acid

The title condensations gave respectively: gem-bisarylated cyclic amines 3a–k or monoarylated unsaturated cyclic amines 4a–g , 1,3-bisarylated cyclohexadienes 6a , 6b , the condensed bicyclo [2,2,2]-octane 8 . In addition the aromatic ketone 9 gave the fluorenone 10 on treatment with polyphosphoric acid (PPA).     

The synthesis of pyrazino[2,3-d]pyridazine and some of its derivatives

Pyrazino[2,3-d]pyridazine (I) was synthesized by two different routes. 5, 8-Dihydroxy-pyrazino[2, 3-d]pyridazine (IV) was converted to 5, 8-dichloropyrazino[2, 3-d]pyridazine (V) and 5, 8-dibromopyrazino[2, 3-d]pyridazine (Va). When V was treated with various benzyl mercaptans and alkoxides the corresponding disubstituted derivatives were obtained. Compound V when allowed to react with aromatic amines gave 5, 8-bisamino-pyrazino[2,3-d]pyridazines, however, with aliphatic amines only mono substituted products were obtained substituted in the 8-position. The reaction of pyrazine-2, 3-dinitrile with hydrazine gave 5, 8-diaminopyrazino[2, 3-d]pyridazine (X).     

Pyrido[2,3-d]pyrimidines 7. Reactions of 1,3-dimethyl-5,7-dichloro-6-nitropyrido-[2,3-d]pyrimidine-2,4-dione with amines. Synthesis of derivatives of triazolo(4′,5′:4,5)pyrido[2,3-d]pyrimidine

The reaction of 5,7-dichloro-6-nitropyrido[2,3-d]-pyrimidine-2,4-dione with amines gave products of the substitution of one or two chlorine atoms by ammo groups. The catalytic reduction of 6-nitro-5,7-disubstituted pyrido[2,3-d]pyrimidines with hydrogen over palladium oxide on carbon leads to 5,6-diamino- and 5,6,7-triaminopyridopyrimidines, the reaction of which with amyl nitrite in acetic acid gives triazolo(4,5:4,5) pyrido[2,3-d]pyrimidines.For communication 6 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 398–401, March, 1993.     

Diastereoselective tandem addition-cyclization reactions of unsaturated tertiary amines initiated by photochemical electron transfer (PET)

Polycyclic molecules and tetrahydroquinoleines were obtained in a tandem reaction involving the diastereoselective addition of alpha-aminoalkyl radicals to (5R)-5-menthyloxy-2[5H]-furanone 1. The facial diastereoselectivity on 1 is >/=90%. The alpha-aminoalkyl radicals were produced from tertiary amines by photochemical-induced electron transfer. When N,N-dialkylanilines 19 were used as starting tertiary amines, a rearomatization step was involved and important side reactions of 1 were observed. A mechanistic study involving isotopic labeling of the starting amine indicated that the byproducts resulted from reduction of 1 during the rearomatization process. An efficient optimization of the reaction was obtained by simply adding acetone or cyclopentanone as mild oxidants to the reaction mixture. The side products resulting from reduction of the furanone 1 were completely suppressed under these conditions, and the yields of the tetrahydroquinolines 21a-i, 22a-f, and 26g-i were doubled.     

Synthesis of new cationic and amphoteric triple-chain F-alkylated amphiphiles derived from 3-[N-[2-(F-alkyl)ethyl] N-alkylamino] propanoic acids

The N-[2-(F-alkyl)ethyl] amines were condensed with acrylic acid to afford the 3-[N-[2-(F-alkyl)ethyl] N-alkylamino] propanoic acids which are double-chain intermediates. To introduce a third chain, these intermediates and n-alkyl amines or n-2-(F-alkyl)ethyl amines were reacted according to three different methods to form triple-chain compounds which are quaternized by reagents such methyl iodide, ethyl bromoacetate and 1,3-propane sultone to form cationic and amphoteric triple-chain perfluoroalkylated surfactants.     

Condensed imidazo-1,2,4-azines. 21. Synthesis of 2-arylfuro(pyrrolo-, thieno-)[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles by cyclization of 2-aroyl-1,2,4-triazino[2,3-a]benzimidazol-4H-3-ones

2-[(-Ethyl-, arylimino)phenethyl]-1,2,4-triazino[2,3-a]benzimidazoles were obtained by reaction of 2-aroylmethyl-1,2,4-triazino[2,3-a]benzimidazol-4H-3-ones with ethyl(aryl)amines or urea. By the action of phosphorus oxychloride, these benzimidazoles cyclize into substituted pyrrolo[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles, heating of which in polyphosphoric acid leads to the formation of furo[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles, while by the action of P₄S₁₀, they are transformed into thieno[2,3-e]-1,2,4-triazino[2,3-a]benzimidazoles.For Communication 20, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1109–1113, August, 1989.     

Simple preparations of Pd6Cl12, Pt6Cl12, and Qn[Pt2Cl8+n], n=1, 2 (Q=TBA+, PPN+) and structural characterization of [TBA][Pt2Cl9] and [PPN]2[Pt2Cl10].C7H8

The hexanuclear Pd6Cl12, i.e., the crystal phase classified as beta-PdCl2, was obtained by reacting [TBA]2[Pd2Cl6] with AlCl3 (or FeCl3) in CH2Cl2. The action of AlCl3 on PtCl42-, followed by digestion of the resulting solid in 1,2-C2H4Cl2 (DCE), CHCl3, or benzene, produced Pt6Cl12.DCE, Pt6Cl12.CHCl3, or Pt6Cl12.C6H6, respectively. Treating [TBA]2[PtCl6] with a slight excess of AlCl3 afforded [TBA][Pt2Cl9], whose anion was established crystallographically to be constituted by two "PtCl6" octahedra sharing a face. Dehydration of H2PtCl6.nH2O with SOCl2 gave an amorphous compound closely analyzing as PtCl4, reactive with [Q]Cl in SOCl2 to yield [Q][Pt2Cl9] or [Q]2[Pt2Cl10], depending on the [Q]Cl/Pt molar ratio (Q=TBA+, PPN+). A single-crystal X-ray diffraction study has shown [PPN]2[Pt2Cl10].C7H8 to contain dinuclear anions formed by two edge-sharing PtCl6 octahedra.