ω-三烷基及ω-吡啶翁基芳乙酮α氢核磁共振研究

用高分辨核磁共振研究了ω-三烷基铵基及ω-吡啶翁基芳乙酮α氢在D2O中的氘交换现象, 证实该类酮在酸性与中性条件下不产生烯醇化, 在弱碱性条件下则产生部分烯醇化。     

α,ω-二碘全氟乙烷和丁烷的一些反应

近年来,以锌为催化剂用超声波进行氟烷基化反应已有不少报道,但反应物限于全氟烷基碘R_F I。对于I(CF_2)_2 I(Ⅰ)、I(CF_2)_4I(Ⅱ)这类α,ω-二碘全氟烷烃未见报道。作者用(Ⅰ)或(Ⅱ)在DMF或THF中,于室温下加入锌粉(锌粉经活化或未活化),立即有气体逸出,若施加超声波,气体更甚。加入碘苯亦无预期产物,这是符合β-断裂、碘极易脱离生成全氟烯烃之说的。     

ω-三烷基铵基及ω-吡啶鎓基芳乙酮α氢核磁共振研究

用高分辨核磁共振研究了ω烷基铵基及ω吡啶基芳乙酮α氢在D_2O中的氘交换现象,证实该类酮在酸性与中性条件下产生烯醇化,在弱碱条件下则产生部分烯醇化。     

α,ω-Bis-N-aziridinoalkanes

By reactions of ,-diamines with 1,2-dihaloethanes there were synthesized ,-bis-N-aziridinoalkanes (la-g) and bis-N-aziridinoethyl ether (II). From 1,3-diaminopropane and dichloroethane bis-aziridine (III) was isolated in addition to (Ia). NMR spectra of the products were studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 882–885, April, 1991.     

A facile synthesis of α,α,ω,ω-tetrahalo-α,ω-dicarboxylic esters

The synthesis of some α,α,ω,ω-tetrachloro and tetrabromo-derivatives of the hypolipidemic 3,3,14,14-tetramethylhexadecanedioic acid from α,ω-dihalo-esters, carbon tetrahalides and lithium diisopropyl amide has been described. Interaction of α,ω-dichloro esters with CBr₄ was shown to give the expected α,ω-dibromo-α,ω-dichloro compounds, but treatment of bis(l-methylethyl) 2,15-dibromo-3,3,14,14-tetramethylhexa-decanedioatewith CCl₄ was found to result in halogen exchange yielding the tetrachloro-diester as the major product.     

αH,αH,ωH-全氟烷氧丙基甲基二氯硅烷的制备和水解反应研究

<正>我们以十六烷基三甲基澳化按为相转移催化剂,将四氟乙烯调聚醇与氛丙烯在氢氧化钠存在下反应,制得三种     

聚全氟三嗪的合成研究Ⅰ.α,ω-二碘代全氟氧杂烷基三嗪单体的合成

以5-碘-3-氧杂-八氟戊碘酰氯(Ⅰ)为原料经八步合成得到三嗪单体——2-三氟甲基-4,6-二(4′-碘-2′-氧杂六氟丁基)-1,3,5-三嗪(Ⅸ).Ⅰ用亚硫酸钾还原生成亚磺酸盐Ⅱ,后者经氢碘酸处理生成5-碘-3-氧杂-六氟戊酸(Ⅲ)。化合物Ⅲ经相应的酯Ⅳ和酰胺Ⅴ转化为5-碘-3-氧杂-六氟戊腈Ⅵ。产物Ⅸ由亚胺脒Ⅷ经酰化脱水环化制备,后者则由腈Ⅵ和脒Ⅶ缩合而得。本文还研究了全氟羧酸的多种酯化方法并提出了一种全氟亚磺酸盐在氢碘酸作用下转化为全氟羧酸的可能机理。     

高分子化学探索性实验:α,ω-羧基聚二甲基硅氧烷的可控合成

以高分子化学实验课程为载体,将学生课外科研活动与高分子化学实验以及任课教师所在科研团队的科研成果有机结合起来,把功能高分子的设计与结构表征提前引入到高分子化学实验中,形成了一整套较为完整、具有探索性和综合性的高分子化学实验实施方案。以α,ω-羧基聚二甲基硅氧烷(α,ω-羧基硅油)的可控合成为例,通过引导本科生独立地进行文献检索、实验方案设计、材料合成和结构表征及实验报告撰写,既提高了他们利用已学的有机化学和高分子化学知识进行综合分析的能力,又培养了其查阅文献、分析文献和形成创新性思维的能力。     

四氢喹啉-4-醇类衍生物的合成

以1,2,3,4-四氢喹啉为初始原料,经N-酰基保护、氧化、脱保护、还原等反应合成了一系列1,2,3,4-四氢喹啉-4-醇类的衍生物,总产率17%~41%,其结构经1H NMR和13C NMR确证。     

15(R,S)-dl-ω-乙基-13,14-去氢前列腺素F2α的合成

本文报道从双羟环氧(4)与3-叔丁氧基癸炔-1的铝试剂(3)在甲苯中开环,再经铂催化氧化、二异丁基铝氢还原、Wittig反应及三氟乙酸水解等反应合成15(R,S)-dl-ω-乙基-13,14去氢前列腺素F_2α,并用活性二氧化锰氧化代替金属铂的催化氧化,获得满意结果。15(R,S)-dl-ω-乙基-13,14-去氢前列腺素F_2α经药理试验表明,有强的溶解黄体及抗生育作用,对平滑肌的收缩作用则较低。对于治疗奶牛持久黄体及诱发母牛同期发情有效。     

全氟及α,α-二氯多氟烷基亚磺酸盐的反应

全氟烷基亚磺酸钠与溴水反应,得到全氟烷基磺酰溴(RfSO2Br),(但在乙腈,乙酸等有机溶剂中与溴反应,则生成溴代全氟烷.在碘化钾水溶液中,全氟烷基亚磺酸钠与碘反应,生成碘代全氟烷.α,α-二氯多币烷基亚磺酸钠在类似条件下与溴水反应,生成1-溴-1,1-二氯多氟烷,与碘在磺化钾水溶液中反应,生成1-碘-1,1-二氯多氟烷.1-溴-1,1-二氯多烷及1-碘-1,1-二氯多氟烷易对烯键加成,也可与连二亚硫酸钠在温和条件下发生亚磺化脱溴及脱碘反应.α,α-二氯二氟乙基亚磺酸钠在强酸中比较稳定,与强碱,氧化剂或还原剂发生反应,得到相应的产物.     

全氟和ω-H-全氟酰基过氧化物与C60的自由基加成反应——全氟和ω-H-全氟烷基化C60的合成

深入研究了C60与全氟酰基过氧化物的反应，通过变温EPR测试证实了此反应的 自由基加成机理．用色谱分析并结合产物的^19F NMR结构鉴定，首次发现由于加成 过程中发生的全氟烷基自由基的β—Scission，生成了新的氟烷基自由基，从而生 成了多种氟烷基化的C60．表面性能研究发现氟烷基化的C60具有优良的疏水、疏油 性．总之，利用C60与全氟酰基过氧化物的反应，成功地对C60进行了全氟烷基化修 饰．     

α,ω-二碘代全氟烷基醚对称三嗪的合成及全氟烷基碘代物的亚磺化反应的初步研究

α,ω-二碘代三嗪(1)由碘代磺酰氟(2)经八步合成得到,各步产率和所用试剂见图式1,     

Synthesis of symmetrical acetylenic hydrocarbons and their α,ω-di-derivatives from α,α,α-trichloro- and α,α,α,ω-tetrachloro-alkanes

Summary By the action of sodium in xylene on polychloro hydrocarbons containing -CCl₂-CCl₂- or- CC1=CC1-, groupings the corresponding symmetrical acetylenic hydrocarbons containing 10,14, and 18 carbon atoms in the molecule were obtained. From ,-disubstituted tetrachloroalkanes by the same method 1,10-diethoxy-5-decyne, 1,14-diethoxy-7-tetradecyne, and 1,14-bisdiethylamino-7-tetradecyne were obtained.The spectra were determined in the Optical Laboratory of the Institute of Heteroorganic Compounds of the USSR by N. A. Chumaevskii, who we thank.     

Mono-Protected Diamines. N-tert-Butoxycarbonyl-α,ω-Alkanediamines from α,ω-Alkanediamines

We wish to report a convenient pathway to N-tert-butoxycarbonyl-α,ω-alkanediamines 2a-e [H₂N(CH₂)χNHBOC; χ=2, 3, 4, 5 and 6; (75–90% yields)] by treatment of the corresponding α,ω-alkanediamine with di-tert-butyl dicarbonate in dioxane as the solvent. Only small amounts of the bis-substituted N.N′-tert-butoxycarbonyl-α,ω-alkanediamines 3a-e were formed (2–9%) which were easily removed by an aqueous workup. The α,ω-alkane-aza-diamine 4 was also mono-protected (62% yield of 5) by the same methodology.     

α,ω-双-(对-氨基苯氧基)-烷类的合成

α,ω-双-(对-氨基苯氧基)-戊烷和庚烷系由对-硝基苯酚与相当的α,ω-二溴烷缩合,再行还原而得;而α,ω-双-(对-甲氨基苯氧基)-戊烷和庚烷的制备,则系以对-(N-对-甲苯磺酰-N-甲氨基)-苯酚或对-(N-乙酰-N-甲氨基)-苯酚代替对-硝基苯酚同法进行缩合,继以水解制得。     

Electrochemical oxidation of tetramethyl esters of α,α,ω,ω-alcaneteracarboxylic acids

Cyclization of esters of butane-1,1,4,4- and pentane-1,1,5,5-tetracarboxylic acids during electrolysis in methanol in the presence of Nal produces, with a yield of 95%, the esters of cyclobutane-1,1,2,2- and cyclopentane-1,1,2,2-tetracarboxylic acids. Under similar conditions, esters of the highest ,,,-alkanetetracarboxylic acids undergo iodation and hydroxymethylation due to electrical oxidation of methanol to formaldehyde. During electrolysis in methanol in the presence of NaOAc, the esters of ,,,-alkanetetracarboxylic acids undergo effective hydroxymethylation, followed by cyclization into substituted five- and six-member lactones, or tetrahydrofurans when structurally possible.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2332–2339, October, 1992.