格林尼亚反应合成全氘代-α-苯乙醇

以重水 (D2 O)及电石 (CaC2 )为原料 ,先制得氘代乙醛 (CD3CDO) ;氘代苯则与溴和金属镁反应生成氘代苯基溴化镁 (C6D5MgBr)。CD3CDO再与C6D5MgBr进行格林尼亚反应 ,并用酸性重水溶液水解 ,最终制得氘代率xD≈ 99%的全氘代 α 苯乙醇 (C6D5—CDODCD3) ,产率 71.2 % (以氘代溴苯计 )。作者介绍了以D2 O、CaC2 及C6D6为原料制备C6D5—CDODCD3 的合成工艺及采用内标相对摩尔校正因子氢核磁共振波谱 (1HNMR)技术表征产物氘代率的方法     

全氘代聚苯乙烯的合成

以氘代苯（Ｃ６Ｄ６）、氘代醋酸（ＣＤ３ＣＯＯＤ）及重水（Ｄ２Ｏ）等市售试剂为原料,经酰化、镍铝合金碱性重水液相还原、脱水及自由基本体聚合等一系列反应,在国内首次合成出了全氘代聚苯乙烯（ＰＳＤ）。该ＰＳＤ材料氘代率达９８．３５％,可望在激光聚变热核靶、低损耗塑料光纤及聚合物相容性研究等领域得到广泛的应用。     

临床试验的氘代药物及其氘代合成策略

综述了临床在研和已上市的20种氘代药物,分析了其氘代合成策略,结果表明氘代甲基CH3-d3是使用频率高和较成功的方法,展望了各种氘代策略的前景。     

新法氘代溴苯-d_5的合成与表征

以氘代苯（Ｃ６Ｄ６）及单质溴（Ｂｒ２）为原料,铁粉（Ｆｅ）及单质碘（Ｉ２）为催化剂,同时改进了常规溴苯合成中粗产物的后处理工序,最终合成出了产率达７２．５％ 、氘代率达９９．２％ 的氘代溴苯（Ｃ６Ｄ５Ｂｒ）。采用付立叶变换红外光谱仪及激光拉曼光谱仪对Ｃ６Ｄ５Ｂｒ的振动光谱特性进行了研究,此外亦采用相对重量校正因子１Ｈ－核磁共振波谱法对样品氘代率的测定进行了探讨。     

氘代聚苯乙烯的合成及表征

在惯性约束聚变(ICF)靶材应用领域,氘代聚合物一直占据着重要位置。本文在氘代苯乙烯(D8,98%)中加入质量分数为其0.4%的引发剂,采用本体聚合方法聚合全氘代聚苯乙烯(D8,DPS),反应温度为70℃,反应时间为72 h,用傅里叶变换红外光谱仪、核磁共振仪对DPS的结构进行表征,综合测试结果表明产物为DPS。采用差式扫描量热仪和热重分析仪分析DPS的热性能,表明DPS的玻璃化转变温度为105℃,5%失重温度为380℃,热性能较好,满足ICF试验使用要求。     

氘代有机物的表征技术

氘代有机物的种类越来越多,氘代基团、氘代率以及含氘量都是分子中需要表征的重要信息。综述了红外光谱、拉曼光谱、质谱、氢核磁共振波谱、分光光度法等在表征以上参数的定性定量方法,并初步总结了氢原子被氘代后体现在红外光谱、质谱上的变化规律。     

氘代氨基甲酸酯类化合物的合成与表征

设计了以有机酚为原料制备氘代氨基甲酸酯类化合物的合成路线。有机酚(Ⅰa~Ⅰc)在Na OH催化作用下,经与三光气(BTC)反应,合成了中间体氯甲酸酯(Ⅱa~Ⅱc),再与一甲胺-D3-盐酸盐缩合反应,制得目标化合物(Ⅲa'~Ⅲc')。设计的合成路线避免使用异氰酸酯,且操作简单,工艺流程短,副产物少,收率可达60%以上,氘同位素丰度没有降低。产物经HPLC、MS、1HNMR和13CNMR表征,结果表明,化学纯度99%,氘同位素丰度99 atom%。     

氘代药物进展

简要地介绍了氘的动力学同位素效应,以及将药物分子中特定的氢替换成氘得到的氘代药物,可以改变药物在体内的代谢速度甚至是代谢途径,达到增加药效和减少副作用的目的。同时还介绍了氘代药物的研究进展和临床情况。尽管到目前为止还没有一个氘代药物被批准上市,但是其临床中表现出的治疗效果还是显著的,相信在不久的未来氘代药物的上市会得到实现。     

钴催化氘代甲氧基化苯甲酰胺衍生物的合成研究

由于C-D键独特的稳定性和标记作用,在化合物中引入氘对于候选药物的合成以及反应机理的研究具有重要意义。芳基醚是一种在药物、溶剂和聚合物前体等方面具有应用前景与价值的化合物,广泛存在于药物中间体和农业生产中。本文根据C-D键和芳基醚类化合物的双重优势,以氘代甲醇为氘源,开发了一种钴(II)/水杨醛配体组成的催化体系,在氧化条件下高效合成了氘代甲氧基化芳烃化合物,该方法无需使用酸碱添加剂,反应条件温和,具有良好的官能团相容性和氘掺入量,各种不同取代的苯甲酰胺衍生物产率中等至良好。     

氘代抗过敏药物赛庚啶的合成研究

论文简要论述了氘代药物的研究意义和利用现代有机化学合成氘代化合物的方法。文章选取了一种常见的传统抗过敏药赛庚啶进行氘代合成改性研究,发现以双(降冰片二烯)四氟硼酸铑(I)为催化剂,氘代甲醇为氘源,在80℃下回流反应48小时,反应能顺利发生氢氘交换反应以87%的产率得到高氘代率的赛庚啶产物,其中氘代率可以达到98%。合成的产物经过气相色谱-质谱和核磁共振氢谱、碳谱和氘谱进行表征确认目标产物结构。     

Synthesis of completely deuterated hydrocarbons

The possibility of synthesizing a new material—completely deuterated hydrocarbons—by the Fischer-Tropsch process has been demonstrated. This is the first step toward the formation of a research-and-production basis for the creation of a pilot plant. There was no isotope effect; consequently, the key characteristics of the synthesis and products were determined by the properties of the catalyst and reaction conditions, irrespective of whether hydrogen or deuterium was used in the starting mixture. Waxes were removed from the catalyst surface under mild conditions; this did not require any special equipment or the transfer of catalyst to another reactor. The chosen catalyst was highly stable and can be used in a pilot plant for the production of completely deuterated waxes. The first evaluation of the properties of the new materials showed that they were promising as solvents for NMR, radioactive labels, targets, neutron flux moderators, etc.     

苯乙酮经Trofimov反应一锅法制备吡咯衍生物的研究

研究了在碳酸氢钠-二甲亚砜催化体系中,酮经Trofimov反应一锅法制备吡咯衍生物。以苯乙酮为原料,生成3-苯基吡咯和1-乙烯基-3-苯基吡咯,反应温度及催化剂的用量对产品收率的影响。其最佳反应条件为:常压,100°C,前者收率为66.2%;后者收率为33.4%。催化剂用量均以NaHCO3/mg:DMSO/mL=420∶10为宜。产物IR及1H NMR均与文献值一致。     

Small-angle neutron scattering from polystyrene—DVB networks containing a delta fraction of deuterated polystyrene: Evidence for aggregation during polymerization

Homopolymer polystyrene-divinylbenzene, PS-DVB, networks were made by free radical chemistry u.v. photopolymerization techniques, and characterized by small-angle neutron scattering (SANS). The networks contained a delta fraction of chains labelled with deuterium. Two different series of samples were made: Method A in which the insertion was made centrally or at the end of the polymerization; Method B in which the delta fraction of deuterated primary chains was inserted at the beginning of the polymerization. Method B samples yielded a molecular weight of about 70,000 g/mole and a radius of gyration of about 120 Å, values in the range expected for single primary chains. Method A samples, however, gave molecular weights of 1–2 million and radii of gyration ranging from 350 to 400 Å. Intrinsic viscosity and gel permeation chromatography (g.p.c.) studies on parallel fractions yielded weight-average molecular weights near 72,000 g/mole for most of the polymerization. These results strongly suggest the existence of aggregation of primary chains synthesized in the same conversion period within the network. A new method of characterizing crosslinking between network chains is proposed, since these experiments count the probability of a chain crosslinking with a chain polymerized immediately before in time.     

含1,2,3-三氮唑肉桂酸衍生物的合成

1,2,3-三氮唑环作为药效基团呈现出多种生物活性,以4-硝基苯甲醛为原料,合成了叠氮基肉桂酸,并以此为原料,CuI为催化剂,与端基炔烃进行1,3-偶极环加成反应,合成含1,2,3-三氮唑功能基的肉桂酸衍生物。     

Reactions and products revealed by NMR spectra of deuterated dimethylsulfoxide with iodomethane in neutral and basic media

Reactions occurring within each one of two mixtures, a mixture of deuterated dimethylsulfoxide, DMSO-d₆, with CH₃I (system I) and another mixture of DMSO-d₆ with CH₃I, NaOH and water (system II), were monitored by 1D and 2D nuclear magnetic resonance (¹H, ¹³C, heteronuclear multiple quantum correlation, heteronuclear multiple bond correlation and diffusion-ordered NMR spectroscopy). The analysis of the spectra as a function of reaction time revealed the formation of methoxy-bis(trideuteromethyl)sulfonium iodide, 3; the precipitation of hexadeuterated trimethyloxosulfonium, 2a; a methyl exchange between DMSO-d₆ and 2a to produce trideuterated dimethylsulfoxide, DMSO-d₃, 4, and nona-deuterated trimethyloxosulfonium iodide, 2b; and the production of small quantities of methanol, 5, trideuterated dimethylsulfide, 6, and dimethyl ether, 7, in both systems. Only system II precipitated deuterated [Na₄(DMSO-d_x)₁₅][(I₃)₃I], 1a, a green solid with metallic shine that corresponds to an isotopomer of 1, which is produced by the self-assembly of DMSO and CH₃I in the presence of NaOH and water.     

Synthesis and polymerization of fluorinated,chlorinated and deuterated vinyl carbonates

The present paper deals essentially with the synthesis of new fluorinated and chlorinated poly(vinylcarbonates). Vinyl carbonates, CH₂=CH-O-CO₂R (where R=CH₂CCl₃, CH₂CF₃, C₂H₄C₆F₁₃ and CD₃) were first prepared by reacting vinyl chloroformate with the corresponding alcohols. Their structures were identified by¹³C NMR. The action of ultraviolet light on these monomers resulted in the corresponding polycarbonates, the refractive indexes and Tg of which were measured. Polycarbonates possess Tg values between those of polyacrylates and polymethacrylates which contain the same substituents.     

Competing Regiochemical Pathways in the Heck Arylation of 1,2‐Dihydronaphthalene

The Heck reaction of aryl iodides with 1,2‐dihydronaphthalene has been examined. Two separate reaction pathways are observed under all the conditions tried. Arylation adjacent to the aromatic ring leads to a subsequent double bond shift such that the product is a 1‐aryl‐1,2‐dihydronaphthalene. The alternative regiochemistry leads to production of the corresponding 3‐aryl‐1,2‐dihydronaphthalene, and labelling studies with specifically deuterated alkenes demonstrate that this is most likely to be the result of a trans Pd‐H elimination pathway. The ratio always varies between 75 : 25 in favour of the 3‐aryl product (Jeffery conditions) to 70 : 30 in favour of the 1‐aryl product.     

氯化聚丙烯／MMA／BA／MAA接枝共聚物的合成

采用溶液法用混合单体甲基丙烯酸甲酯（MMA）、丙烯酸丁酯和2-甲基丙烯酸（MAA）对氯化聚丙烯（cmm）进行接枝改性，考察了反应温度、反应时间、引发剂浓度和单体浓度等因素对接枝率的影响，并对接枝产物进行了傅立叶变换红外光谱分析。确定了理想的工艺条件：反应温度为105℃，反应时间为5h，m（CPP）／m（单体）／m（BPO）为1：0．3：0．0：3。