N—BOC—8—氨甲基—2—萘甲酸的改进合成法

以２－萘甲酸为原料，经硝化，酯化，重氮化，选择性催化氢化，ＢＯＣ酸酐保护等六步反应，完成了Ｎ－ＢＯＣ－８氨甲基－２－萘甲酸（１ａ）的合成，为化合物１的合成提供了新的合成途径。     

Simple and Selective Removal of the t‐Butyloxycarbonyl (Boc) Protecting Group on Indoles,Pyrroles, Indazoles,and Carbolines

A highly selective and efficient deprotection of the N‐t‐butoxy carbonyl (N‐Boc) group on indoles, pyrroles, indazoles, and carbolines has been achieved in high yields using a catalytic amount of NaOMe as a base in dry MeOH, at ambient temperature.     

Forensic differentiation of biogenic organic compounds from petroleum hydrocarbons in biogenic and petrogenic compounds cross-contaminated soils and sediments

“Total petroleum hydrocarbons” (TPHs) or “petroleum hydrocarbons” (PHCs) are one of the most widespread soil pollutants in Canada, North America, and worldwide. Clean-up of PHC-contaminated soils and sediments costs the Canadian economy hundreds of million of dollars annually. Much of this activity is driven by the need to meet regulated levels of PHC in soil. These PHC values are legally required to be assessed using standard methods. The method most commonly used in Canada, specified by the Canadian Council of Ministers of the Environment (CCME), measures the total hydrocarbon concentrations in a soil by carbon range (Fraction 1: C₆–C₁₀; Fraction 2: C₁₀–C₁₆, Fraction 3: C₁₆–C₃₄: and Fraction 4: C₃₄+). Using the CCME method, all of the materials extractible by a mixture of 1:1 hexane:acetone are considered to be petroleum hydrocarbon contaminants. Many hydrocarbon compounds and other extractible materials in soil, however, may originate from non-petroleum sources. Biogenic organic compounds (BOCs) is a general term used to describe a mixture of organic compounds, including alkanes, sterols and sterones, fatty acids and fatty alcohols, and waxes and wax esters, biosynthesized by living organisms. BOCs are also produced during the early stages of diagenesis in recent aquatic sediments. BOC sources could include vascular plants, algae, bacteria and animals. Plants and algae produce BOCs as protective wax coating that are released back into the sediment at the end of their life cycle. BOCs are natural components of thriving plant communities. Many solvent-extraction methods for assessing soil hydrocarbons, however, such as the CCME method, do not differentiate PHCs from BOCs. The naturally occurring organics present in soils and wet sediments can be easily misidentified and quantified as regulated PHCs during analysis using such methods. In some cases, biogenic interferences can exceed regulatory levels, resulting in remediation of petroleum impacts that are not actually present. Consequently, reliance on these methods can trigger unnecessary and costly remediation, while also wasting valuable landfill space. Therefore, it is critically important to develop new protocols to characterize and differentiate PHCs and BOCs in contaminated sediments. In this study, a new reliable gas chromatography–mass spectrometry (GC–MS) method, in combination with a derivatization technique, for characterization of various biogenic compounds (including biogenic alkanes, sterols, fatty acids and fatty alcohols) and PHCs in the same sample has been developed. A multi-criteria approach has been developed to positively identify the presence of biogenic compounds in soil and sediment samples. More than thirty sediment samples were collected from city stormwater management (SWM) ponds and wetlands across Canada. In these wet sediment samples, abundant biogenic n-alkanes, thirteen biogenic sterols, nineteen fatty carboxylic acids, and fourteen fatty alcohols in a wide carbon range have been positively identified. Both PHCs and BOCs in these samples were quantitatively determined. The quantitation data will be used for assessment of the contamination sites and toxicity risks associated with the CCME Fraction 3 hydrocarbons.     

NMR和XAFS方法研究溶液中杯芳冠醚与碱金属离子配位化学

给出了1,3-二辛氧基杯[4]芳烃冠醚-6(25,27-bis-octyloxy-calix[4]arene-26,28-crown-6, BOC6)和杯[4]芳烃双冠醚-6(1,3-alternate biscrown-6, BisC6)晶体结构参数, 用NMR(CDCl₃作溶剂)和XAFS(X-ray absorption fine structure)方法研究了邻硝基苯甲醚(o-nitro-phenyl methyl ether, NPME)和正辛醇(n-octyl alcohol, OA)溶液中BOC6和BisC6与碱金属离子的配位行为. 结果表明: 铯离子的嵌入使得杯芳冠醚分子中冠醚链的对称性明显提高; 在溶液中,配合物分子中铯离子的配位数为7, 7个氧的配位是一种稳定结构.     

Electrophoretic separation strategy for chiral pharmaceuticals using highly-sulfated and neutral cyclodextrins based dual selector systems

The enantiomeric separation of chiral pharmaceuticals was investigated using dual systems with mixtures of cyclodextrin derivatives. The dual cyclodextrin systems, consisting of one highly-sulfated (α-, β-, and γ-HSCD) and one neutral cyclodextrin, i.e. either heptakis (2,3,6-tri-O-methyl)-β-CD (TMCD), heptakis (2,6-di-O-methyl)-β-CD (DMCD) or hydroxypropyl-β-CD (HPCD), are tested on 25 pharmaceutical compounds with different acid-basic properties (16 basics, 8 acids and 1 neutral). The influence on the separation of the type and concentration of neutral CD in highly-sulfated cyclodextrins-based dual selector systems, is investigated. For 11 of 16 basic compounds, a better separation is obtained with the CD mixtures compared to the use of only a highly-sulfated CD. Mixtures with TMCD give better results than those with DMCD and HPCD. Results showed that dual CD systems are useful to achieve and to optimise chiral separations of compounds not (sufficiently) separated with HSCDs alone. For example, ibuprofen was not resolved with α-, β- or γ-HSCD, but could be separated with the mixture 25 mM TMCD and 5% HS-β-CD. Based on the obtained results, a dual CD systems based separation strategy is defined.     

Selective Mono‐BOC Protection of Diamines

A facile route for mono‐BOC protection of symmetrical and unsymmetrical diamines was developed by sequential additions of 1 mol of HCl and 1 mol of (BOC)₂O followed by neutralization.     

Aqueous phosphoric acid as a mild reagent for deprotection of the t-butoxycarbonyl group

Aqueous phosphoric acid (85 wt%) is an efficient and mild reagent for the deprotection of N-BOC groups. Acid sensitive functionalities including benzyl and methyl esters, TBDMS ether, CBZ and isopropylidene groups are compatible with the reaction conditions. The reactions are high yielding, and the workup is convenient.     

An optimised synthesis of SG3376, a non-cleavable antibody-drug conjugate pyrrolobenzodiazepine drug-linker

In recent years, antibody-drug conjugates (ADCs) have been evaluated in a growing number of clinical trials. Preclinical evaluation and the synthetic accessibility of cleavable pyrrolobenzodiazepine drug-linkers, such as talirine and tesirine, have been previously described. This article details how the synthesis of SG3376, a non-cleavable pyrrolobenzodiazepine drug-linker, has been optimised to provide access to late-stage versatile intermediates in a robust and scalable fashion. Of particular importance was the selective deprotection of primary N-Boc in the presence of secondary N-Boc and secondary O-TBS. SG3376 was conjugated to trastuzumab and the resulting ADC was found to have potent cytotoxic activity in a number of HER2-positive cancer cell lines.     

Navigation signal structure based on complex carrier modulation

Signal structure design is an important part of satellite navigation system research,which directly affects navigation performance.Signal performance parameters are analyzed and performances of BPSK modulated signals and BOC modulated signals are compared.Aiming at requirements of high navigation precision and high anti-jamming ability,a new navigation signal structure based on complex carrier modulation is proposed and performances of the signal are researched with different parameters.A synchronization al...     

氨基酸卟啉衍生物的合成

以对硝基苯甲醛、吡咯为起始物，经缩合成环得到了四（4－硝基苯基）卟啉（TNPP），以此为基础依次合成了四（4－氨基苯基）卟啉（TAPP）及带有缬氨酸侧链的卟啉类化合物TAPP－Val-BOC,TAPP-Val，其结构经紫外、红外和^1H核磁等得到了证实。同时通过实验数据对卟啉成环反应的影响因素进行了探讨，从而确定了反应进行的最佳条件。