Chemistry of Pentafluorosulfanyl Derivatives and Related Analogs: From Synthesis to Applications

Pentafluorosulfanyl (SF₅)-containing compounds and corresponding analogs are a highly valuable class of fluorine-containing building blocks owing to their unique properties. The reason for that is the set of peculiar and tremendously beneficial characteristics they can impart on molecules once introduced onto them. Despite this, their application in distinct scientific fields remains modest, given the extremely harsh reaction conditions needed to access such compounds. The recent synthetic approaches via S−F, and C−SF₅ bond formation as well as the use of SF₅-containing building blocks embody a “stairway-to-heaven” loophole in the synthesis of otherwise-inaccessible chemical scaffolds only a few years ago. Herein, we report and evaluate the properties of the SF₅ group and analogs, by summarizing synthetic methodologies available to access them as well as following applications in material science and medicinal chemistry since 2015.     

Discovery of Novel Symmetrical 1,4-Dihydropyridines as Inhibitors of Multidrug-Resistant Protein (MRP4) Efflux Pump for Anticancer Therapy

Despite the development of targeted therapies in cancer, the problem of multidrug resistance (MDR) is still unsolved. Most patients with metastatic cancer die from MDR. Transmembrane efflux pumps as the main cause of MDR have been addressed by developed inhibitors, but early inhibitors of the most prominent and longest known efflux pump P-glycoprotein (P-gp) were disappointing. Those inhibitors have been used without knowledge about the expression of P-gp by the treated tumor. Therefore the use of inhibitors of transmembrane efflux pumps in clinical settings is reconsidered as a promising strategy in the case of the respective efflux pump expression. We discovered novel symmetric inhibitors of the symmetric efflux pump MRP4 encoded by the ABCC4 gene. MRP4 is involved in many kinds of cancer with resistance to anticancer drugs. All compounds showed better activities than the best known MRP4 inhibitor MK571 in an MRP4-overexpressing cell line assay, and the activities could be related to the various substitution patterns of aromatic residues within the symmetric molecular framework. One of the best compounds was demonstrated to overcome the MRP4-mediated resistance in the cell line model to restore the anticancer drug sensitivity as a proof of concept.     

Naphthyl azomesogens with lateral chloro groups

A homologous series of azomesogens, 2″-[4-(4′-n-alkoxybenzoyloxy)-2-chlorophenylazo] naphthalenes, with lateral chloro groups was synthesised. All the homologues synthesized exhibit enantiotropic nematic mesophase. The mesomorphic properties of the present series are compared with other structurally related series to evaluate the effect of lateral chloro group and its position on mesomorphism This paper was presented at the 10th National Conference on Liquid Crystals held at Bangalore, India during 9–11 October 2003.     

Nucleophilic chain substitution on perfluoroketene dithioacetals by ethyl 2-trimethysilyl acetate. Application to the synthesis of 2-trifluoromethyl succinic acid derivatives

A highly efficient substitution of the vinyl fluoride of perfluoroketene dithioacetals was achieved using trimethylsilylacetate to give 2-perfluoroalkyl succinic acid derivatives and 2-trifluoromethyl succinimides. This chain process was initiated by a catalytic amount of fluoride salt, whereas reaction failed with the corresponding lithium enolate.     

Synthesis and refractive‐index control of fluoropolymers by the polyaddition of bis(epoxide)s and triazine di(aryl ether)s

The polyaddition of fluorine‐containing bis(epoxide)s and fluorine‐containing triazine di(aryl ether)s were examined to give the corresponding fluorine‐containing poly(cyanurate)s. It was observed that the synthesized fluoropolymers had good thermal stabilities and good film‐forming properties. The glass transition temperatures (T_g's) and refractive‐indices (n_D's) of synthesized polymers were determined by differential scanning calorimetry and ellipsometry, respectively, and it was found that the values of T_g's and n_D's were supported by their fluorine containing ratios and skeletons. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4421–4429, 2007     

Effects of diamines and their fluorinated groups on the color lightness and preparation of organosoluble aromatic polyimides from 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]‐hexafluoropropane

To investigate the position and amount of the CF₃ group affecting the coloration of polyimides (PIs), we prepared 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]hexafluoropropane ( 2 ) with four CF₃ groups with 2‐chloro‐5‐nitrobenzotrifluoride and 2,2‐bis(4‐hydroxyphenol)hexafluoropropane. A series of soluble and light‐colored fluorinated PIs ( 5 ) were synthesized from 2 and various aromatic dianhydrides ( 3a – 3f ). 5a – 5f had inherent viscosities ranging from 0.80 to 1.19 dL/g and were soluble in amide polar solvents and even in less polar solvents. The glass‐transition temperatures of 5 were 221–265 °C, and the 10% weight‐loss temperatures were above 493 °C. Their films had cutoff wavelengths between 343 and 390 nm, b* values (a yellowness index) ranging from 5 to 41, dielectric constants of 2.68–3.01 (1 MHz), and moisture absorptions of 0.03–0.29 wt %. In a comparison of the PI series 6 – 8 based on 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane, we found that the CF₃ group close to the imide group was more effective in lowering the color; this means that CF₃ of 5 , 7 , and 8f was more effective than that of 6c . The color intensity of the four PI series was lowered in the following order: 5 > 7 > 6 > 8 . The PI 5f , synthesized from diamine 2 and 4,4′‐hexafluoroisopropylidenediphthalic anhydride, had six CF₃ groups in a repeated segment, so it exhibited the lightest color among the four series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 922–938, 2003     

含氟碳菁染料聚集行为的研究

本文对五种不同结构的含氟碳菁染料的甲醇溶液及吸附在碘溴化银T 颗粒表面的聚集行为进行了研究 ,测定了照相性能 ,计算了增感倍率。Dye1 ,Dye2 ,Dye3在甲醇溶液中测得的单分子态吸收曲线 ,当取代基从C2 H5→CH3→无取代基时 ,最大吸收峰对应的波长向短波方向移动 ;乙基取代基的增感染料 (Dye1 )吸附在碘溴化银表面形成的J 聚集态峰值较高 ,对应的增感倍率也高。没有取代基的增感染料 (Dye3)不形成J 聚集 ,增感倍率低 ,有减感作用。Dye4与Dye5相比 ,Dye4具有尖而窄的J 聚集反射光谱 ,增感倍率高。结果表明 :不同结构的增感染料吸附在卤化银颗粒上形成的J 聚集态不同 ,吸收谱带窄的J 聚集态增感染料具有较高的增感倍率。     

Photorefractive Four-Wave Mixing Switches Utilizing Pockels Effect -Longitudinal and Lateral Switches-

We carried out detailed calculations for photorefractive wave-mixing switches based on one of three crystals with high electro-optic coefficients, namely, BaTiO₃, Strontium Barium Niobate (SBN (0.75)), and Potasium Sodium Strontium Barium Niobate (KNSBN). A comparison of results for the three crystals shows that a 0_-cut BaTiO³ crystal is suitable for a longitudinal switch and requires a voltage of about 80 for a 2-mm-thick crystal to induce sufficient phase mismatch. The electrodes must be transparent for the incident and diffracted beams. A 45_-cut SBN (0.75) crystal, however, is suitable for a lateral switch and requires a voltage of about 150 for a 1-mm-wide crystal. The electrodes do not need to be transparent.     

透镜初级球差的横向剪切干涉条纹研究

利用玻璃平行平板构成简单的横向剪切干涉仪可以观察到单薄透镜形成的准直光束的剪切干涉条纹,由干涉条纹分布求出对应的几何像差和离焦量.用焦距为190 mm的单薄透镜做实验,实验结果与计算机模拟结果符合,说明可以从剪切干涉条纹的分布求出透镜的轴向调整误差和初级球差.     

横向放大率法测定光具组的基点

介绍了用横向放大率法确定两薄透镜组成的光具组基点的原理和方法,该方法采用线阵光电耦合器件(CCD)测量物经光学系统成像的横向放大率,进一步提高了测量精度.