固相氯化法合成氯化聚乙烯的红外光谱研究

本文研究在不同条件固相氯化聚乙烯(CPE)的红外光谱,探讨了一步和两步氯化合成的CPE的结构差别,着重讨论了两步氯化的CPE结构特点。从观察表征结晶结构和—(CH_2)_n—链段氯分布的特征频率变化表明,低温固相氯化主要发生在无定形区,并且在CPE中形成高氯化和低氯化链段(或未氯化)的嵌段结构。在两步固相氯化时,晶区受到较大程度的破坏,氯化作用已不局限在无定形区,其结晶结构的破坏主要同第二步氯化程度有关,即使CPE氯含量相同,若前后两步氯化程度不同,结构有很大差异。     

Synthesis of a selective estrogen receptor β-modulator via asymmetric phase-transfer catalysis

An efficient asymmetric synthesis of selective estrogen receptor β-modulator (S)-4-bromo-9a-butyl-8-chloro-6-fluoro-7-hydroxy-1,2,9,9a-tetrahydro-fluoren-3-one was developed. The route features a chemoselective aromatic chlorination reaction, an asymmetric phase-transfer-catalyzed alkylation of an indanone with efficient ee upgrade by racemate crystallization, and a robust bromination reaction using imidazole as an in situ bromine trap to avoid overreaction. The synthesis proceeds in 34% yield over 8 steps from 2-fluoroanisole, and provides material with >99.5% ee.     

Aquatic degradation of triclosan and formation of toxic chlorophenols in presence of low concentrations of free chlorine

The degradation of 2-(2,4-dichlorophenoxy)-5-chlorophenol (triclosan) in chlorinated water samples was investigated. Sensitive determination of the parent compound and its transformation products was achieved by gas chromatography with mass spectrometry detection after sample concentration, using a solid-phase extraction sorbent and silylation of the target compounds. Experiments were accomplished using ultrapure water spiked with chlorine and triclosan concentrations in the low mg/l and ng/ml ranges respectively. Chlorination of the phenolic ring and cleavage of the ether bond were identified as the main triclosan degradation pathways. Both processes led to the production of two tetra- and a penta-chlorinated hydroxylated diphenyl ether, as well as 2,4-dichlorophenol. The formation of 2,3,4-trichlorophenol was not detected in any experiment; however, significant amounts of 2,4,6-trichlorophenol were noticed. All of these five compounds were also identified when triclosan was added to tap-water samples with free chlorine concentrations below 1 mg/l. Minor amounts of three di-hydroxylated phenols, containing from one to three atoms of chlorine in their structures, were also identified as unstable triclosan chlorination by-products. The analysis of several raw wastewater samples showed the co-existence of important concentrations of triclosan and its most stable by-products (2,4-dichlorophenol and 2,4,6-trichlorophenol), reinforcing the potential occurrence of the described transformations when products containing triclosan are mixed with chlorinated tap water.     

Concise Synthesis of Ximenynic Acid

Abstract

An improved synthesis of ximenynic acid (1) starting from castor oil has been developed with the direct chlorination of ricinstearolic acid as the key step. By this modification, the synthetic route was more concise and economic. The separation of geometric somers was achieved by repeated urea fractionation.

Supplemental materials are available for this article. Go the publisher's online edition of Synthetic Communications to view the free supplemental file.     

Oxidation for unsymmetrical bromo-1,10-phenanthrolines and subsequent hydroxylation,decarbonylation and chlorination reactions

A systematic investigation on the oxidation of unsymmetric bromo-phens is presented herein, where the reaction temperature is found to be the key parameter to generate oxidation or oxidation-bromination products. The regioselective C3-brominated compounds are produced in moderate yields in the cases of 2-bromo-phen and 4-bromo-phen. Subsequent hydroxylation and decarbonylation for bromo-phds are also studied, where a series of bromo-diazafluorenones and phen-triones have been isolated. Furthermore, various chlorination products have been obtained by treating bromo-phds or bromo-phts with excess POCl₃.     

α‐Chlorination of Carboxylic Acids Using Trichloroisocyanuric Acid

Abstract

Carboxylic acids are chlorinated in the α position by heating with trichloroisocyanuric acid after formation of a small amount of the acid chloride using phosphorus trichloride.     

Phosphonium salt induced stereoselective allylic rearrangement during chlorination of α-hydroxyallylphosphinates

α-Hydroxyallylphosphinates were stereoselectively converted to γ-chloro allylphosphinates when treated with Ph₃P and CCl₄, via substitution of hydroxyl and migration of double bond. The reaction was promoted by phosphonium cation that acted as Lewis acid.     

One‐Pot Regioselective Synthesis of Novel Oximino Ester‐Containing 1‐Aryl‐4‐chloro‐3‐oxypyrazoles as Potential Fungicides

A novel, functional‐group‐tolerant, and highly regioselective one‐pot synthesis of six 4‐chloro‐1‐aryl‐3‐oxypyrazoles, 8a – 8f , containing an oximino ester moiety has been developed. Their structures were characterized by ¹H‐ and ¹³C‐NMR, IR, MS, and elemental analyses. The regioselectivity of the reaction was also determined by single‐crystal X‐ray diffraction analysis of product 8d . The reaction pathway, proposed with the aid of DFT calculations, likely proceeds via a DMF‐catalyzed mechanism, which involves an electrophilic attack by SOCl₂ and two nucleophilic substitutions by benzyl bromide (BnBr) and Cl^?, respectively, as the key steps. A preliminary in vitro bioassay indicated that most compounds exhibited good fungicidal activities against Sclerotinia sclerotiorum and Gibberella zeae. Especially, 8d and 8e displayed higher or similar fungicidal activities compared with pyraclostrobin at the concentration of 10 μg/ml.     

金属离子对在饮用水氯化过程中形成消毒副产物的影响的研究进展

饮用水氯化消毒的安全性问题一直是水处理领域的研究热点之一.由于天然水体中矿物质的普遍存在以及微量重金属污染的经常发生,开展金属离子对消毒副产物形成的影响规律研究,对于实际饮用水消毒副产物的控制及其对人类健康的影响评价都具有重要意义.本文以目前研究较多的一些典型金属离子和金属氧化物（如铜离子、铁离子、二氧化锰和二氧化铅等...