Aromatic polyamides containing keto-benzocyclobutene pendants

A series of novel benzocyclobutene (BCB)-pendanted polyamides (inherent viscosities: 0.20–0.69 dL/g) was synthesized from 3,5-diaminophenyl-4-benzocyclobutenyl ketone, and terephthaloyl, isophthaloyl, 4,4′-oxydibenzoyl chlorides, as well as 4,4′-(o-phenylenedioxy)dibenzoyl chloride. The DSC studies demonstrated that the BCB crosslinking exothermic transition occurred at nearly the same temperature (max. ∼︁ 275°C) for all the four polyamides, and they were thermally stable up to 380°C in helium, where the weight loss started to occur. TGA and DSC studies in air indicated that the polymers, in contrast to the model compound, showed evidence of oxidation just prior to or occurring simultaneously with the BCB crosslinking reaction. This could be attributed to the oxidation of the reactive diene generated from the ring-opening of the BCB competing with the process of two BCB pendant units approaching each other for crosslinking reaction. Preliminary examination of the BCB-pendanted polyamide regenerated from a methanesulfonic acid solution indicates that the BCB ring is quite stable (DSC evidence) in the strong acid medium. © 1996 John Wiley & Sons, Inc.     

Ring-opening polymerization of macrocyclic aryl ether ketone oligomers containing the 1,2-dibenzoylbenzene moiety

Facile ring-opening polymerization of cyclic aryl ether oligomers containing the 1,2-dibenzoylbenzene moiety to form high molecular weight linear polymers in the presence of a nucleophilic initiator is described. The polymerization can be initiated in the melt in the presence of a nucleophilic initiator such as potassium carbonate, cesium fluoride, and alkali phenoxides. Various alkali phenoxides were investigated as potential nucleophilic initiators. The polymerization reaction rate in the melt increases in the order of K⁺ > Na⁺ > Cs⁺, and in the order of ⁻OPhPhO⁻ > PhO⁻ > PhOPhO⁻ > PhPhO⁻. However, the polymerization in an aprotic dipolar solvent is faster in the presence of cesium phenoxide than in the presence of potassium phenoxide. Polymerization of the cyclic oligomers in solution demonstrates that the ring-opening polymerization proceeds via a chain-growth mechanism and involves a transetherification reaction between linear and cyclic aryl ether oligomers. The ring-chain equilibrium is much more favorable towards linear polymers. Since little or no ring strain exists in the cyclic system, the transetherification reactions are indiscriminate with regards to cyclic or linear chains and the interchain equilibration is also a facile process during polymerization. This intermolecular transetherification has been demonstrated by using low molecular weight aryl ethers to control the molecular weight of the polymer formed via ring-opening polymerization. © 1996 John Wiley & Sons, Inc.     

二异丙基酮定性定量方法的研究

采用色谱—质谱联用技术对酸—酸化反应制得的二异丙基酮化冷凝液进行了系统的定性,并且在色谱仪上利用外标法和面积归一化法对主要组分进行了定量方法的比较,得到了较好的定性定量结果。     

(Liquid + liquid) equilibria of (water + propionic acid + methyl isoamyl ketone or diisobutyl ketone or ethyl isoamyl keton) at T = 298.2 K

(Liquid + liquid) equilibrium (LLE) data for (water + propionic acid + solvent) were measured at T = 298.2 K and atmospheric pressure. The solvents were methyl isoamyl ketone (5-methyl-2-hexanone), ethyl isoamyl ketone (5-methyl-3-heptanone) and diisobutyl ketone. The tie-line data were correlated by means of the NRTL and UNIQUAC equation, and compared with results predicted by the UNIFAC method. A comparison of the extracting capabilities of the solvents was made with respect to distribution coefficients, separation factors, and solvent free selectivity bases.     

Sodium dithionite initiated addition of 1-bromo-1-chloro-2,2,2-trifluoroethane to allylaromatics: Facile synthesis of conjugated dienes substituted with terminal CF3 group

Sodium dithionite effectively promotes the addition of 1-bromo-1-chloro-2,2,2-trifluoroethane to the terminal double bond of allylbenzenes 1. The reactions proceeded in MeCN/H₂O to give a 3:1 mole ratio of diastereoisomers of 1-(2-bromo-4-chloro-5,5,5-trifluoropentyl)benzenes 2 as the main products together with small amounts of its reductive debromination products 3. Total yields of 2 and 3 were dependent on the nature of the aromatic ring substituents in 1. Treatment of adducts 2 with DBU in refluxing hexanes resulted in double dehydrohalogenation affording, in good yields, conjugated dienes 4 (1,1,1-trifluoro-5-phenyl-2,4-pentadienes) terminated with the CF₃ group at the one end and the phenyl group at the opposite end. These dienes were found to be sufficiently reactive to undergo Diels-Alder condensation with active dienophiles to give trifluoromethylated carbocycles. The reactions of CF₃CHClBr with allylheterocycles were less successful and lead to low yields of mixtures of hardly separable compounds or to polymeric resins.     

Synthesis of 2-arylacrylic esters from aryl methyl ketones via Wittig reaction/singlet oxygen ene reaction

An efficient synthetic method has been developed for the synthesis of 2-arylacrylic esters from the corresponding aryl methyl ketones via Wittig reaction and singlet oxygen ene reaction. Wittig reaction to aryl methyl ketones with (methoxymethyl)triphenylphosphonium chloride in basic condition afforded the methyl enol ethers, and then 2-arylacrylic esters were obtained by singlet oxygen ene reaction, followed by tosylation and elimination in one-pot to the methyl enol ethers in good yields.     

Novel and Efficient One Pot Condensation Reactions between Ketones and Aromatic Alcohols in the Presence of CrO3 Producing α,β‐Unsaturated Carbonyl Compounds

We report a new, effective and simple method for preparing α,β‐unsaturated carbonyl compounds by reacting ketones and aromatic alcohols at 56°C in the presence of CrO₃ (CrO₃ acts as an oxidant and also a catalyst) for around 10 h. The condensation reactions occurred effectively among a wide combination of ketones and alcohols. The procedure is simple and the yields can be high up to 98%. And a probable mechanism is proposed.     

An improved palladium(II)-catalyzed method for the synthesis of aryl ketones from aryl carboxylic acids and organonitriles

A palladium(II)-catalyzed decarboxylative protocol for the synthesis of aryl ketones has been developed. The addition of TFA was shown to improve the reaction yield and employing THF as solvent enabled the use of solid nitriles and in only a small excess. Using this method, five different benzoic acids reacted with a wide range of nitriles to produce 29 diverse (hetero)aryl ketone derivatives in up to 94% yield.     

2,4,6-Tris(4-iodophenoxy)-1,3,5-triazine as a new recyclable “iodoarene” for in situ generation of hypervalent iodine(III) reagent for α-tosyloxylation of enolizable ketones

The synthesis of 2,4,6-tris[(4-iodo)phenoxy)]-1,3,5-triazine 6, as a new recyclable nonpolymeric analogue of iodobenzene is achieved using the reaction of 2,4,6-trichloro-1,3,5-triazine with 4-iodophenol in the presence of KOH. The application of 6 as a recyclable ‘iodoarene’ is demonstrated for α-tosyloxylation of enolizable ketones via in situ generation of hypervalent iodine(III) species using PTSA and MCPBA as the terminal oxidant. The recyclability of the reagent 6 was possible owing to the facile recovery and reuse from the reaction mixture due to its near insolubility in methanol.     

含羧酸共生稀土光敏剂的低密度聚乙烯膜紫外光氧化降解

含羧酸共生稀土光敏剂的低密度聚乙烯膜紫外光氧化降解林宜超（福建省测试技术研究所福州３５０００３）近年来，许多作者先后研究并开发出含硬脂酸铈（ＣｅＳｔ３）光敏剂的可控光降解低密度聚乙烯（ＬＤＰＥ）［１，２］、高密度聚乙烯［３］、聚丙烯［４］、聚苯乙烯...