Efficient Allylation of Nucleophiles Catalyzed by a Bifunctional Heterogeneous Palladium Complex‐Tertiary Amine System

We demonstrate the synergistic catalysis of a silica‐supported diaminopalladium complex and a tertiary amine (SiO₂/diamine/Pd/NEt₂) as well as synthetic scope of the Tsuji–Trost reaction of 1,3‐dicarbonyls, phenols, and carboxylic acids with allyl carbonate and acetates. The synergistic catalysis of SiO₂/diamine/Pd/NEt₂ exhibited wide applicability and high activity for the Tsuji–Trost reaction. For example, the reaction of ethyl 3‐oxobutanate with allyl methyl carbonate afforded the allylated product in >99% yield at 70 °C for 5 h. The yield of allylated products was 26% for SiO₂/diamine/Pd, without immobilization of the tertiary amine group. In the reaction of 1.0 mmol of ethyl 3‐oxobutanate using 0.60 μmol of Pd in SiO₂/diamine/Pd/NEt₂, the turnover number (TON) of Pd reached up to 1070 within 24 h. Phenols with electron‐withdrawing groups, such as nitro and chloro groups, on the para position resulted in high product yields. The SiO₂/diamine/Pd/NEt₂ catalyst was reusable at least 4 times without appreciable loss of its activity and selectivity in the reaction of p‐chlorophenol.     

Pseudo‐Hydroxide Extraction in the Separation of Sodium Hydroxide from Aqueous Solutions Using Alkyl Phenols

Abstract

Pseudo‐hydroxide extraction of sodium hydroxide from aqueous solution using four alkyl phenols of nearly identical molecular weight in 1‐octanol at 25°C was examined to understand the effect of alkyl substituents. The order of extraction strength among the four alkyl phenols tested was 4‐tert‐octylphenol>3,5‐di‐tert‐butylphenol>2,4‐di‐tert‐butylphenol>2,6‐di‐tert‐butyl‐4‐methylphenol. A good correlation with phenol pK _a was observed, indicating that extraction strength is determined by phenol acidity, as modified by steric effects in proximity to the phenol –OH group. The effective partition ratios (P _eff) of two phenols from 1 M NaOH solution were determined, showing that the phenols remain predominantly in the 1‐octanol phase even when converted to their sodium salts. However, the hydrophobicity of the tested phenols may not be sufficient for process purposes. The equilibrium constants for the governing extraction equilibria were determined by modeling the data using the program SXLSQI, supporting the cation‐exchange extraction mechanism. The proposed mechanism consists of two simple sets of equilibria for

1. Ion‐pair extraction to give Na⁺OH^? ion pairs and corresponding free ions in 1‐octanol the phase and

2. Cation exchange by monomeric phenol molecules (HAs) to form monomeric organic‐phase Na⁺A^? ion pairs and corresponding free organic‐phase ions.

沉淀法回收煤焦油和含酚废水中酚类的研究

首次采用沉淀法系统地研究了金属离子对酚类的回收过程，结果表明，该法对焦油中总酚回收率为８９．７％，各组分回收率为８７．２％－９２．５％，该法亦可用来回收含酚废水中酚类、脱酚率＞９５％，因此，本研究为焦油和含酚废水中酚类回收开辟了新路。     

催化裂化汽油选择性加氢脱硫前后组成分析

采用色谱、质谱、元素分析、电位计等分析手段研究了中国石化石家庄炼油化工股份有限公司催化裂化汽油选择性加氢脱硫前后组成的变化。结果表明:加氢前后汽油中的氮化物均主要为碱性氮化物,加氢后总氮质量分数减少12.1个百分点,碱性氮化物质量分数减少8.3个百分点;汽油中的酚类主要为C1~2苯酚,苯酚和C3苯酚含量很少,加氢前后汽油中酚类的质量分数分别为0.14%和0.05%;加氢前汽油中的硫化物主要为噻吩和硫醚,硫醇含量较少且为C5~8硫醇;加氢后汽油中的硫化物主要为噻吩和硫醇,硫醚含量较少;加氢前后,硫醇质量分数由48.9×10-6降低到15.6×10-6,总硫质量分数由924.6×10-6降低到43.0×10-6;加氢后汽油的异构烷烃质量分数增加5.55个百分点,烯烃质量分数降低10.12个百分点(饱和率为31%),环烷烃质量分数增加2.95个百分点。     

Tannin levels in leaves of some oak species at different stages of maturity

Total phenolics, condensed tannins, degree of polymerisation, protein precipitation capacity, protein precipitable phenolics and specific activity (protein bound per unit tannins) were determined in the leaves of four oak species at different stages of maturation (4 days old to 1 year old). The content of total extractable phenols was higher in younger leaves in Quercus ilex Linn, Quercus semecarpifolia Sm and Quercus serrata Roxb, whereas in Quercus glauca Thumb the content was higher in the mature leaves. In all species studied, condensed tannins increased with maturation. Protein precipitation capacity had a trend similar to that of total phenols. In Q serrate and Q semecarpifolia the apparent degree of polymerisation increased, and the content of protein precipitable phenolics and specific activity decreased as the leaves matured. The decrease in protein precipitation capacity with maturation in these two species may be explained by both the decrease in the content and the change in the nature of phenols capable of binding proteins. Protein precipitation capacity was not detectable in Q ilex leaves. Protein precipitation capacity in the mature leaves decreased in the order of Q serrata > Q semecarpifolia > Q glauca > Q ilex.     

Effect of the Extraction Technique and Operational Conditions on the Recovery of Bioactive Compounds from Chestnut (Castanea sativa) Bur and Shell

The aim of this work was to study the extraction of phenolic compounds from chestnut bur and shell, both waste products of chestnut processing in the food industry. Two extraction techniques were compared—maceration with solvents and microwave-assisted extraction. The influence of the solvent used (water, 50% MeOH or 50% EtOH) and temperature (25-50-75°C) on extraction yield and extract total phenols content and FRAP, DPPH, and ABTS antioxidant activities was studied. In the conventional extraction, the yield was significantly higher for the bur (8.54–19.58%) than for the shell (2.91–13.27%); however, the shell extracts showed substantially greater properties. The best extract properties were achieved at 75°C using 50% MeOH for the bur and water for the shell and phenolic compounds with demonstrated antioxidant properties, as gallic acid esters of glucose and ellagic acid, were identified in these extracts by RP-HPLC-ESI-TOF. In addition, the aqueous extracts showed ability to inhibit the growth of gram positive and negative bacteria but not fungi. The kinetic of the extraction process was well fitted by the Peleg's model. The non-conventional microwave-assisted extraction slightly improved the chestnut bur extraction by reducing the extraction time.     

Bioactive compounds in lettuce: Highlighting the benefits to human health and impacts of preharvest and postharvest practices

Lettuce is one of the most commonly consumed leafy vegetables worldwide and is available throughout the entire year. Lettuce is also a significant source of natural phytochemicals. These compounds, including glycosylated flavonoids, phenolic acids, carotenoids, the vitamin B groups, ascorbic acid, tocopherols, and sesquiterpene lactones, are essential nutritional bioactive compounds. This review aims to provide a comprehensive understanding of the composition of health-promoting compounds in different types of lettuce, the potential health benefits of lettuce in reducing the risks of chronic diseases, and the effect of preharvest and postharvest practices on the biosynthesis and accumulation of health-promoting compounds in lettuce.     

Biochemical changes of fresh-cut pineapple slices treated with antibrowning agents

The effectiveness of ascorbic acid (AA), isoascorbic acid (IAA) and N‐acetyl‐cysteine (AC) in inhibiting browning of fresh‐cut pineapple slices that were stored for up to 14 days at 10 °C, were studied. Slices treated with IAA and AA maintained higher levels of sugars and vitamin C than AC and controls. A low reduction of total phenolic content in treated slices was correlated with a lower polyphenol oxidase activity. IAA and AA slowed the degradation rates of sugars, vitamin C, and phenolic content, whereas AC was less effective in affecting these processes. A higher content of AA and IAA was associated with better compositional quality parameters and appearance of the pineapple slices during the storage period.     

COLORIMETRIC DETERMINATION OF PHENOLS IN PEATED MALTS USING A MODIFIED KLEBER'S METHOD

Kleber's method was modified to determine the amount of volatile phenolic compounds, that is, the pasting degree of peated malt. Steam distillation was done using a specially designed apparatus directly with the malt instead of the wort. The modified Kleber's method, when compared with Macfarlane's method by quantitative analysis using gas chromatography, was more sensitive and showed higher reproducibility and accuracy.     

结球甘蓝不同品种及部位中主要生物活性物质含量比较

对春大将、帕特、汉城和春优4种结球甘蓝(Brassica oleracea var.capitata L.)以及帕特甘蓝的不同部位中硫代葡萄糖苷、异硫氰酸盐(isothiocyanate,ITCs)、总酚和抗坏血酸等主要生物活性物质含量进行比较。结果表明:各品种中脂肪族硫苷含量均最高。其中帕特甘蓝中总硫苷、脂肪族硫苷均高于其他3个品种,且其不同部位中总硫苷含量以外部叶为最高,而中部叶中含量最低。帕特甘蓝中ITCs和总酚含量最高,汉城甘蓝中抗坏血酸含量高于其他3个品种;春大将甘蓝中黑芥子酶(myrosinase,MYR)活性最高,帕特和春优甘蓝中其活性差异不显著,汉城甘蓝中最低。帕特甘蓝中ITCs和抗坏血酸含量以外部叶为最高,总酚含量则在内部叶中最高,MYR活性在中部叶和内部叶中显著高于外部叶。可见,帕特甘蓝可作为功能性食品的原料加以开发利用。