Selective hydroxymethylation of guaiacol in the presence ofβ-cyclodextrin

Studies on the effect of-cyclodextrin (BCD) and its derivatives on the selectivity in hydroxymethylation of guaiacol by formaldehyde was carried out. Fairly high selectivity with respect to isovanillyl alcohol formation was achieved. Significantly, the selectivity-enhancing effects of 2,6-di-O-methyl-BCD was much larger, giving rise to 22% more of isovanillyl alcohol formation than BCD and its polymer. UV, fluorescence,¹H-NMR spectroscopic and potentiometric studies were also carried out to determine the orientation of guaiacol inside the BCD cavity.     

Ammeline–melamine–formaldehyde resins. Preparation and properties

Ammeline–melamine–formaldehyde resins (AMF Resins) containing 5–100 mol % of ammeline, were synthesized by polymerization of the preformed sodium salt of ammeline, melamine, and formaldehyde in basic medium by three methods. These resins, when cured, constitute a new class of thermosets. The rate of hydroxymethylation of the amino groups of the ammeline salt with formaldehyde was somewhat larger then that of the amino groups on melamine. At higher pH values ammeline insolubility was not a problem. The AMF resin composition was approximately equal to the mol ratio of the components originally charged. Both ammeline and melamine were consumed over the entire reaction period. Thus, it is possible to make approximately uniform random ammeline-melamine-formaldehyde resins (AMF) with any mol ratio of ammeline salt to melamine. By controlling the pH of the solution from which the resins were isolated, the (SINGLE BOND) O⁻ Na⁺/(SINGLE BOND) OH ratio could be varied. Resin melting points varied widely with the mol fraction of ammeline and the (SINGLE BOND) O⁻ Na⁺/(SINGLE BOND) OH ratio. AMF resin solubilities, shelf lives, cloud points, and water tolerance depended upon the method of preparation, pH, and other factors. The sodium salt of ammeline was hydroxymethylated in water more readily than ammeline. More highly methylolated ammeline species were readily formed in solution but upon precipitation only bis-N-hydroxymethylammeline was isolated. © 1996 John Wiley & Sons, Inc.     

A chemoselective hydroxymethylation: new route for the synthesis of 6-aroyl-4-(4H-triazol-3-yl)thiomorpholin-3-ones

Treatment of 2-(2-oxo-2-arylethylthio)-N-(4H-1,2,4-triazol-3-yl)acetamides with paraformaldehyde in the presence of a base has led to a tandem chemoselective hydroxymethylation followed by cyclization yielding a set of novel 6-aroyl-4-(4H-triazol-3-yl)thiomorpholin-3-ones. The thiomorpholine ring has been found to have a boat like conformation in these compounds as evidenced by NOESY NMR spectrum.     

芴的9位羟甲基化反应产物的影响因素

以聚甲醛为羟甲基化试剂,研究了碱的种类、反应温度和反应时间等因素对芴与聚甲醛发生羟甲基化反应产物类型的影响。 结果表明,提高碱的强度有利于生成9,9-双羟甲基芴,升高温度和延长反应时间则有利于生成9,9′-亚甲基双芴。 通过控制反应条件,有可能优先生成9-芴甲醇或9,9-双羟甲基芴或联产这2个化合物。     

谷朊蛋白的改性及其作为纸张增强剂的性能

采用廉价可生物降解的小麦谷朊蛋白为原料,经过羟甲基化和阳离子化改性合成类似聚酰胺聚胺环氧氯丙烷(PPE)的纸张增强剂. 经改性后,谷朊蛋白带有氮杂环丁烷结构、表氯醇和环氧基团3种功能基团,可与纤维形成共价键,且能发生自身交联,在纤维周围形成三维交联网络结构,提高纸张干、湿强度. 通过单因素试验,研究了甲醛、甲酸、温度、反应时间和环氧氯丙烷5种反应因素对纸张强度的影响. 优化合成条件下制备改性谷朊蛋白可使纸张干抗张强度提高35%,湿强保留率达20%. 改性后谷朊蛋白显阳离子性,加入纸浆中,可使得浆料体系Zeta电位升高,改善浆料的留着率,明显提高纸张强度. 结果表明,经羟甲基化和环氧氯丙烷加成改性的谷朊蛋白可以作为纸张的干强剂和湿强剂.     

Selective Production of Linear Aldehydes and Alcohols from Alkenes using Formic Acid as Syngas Surrogate

Performing carbonylation without the use of carbon monoxide for high-value-added products is an attractive yet challenging topic in sustainable chemistry. Herein, effective methods for producing linear aldehydes or alcohols selectively with formic acid as both carbon monoxide and hydrogen source have been described. Linear-selective hydroformylation of alkenes proceeds smoothly with up to 88 % yield and >30 regioselectivity in the presence of single Rh catalyst. Strikingly, introducing Ru into the system, the dual Rh/Ru catalysts accomplish efficient and regioselective hydroxymethylation in one pot. The present processes utilizing formic acid as syngas surrogate operate simply under mild condition, which opens a sustainable way for production of linear aldehydes and alcohols without the need for gas cylinders and autoclaves. As formic acid can be readily produced via CO₂ hydrogenation, the protocols represent indirect approaches for chemical valorization of CO₂.     

Regioselective synthesis of gentisyl alcohol-type marine natural products

Gentisyl alcohol-type natural products, possessing various important biological properties, have been synthesized from 4-methoxyphenol by using a selective phenol monohydroxymethylation/monochlorination, a CAN oxidation and a sodium dithionite reduction as the key steps. The natural product synthesis is efficient, atom- and step-economical, and requires no protecting groups.     

Oxidation Reactions of Azines. 10. Synthesis, Structure, and Oxodihydroxylation of 3-Hydroxymethyl-1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine

It has been established that oxidation of a mixture of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine and dicyanomethane or formaldehyde with manganese dioxide gives 3-hydroxymethyl-1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine, the structure of which was confirmed by X-ray structural analysis. Some oxidative conversions by potassium permanganate of the product formed and its esters have been studied. These included lactamization, aromatization, and oxodihydroxylation.     

三聚氰胺甲醛树脂合成—盐酸的催化作用及对产物稳定性的影响

三聚氰胺 (MA)在含有HCl的水溶液中与甲醛 (FA)进行羟甲基化反应。HCl与MA以等摩尔比结合 ,在反应过程中逐渐析出 ,至反应完毕仍保留半结合量。氢离子浓度对三聚氰胺甲醛树脂 (MF)溶液的稳定性有重要的影响