Palladium(II)‐Catalyzed Direct ortho‐C?H Acylation of Anilides by Oxidative Cross‐Coupling with Aldehydes using tert‐Butyl Hydroperoxide as Oxidant

An efficient palladium‐catalyzed C H acylation with aldehydes using tert‐butyl hydroperoxide (TBHP) transforms various anilides into synthetically useful 2‐aminobenzophenone derivatives under mild conditions (40 °C, 3 h). The acylation reaction exhibits excellent regioselectivity and functional group tolerance, and simple aromatic aldehydes, functionalized aliphatic aldehydes and heteroaromatic aldehydes are effective coupling partners. The acylation reaction is probably initiated by a rate‐limiting electrophilic C H cyclopalladation (k_H/k_D=3.6; ρ⁺=−0.74) to form an arylpalladium complex, followed by acyl radical functionalization.     

颜料分散用马来酸酐-乙醇胺-苯乙烯水性高分子助剂的合成

以乙酸乙酯为溶剂,马来酸酐、乙醇胺、苯乙烯为单体,过氧化苯甲酰为引发剂,采用溶液聚合法合成了聚羧酸型马来酸酐–乙醇胺–苯乙烯(MA–EA–St)高分子分散剂,研究了聚合反应温度和时间、引发剂用量及酰化马来酸酐与苯乙烯的摩尔比对TiO2颗粒悬浮率的影响,获得了较佳的聚合反应条件为:n(酰化马来酸酐)∶n(苯乙烯)=1.25,聚合反应温度75°C、时间5 h,引发剂用量占单体总质量的2%。当此条件下合成的MA–EA–St分散剂用量为2.5 g/L时,TiO2颗粒的悬浮率为97.42%,达到较佳的分散效果。     

AlPW12O40/TiO2催化苯甲醚乙酰化反应

以钛酸丁酯、磷钨酸、硝酸铝为主要原料,采用溶胶-凝胶法制备了AlPW12O40/TiO2复合催化剂.考察了对苯甲醚乙酰化反应制备对甲氧基苯乙酮的催化活性.实验结果表明:AlPW12O40负载量、催化剂用量、反应物配比、反应时间及反应温度等是影响催化效果的重要因素.反应的适宜条件为:AlPW12O40负载量为35％,乙酸酐与苯甲醚物质的量之比为2.5,催化剂用量为反应物总质量的3％,反应温度100℃,反应60 min,苯甲醚转化率可达到84.5％.催化剂易于分离,重复使用仍有较高催化活性.     

New Approach to Synthesis of Naftidrofuryl

A new method of synthesizing N, N- （dlethylamino） ethyl-2- （ 1-naphthylmethyl）-3-tetrahydrofurfuryl propionate was proposed. The key inermediate diethyl tetrahydrofurfuryl propionate was synthesized by aeylation of ρ-toluenesulfo-chloride with tetrahydrofurfuryl alcohol, then by alkylation of tetrahydro-furfuryl ρ- toluenesulfonate with diethyl malonate. The yield of N, N-（diethylamino）ethyl-2-（1-naph, hyl-me, hyl）-3-tetrahydrofurfuryl propionate was raised from 34.0 % to 46.4 % ; the reaction time was greatly shortened. The method described is feasible with higher yield, and has industrial prospects.     

月桂酸纤维素酯的酰化法制备及其成膜性能

将棉浆粕纤维素溶解在离子液体([Bmim]Cl)中获得纤维素/[Bmim]Cl均相溶液后,在4-二甲氨基吡啶的催化作用下,通过纤维素与月桂酰氯的酰化反应制备了月桂酸纤维素酯(LACE)。采用FT-IR、1H NMR、XRD、TG等表征方法研究了产物结构及热稳定性;考察了产物取代度的影响因素;并选择具有不同取代度的LACE溶解在CHCl3中配成不同浓度的制膜液,采用延流法制膜,通过考察制膜条件与薄膜力学性能的关系以及薄膜形貌特征,研究了LACE的成膜性能。结果表明:95℃下,反应物以物质的量比为n(AGU)∶n(DMAP)∶n(LC)=1∶0.03∶3投料并反应4 h,所得产物具有较高取代度,在非极性溶剂中溶解性能优良,且无需加入增塑剂就可模塑成型。     

Fully Enzymatic Resolution of Chiral Amines: Acylation and Deacylation in the Presence of Candida antarctica Lipase B

A fully enzymatic methodology for the resolution of chiral amines has been demonstrated. Candida antarctica lipase B (CaLB)‐catalyzed acylation with N‐methyl‐ and N‐phenylglycine, as well as analogues having the general formula R¹ X CH₂CO₂R² (R¹=Me, Ph; X=O, S) afforded the corresponding enantioenriched amides, which were subsequently enzymatically hydrolyzed. Surprisingly, CaLB also proved to be the catalyst of choice for this latter step. The heteroatom in the acyl donor profoundly influences both the enzymatic acylation and deacylation; the O‐substituted reagents performed best with regard to enantioselectivity as well as reaction rate in synthesis and hydrolysis.     

Palladium‐Catalyzed N‐Demethylation/N‐Acylation of Some Morphine and Tropane Alkaloids

Hydrocodone was converted to various N‐acyl derivatives via a one‐pot N‐demethylation/N‐acylation protocol catalyzed by palladium(II). The procedure has also been successfully applied to several N‐methyltropane alkaloids. A plausible mechanism is suggested.     

Study of the acyl transfer reaction: Structure and properties of glycerol carbonate esters

A series of glycerol carbonate esters derived from glycerol carbonate was synthesised by acylation of glycerol carbonate in the presence of aliphatic acyl chlorides. These compounds are characterised polyoxygenated by an endocyclic diester function and an exocyclic ester function. Physical and physicochemical properties of glycerol carbonate esters are determined. These compounds present a good thermal and oxidation stability. They exhibit surfactant properties towards water/soybean oil interface. The polyfunctional properties enable developments in existing industrial applications as well as in new niche markets.     

3,4二氢2H苯并[b][1,4]二氧杂环庚7醇的结构鉴定及抗氧化性研究

以邻苯二酚、1,3-二溴丙烷为起始原料,在碱性回流条件下经环化反应得到3,4-二氢-2H-1,5-苯并二氧环丙,然后通过Friedel-Crafts酰基化反应得到7-乙酰基-3,4-二氢-1,5-苯并二恶庚,之后经Bayer-Villiger氧化、水解酸化及柱层析分离得到目标产物,总产率28.5%。采用红外光谱(IR)、质谱(MS)以及核磁共振(1H-NMR,13C-NMR)对终产物进行结构鉴定,确定目标产物为3,4-二氢-2H-苯并[b][1,4]二氧杂环庚-7-醇。测定其在油脂中的抗氧化能力,结果表明其在动植物油脂中均具有一定的抗氧化性。