失水山梨醇单月桂酸酯的一步法合成

失水山梨醇单月桂酸酯(商品名Span20)用途广泛[1 4]。传统方法[5]生产出的产品色泽深、副产物多、单酯质量分数低、熔融状态下多呈浑浊状态、质量不稳定,仅能用于石油、采矿和纤维等行业,用于食品、医药、化妆品的这类产品绝大部分依赖进口。本文以山梨醇和月桂酸为原料,采用一步法合成的目标产物为乳白色,单酯质量分数大于90%。并对合成方法进行了对比,探讨了各主要影响因素对目标产物色泽和三项指标(酸值、羟值、皂化值)的影响。梨醇的醚化和酯化反应产物是一个复杂的混合物:不仅有单酯及其异构体,还会存在其它二酯、多酯及相应异构…     

失水山梨醇脂肪酸酯-聚乙二醇嫁接的聚乙烯醇化磁性药物载体的制备及应用

通过丁二酸酐将失水山梨醇脂肪酸酯(Span80)和聚乙二醇(PEG400)联接在一起,合成了一种新的非离子表面活性剂.然后将其嫁接在聚乙烯醇(PVA)化的Fe3O4磁性粒子上,合成了一种新型靶向药物载体.这种载体兼备了Span80/PEG400类脂囊泡和磁性材料的特点,具有良好的稳定性和靶向作用.将这种新型载体用于两性霉素的包封,包封率可达96.6%,且方法简便.实验过程中采用了FTIR, NMR, XRD和TEM等多种手段进行表征.     

2—亚甲基丁二酯酐和甲基丙烯酸甲酯的共聚反应研究

２－亚甲基－丁二酯酐和甲基丙烯酸甲酯在四氢呋喃中以过氧化二苯甲酰作引发剂进行自由基共聚合。由作图法求得这两种单体在６６℃的共聚竞聚率：ｒ１＝４．２２，ｒ２＝０．６４，表明它们趋于嵌均共聚。用粘度法和ＧＰＣ测量了共聚物的分子量和分子量分布。     

疏水链长对聚氧乙烯失水山梨醇脂肪酸酯界面扩张流变性质的影响

利用悬挂滴方法研究了系列聚氧乙烯失水山梨醇脂肪酸酯(Tween X)在正癸烷-水界面的扩张流变性质.实验结果表明,疏水烷基链长较短的Tween20分子在界面上吸附量较大,分子排列更紧密,Tween40和Tween60具有大致相同的"有效截面积",导致饱和吸附时界面张力(γcmc)比较接近.Tween X浓度大于临界胶束浓度(cmc)时,由于Tween20分子排列的更加紧密,模量和弹性大于Tween40和Tween60.当Tween X的疏水烷基链长达到一定长度时,Tween X的界面膜性质受疏水链长的影响减弱,Tween40和Tween60的扩张参数相差不大.     

离子液体中乙酸异山梨醇酯的合成

以1-丁基-3-甲基咪唑六氟磷酸盐离子液体为溶剂,对新一代长效抗心绞痛药物单硝酸异山梨酯中间体异山梨醇进行了萃取分离,避免了使用高真空高温蒸馏;以酸性离子液体N-甲基咪唑硫酸氢盐为溶剂和催化剂,合成了中间体2-乙酸异山梨醇酯,产物结构经红外光谱确证.异山梨醇收率80%,2-乙酸异山梨醇酯收率86%.     

脂肪酶催化合成L-抗坏血酸脂肪酸酯和D-异抗坏血酸脂肪酸酯

用固定化脂肪酶Lipozyme 435作催化剂,分别用直接酯化法和酯交换法合成L-抗坏血酸脂肪酸酯和D-异抗坏血酸脂肪酸酯.产物结构经IR、1HNMR、13CNMR和MS表征.结果表明,对于同一目标化合物,相似条件下,直接酯化法的效果优于酯交换法,原料脂肪酸和脂肪酸甲酯均可回收循环使用.     

含异山梨醇结构单元聚酰亚胺的合成与表征

以异山梨醇为原料,合成了含异山梨醇的二胺单体.将该单体与4,4′-(六氟异丙基)双邻苯二甲酸二酐(6FDA)反应,制备了含异山梨醇结构单元的聚酰亚胺.采用红外光谱、氢核磁共振、紫外光谱和热分析等手段,对产物的结构、热性能及光学性能等进行了表征.结果表明,所得到的聚酰亚胺具有较好的热稳定性和光学性能、并在极性溶剂中具有较好的溶解性.     

HPLC测定山梨醇水溶液中山梨醇和甘露醇含量

采用HPLC法,以超纯水为流动相,用Sugar-pakⅡ(Waters)色谱柱和示差拆光检测器,准确地分离和测定了山梨醇水溶液中山梨醇和甘露醇的含量,变异系数1.42%,回收率99.89%。     

蔗糖脂肪酸酯的气相色谱测定

蔗糖脂肪酸酯是一种无毒、安全、无刺激、无污染的非离子表面活性剂,它在食品、化妆品、洗涤剂及医药卫生用品方面有着广泛的用途。在其制备过程中,由于所用原料及反应条件不同,蔗糖酯中疏水基的链长分布及单、双酯的比例也不尽相同,因此,亲水-亲油平衡(HLB)值也各有差异。为了选择合乎要求的蔗糖脂肪酸酯,或在生产过程中对产品进行控制,测定其疏水基链长分布及单、双酯的比例就显得十分重要。 测定蔗糖酯亲水、疏水基组成的方法,一般采用预先皂化或氢化锂铝还原分解     

偕二酸酯的无溶剂合成

以醛和酸酐为原料,溴化锌为催化剂,无溶剂条件下高产率地合成了偕二酸酯(其中醛与苯甲酸酐的反应是首次报道)。部分产物的结构经NMR,IR和MS表征。     

Free Radical Formation of p-Nitrophenacyl Esters of Carboxylic Acids and Their Detection by High-Performance Liquid Chromatography with Electron Spin Resonance

Abstract

p-Nitrophenacyl esters derived from p-nitrophenacyl bromide and carboxylic acids were determined by high-performance liquid chromatography with electron spin resonance. p-Nitrophenacyl bromide was used as the pre-column reagent to determine the carboxylic acids. The p-nitrophenacyl esters gave free radicals by hydrolysis with alkaline solution, and then the free radicals were detected with electron spin resonance. The separation of these esters was achieved within 20 min.     

用裂解色谱法鉴定羧酸酯的结构

 研究了用裂解气相色谱法鉴定羧酸酯结构的方法。对一些一元酸酯和二元酸酯进行了普通裂解和与碱石灰混合后的裂解，依据裂解产物可确定酯的母体酸和母体醇。直接从薄层板上取分离后的组分，不用去除吸附剂就能进行鉴定，可用于常见羧酸酯的剖析工作。     

(2,2-双二茂铁基丙烷)-6-甲酸酯的合成与表征

以2，2-双二茂铁基丙烷作为母体制得对应的甲酸，并以此合成了一系列未见文献报道的（2，2-双二茂铁基丙烷）-6．甲酸酯，其结构经1^H NMR，IR及元素分析表征。     

Convenient Synthesis of tert‐Butyl Esters of Indole‐5‐carboxylic Acid and Related Heterocyclic Carboxylic Acids

The tert‐butyl esters of indole‐5‐carboxylic acid and related compounds such as benzofuran‐ and benzothiophene‐5‐carboxylic acid were readily accessed by reacting the appropriate carboxylic acids with tert‐butyl trichloroacetimidate. To obtain the tert‐butyl esters of the 5‐carboxylic acids of 1H‐benzotriazole and 1H‐benzimidazole, position 1 of these heterocycles had to be protected by acetylation prior to reaction with tert‐butyl trichloroacetimidate. Cleavage of the acetyl residue of the obtained intermediates by dilute aqueous NaOH in ethanol led to the desired tert‐butyl 1H‐benzotriazole‐and 1H‐benzimidazole‐5‐carboxylates.     

Decarboxylative Conjunctive Cross‐coupling of Vinyl Boronic Esters using Metallaphotoredox Catalysis

The synthesis of complex alkyl boronic esters through conjunctive cross‐coupling of vinyl boronic esters with carboxylic acids and aryl iodides is described. The reaction proceeds under mild metallaphotoredox conditions and involves an unprecedented decarboxylative radical addition/cross‐coupling cascade of vinyl boronic esters. Excellent functional‐group tolerance is displayed, and application of a range of carboxylic acids, including secondary α‐amino acids, and aryl iodides provides efficient access to highly functionalized alkyl boronic esters. The decarboxylative conjunctive cross‐coupling was also applied to the synthesis of sedum alkaloids.     

Direct Transformation of Esters into Arenes with 1,5‐Bifunctional Organomagnesium Reagents

A direct transformation of carboxylic acid esters into arenes with 1,5‐bifunctional organomagnesium reagents is described. This efficient and practical method enables the one‐step defunctionalization of various carboxylic acid esters to prepare benzene, anthracene, tetracene, and pentacene derivatives. A double nucleophilic addition of the 1,5‐organodimagnesium reagent to the ester is followed by an immediate 1,4‐elimination reaction that leads to the direct [5+1] formation of a new aromatic ring.     

Direct Transformation of Esters into Heterocyclic Fluorophores

Despite the manifold use of heterocyclic fluorophores, only a fraction of the desired dye diversity can be accessed by contemporary synthetic approaches. Herein, we describe a modular method that converts various carboxylic acid esters directly into a broad spectrum of heteroanthrylium fluorophores. The double addition of heteroatom‐bridged 1,5‐bifunctional organomagnesium reagents to esters leads to the formation of acridinium, xanthylium, and SiR fluorophores after dehydrative acidic work‐up. This one‐step synthetic method provides access to organophotoredox catalysts for dual catalysis with nickel and dyes amenable to fluorescence enhancement.     

Oxidation of Alkynyl Boronates to Carboxylic Acids,Esters, and Amides

A general efficient protocol was developed for the synthesis of carboxylic acids, esters, and amides through oxidation of alkynyl boronates, generated directly from terminal alkynes. This protocol represents the first example of C(sp)?B bond oxidation. This approach displays a broad substrate scope, including aryl and alkyl alkynes, and exhibits excellent functional group tolerance. Water, primary and secondary alcohols, and amines are suitable nucleophiles for this transformation. Notably, amino acids and peptides can be used as nucleophiles, providing an efficient method for the synthesis and modification of peptides. The practicability of this methodology was further highlighted by the preparation of pharmaceutical molecules.     

Oxidation of Alkynyl Boronates to Carboxylic Acids,Esters, and Amides

A general efficient protocol was developed for the synthesis of carboxylic acids, esters, and amides through oxidation of alkynyl boronates, generated directly from terminal alkynes. This protocol represents the first example of C(sp)−B bond oxidation. This approach displays a broad substrate scope, including aryl and alkyl alkynes, and exhibits excellent functional group tolerance. Water, primary and secondary alcohols, and amines are suitable nucleophiles for this transformation. Notably, amino acids and peptides can be used as nucleophiles, providing an efficient method for the synthesis and modification of peptides. The practicability of this methodology was further highlighted by the preparation of pharmaceutical molecules.     

One-Pot Synthesis of Phenacyl Esters from Acetophenone, [Bmim]Br3, and Potassium Salts of Carboxylic Acids Under Solvent-Free Conditions

One-pot synthesis of phenacyl esters from acetophenone, [Bmim]Br₃, and potassium salts of carboxylic acids under solvent-free conditions gave the corresponding phenacyl esters with excellent yields.