A highly regioselective synthesis of δ-lactones from meadowfoam fatty acids

Meadowfoam fatty acids, when treated with mineral acid catalysts in the presence of polar nonparticipating solvents, undergo a facile ring closure to form δ-lactones. Perchloric and sulfuric acids catalyze the cyclization at concentrations of 0.6–13 mole equivalents, both neat and in the presence of solvent. Under constant acid concentrations, methylene chloride was found to increase the rate of reaction, the regioselectivity for the formation of δ-lactone, and the overall yield. In the absence of solvent, increased acid concentration improved the yield of lactone but reduced regioselectivity for the δ-isomer. Solvent polarity plays a significant role in the regioselectivity of the cyclization for δ-lactone, with solvents of higher dielectric strength providing larger δ/γ ratios (38:1) and higher yields up to 92%.     

Continuous deacylation of amides in a high-temperature and high-pressure microreactor

The deacylation of amides, which is widely employed in the pharmaceutical industry, is not a fast reaction under normal conditions. To intensify this reaction, a high-temperature and high-pressure continuous microreaction technology was developed, whose space-time yield was 49.4 times that of traditional batch reactions. Using the deacylation of acetanilide as a model reaction, the effects of the temperature, pressure, reaction time, molar ratio of reactants, and water composition on acetanilide conversion were carefully studied. Based on the rapid heating and cooling capabilities, the kinetics of acetanilide deacylation at high temperatures were investigated to determine the orders of reactants and activation energy. This microreaction technology was further applied to a variety of other amides to understand the influence of substituents and steric hindrance on the deacylation reaction.     

Solid acid (superacid) catalyzed regioselective adamantylation of substituted benzenes

Adamantylation of substituted benzenes with 1-bromo-adamantane was catalyzed by solid acids including acidic ion exchange and ionomer resins, HY zeolite, sulfated zirconia and supported superacids on HY zeolite and SiO₂. Adamantylation generally takes place in excellent yield giving predominantly para products without formation of byproducts. The reactions did not require the usual workup of Friedel-Crafts reactions as catalysts were simply filtered of. Cross-linked polystyrene resin sulfonic acid (Amberlyst) was found particularly suitable as besides its high catalytic activity, high regioselectivity was observed with almost exclusive formation ofp-adamantylated benzenes. AMI, PM3 and MNDO semiempirical calculations of heats of formation showed that of all regioisomers, the para isomer is the most stable. The temperature dependence of adamantylation was also investigated allowing the optimization ofp-substituted product in high yield and excellent selectivity. Lack of isomerization of 1-p-tolyla-damantane using solid (Amberlyst, Nafion-H) and liquid acids (neat and modified trifluoromethanesulfonic acid) indicates absence of product isomerization, while the intramolecular rearrangement of the intermediate arenium complex is still possible.Catalysis by solid superacids, Part 30. For part 29, see ref.[1A].     

COSMO‐based computer‐aided molecular/mixture design: A focus on reaction solvents

In this article, we investigate reaction solvent design using COSMO‐RS thermodynamics in conjunction with computer‐aided molecular design (CAMD) techniques. CAMD using COSMO‐RS has the distinct advantage of being a method based in quantum chemistry, which allows for the incorporation of quantum‐level information about transition states, reactive intermediates, and other important species directly into CAMD problems. This work encompasses three main additions to our previous framework for solvent design (Austin et al., Chem Eng Sci. 2017;159:93–105): (1) altering the group contribution method to estimate hydrogen‐bonding and non‐hydrogen‐bonding σ‐profiles; (2) ab initio modeling of strong solute/solvent interactions such as H‐bonding or coordinate bonding; and (3) solving mixture design problems limited to common laboratory and industrial solvents. We apply this methodology to three diverse case studies: accelerating the reaction rate of a Menschutkin reaction, controlling the chemoselectivity of a lithiation reaction, and controlling the chemoselectivity of a nucleophilic aromatic substitution reaction. We report improved solvents/mixtures in all cases. © 2017 American Institute of Chemical Engineers AIChE J, 63: 104–122, 2018     

纳米固体酸催化一硝基氯苯区域选择性合成

采用纳米化学技术制备了新型的纳米复合固体超强酸催化剂Fe2O3/SO42-,并用XRD、TEM进行了表征。结果表明:所研制的Fe2O3/SO42-催化剂为晶态纳米粒子,平均粒径为40 nm,分散性较好;以Fe2O3/SO42-为催化剂时,氯苯硝化的区域选择性和活性提高。最佳反应条件为:催化剂活化温度600℃,反应温度50℃,n(硝酸)/n(氯苯)=3.5,m(氯苯)/m(催化剂)=20,反应时间6 h,产物收率为78.7%,对位一硝基氯苯与邻位一硝基氯苯之比(P/O)可达4.8。     

Regioselective analysis of the fatty acid composition of triacylglycerols with conventional high-performance liquid chromatography

A new method for regioselective analysis of triacyglycerols via conventional high-performance liquid chromatography (HPLC) has been developed. The method is simple and avoids the time-consuming purification processes normally characteristics of regioselective analyses. The procedure utilizes an sn-1,3-specific lipase from Rhizopus arrhizus to deacylate the fatty acid residues located at the sn-1 and sn-3 positions of triacylglycerols. The fatty acid residues esterified at the sn-2 position are determined by subtraction of the results of the sn-1,3 analysis from an overall composition analysis based on complete saponification of the original sample. The fatty acid mixtures are converted to p-bromophenacyl esters and analyzed using conventional HPLC techniques. The analytical procedure has been verified using a standard structured triacylglycerol. The analytical results for three edible vegetable oils are compared with those obtained via the method proposed by P.J. Williams and co-workers.     

Enzyme‐catalyzed regioselective synthesis of sugar esters and related compounds

In this review, a comprehensive and illustrative survey is made of the regioselective synthesis of esters of sugars and related compounds using lipases. The main emphasis has been given to the screening and use of commercially available lipases for the enzymatic esterification of neutral monosaccharides, disaccharides, sugar alcohols and their selected ether and ester derivatives. The effect of solvents and solubilizing agents in improving the yields of the resultant sugar fatty acid esters has been incorporated. Further, solvent‐free esterification with molten fatty acids, use of ionic liquids and microwave radiations for improvement in the methodology have also been discussed. Copyright © 2006 Society of Chemical Industry     

铌酸及其改性催化剂上甲苯的区域选择性硝化

研究了铌酸催化剂上甲苯硝化反应的区域选择性。结果表明,当反应温度为40℃,反应时间为60 min时,以CCl4为溶剂,以质量分数为95%的硝酸为硝化剂,在醋酐存在条件下,经300℃焙烧3 h后的铌酸催化剂,对甲苯硝化表现出了强的区域选择性;催化剂用量为0.8 g,甲苯硝化产物邻对位摩尔比达1.20,较硝硫混酸的1.67显著降低,产物得率达99.7%。且该催化剂循环使用5次,催化活性变化很小。制备了4种改性铌酸催化剂,结果分析表明,改性铌酸催化剂对甲苯硝化均表现出了比铌酸催化剂强的区域选择性,分别以硫酸铈改性的固体铌酸、硫酸铈和磷酸改性的铌酸、硝酸改性的铌酸、硝酸和磷酸改性的铌酸为催化剂,甲苯硝化产物的邻对位摩尔比可分别达1.15,1.11,1.09,1.04。     

tert-Butyl Nitrite Promoted Visible-Light-Induced Steric-Hindrance-Regulated Concurrent Cross-Coupling and Regioselective Nitration of 3-Alkylidene-2-oxindoles

A tert-butyl nitrite (TBN) promoted visible-light-induced one-pot C−N cross coupling reaction of 3-alkylidene-2-oxindoles with benzene-1,2-diamine was explored. Simultaneously, the indoline motif of 3-alkylidene-2-oxindoles as well as 3-ylidene oxindoles are regioselectively nitrated at the C-6 position by in-situ formed NO₂ radical. (E)-3-(2-(aryl)-2-oxoethylidene)oxindole and (E)-3-ylidene oxindole produce distinct nitrated diastereomeric coupling products, a phenomenon influenced by the steric bulk of the functional group. The experimental findings suggest the potential involvement of a radical pathway in this reaction.     

Novel Brønsted acidic ionic liquids catalyzed one-pot reaction of highly green regioselective thiocyanation of N-containing aromatic and heteroaromatic compounds at room temperature

In this method, a novel Brønsted acidic ionic liquid silica-supported pyridinium sulfonic acid thiocyanate {SiO₂@[Pyridine-SO₃H]SCN} and sulfonic acid-functionalized pyridinium chloride {[PSA]Cl} were easily synthesized and characterized. In the first method, {SiO₂@[Pyridine-SO₃H]SCN as a novel and environmentally friendly catalyst with one acidic functional group and one thiocyanation agent group was ef?ciently used for the synthesis of aryl and heteroaryl thiocyanates via the condensation of anilines, indoles, pyrroles, and their derivatives in the presence of H₂O₂ as a green oxidant in EtOH:H₂O (1:1) at room temperature. In the second method, {[PSA]Cl} as a new ionic liquid and environmentally friendly catalyst with one acidic functional group was used for the simple and efficient synthesis of aryl and heteroaryl thiocyanates via the condensation of anilines, indoles, pyrroles, and their derivatives with NH₄SCN in the presence of H₂O₂ as a green oxidant in EtOH:H₂O (1:1) at room temperature. A simple experimental procedure, clean reaction profile, use of an inexpensive catalyst, and recyclability of the catalyst are some of the advantages of the procedure. Also, one of the advantages of the first method is the non-usage of NH₄SCN or KSCN in the reaction.