离子液体与微波协同促进有机合成反应

介绍了离子液体作溶剂、助溶剂、催化剂和反应试剂与微波协同促进有机合成的研究进展。离子液体与微波协同促进有机合成反应,缩短了反应时间,提高了反应的选择性和产率,对环境更加友好。     

Microwave-assisted Synthesis and Crystal Structure of 3-Acetamido-1-phenyl-4-（2,6-dichloro）benzylidene-5-pyrazolone

The title compound,3-acetamido-1-phenyl-4-(2,6-dichloro)benzylidene-5-pyrazolone(C18H13Cl2N3O2,Mr = 374.21),has been synthesized by one-step condensation of 2,6-dichloroben-zaldehyde with acetic anhydride and 3-amino-1-phenyl-5-pyrazolone under microwave irradiation.The compound was characterized by means of IR and 1H NMR.Its crystal and molecular structure were determined by X-ray diffractometry.It belongs to the orthorhombic system,space group Pbca,with a = 12.5312(13),b = 8.5495(9),c = 31.110(3) ,V = 3332.9(6) 3,Z = 8,Dc = 1.492 g/cm3,λ = 0.71073 ,μ(MoKα) = 0.407 mm-1,F(000) = 1536,the final R = 0.0394 and wR = 0.0984.A total of 15894 reflections were collected,of which 3630 were independent(Rint = 0.0362).There exist three planes in the molecular structure.X-ray analysis reveals that the dihedral angles between planes 1 and 2,1 and 3 and 3 and 2 are 80.89,74.29 and 20.57°,respectively.     

Ultrasound assisted,VOSO4 catalyzed synthesis of 4-thiazolidinones: Antimicrobial evaluation of indazole-4-thiazolidinone derivatives

A simple and expedient multicomponent protocol was developed to synthesize 4-thiazolidinones by employing VOSO₄ as a catalyst under ultrasonic irradiation. The significant features of this protocol includes shorter reaction time, high yields, low catalyst loading, and also the catalyst can be recovered and reused up to next four cycles without significant loss in catalytic activity. All the synthesized novel indazole compounds were evaluated for their antibacterial and anti-biofilm activities. Compounds 9n, 9o and 9q showed promising activity (MIC value of 3.9?µg/mL) against K. planticola (MTCC 530). They also exhibited significant bactericidal activity against K. planticola (MTCC 530) (MBC value of 15.6?µg/mL). Additionally, 9n, 9o and 9q inhibited biofilm formation (IC₅₀ values ranging between 20.28–20.79?μg/mL) in this organism.     

Synthesis of organosilyl compounds-containing 1,2,4,5-tetraaryl imidazoles sonocatalyzed by M/SAPO-34 (M = Fe,Co, Mn,and Cu) nanostructures

The one-step synthesis of silylated 1,2,4,5-tetraaryl imidazoles by use of a series of M/SAPO-34 (M: Fe, Co, Mn, and Cu) nanocatalysts and subsequent silylation reactions is described. Cu/SAPO-34 catalyst has the highest activity in improving the efficiency of the heterogeneous cyclo-condensation of an aldehyde, benzil, ammonium acetate and a primary aromatic amine in water under ultrasonic irradiation. Some of imidazole derivatives are studied with a view to the synthesis of a series of new, multi-substituted imidazoles containing organosilyl groups including carbosilanes (Si–C) and silyl ethers (Si–O).     

“一锅法”合成11,11′-双(8,11-二氢苯并[f]呋喃并[3,4-b]喹啉-10-酮)(英文)

微波辐射下,不使用催化剂,在醋酸和DMF的混合溶剂中二醛、季酮酸和萘胺反应,"一锅法"合成11,11′-双(8,11-二氢苯并[f]呋喃并[3,4-b]喹啉-10-酮)。所合成化合物的结构经红外光谱、核磁共振光谱和高分辨率质谱予以确证。该方法具有产率高、操作简单、反应时间短等优点。     

微波辐射下秸秆纤维微观结构的变化

利用原子力显微镜(AFM)对微波处理前后秸秆纤维表面的变化进行了研究,并结合XRD和FTIR研究了处理前后其化学结构及结晶形态的变化情况。结果表明,未经微波处理的秸秆纤维表面比较光滑,平均粗糙度(Ra)为(86.7±6.335)nm,均方根粗糙度(Rq)为(141.1±9.055)nm;经微波处理的秸秆纤维表面比较粗糙,并出现许多细小孔洞,其Ra为(445.0±28.14)nm,Rq为(558.9±33.458)nm,微波辐射处理前后秸秆纤维的表面形态差异较大。经微波辐射处理后,秸秆纤维在2θ=22.3°处的衍射峰移至21.8°,且峰宽稍有增加,在38.1°、44.3°、64.6°、78.9°处出现的4个衍射峰,除强度稍有增强,其峰形和位置与未经处理秸秆纤维的衍射峰基本一致,表明微波处理没有改变纤维的结晶形态。FTIR光谱表明,微波处理样中未产生新的官能团,但分子间氢键及分子内氢键发生变化。微波作用未引起秸秆纤维化学结构的变化。     

Solid phase synthesis of a molecular library of pyrimidines, pyrazoles, and isoxazoles with biological potential

A small molecular library of 40 pyrimidine, pyrazole, and isoxazole derivatives, bearing structural features for a promising binding of therapeutically interesting enzymes, was designed and prepared. An efficient and straightforward solid phase synthesis was envisaged and carried out on a Rink amide resin. The assistance of microwave heating in any step reduced the reaction time, increased the reaction yields, and allowed an easy work-up and purification of the targeted compounds.     

Hot or not—the influence of elevated temperature and microwave irradiation on the solid phase synthesis of an affibody

Despite the advances of solid phase peptide synthesis (SPPS) the synthesis of long peptides is still challenging. Microwave irradiation and conventional heating are considered to improve the efficiency of SPPS. It has been shown that conventional heating and heating by microwave irradiation improves the efficiency of solid phase synthesis of peptides that are prone to aggregation as compared to the synthesis at room temperature. In this Letter, the influence of elevated temperature and microwave irradiation on the homogeneity of the synthesis product of a 58-mer peptide affibody has been compared. A detailed analysis by high resolution HPLC and LC-MS mass spectrometry using a high-mass resolution Orbitrap Exactive mass spectrometer was performed. This study revealed that neither thermal heating nor microwave heating improves the yield and purity of the crude product as compared to the synthesis at room temperature. In contrast, the formation of undesirable side products rather increased by microwave irradiation. These results indicate that neither heating nor microwave enhancement of solid phase synthesis does allow a significant improvement of peptide sequences with a low aggregation potential.     

Light-induced degradation of the active layer of polymer-based solar cells

Polymer-based organic solar cells are known to offer a poor stability in real use conditions, and the photodegradation of the active organic layer plays an important role in the reduced lifetime of the devices. This paper focuses on the photodegradation of two conjugated polymers used in organic solar cells, namely poly(2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene (MDMO-PPV) and poly(3-hexyylthiophene) (P3HT), and their blends with [60]PCBM (methano-fullerene[6,6]-phenyl C61-butyric acid methyl ester), a fullerene derivative. MDMO-PPV and P3HT thin films were submitted to photoageing (λ > 300 nm) in the presence and in the absence of oxygen. The mechanisms by which these polymers degrade were elucidated. P3HT, pristine and blended with PCBM, was shown to be much more stable under illumination than MDMO-PPV. The results showed that, if deposited on an inert substrate and well protected from oxygen with a convenient encapsulation, P3HT:PCBM based active layer should be intrinsically stable for several years in use conditions.     

Unexpected formation of new photochromic compounds derived from 3,3-diphenyl-3H-naphtho[2,1-b]pyran-1-one

Two new unexpected photochromic compounds were obtained from naphtho[2,1-b]pyran-1-one 1. The reaction of this ketone with the silyl enol ether methyl trimethylsilyl dimethylketene acetal, catalyzed by TiCl₄, afforded the photochromic dihydronaphtho[2,1-b]pyranone 2. The Reformatsky reaction of ketone 1 with ethyl bromoacetate led to the formation of the expected alcohol that under acid treatment gave, unexpectedly, the novel photochromic benzocoumarin 6. UV irradiation compounds 2 and 6 in solution provided thermally stable photoproducts that returned to the initial uncoloured forms under visible irradiation. The photochromic behaviour of these compounds and the structures of the photoproducts formed in these reactions were characterized by 1D and 2D NMR.