在N-甲基吡咯烷酮(NMP)促进下,取代肉桂酸(1a～1g)与二氯亚砜(SOCl2)在20℃酰氯化反应0.5 h,再加入甘氨酸乙酯盐酸盐,在40℃下酰胺化反应4 h,n(取代肉桂酸)/n(SOCl2)/n(甘氨酸乙酯盐酸盐)=1.0/1.2/1.4,合成了一系列取代肉桂酰甘氨酸乙酯(2a～2g),其结构经1H NMR、13C NMR、IR和MS(EI)确证.并探讨了NMP促进取代肉桂酰甘氨酸乙酯反应可能的机理.

A visible-light-mediated tandem sulfonylation/cyclization of vinyl azides with sulfonyl hydrazines was developed that provides an efficient and simple strategy for the synthesis of valuable 6-(sulfonylmethyl)phenanthridines with a broad substrate scope and satisfactory yields under mild conditions.

A novel copper-catalyzed oxidative cross-coupling reaction between N-arylglycine esters and Sily1 enol ethers for the synthesis of beta-acyl-alpha-amino acid esters has been developed. The features of this reaction are high reaction yields, mild reaction conditions (such as room temperature environments and inexpensive catalysts, etc.) and smooth operation in aqueous medium.

A blue fluorescent material 2-[4- (4- (9H-carbozol-9-yl) phenyl) phenyl]-4, 5-diphenyl-1H-imidazole had been synthesized by suzuki coupling of 4- (9H-carbozol-9-yl) phenylboronic acid with 4, 5-diphenyl-2- (4-bromophenyl) imidazole, which prepared from a benzil, 4-bromobenzaldehyde and an ammonium acetate by condensation reaction.The structure was characterized by IR, 1H NMR, 13C NMR and MS.The optical properties, electrochemical behaviour and thermal stability of the target product were investigated by UV-Vis absorption spectra, fluorescence emission spectra, cyclic voltammetry, TGA, DSC and theoretical calculations.The results indicated that the UV-Vis absorption peaks were observed at 341 nm, and the fluorescence emission peaks were showed at 416 nm.The HOMO and LUMO energy levels of the target product were estimated to be 5.29 eV and 2.11 eV, respectively.TGA and DSC analysis showed that the target product possesses good thermal stability.

在N,N-二甲基乙酰胺(DMAC)促进下,取代肉桂酸(1a～1k)与二氯亚砜(SOCl2)在25℃酰氯化反应0.5h,再加入甘氨酸甲酯盐酸盐在40℃下酰胺化反应3h,合成了11个取代肉桂酰甘氨酸甲酯(2a～2k),产率80.01％～91.12％,其结构经1 H NMR、13C NMR、IR和EI-MS确证,并探讨了DMAC促进取代肉桂酰甘氨酸甲酯反应可能的机理.

研究了N,N-二甲基乙酰胺(DMAc)促进的取代苯甲酸/肉桂酸/巴豆酸(1a～1m)与羟胺的生成羟肟酸的反应,得到了一系列不同取代的羟肟酸(2a～2m).产物2a～2m经1 H NMR、13C NMR、IR和MS表证.提出了DMAc协同促进羟肟酸合成反应的可能机理.

A series of chiral warfarin compounds were synthesized by the Michael reaction of 4-hydroxycoumarin with benzylideneacetones at -20℃ for 24 h.The yields and ee value of target com-pounds were 80%~97%and 80%~95%,respectively.The structures were confirmed by 1H NMR, 13 C NMR,IR and HR-MS(ESI).

Ascorbicylibuprofenate and isoascorbicylibuprofenate was synthesized via acyl chlorination of ibuprofen with SOCl2 in N-methyl pyrrolidone(NMP),followed by esterification with ascorbic acid or isoascorbic acid.The effect of such factors as NMP amount,acyl chlorination time,esterification time and molar ratio of reactants on the yield of ascorbicyl 2-(4-isobutylphenyl) propanoate was investigated.It was found that the yield could reach 86.20％ under the optimal reaction conditions 5 mmol of ibuprofen,5 mL NMP,and n(ibuprofen) ∶n(SOC12) ∶n(VC)=1.0∶1.2∶1.4,acyl chlorination at 25 ℃ for 0.5 h,esterification reaction at 25 ℃ for 10 h.The title compound was characterized by 1HNMR,13CNMR,IR and ESI-MS.

4-(4-Aminophenyl)-5-ethoxycarbonyl-6-methyl-3,4-dihydropyrimidin-2(1H)-one (AEMD) single crystal was obtained and determined by X-ray single crystal diffraction. This compound crystallizes in a monoclinic P2(1)/c space group with a=1. 1237(4) nm,b=0. 5799(2) nm,c=2. 2394(7) nm,α=90°,β=91. 048(5)°,γ=90°,Z=4. The interactions between AEMD and bovine serum albumin ( BSA ) were investigated using fluorescence spectroscopy. The results revealed that AEMD could quench the BSA fluorescence. The corresponding thermodynamic parameters (ΔH<0 andΔS<0 ) showed that the AEMD and BSA interaction occurred mainly by hydrogen bond formation and van der Waals forces. The binding distance was estimated to be about 2. 19 nm according to F?rster′s non-radioactive energy transfer theory. Besides,the synchronous fluorescence demonstrated that AEMD induced conformational changes of BSA.

NMP-mediated chlorination of aliphatic alcohols has been developed for the synthesis of alkyl chlorides. This facile, efficient and practical approach used simple and readily available aryl sulfonyl chlorides as the chlorination reagent for the construction of C–Cl bond in good to excellent yields with mild conditions and broad substrate scope.

考察了一系列手性吡咯烷叔胺硫脲催化剂对4-氯代乙酰乙酸乙酯与亚胺的不对称Mannich/Cyclization串联反应的催化性能,合成了一系列具有潜在生物活性的手性特窗酸类衍生物,产率62％～92％,对映选择性68％～96％,产物结构经1 H NMR,13 C NMR,IR和HR-MS确证.并对反应条件进行了优化,对反应机理进行了推测.

Ibuprofenamide(3a~3i)were synthesized through acyl chlorination of ibuprofen with SOCl2at 25℃ for 0.5 h in N-meth-yl pyrrolidone,followed by amidation with substituted anilines(2a~2i)at 25℃ for 3 h,and(4a~4f)instead of substitute(2a~2i) at 25℃ for 8 h,then ibuprofenate(5a~5f)were obtained.The title compound(3a~3i,5a~5f)was characterized by 1H NMR,13C NMR,IR and EI-MS.The proposed mechanism for the NMP-promoted of carboxylic acid with thionyl chloride was put forward.The main advantages of the developed methodology were under mild reaction conditions,simple work-up procedure and short reaction time.

A facile and efficient protocol has been developed for sulfonylation/cyclization of vinyl azides under photoredox conditions.

A mild,convenient,and economical approach for the construction of amides and lactams from ketoximes via Beckmarn rearrangement by using a new type of Vilsmeier reagents generated in situ from thionyl chloride and 1-methyl-pyrrolidin-2-one was reported.Various amides and lactams bearing different substituents were obtained in good to excellent yields under mild conditions,and the gram scale reaction was achieved without the loss of the yield.Moreover,it can be used in the synthesis of 2-methylbenzoxazole from 1-(2-hydroxyphenyl)ethanone oxime.

Twenty two cinnamyl carboxylates(2a~2v, among them 2j, 2k, 2o, 2t and 2v were novel compounds) were synthesized by the N,N-dimethylacetamide( DMAc)-promoted reaction of carboxylic (1a~1v) with SOCl2 and cinnamyl alcohol, respectively. The structures were characterized by 1 H NMR, 13C NMR, IR and MS(EI). Effects of the dosage of crotonic acid(1i), cinnamic alcohol, SOCl2 and DMAc on yield of cinnamyl crotonate(2i) and the addition protocol of alcohol on products composition were investigated, using the synthsis of 2i as example. The results indicated that under the optimized reaction conditions(1i 1. 0 eq. , cinnamic alcohol 1. 3 eq. , SOCl21. 3 eq. , DMAc 2 mL, CH2Cl26 mL, adding benzyl alcohol after acylation), the yield of 2i was 82. 2%. The co-promoted mechanism of DMAc was confirmed by 1 H NMR tracing results.

Menthyl benzoate and its derivatives were synthesized from the corresponding benzoic acid,which react with menthol by using the combination of thionyl chloride (SOCl2) and N,N-dimethylacetamide (DMAc) in dichloromethane (CH2Cl2) under the room temperature.The method proposed here has multiple advantages,such as mild condition,easy procedure,cheap ingredients and high yield,which provide a new and practical protocol for the synthesis of menthyl benzoate and its derivatives.The structures of products were characterized by 1H NMR,13C NMR,and MS.

在N,N-二甲基乙酰胺(DMAc)的促进下,棕榈酸与SOCl2反应生成棕榈酰氯.酰氯不分离直接与L-抗坏血酸反应得到L-抗坏血酸棕榈酸酯.结果表明,在15mL DMAc和5mL CH2Cl2体系中,10℃下酰氯化反应0.5h后,接着在25℃下酯化反应6h,棕榈酸10mol,n(棕榈酸):n(SOCl2):n(L-抗坏血酸)=1.0:1.3:1.2,反应收率为90.29%.本方法操作简便,反应条件温和,反应时间短,收率较高.

A mild, convenient, and economical approach for the construction of amides and lactams from ketoximes via Beckmann rearrangement by using a new type of Vilsmeier reagents generated in situ from thionyl chloride and 1-methyl-pyrrolidin-2-one was reported. Various amides and lactams bearing different substituents were obtained in good to excellent yields under mild conditions, and the gram scale reaction was achieved without the loss of the yield. Moreover, it can be used in the synthesis of 2-methylbenzoxazole from 1-(2-hydroxyphenyl) ethanone oxime.

在N,N-二.甲基乙酰胺(DMAc)和CH2Cl2体系中,乙酸与SOCl2在0℃下反应20 min,制得的乙酰氯不经提纯直接与加入的苯胺在25℃下反应5h,得到了一系列取代乙酰苯胺化合物.优化条件下,反应产率为83％～ 97％.目标化合物的结构经1HNMR、13CNMR、IR和MS确证,提出了DMAc协同促进乙酰苯胺合成反应的可能机理.