1,5-二甲基-2-(S)-(1''''-苯基乙基)-2-氮杂-8-氧杂-双环[3.3.0] 辛烷-3,7-二酮的合成及其结构表征

利用2,3-丁二酮与丙二腈缩合形成双甲基双氰基环并内酰胺,经酸性水解得到双甲基环并内酯,然后和(S)-(-)-(1-苯基乙基)胺反应生成1,5-二甲基-2-(S)-(1′-苯基乙基)-2-氮杂-8-氧杂-双环[3.3.0]辛烷-3,7-二酮,通过元素分析、红外光谱、核磁共振氢谱和质谱对其结构进行了表征.用X射线单晶衍射法测定了目标产物的晶体结构,结果表明,晶体属单斜晶系,P21空间群,a=0.8777(18)nm,b=1.0102(2)nm,c=0.9009(18)nm,β=118.75(3)°,V=0.7003(2)nm3,Dc=1.296 g·cm-3,μ=0.089 mm-1,F(000)=292,Z=2,R1=0.0393,wR2=0.0955.     

2-氰基-2,3,3-三甲基-5-硫代-吡咯烷的合成新法

以3,3-二甲基-4-戊烯酸甲酯为原料, 经过6步反应合成了目标产物2-氰基-2,3,3-三甲基-5-硫酮-吡咯烷, 反应的总收率约为37%, 其中关键步骤为分子内环化和碘化氢消除反应. 通过元素分析, ¹H NMR, IR和MS对所合成化合物的结构进行了表征.     

3-甲基-4-乙氧甲酰-2-环己烯酮合成方法的改进

甲基乙氧羰基环己烯酮;多聚甲醛;3-甲基-4-乙氧甲酰-2-环己烯酮合成方法的改进     

3-亚甲基六氢苯并呋喃-2(3H)-酮的简便合成

以氧化环己烯为原料,在正丁基锂作用下与乙腈经开环反应制得2-羟基环己基乙腈(2);2依次经水解、内酯化、二甲胺甲基化、甲基化和Hofmann降解反应合成了α-亚甲基-γ-丁内酯类化合物--3-亚甲基六氢苯并呋喃-2(3H)-酮,总收率30.4%,其结构经¹H NMR,¹³C NMR和HR-MS(EI)确证。     

1-(2, 6, 6-三甲基-1-环己烯基-)-3-甲基-2-丁烯-4-醛合成新工艺

1-(2; 6; 6-三甲基-1-环己烯基-)-3-甲基-2-丁烯-4-醛合成新工艺;(三甲基环己烯基)甲基丁烯醛;卡宾反应; β-紫罗兰酮;三甲基溴化硫     

无催化剂条件下2-氨基-3-氰基-4-芳基-7,7-二甲基-5-氧代-5,6,7,8-四氢-4H-苯并吡喃的合成

芳亚苄基丙二腈;二甲基环己二酮;无催化剂条件下2-氨基-3-氰基-4-芳基-7;7-二甲基-5-氧代-5;6;7;8-四氢-4H-苯并吡喃的合成     

由α-氰基二硫缩烯酮制备多取代喹唑啉酮化合物

以α-氰基乙酸甲酯为起始原料,经与二硫化碳、碘甲烷反应先得到α-氰基二硫缩烯酮1,1与苯乙酮2反应得2H-吡喃-2-酮-3-腈化物3,碱诱导下3再与丙二腈经环转化得到多取代邻氨基芳香腈4,4与酮5在氢氧化钠催化下环化得到多取代喹唑啉酮目标物6.这组连续转化合成多取代喹唑啉酮的反应具有原料简便、反应温和等优点.     

芳亚甲基丙二腈和4-羟基喹啉-2-酮反应的研究

以芳亚甲基丙二腈和4-羟基喹啉-2-酮为原料,在六氢吡啶催化下以乙醇为溶剂,80℃合成了一系列新的2-氨基-3-氰基-4-芳基5,6-二氢化-4H-吡喃并[3,2-c]喹啉-5-酮衍生物,反应条件温和,产率较高,并通过单晶X射线衍射分析确证产物的结构.     

硫代丁内酯拼接吡唑啉酮双螺环化合物的合成

以3-异硫氰酸酯取代的硫代丁内酯1为合成子,在有机催化剂DABCO作用下,与各种取代的吡唑啉酮烯烃2发生Michael加成与环化反应,获得了9个未见文献报道的新型硫代丁内酯拼接吡唑啉酮双螺环化合物3a～3i,产率70%～77%,dr 2/1～9/1,其结构经¹H NMR,¹³C NMR和HR-MS(ESI-TOF)表征,通过单晶进一步确定了化合物3c的构型。该类化合物含有螺环丁内酯和螺环吡唑啉酮生物活性骨架,对医药行业具有重要的潜在价值。     

2-氰基-3-取代氨基-3-(2-甲基苯基)丙烯酸乙酯的合成和杀菌活性

2-甲基苯甲酰氯与氰乙酸乙酯反应得到2-氰基-3-羟基-3-(2-甲基苯基)丙烯酸乙酯, 经氯化得到2-氰基-3-氯-3-(2-甲基苯基)丙烯酸乙酯, 再用三乙胺处理合成了11个2-氰基-3-取代氨基-3-(2-甲基苯基)丙烯酸乙酯类目标化合物. 生物活性研究表明这类新化合物具有良好的杀菌活性.     

新型色满酮并环己烷螺环氧化吲哚类化合物的合成

以色酮 氧化吲哚合成子与硝基苯乙烯,在催化剂DBU作用下,在二氯甲烷中发生Michael/Michael加成环化反应,合成了9个未见文献报道的新型色满酮并环己烷螺环氧化吲哚类化合物3a~3i产率72%~87%, dr值4/1~2/1, 其结构经¹H NMR, ¹³C NMR和HR-MS（ESI-TOF）表征确定。     

Reactions of hydro(pero)xy derivatives of polyunsaturated fatty acids/esters with nitrite ions under acidic conditions. Unusual nitrosative breakdown of methyl 13-hydro(pero)xyoctadeca-9,11-dienoate to a novel 4-nitro-2-oximinoalk-3-enal product

13(S)-hydroperoxy- and 13(S)-hydroxyoctadeca-9,11-dienoic acids (1a/b), 15(S)-hydroperoxy- and 15(S)-hydroxyeicosa-5,8,11,13-tetraenoic acids (2a/b), and their methyl esters reacted smoothly with NO2- in phosphate buffer at pH 3-5.5 and at 37 degrees C to afford mixtures of products. 1b methyl ester gave mainly the 9-nitro derivative 3b methyl ester (11% yield) and a peculiar breakdown product identified as the novel 4-nitro-2-oximinoalk-3-enal derivative 4 methyl ester (15% yield). By GC-MS hexanal was also detected among the products. Structures 3b and 4 methyl esters were secured by 15N NMR analysis of the products prepared from 1b methyl ester upon reaction with Na15NO2. 4 methyl ester (14% yield) was also obtained from 1a methyl ester along with the nitrated hydroperoxy derivative 3a methyl ester (10% yield). Under the same conditions, 2a/b methyl esters gave mainly the corresponding nitrated derivatives 5a/b, with no detectable breakdown products, whereas the model compound (E,E)-2,4-hexadienol (6) afforded two main nitrated derivatives identified as 7 and 8. A reaction pathway for 1a/b methyl esters was proposed involving conversion of nitronitrosooxyhydro(pero)xy intermediates which would partition between two competing routes, viz., loss of HNO2, to give 3a/b methyl esters, and a remarkably facile fission leading to 4 methyl ester and hexanal.     

几种新的4-酰代吡唑啉酮衍生物的合成与结构

利用4-酰代吡唑啉酮与氨基硫脲类化合物反应制备了新的吡唑啉酮类衍生物,并用IR,NMR,MS和元素分析进行表征,最后用X射线四圆衍射对其中的2个化合物进行了晶体结构测定。     

Synthesis of New N‐alkyl‐5‐formyl‐2‐methylpyrrole Derivatives from Glucosamine

Glucosamine hydrochloride 1 was treated with 1,3‐dicarbonyl compounds to obtain 2‐methyl‐5‐(1,2,3,4‐tetrahydroxy‐butyl) pyrrole 2a and 2b , respectively. Under the role of NaIO₄, 2a and 2b were successfully transformed into the related 5‐formal pyrrole derivative 3a and 3b , respectively. Compounds 4a – 4d and 5a – 5e were obtained by reacting 3a and 3b with chlorinated hydrocarbons by alkylation reactions, respectively. The structures of all new products were confirmed by IR, NMR, and HRMS spectra.     

Enantioselective radical cyclisation reactions of 4-substituted quinolones mediated by a chiral template

Six 4-substituted quinolones 6-8, which bear an ω-iodoalkyl chain, were prepared and subjected to reductive radical cyclisation conditions employing BEt(3)/O(2) as the initiator and either Bu(3)SnH or TMS(3)SiH as hydride source. 4-(4-Iodobutyl)-quinolone (6a) and 4-(3-iodopropylthio)-quinolone (8a) gave the respective 6-endo-cyclisation products in good yields. 4-(3,3-Dimethyl-4-iodobutyl)-quinolone (6b) cyclised in a 5-exo-fashion, while the other substrates delivered only reduction products. The cyclisation reactions could be conducted in the presence of a chiral template (1) with high enantiomeric excess (94-99% ee). The association behaviour of substrate 6a to 1 was studied by NMR titration experiments. In the enantioselective cyclisation of 6b a significant nonlinearity was observed when comparing the product ee with the ee of the template.     

无溶剂自催化合成吡咯或吲哚Michael加成产物

在吡咯或吲哚自身N－H的催化下,在无溶剂条件下合成了3个吡咯和5个吲哚Michael加成产物(2a～2c和3a～3e,其中2b和3a～3e为新化合物),收率80%～92%, 3a~3c的d/r值分别为3.8 : 1, 1.3 : 1和1.1 :1,其结构经¹H NMR, ¹³C NMR, IR和HR-MS(ESI)表征。     

嘌呤6位含氟基团取代衍生物的合成

以6-氯嘌呤衍生物和6-溴嘌呤衍生物为原料, 通过卤素交换反应制得6-氟嘌呤衍生物; 通过烷氧基化反应制得6-三氟乙氧基嘌呤衍生物, 通过三氟甲基化反应制得6-三氟甲基嘌呤衍生物, 所有化合物的结构均经过1H NMR, MS和元素分析表征. 分析了所得化合物对稻草芽孢杆菌、黑曲酶和热带假丝酵姆的抑菌活性, 结果表明: 化合物2b, 4b对稻草芽孢杆菌(Bacillus subtillis)有比较好的杀菌效果, 化合物4a, 4b对黑曲酶(Aspergillus niger)有比较好的杀菌效果, 化合物3b, 4b对热带假丝酵姆(Cardida tropicals)有比较好的杀菌效果.     

第五、六族元素的有机化合物在有机合成中应用的研究 XVII.胂叶立德与氟代烯烃的反应

Reaction of perfluoropropylene (2a) with cyanomethylene- triphenylarsorane (1b) gave cyano-2, 3, 3, 3-tetrafluoropropionylmethylene-triphenylarsorane (4b), and with benzoylmethylene-(1c) and acetylmethylene-triphenylarsorane (1d) gave benzoyl-(3c) and acetyl-(trans-perfluoropropen-1-yl)- methylene-triphenylarsorane (3d), respectively 3c and 3d could be converted to benzoyl-(4c) and acetyl-2, 3, 3, 3-tetrafluoropropionyl -methylene triphenylarsorane (4d), respectively by refluxing with moist benzene. Reaction of carbomethoxymethylene- triphenylphosphorane (1e) with perfluoropropylene was similar to that of arsorane. However, benzoylmethylene-and acetylmethylene- triphenylphosphorane were unreactive towards perfluoropropylene. Reaction of carbomethoxymethylene-triphenylarsoraen (1a) with trifluorochloroethylene gave carbomethoxyfluoroacetylmenthylene- triphenylarsorane (4f) in low yield. when the residue was treated with methanol, difluorotriphenylarsorano and methyl- fluorochloroacetate (8) were obatined. The structures of the aforementioned products are ascertained by elemental analyses, IR, ^1H NMR, ^1^9F NMR and mass spectra.     

Synthesis of Bis Azole,Diazole, and Triazole Derivatives from N‐(4‐Chloro/Iodophenyl)‐N‐carboxyethyl‐β‐alanine Dihydrazides

A new potentially biologically active N‐(4‐chloro/iodophenyl)‐N‐carboxyethyl‐β‐alanine derivatives ( 2 , 2a , 2b , 3 , 3a , 3b , 4 , 4a , 4b , 8 , 8a , 8b , 9 , 9a , 9b ) and products of their cyclization 6 , 6a , 6b , 7 , 7a , 7b , 10 , 10a , 10b , 11 , 11a , 11b were obtained and characterized by the methods of ¹H‐NMR, ¹³C‐NMR, IR, mass spectroscopy, and elemental analysis.     

Synthesis of optically active 2-alkoxy-2H-pyran-3(6H)-ones. Their use as dienophiles in Diels-Alder cycloadditions.

Optically active 2-alkoxy-2H-pyran-3(6H)-ones (4a-d) were synthesized in one step by the tin(IV) chloride-promoted glycosylation and rearrangement of the 2-acetoxy-3,4-di-O-acetyl-D-xylal (3) prepared from D-xylose (1). The absolute configuration of the new stereocenter at C-2 was determined by chemical transformation of the dihydropyranones 4a and 4b into the known alkyl pentopyranosides (7a and 7b, respectively). Also, from (1)H NMR experiments using a chiral ytterbium shift reagent, the enantiomeric excesses for 4a (>86%) and 4b (>77%) were established. Enantiomerically pure 4c and 4d were obtained by reaction of 3 with chiral 2-octanol (R and S, respectively). Dihydropyranones 4a-d were employed as dienophiles in Diels-Alder cycloadditions with 2,3-dimethylbutadiene and butadiene. Under thermal conditions, only moderate yields (approximately 50%) of cycloadducts 9a-c and 10a were respectively obtained with good diastereofacial selectivity (>80%). Optimized Lewis acid promoted cycloadditions led to 9a-d and 10a,c in higher yields (approximately 80%) and with higher diastereoselectivities (>94%). The major products were formed by approach of the dienes from the less hindered face of the dihydropyranones, and the minor products (such as 11a) were formed by addition from the opposite side. Furthermore, cycloadduct 9a was stable in an alkaline solution, whereas 11a underwent epimerization under the same conditions.