马拉赛昂类型化合物的制备

等克分子的二硫代磷酸-O,O-二乙酯与溴代丙二酸二乙酯在氢氧化钠的存在下分别用乙醇和丙酮为溶剂回馏,产生 S-双(乙氧甲酰)次甲基-O,O-二烷基二硫代磷酸酯(Ⅷ)(R 为 C_2H_(?)—,(?)-C_6H_7—,n-C_6H_7—,n-C_4H_9—,ClC_2H_4—)。初步昆虫试验结果证明 R 为乙基的化合物对拟谷盗有毒杀作用。     

C1—C6一元脂肪酸及乳酸的气相色谱分析新方法

测定C_1～C_6脂肪酸及乳酸的量,在食品饮料、医药卫生、生物工程及农业、饲料工业等领域具有重要意义。用气相色谱法测定这些酸的含量,多将它们转变为对应的甲酯、乙酯、异丙酯、丁酯或苄酯等热稳定性好、易挥发的酯衍生物后再进行分析。本文采取室温下,在二甲基乙酰胺中利用题示各酸的四甲基铵盐与2—碘代丙烷反应制备各酸相应的异丙酯,     

(S)-(+)-2,2-二甲基环丙烷甲酰胺的不对称合成

以环己二胺作为手性源,与3,5-二叔丁基水杨醛经缩合反应制得Salen配体(R,R)-N,N'-二(3,5-二叔丁基水杨醛)-1,2-环己二胺(6);甘氨酸乙酯盐酸盐经重氮化和6与三氟甲烷磺酸亚铜催化的不对称环丙烷化反应制得(S)-(+)-2,2-二甲基环丙烷甲酸乙酯(9);9经水解、酰氯化和氨解反应合成了(S)-(+)-2,2-二甲基环丙烷甲酰胺,ee值82%,总收率55.4%,其结构经1H NMR和IR确证。     

脂蛋白脂酶激活剂艾溴利平类似物的合成

合成了两个新型的艾溴利平类似物——N-2 -硝基-4-氯苯基-4-[(膦酸二乙酯基)甲基]苯甲酰肼(5,总收率28.1％)和N-2-四氮唑基-4-氯苯基-4-[(膦酸二乙酯基)甲基]苯甲酰胺(7,总收率30.5％).以对氯甲基苯甲酸为原料,经酯化、水解和酰氯反应制得中间体4-[(膦酸二乙酯基)甲基]苯甲酰氯(4);4与2-硝基-4-氯苯肼盐酸盐反应合成了5.4先与2-氨基-5-氯苯腈反应制得N-2-氰基-4-氯苯基-4-[(膦酸二乙酯基)甲基]苯甲酰胺(6);6再与叠氮化钠反应合成了7.其结构经1 H NMR和IR表征.     

沙枣花净油化学成份的研究

用GC-MS-DS技术对沙枣花净油的化学成份进行了研究。其主要成份为反式肉桂酸乙酯。其它成份有:3-甲基己醛、苯甲醛、壬醛、苯甲酸乙酯、癸醛、苯乙酸乙酯、7-甲基十三烯-6、顺式肉桂酸乙酯、肉桂酸甲酯、肉桂酸异丙酯、正十七烷、苯乙烯基异丙基酮、6,10,14-三甲基十五酮-2、棕榈酸乙酯、棕榈酸、正二十一烷、油酸乙酯、硬酯酸乙酯、正二十八烷和花生油酸乙酯。     

取代苯甲醛类的Knoevenagel反应的研究

苯环上有吸电子基团(p-或m-HO_2,p-CN,m-Br)取代的苯甲醛与甲基丙二酸在吡啶催化下,生成α-甲基-β-羟基苯丙酸类化合物;在六氢吡啶催化下则得到α-甲基肉桂酸类化合物。取代苯甲醛与丙二酸无论用吡啶或六氢哟啶催化均生成肉桂酸类化合物;与丙二酸二乙酯缩合时也无论用吡啶或六氢吡吡催化均生成苄叉丙二酸二乙酯。     

六水合三氯化铁催化3-甲基环己酮与丙酮酸乙酯交叉羟醛缩合制备薄荷内酯

用FeCl3·6H2O催化3-甲基环己酮与丙酮酸乙酯交叉羟醛缩合,制得2-(2-氧代-4-甲基环己叉基)丙酸乙酯和7a-羟基薄荷内酯,皂化后用硼氢化钠还原、酸化制得(±)-薄荷内酯,产率为51%。考察了3-甲基环己酮的烯醇式异构化的位置选择性和粗产物中(±)-薄荷内酯与(±)-异薄荷内酯异构体的比例。     

水性可聚合二苯甲酮光引发剂的简便合成

以甲基丙烯酸-N,N-二甲基氨基乙酯为亲核试剂,分别与4-溴甲基二苯甲酮和4,4’-二(溴甲基)二苯甲酮在20℃下反应,并过简单的过滤,得到了两种水性可聚合二苯甲酮类光引发剂:4-[N-(2-甲基丙烯酰氧基乙基)二甲基溴化铵甲基]二苯甲酮(收率79.2%)和4,4’-双[N-(2-甲基丙烯酰氧基乙基)二甲基溴化铵甲基]二苯甲酮(收率79.7%)。产物用NMR、IR和元素分析进行了表征。     

(R)-3,3-二甲基-2-羟基-4-氧代丁酸乙酯的不对称合成

研究了异丁醛与乙醛酸乙酯不对称羟醛缩合反应合成(R)-3,3-二甲基-2-羟基-4-氧代丁酸乙酯,考察了催化剂种类及用量、反应时间、反应溶剂对羟醛缩合反应的影响。确定较佳反应条件为:L-组氨酸作催化剂,用量为乙醛酸乙酯物质的量的30%,乙二醇为溶剂,反应时间24h。(R)-3,3-二甲基-2-羟基-4-氧代丁酸乙酯的收率达75%,ee值为73%。产物结构经1H NMR,GC-MS进行了表征。     

2-溴甲基取代的[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸乙酯的合成(英文)

6-甲基-[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸乙酯(1)与N-溴代丁二酰亚胺(NBS)在150W白炽灯照射的条件下有效的发生自由基溴化反应,以较好的收率(75%)得到想要的单溴化产品6-(溴甲基)-[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸乙酯(2)。本文所开发的自由基溴化方法与文献相比,单溴化产品的收率提高了46%。另外,该溴化反应中所生成的少量副产品也进行了分离提纯,其结构经波谱分析证实为9-溴-6-甲基-[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸乙酯(3)。     

Synthesis of 1,4-dihydro-2-methyl-4-oxo-nicotinic acid: Ochiai's route failed

The synthesis of 1,4-dihydro-2-methyl- and 1,4-dihydro-1,2-dimethyl-4-oxo-nicotinic acids was accomplished following a route other than Ochiai's procedure, which yielded the isomer 1,6-dihydro-2-methyl-6-oxo-nicotinic acid ethyl ester, and not the 4-oxo-derivative, as reported. Analytical data confirmed the identity of the two isomer oxo-nicotinic acids. UV-vis and potentiometric preliminary data showed that Al(III) does not form complexes with 1,6-dihydro-2-methyl-6-oxo-nicotinic acid ethyl ester in solution, as expected, but with 1,4-dihydro-2-methyl-4-oxo-nicotinic acid.     

4-Hydroxyquinolones-2. 91. Synthesis and properties of ethyl 1-R-4-hydroxy-6-methyl-2-oxo-dihydropyridine-5-carboxylates

The reaction of ethyl aminocrotonates with derivatives of malonic acid is a suitable method for the preparation of ethyl 4-hydroxy-6-methyl-2-oxo-1,2-dihydropyridine-5-carboxylates. One of the synthesized materials has been studied by X-ray crystallography. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, 217–223, February, 2006.     

Selection of Planar Chiral Conformations between Pillar[5,6]arenes Induced by Amino Acid Derivatives in Aqueous Media

Chiral α-amino acids play critical roles in the metabolic process in nearly all life forms. So far, chiral recognition of α-amino acids has mainly focused on the determination of l /d enantiomers. Herein, selection of planar chiral conformations between water-soluble pillar[5]arene WP5 and pillar[6]arene WP6 was observed due to α-side chain or ethyl ester moieties of l -α-amino acid ethyl ester hydrochlorides binding with WP5 and WP6 , respectively. Therefore, α-side chain and ethyl ester moieties of l -α-amino acid ethyl ester hydrochlorides were recognized by observing the induced CD signal and its inversion. This is a rare example of being able to detect the chiral region around α-carbon of a chiral α-amino acid molecule.     

Synthesis of new 1,3,5-thiadiazine and 1,3,5-triazine derivatives and their antimicrobial activity

Interaction of ethyl chloroformate with γ-N-substituted trithioallophanic acids has been found to yield the corresponding 6-oxo-5-aryl-2,4-dithio-hexahydro-l,3,5-thiadiazines. These on reaction with amines yield 1,3,5-triazines. γ-N-substituted β-oxo-dithio-allophanic acid with ethyl chloroformate similarly yields 4,6-dioxo-5-aryl-2-thio-1,3,5-thiadiazine. Antimicrobial activity of thiadiazines has been reported.     

Rapid analysis of free medium-chain fatty acids and related ethyl esters in beer using SPE and HRGC

A modification of a procedure by Hage [1] is proposed for the gas chromatographic evaluation of the content of free medium-chain fatty acids and related ethyl esters in beer. The method involves extraction of free fatty acids and ethyl esters by SPE using C₁₈ bonded phase columns, derivatization of free fatty acids and related ethyl esters with diazomethane, and GC analysis using an SP-2340 capillary column. The results obtained have shown the method to be rapid and highly reproducible. The technique has been compared with other methods used for determination of free fatty acids.     

An unexpected reaction of 2-vinyloxyethyl isothiocyanate with halocarboxylic acids

Reactions of 2-vinyloxyethyl isothiocyanate with aliphatic halocarboxylic acids give rise to their 1-(2-isothiocyanatoethoxy)ethyl esters in quantitative yields. An unusual rearrangement of 1-(2-isothiocyanatoethoxy)ethyl chloro(bromo)acetate and 3-bromopropanoate to 5-aza-7-chloro(bromo)-4-oxo-3-thiaheptanoic and to 6-aza-8-bromo-5-oxo-4-thiaoctanoic acids, respectively, was observed. Monohalocarboxylic acids and their esters were shown to readily alkylate l,3-oxazolidine-2-thione to form the same thiaheptanoic and thiaoctanoic acids and their esters.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–354, February, 1993.     

磷钨酸-拟薄水铝石负载催化剂合成对羟基苯甲酸乙酯

以拟薄水铝石固载的磷钨酸为催化剂,通过对羟基苯甲酸乙酯的合成产率及磷钨酸的溶脱率的测定,考察催化剂的催化性能和固载程度。结果表明,对羟基苯甲酸乙酯的合成最高产率达到83.8%,溶脱率为2.8%。重复使用6次后,总的溶脱率为12.5%。由此可见,该催化剂是一种固载程度良好的环境友好型催化剂。     

Preparation of Some Glycosyl Amino Acid Building Blocks via Click Reaction and Construction of a Glycotetrapeptide Library Using Spot Synthesis

The copper-catalyzed 1,3-dipolar cycloaddition reaction between ethyl 2,3,4-tri-O-actetyl-6-azido-6-deoxy-1-thio-β -d-glucopyranoside (2), ethyl 2,3,4-tri-O-actetyl-6-azido-6-deoxy-1-thio-β -d-galactopyranoside (4), methyl 2,3,4-tri-O-acetyl-6-azido-6-deoxy-α -d-mannopyranoside (7), and methyl 2,3,6-tri-O-acetyl-2-azido-2-deoxy-β -d-glucopyranoside (9), and tert-butyl-protected Fmoc-asparaginic acid propargylamide (10) gave the corresponding protected glycosyl amino acid building blocks 11, 13, 15, and 17 in 67% to 95% yield. The latter were converted into the corresponding pentafluorophenyl esters 12, 14, 16, and 18, which were used for a spot synthesis of a combinatorial library containing 256 glycotetrapeptides. The library was screened for lectin-binding affinity with the lectins Concanavalin A (Con A), phaseolus vulgaris (PHA-E), and galantus nivalis (GNA).     

Heterocycles [<Emphasis Type="Italic">h</Emphasis>]-fused to 4-oxoquinoline-3-carboxylic acid. Part VII: synthesis of some 6-oxoimidazo[4,5-<Emphasis Type="Italic">h</Emphasis>]quinoline-7-carboxylic acids and esters

Abstract  A series of ethyl 2-(substituted)-9-cyclopropyl-4-fluoro-6-oxo-1H-imidazo[4,5-h]quinoline-7-carboxylates has been prepared from ethyl 7,8-diamino-1,4-dihydroquinoline-3-carboxylate via thermally induced reactions with model alkanoic acids or via microwave-assisted cyclocondensation with some arene carboxaldehydes. Acid-catalysed hydrolysis of the resulting ester derivatives furnished the corresponding imidazoquinoline-7-carboxylic acids. The structures of these new acid and ester derivatives are based on microanalytical and spectral (IR, MS, and NMR) data. Graphical abstract