3-[2,6-二氯-4-(3,3-二氯烯丙氧基)苯氧基]丙基吡唑-5-羧酸酯类衍生物的合成及杀虫活性

以3-[2,6-二氯-4-(3,3-二氯烯丙氧基)苯氧基]丙醇和5-吡唑甲酸衍生物为原料,设计并合成了14个未见报道的3-[2,6-二氯-4-(3,3-二氯烯丙氧基)苯氧基]丙基吡唑-5-羧酸酯类衍生物.目标化合物的结构经IR,1HNMR和元素分析测定确认.初步杀虫活性测试结果表明,该类化合物对鳞翅目害虫具有较好的杀虫活性.     

The synthesis of some dialkyl 4-(3-substituted amino)phenyl-1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylates

Dialkyl 4-(3-aminophenyl)-1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylates 1 were transformed into alkyl 4-(3-(((2-benzoylamino-2-methoxycarbonyl)ethenyl)amino)phenyl)-1,4-dihydro-2,6-dimethyl-pyridine-3,5-dicarboxylates 4 and with 2,2-disubstituted-1-dimethylaminoethenes 7 into dimethyl 4-(3-(((2,2-diacyl- or 2-acyl-2-alkoxycarbonyl)ethenyl)amino)phenyl)-1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylates 8 and their ethyl methyl analogues 9.     

Synthesis and Crystal Structure of Ethyl 1-（2-bromoethyl）-3-（4-meth-oxyphenyl）-1H-pyrazole-5-carboxylate

The title compound ethyl 1-(2-bromoethyl)-3-(4-methoxyphenyl)-1H-pyrazole-5-carboxylate 1 has been synthesized and structurally characterized by single-crystal X-ray diffraction.The crystal is of monoclinic(C15H17BrN2O3,Mr = 353.22),space group C21 with a = 24.691(7),b = 6.7678(17),c = 17.884(5) ,β = 97.184(5)o,V = 2965.1(13) 3,Z = 8,Dc = 1.583 g.cm-3,F(000) = 1440,μ = 2.784 mm-1,the final R = 0.0260 and wR = 0.0596 for 2684 observed reflections with I > 2σ(I).All the carbon atoms in the molecule are nearly coplanar except C(15),with a large conjugated system among the carbonyl group,pyrazole ring and the benzene ring.Three non-classical intermolecular hydrogen bonds help to stabilize the crystal lattice.The regioselectivity was rationalized based on the coordination of potassium ion with the N-anion and the carbonyl oxygen atom.     

2-(取代哌嗪-1-甲基)-3-喹啉甲酸乙酯及其衍生物的合成、 表征及晶体结构

以邻硝基苯甲醛为起始原料, 经还原、Friedländer 缩合反应合成2-甲基-3-喹啉甲酸乙酯(2), 2经N-溴代丁二酰亚胺(NBS)溴代得到化合物3, 3再与N-取代哌嗪5a～5p 发生SN2亲核取代反应, 合成一系列2-(取代哌嗪-1-甲基)-3-喹啉甲酸乙酯及其衍生物6a～6p. 它们的结构通过元素分析, IR, 1H NMR, 13C NMR和MS进行了鉴定和表征, 并用X射线衍射法测定了化合物6n的晶体结构.     

5-(4-叔丁氧基羰基哌嗪基)苯并呋喃-2-甲酸乙酯的合成

5-溴苯并呋喃-2-甲酸乙酯与4-叔丁氧基羰基哌嗪进行Buchwald-Hartwig偶联反应,若催化剂是Pd(OAc)2/BINAP,碱是Cs2CO3,则产物主要是5-(4-叔丁氧基羰基哌嗪基)苯并呋喃-2-甲酸乙酯,转化率达70%;若催化剂是Pd(dba)2/P(t-Bu)3,碱是叔丁醇钾,则产物中几乎没有5-(4-叔丁氧基羰基哌嗪基)苯并呋喃-2-甲酸乙酯.文中讨论了影响这个Buchwald-Hartwig偶联反应的因素.     

Functional Derivatives of 4-Formyl-2-methoxyphenyl Pyridine-4-carboxylate

Russian Journal of Organic Chemistry - Acylation of vanillin with isonicotinoyl chloride gave 4-formyl-2-methoxyphenyl pyridine-4-carboxylate which was converted into a number of functional...     

Synthesis,Crystal Structure and Fungicidal Activity of Ethyl 2-(3-(4-Fluorobenzamido)phenyl)-4-((4-fluorobenzoyl)oxy)thiazole-5-carboxylate

The target compound, ethyl 2-(3-(4-fluorobenzamido)phenyl)-4-((4-fluorobenzoyl)oxy) thiazole-5-carboxylate, was synthesized by four-step procedures including N-protection, thionation, cyclization and acylation. Its structure was characterized by 1 H NMR, ~(13)C NMR, HRMS and single-crystal X-ray diffraction. The target compound crystallizes as monoclinic crystal system, space group C2/c with a = 9.6097(19), b = 14.246(3), c = 33.070(7) ?, V = 4515.1(16) ?~3, Z = 8, Dc = 1.496 Mg/m~3, F(000) = 2096 and μ = 0.203 mm~(-1). There are 21864 reflections measured(4.94≤2θ≤55.96°), of which 5357 were unique(Rint = 0.1418) and used in all calculations. The final R = 0.0581(I 2σ(I)) and wR = 0.1453(reflections). The target compound showed over 50% of growth inhibition against Physalospora piricola, Rhizoctonia cerealis and Sclerotinia sclerotiorum.     

1-(嘧啶基-4)-3-(2,6-二氟苯甲酰基)脲衍生物的合成与生物活性

为了寻找高效、低毒、低残留的环境友好杀虫剂, 设计并合成了12个新的1-(嘧啶基-4)-3-(2,6-二氟苯甲酰基)脲衍生物6a～6l, 其结构经IR, ¹H NMR, LC/MS和元素分析确证. 初步生物活性测试结果表明, 部分化合物具有明显的杀虫活性, 如6g在100 mg/L浓度下, 对粘虫(Mythimna sepatara)具有100%的杀虫活性.     

Synthesis,Crystal Structure and Photoluminescence of Ethyl Coumarin-3-carboxylate Derivatives

The ethyl coumarin-3-carboxylate(1) and its two derivatives,ethyl 7-methoxy-2-oxo-2H-chromene-3-carboxylate(2) and ethyl 7-(3-methylbut-2-enyloxy)-2-oxo-2H-chromene-3-carboxylate(3),were synthesized,characterized and their UV-vis spectra and photoluminescence were investigated.Compound 2 crystallizes in the monoclinic system with space group C2/c,a = 25.884(4),b = 6.8365(11),c = 13.816(2) ,β = 104.876(2)°,V = 2362.9(7) 3,Z = 8,Dc = 1.396 g/cm3,Mr = 248.23,F(000) = 1040 and μ = 0.108 mm–1.Compound 3 crystallizes in the monoclinic system with space group P21/c,a = 15.685(6),b = 8.373(3),c = 13.063(5) ,β = 111.862(6)°,V = 1592.2(10) 3,Z = 4,Dc = 1.261 g/cm3,Mr = 302.31,F(000) = 640 and μ = 0.093 mm–1.Both the absorption and emission of the two derivatives were stronger than that of ethyl coumarin-3-carboxylate due to the larger conjugation of their electron donor group moiety at the 7-position.Under ultraviolet light excitation,the two derivatives exhibit strong blue-violet emission.     

2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基丙烯腈衍生物的合成及生物活性

为了寻找生物活性良好的噻唑基丙烯腈类化合物, 利用2-[4-(2,6-二氟苯基)噻唑-2-基]乙腈(3)分别与取代氯甲酸酯4和取代苯基异氰酸酯6在碱存在下反应, 合成了8个2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基-3-烃氧基丙烯腈化合物5和7个2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基-3-取代苯胺基丙烯腈化合物7, 均为首次报道的丙烯腈类化合物. 化合物结构经1H NMR, IR, MS和元素分析表征. 初步生物活性测定结果表明, 在试验浓度下, 目标化合物均具有一定的杀虫和抑菌活性, 其中化合物5f和5h在100 mg/L浓度下对炭疽病菌的抑制率达95%; 化合物5g和7d在250 mg/L浓度下对棉红蜘蛛的致死率达85%.     

Intramolecular 6-endo-dig-Cyclization of Ethyl 5-Aminomethyl-4-(1,2,3-thiadiazol-4-yl)furan-2-carboxylate

The reaction of 5-aminomethyl-4-(1,2,3-thiadiazol-4-yl)furan-2-carboxylic acid ethyl ester with bases has given ethyl 5-sulfanylidene-4,5,6,7-tetrahydrofuro[2,3-c]pyridine-2-carboxylate as a result of intramolecular 6-endo-dig-cyclization of thioketene generated in situ with an internal CH₂NH₂ nucleophile. The obtained ester has been alkylated with iodomethane at the sulfur atom to form ethyl 5-methylsulfanyl-4,7-dihydrofuro[2,3-c] pyridine-2-carboxylate. The Hantzsch reaction with ω-bromoacetophenone has resulted in the formation of 7-ethoxycarbonyl-3-phenylfuro[3,2-d[1,3]thiazolo[3,2-a]pyridin-4-ium bromide.

     

Functionalization of Ethyl 6-Amino-4-(4-chlorophenyl)-5-cyano-2-methyl-4H-pyran-3-carboxylate: Facile Synthesis of a New Series of Pyrano[2,3-d]pyrimidine Derivatives

Russian Journal of General Chemistry - Herein, synthesis of a new series of pyrano[2,3-d]pyrimidine scaffolds is presented. Ethyl 6-amino-4-(4-chlorophenyl)-5-cyano-2-methyl-4H-pyran-3-carboxylate...     

Synthesis and Crystal Structure of Ethyl 2,7,7-Trimethyl-4-(4＇-methylphenyl)-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate in Aqueous Medium

The title compound (C22H27NO3) was obtained by the reaction of 4-methylbenzal- dehyde, dimedone, ethyl acetoacetate and ammonium acetate in water in the presence of triethyl- benzylammonium chloride (TEBA). The crystal is of orthorhombic, space group Pbcn with a = 18.242(2), b = 15.651(1), c = 14.207(2) (A), V = 4056.15(64) (A)3, Mr = 353.45, Z = 8, Dc = 1.158 g/cm3, μ = 0.076, λ(MoKα) = 0.71073 (A) and F(000) = 1520. The final R = 0.0453 and wR = 0.0436 for 1156 observed reflections with I > 2((Ⅰ). X-ray analysis revealed that the pyridine ring is of boat conformation and the six-member ring fused with it adopts half-chair conformation.