螺{1-溴-4-L-孟氧基-5-氧杂-6-氧代双环[3.1.0]己烷-2,3′-(4′-呋喃甲醇基-5′-孟氧基丁内酯)}的合成及其晶体结构

α-呋喃甲醇与手性试剂5-(L-孟氧基)-3-溴-2(5H)-呋喃酮于室温进行串联的不对称双M ichael加成/分子内亲核取代反应,合成了含有4个新手性中心的螺环/环丙烷标题化合物(1,C33H47B rO8,M r=651.62)。其结构经1H NMR,13C NMR,IR,MS,元素分析和四园单晶X-射线衍射仪表征。1属正交晶系,P2(1)2(1)2(1)空间群,a=10.166(2),b=14.980(3),c=23.202(5),α=90°,β=90°,γ=90°,V=3533.4(12)3,Z=4,Dc=1.225 Mg.m-3,μ=0.074 mm-1,F(000)=1376,偏离因子R=0.0701,wR=0.1149。1的分子中共有6个环,12个手性中心,2个六元环呈椅式构象,3个五元环呈信封式构象,4个新生成的手性中心的构型分别是(S)-C1,(S)-C3,(R)-C3,′(R)-C4′。     

螺[1-氯-4-l-孟氧基-5-氧杂-6-氧代双环[3·1·0]己烷-2,3'-(4'-吗啉基-5'-l-孟氧基丁内酯)]合丙酮的合成及晶体结构

利用新手性源,5-(l-孟氧基)-3-氯-2(5H)-呋喃酮4与亲核试剂吗啉通过串联不对称双Michael加成/分子内亲核取代反应合成了一般方法难以得到的含有多个手性中心的螺-环丙烷双内酯化合物C32H50O7NCl.其单晶为C32H50O7NCl(OC3H6)0.5,正交晶系, 空间群为P212121, 晶胞参数a = 17.149(3), b = 20.384(4), c = 10.831(2) , V = 3786.1(12) 3, Z = 4, Dc = 1.097 g/cm3, F(000) = 1352, μ= 0.144 mm-1; 射线类型为MoK?( = 0.71073 ?, 偏离因子R = 0.0755, wR = 0.1956, 独立衍射点3710个, 其中可观测点数2318个.分子中共有六个环, 12个手性中心, 3个六元环呈椅式构象, 两个五员内酯环呈信封式构象, 并分别与环丙烷形成[2.4]螺环和 [3.1.0] 稠环, 4个新生成的手性中心的绝对构型为C(3)(S), C(4)(S), C(5)(R), C(8)(R).     

螺〔1-溴-4-l-孟氧基-5-氧杂-6-氧代双环〔3.1.0〕己烷2,3’-(4’-甲氧基5’孟氧基丁内酯)〕的晶体结构

本文报道了利用新手性源合成的标题化合物C2 9H45 BrO7(Mr=5 85 .5 6 )的晶体结构 ,该晶体属正交晶系 ,空间群为P2 1 2 1 2 1 ,晶胞参数a =9.748(4) ,b =12 .5 37(5 ) ,c =2 5 .85 1(9) ,V =315 9(2 ) 3,Z =4,Dx=1.2 31g/cm3,μ =1.341mm- 1 ,F(0 0 0 ) =12 40 ,偏离因子R =0 .0 475 ,Rw=0 .0 6 0 9;分子中共有 5个环 ,12个手性中心 ,2个六元环呈椅式构象 ,2个五元内酯环呈信封式构象 ,并分别与环丙烷形成〔2 .4〕螺环和〔3 .1.0〕稠环 ,4个新生成的手性中心的绝对构型为C(13) (S) ,C(14 ) (S) ,C(15 ) (R) ,C(16 (R) ,无任何对称因素     

螺[1-溴-4-(1R,2S,5R)-l-孟氧基-5-氧杂-6-氧代双环[3.1.0]己烷-2,2'-(3'-α-膦酸二乙酯基-(S)-苯甲氧基-4'-l-(1R,2S,5R)-孟氧基丁内酯)]的晶体结构

报道了标题化合物合成和晶体结构。X-射线结构分析表明,该化合物的分子式为C39H58BrO10P,Mr = 797.74,晶体属于单斜晶系,空间群为P21,晶胞参数a = 12.858(3), b = 25.130(5), c = 14.125(3) ? = 105.15(3), V = 4405(2) ?, Z = 4, Dc = 1.203 g/cm3, ?= 1.019 mm-1, F(000) = 1688,R = 0.0726, wR = 0.1201,共收集到9691个独立衍射点,其中可观测点5638个(I≥2s(I))。每个分子中有6个环,13个手性中心,2个五员环呈信封式构象,并分别与三员环组合成[2.4]螺环和[3.1.0]桥环化合物,4个新生成的手性中心的绝对构型为C(6)(S), C(7)(S), C(3)(R), C(2)(R),新引入的磷酸酯官能团C(9)为S构型。     

3-(3,4-亚甲二氧基)苯基-6-孟氧基-6,6a-二氢-呋喃并[3,4-d]异噁唑啉-4(3aH)-酮的合成和晶体结构

标题化合物是由5-(R)-(l-孟氧基)-2(5H)-呋喃酮与3,4-亚甲二氧基苯甲醛肟在次氯酸钙作为氧化剂的条件下,进行的区域选择性原位1,3-偶极环加成反应得到。结构通过单晶X-射线衍射法确定, C22H27NO6其晶体属正交晶系, 空间群为P212121, Mr = 401.45, a = 6.2600(3), b = 10.7300(11), c = 31.2160(25) , V = 2096.8(3) 3, Z = 4, Dc = 1.272 g/cm3, μ = 0.09 mm-1, F(000) = 856。最终的可靠因子为R f = 0.073, wR = 0.186。在分子结构中,平面1(异噁唑啉环)与平面2(呋喃酮环)之间的二面角为67.4°, 孟氧基中的环己烷环为椅式构象,呋喃酮并异噁唑啉环上的3个手性中心的构型为SC3a, RC6, RC6a。     

(1R,4S,5S)-6-环己基-4-[(1R,2S,5R)-5-甲基-2-异丙基环己氧基]-3-氧杂-6-氮杂双环[3.1.0]-2-己酮的合成及结构表征

环已胺与差向异构体5-[(1R,2S,5R)-5-甲基-2-异丙基环己氧基]-3-溴-2(5H)-呋喃酮发生不对称Mi-chael加成-分子内亲核取代反应,并经柱层析分离,得到一对手性氮杂环丙烷-丁内酯衍生物,其中的标题化合物为首次得到的新手性化合物,产率17%,其结构经IR、1H NMR、13C NMR和HRMS进行了表征。     

新型硅基桥连双(环戊二烯基)四羰基二铁类配合物的合成

以六甲基二硅烷为原料,经氯代、格式反应和锂化反应制得双(环戊二烯基)配体(C5H5)2MeSiSiMe2R(3a^3c),将该配体分别与五羰基铁在对二甲苯中回流反应,合成了3种新型的硅基桥连双(环戊二烯基)四羰基二铁类配合物[η^5,η^5-C5H4MeSi(SiMe2R)C5H4]Fe2(CO)2(μ-CO)2[R=p-C6H4CH3(4a),R=p-C6H4OCH3(4b),R=CH2C6H5(4c)],其结构经1H NMR,13C NMR,IR和元素分析表征。并用X-射线单晶衍射法确定了配合物4b的分子结构。结果表明:4b(CCDC:1942618)属单斜晶系,Cc空间群,晶胞参数a=18.591(3)A,b=10.3080(10)A,c=14.136(2)A,α=90°,β=117.262(6)°,γ=90°,V=2408.1(6)A^3,Z=4,F(000)=1152,Dc=1.546 g·cm^-3,μ=1.338 mm^-1,R1=0.0351,wR2=0.0754。     

三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯的合成、结构和体外抗癌活性

利用三有机锡氢氧化物和手性配体(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸(HL)反应合成了3个三有机锡(4R)-3-[[(2S)-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯R3SnL[1,R=c-C6H11(a),C6H5(b),C6H5C(CH3)2CH2(c)],通过元素分析、IR、1H NMR和X-射线单晶衍射表征了其结构。化合物1a属正交晶系,P212121空间群;化合物1b属单斜晶系,P21空间群。二者均为由羧基氧和内酰胺羰基氧桥联配位形成的右螺旋链状有机锡配位聚合物,锡原子具有五配位[SnC3O2]畸变三角双锥构型。化合物1a和1b对体外2种人癌细胞Colo205和Bcap37增殖均有强的抑制作用,其活性为1b1a。     

手性5-(R)-(1′R,2′S,5′R)-孟氧基丁内酯并[3,4-b]-2(S)-6(R)-1-N-环己基氮杂环丙烷的合成及晶体结构

环己胺与手性元5-(R)-(1′R,2′S,5′R)-孟氧基-3-溴-2(5H)-呋喃酮的不对称M ichael加成/分子内亲核取代反应,得到含有两个新手性中心的氮杂环丙烷/稠合丁内酯标题化合物。对其进行了谱学表征和X-射线单晶衍射测定。标题化合物分子式为C20H33NO3,M r=335.47,三斜晶系,P1空间群,晶胞参数:a=5.438(11)。A,b=8.117(2)。A,c=11.572(2)。A,α=96.84(3)°,β=94.48(3)°,γ=101.86(3),°V=493.5(2)。A3,Z=1,D c=1.129g/cm3,R=0.0867,wR=0.2344。     

N,N′-二[3-氯-5S-(l-孟氧基)-2(5H)-4-呋喃酮基]-1,4-丁二胺的合成及晶体结构(英文)

合成了N,N′-二[3-氯-5S-(l-孟氧基)-2(5H)-4-呋喃酮基]-1,4-丁二胺,并通过IR,1H NMR,MS和X射线单晶衍射对其进行了表征.X射线单晶衍射结果表明:标题化合物的不对称结构单元中包含一个平面的呋喃酮环和一个椅式的环己烷环,四个手性中心.标题化合物通过N—H…O分子间氢键作用实现空间堆积.     

SYNTHESIS OF 4,5-SECOCHOLESTANE AND 4-METHYL-4,5-SECOCHOLESTANE

The synthesis of 4,5-secocholestane and 4-methyl-4,5-secocholestane fromcholesterol are reported.     

Synthesis of ribonucleosides of 4(5)-cyano-5(4)-methylimidazole and related 4-substituted-5-methylimidazole ribosides

4-Cyano-1-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-5-methylimidazole ( 4 ) and its corresponding 5-cyano-4-methyl substituted isomer ( 5 ) have been obtained by ribosylation of 4(5)-cyano-5(4)-methylimidazole ( 3 ) via the mercuric cyanide method or by ribosylation of the trimethylsilyl derivative of 3 . Treatment of 4 with methanolic ammonia, ammonium chloride in liquid ammonia and potassium hydrosulfide provided 4-cyano-1-β-D-ribofuranosyl-5-methylimidazole ( 6 ), 1-β-D-ribofuranosyl-5-methylimidazole-4-carboxamide ( 2 ) and 1-β-D-ribofuranosyl-5-methylimidazole-4-thiocarboxamide ( 11 ) respectively. Reaction of 6 with hydroxylamine afforded the corresponding 4-carboxamidoxime substituted nucleoside ( 13 ) which on catalytic reduction in the presence of ammonium chloride, was transformed into 1-β-D-ribofuranosyl-5-methylimidazole-4-carboxamidine ( 14 ) as hydrochloride salt.     

Synthesis of 4-aroyl-5-nitro-1H-imidazoles and 4-aroyl-5-aminoimidazoles

The reaction of α-(aryl)-4-morpholineacetonitriles (masked aroyl anion equivalents) with N-protected 4(5)-bromo-5(4)-nitro-1H-imidazoles gave 4-aroyl-5-nitroimidazoles which were reduced to afford 4-aroyl-5-aminoimidazoles.     

Halogenide der Seltenerdmetalle Ln4X5Z. Teil 3: Das Chlorid La4Cl5B4 – Präparation,Struktur und Verwandtschaft zu La4Br5B4, La4I5B4

Rare Earth Halides Ln₄X₅Z. Part 3: The Chloride La₄Cl₅B₄ – Preparation, Structure, and Relation to La₄Br₅B₄, La₄I₅B₄ La₄Cl₅B₄ is synthesized by reaction of LaCl₃, La metal and boron in sealed Ta containers at 1050 °C < T < 1350 °C. It crystallizes in the monoclinic space group C2/m with a = 16.484(3) Å, b = 4.263(1) Å, c = 9.276(2) Å and β = 120.06(3)°. Ce₄Cl₅B₄ is isotypic, a = 16.391(3) Å, b = 4.251(1) Å, c = 9.180(2) Å and β = 120.20(3)°. The La atoms form strings of trans-edge shared La octahedra, and the B atoms inside the strings form B₄-rhomboids, which are condensed to chains via opposite corners. The Cl atoms interconnect the channels according to La₂La_4/2Clⁱ⁻ⁱ_6/2Cl^i−a_2/2Cl^a−i_2/2. The crystal structures of the bromide and the iodide are comparabel, however, the interconnection of the strings is different in the three structure types, as 14 Cl, 13 Br and 12 I atoms surround the La₆ octahedra.     

C-alkyl-4-nitropyrazoles from 5-chloro-4-nitropyrazoles

5-Chloro-4-nitro-1H-pyrazoles reacted with arylsulfonyl-, cyano-, and acetylacetic acid esters in DMSO in the presence of potassium carbonate to give 5-[alkoxycarbonyl(acetyl, cyano, or arylsulfonyl)-methyl]-substituted 4-nitropyrazoles which may be promising from the viewpoint of preparation of other functionalized pyrazole derivatives and bicyclic ensembles.     

Synthesis of analogs of 5(4)-aminoimidazole-4(5)-carboxamide

In order to obtain 5(4)-aminoimidazole-4(5)carboxamide antagonists, the.hydrazides of 5(4)-aminoimidazole-4(5)-carboxylic acid and 5(4)-aminoimidazole-4(5)hydroxamic acid were synthesized, and the reaction of 5(4)-bromo-4(5)sulfamoylimidazole with amines was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1421–1422, October, 1971.