(+)-1R,3R,5S-1,8,8-三甲基-3-甲硫基-3-氧代-2,4,3-二氮磷杂二环[3,2,1]辛烷的合成、晶体结构和分子的绝对构型

合成标题化合物的结构经X射线分析,其晶体空间群为P_(2_1),晶胞参数a=0.7566(1)、b=0.7708(2)、c=1.0255(1)nm,β=98.60(1)°,Z=2.分子骨架由磷、氮船式七元环组成,P—S键为e键,P—O键为a键。分子绝对构型根据分子中P、S原子对Cu Ka射线的反常散射效应确定。     

(+)-1R,3R(3S),5S-2,4,3-二氮磷杂二环[3.2.1]辛烷衍生物的不对称合成

用(+)-顺式-1R,3S-1,2,2-三甲基-1,3-环戊二胺1为手性诱导试剂分别和几类硫代磷酰二氯2a—k反应,合成了11个新型的含手性磷原子的(+)-1R,3RS,5S-2,4,3-二氮磷杂二环[3.2.1]辛烷的衍生物3a-k.3(1R,3Rs,5S)由两个不等量的非对映异构体3’(1R,3R,5S)和 3"(1R,3S,5S)组成,d.e.值对 3’为 6.2—83.6％,对3"为50.4—100％,表明3的合成是经过不对称反应实现的.苯氧基硫代磷酰二氯2e和1的反应具较高的光学选择性,产物中R磷原子异构体3’e的含量占90％;N,N-二烷基胺基硫代磷酰二氯2h,2i和1反应时,只得到含S磷原子的异构体3"h和3"i,为立体专一性反应.     

1-氮杂-2,8-二氧杂二环[3.3.0]-辛烷类化合物合成的新方法

以苯基-3,5-二(甲氧基羰基)-2-异(口恶)唑啉-N-氧化物为偶极体,丙烯酸乙酯为亲偶极体,通过[3+2]环加成反应,简便地合成了含有多官能团的1-氮杂-2,8-二氧杂二环[3.3.0]-辛烷类化合物。该反应条件温和,产率较高(50%～93%).化合物的结构经元素分析,¹H NMR,¹³C NMR,IR和MS确认和表证,并对其波谱性质进行了讨论。     

基于[3+2]环加成反应的氮杂螺[3,4]环辛烷的合成

哌嗪、吗啉是小分子药物中常见的结构片段,2,6-二氮杂螺[3,4]环辛烷和2-氧-6-氮杂螺[3,4]环辛烷等四元螺环化合物作为其类似物,在药物化学领域具有良好的应用前景.本研究以廉价易得的丙二酸二乙酯或丙烯酸乙酯为起始原料,经[3+2]环加成反应,可便捷高效地完成6-苄基-2,6-二氮杂螺[3,4]环辛烷和2-氧-6-氮杂螺[3,4]环辛烷克级水平的合成.     

3-氧杂-8-氮杂双环[3.2.1]辛烷盐酸盐的合成

以己二酸为初始原料,依次经酰氯化,溴代,苄胺环合,水解,还原,脱水环合,氢解脱苄和成盐等8步反应,合成了3-氧杂-8-氮杂双环[3.2.1]辛烷盐酸盐,总收率23%,纯度100%,其结构经1H NMR确证。     

1,4-二氮杂双环[2.2.2]辛烷催化的有机化学反应

综述了有机小分子催化剂1,4-二氮杂双环[2.2.2]辛烷(DABCO)在有机合成反应中的应用与发展。这种有机小分子催化的反应大多数条件温和、操作简单;相对过渡金属而言,对环境友好;在一定条件下,这种催化剂可以回收再利用。     

2,6-二氧杂双环[3.2.1]辛烷类衍生物的串联合成

以2-甲基-4-戊烯-1,2-二醇和芳香醛为原料, 三氯化铟为催化剂, 得到了一系列1,3-二取代2,6-二氧杂双环[3.2.1]辛烷类衍生物. 整个反应采用一锅法, 反应条件简单且产率高. 所有的化合物均用¹H NMR, ¹³C NMR和质谱法进行了表征, 并用NOESY确立了分子的相对构型.     

1，4-二氮杂二环[2.2.2]辛烷-1，4-二乙酸配合物的合成、结构与磁性

合成了{[M(L)₂(H₂O)₂](ClO₄)₂·4H₂O}_n(M=Cu 1,Co 2;L=1,4-二氮杂二环[2.2.2]辛烷-1,4-二乙酸),并进行了元素分析、红外、热重、变温磁化率等表征。单晶结构表明这2个配合物属于单斜晶系,P2₁/c空间群。Cu(Ⅱ)和     

ASYMMETRIC SYNTHESIS OF THE DERIVATIVES OF (+)-1R,3R(3S), 5S-2,4,3-DIAZAPHOSPHABICYCLO [3.2.1] OCTANE

A new series of dextrorotatory derivatives of 1R,3RS,5S-1,8,8-trimethyl-2,4,3-diazaphosphabicyclo [3.2.1] octane with a newly formed chiral phosphorus atom has been prepared by an asymmetric reaction of (+)-cis-1R,3S-1,2,2-trimethyl-1,3-cyclopentadiamine with some thiophosphoryl dichlorides. The optically active products consisted of two unequal amounts of diastereomers,(1R, 3R, 5S) isomers and(1R, 3S, 5S) isomers. Two regioselective reactions took place when phenoxy thiophosphoryl dichloride and N,N-dialkylamino thiophosphoryl dichlorides were chosen as the reagents for the reaction. The content of (1R, 3R, 5S) isomers in the product was over 90% for the former and there were only (1R, 3S, 5S) isomers obtained for the latter.     

Synthesis and Crystal Structure of 1,2,4,6-Tetraphenyl-2-hydroxy-8-azabicycle[3,2,1]octane

1 INTRODUCTIONAtrope alkaloids, which exist in eggplant plants, such as atrope and scopolamine, are used as a series of important drugs in medical science [1,2]. The typical character of atrope alkaloid is that these compounds contain the main skeleton of 8-azabicycle[3,2,1]octane , which results in the very complicated synthetic routine[3]. During our research for the reaction of 1,3,5,7-tetraphenyl-4- nitro-1,7-heptadione with low-valent titanium reagent, we easily synthesized the title …     

Synthesis and Crystal Structure of （2S,5S）-1-Aza-2-（2-pyridyl）-3-oxa-4,4-diphenylbicyclo [3.3.0] Octane

1 INTRODUCTION The catalytic asymmetric synthesis has been a challenging subject in organic synthesis. The deve- lopment of efficient enantioselective catalysts appli- cable to a wide range of carbon-carbon bond form- ing reactions represents a pivotal …     

(+)-O-萘基环状磷酰二胺酯的合成、晶体结构及绝对构型

合成了目标化合物(+)-O-萘基环状磷酰二胺酯,其结构由¹HNMR,³¹PNMR及元素分析确定,并在273K下进行了X射线衍射晶体结构分析.该化合物晶体属正交晶系,P2₁2₁2₁空间群,晶胞参数a=1.0028(4)nm,b=1.1406(4)nm,c=2.4455(8)nm,V=2.7971(18)nm₃,Z=4,Dc=1.212g/cm³,F(000)=1088,μ=0.129mm^-1.晶体的结构收敛最终偏离因子R和wR分别为0.0585和0.0827.Flackx参数为0.03(12).目标化合物中磷原子的绝对构型为S.     

Synthesis and Crystal Structure of 1-（4-Fluorophenyl）-2-hexylthiobenzo[4,5]-furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5（1H）-one

The crystal structure of the title compound 1-(4-fluorophenyl) -2-hexylthio-benzo [4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5(1H) -one(C23H21FN4O2S,Mr = 436.5) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 13.9854(3) ,b = 17.2678(4) ,c = 18.1828(5) ,β = 99.364(2) °,V = 4332.58(18) 3,Z = 4,Dc = 1.338,F(000) =1824,μ = 0.185 mm-1,MoKa radiation(λ = 0.71073) ,R = 0.0538 and wR = 0.1162 for 4728 observed reflections with I > 2σ(I) . X-ray diffraction analysis reveals the fused rings of benzo[4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a] pyrimidin-5(1H) -one system are nearly coplanar. The crystal packing is mainly stabilized by weak intermolecular C-H···O hydrogen bond and π-π interactions.     

Synthesis and Crystal Structure of 2,10-Di-tert-butylindolo[3,2,1-jk]carbazole

The title compound, 2,10-di-tert-butylindolo[3,2,1-jk]carbazole (C26H27N, Mr=353.49), has been synthesized by palladium-catalyzed intramolecular arylation and characterized by 1H NMR, 13C NMR and X-ray crystal structure determination. The crystal crystallizes in the monoclinic system, space group P21/c with a=13.6409(5), b=11.6706(4), c=13.1678(5), β=100.6180(10)°, V=2060.39(13)3 , Z=4, Dc=1.140 mg/m3 , μ=0.065mm-1 , F(000)=760, the final R=0.0456 and wR=0.1209 for 3012 observed reflections (I > 2σ(I)).     

四氢咪啶[2,1-a]并-2,3-二苯基-1,4-二氮杂-3-环己烯的合成与结构

对由二乙烯三胺与联苯甲酰合成的标题化合物进行了MS、IR、UV、NMR谱的表征及X射线单晶衍射结构分析.该化合物M_r=277.39,晶体属P2_1/n空间群,晶胞参数a=0.9442(2)nm,b=1.4344(4)nm,c=1.1824(3)nm.β=112.92(2)°,Z=4,D_c=1.25g·cm~(-3).晶体结构由直接法解出,1827个可观察衍射参与最小二乘法修正,最终偏差因子R=0.050.结果表明标题化合物是一非平面型,具有部分不饱和键的氮杂稠二环化合物,其母体六元环为椅式构型、五元环为半椅式构型,2个取代苯基间的夹角为73.5°.     

2-[3-苯氧甲基-4-苯基-[1,2,4]三唑-5-硫基]乙酰胺的合成、晶体结构表征及生物活性

在微波辐射下, 由苯氧乙酰肼出发, 合成了一系列三唑类衍生物, 利用单晶X射线衍射法测定了化合物5f的单晶结构. 化合物5f通过分子间氢键及范德华力形成了三维网状结构的超分子. 这些化合物对植物根的生长具有比较明显的促进活性.     

Synthesis, Crystal Structure and Fungicidal Activity of 3- ( 4- Chloro- 3- ethyl- 1 -methyl- 1 H- pyrazol- 5-yl ) - 6- (E) phenylvinyltriazolo [ 3, 4-b ] - 1,3, 4-thiadiazole

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