2,8,9-三氧杂-5-氮杂-1-硼杂双环[3,3,3]十一碳烷的合成

本文报导了具有N→B配位键的2,8,9-三氧杂-5-氮杂-1-硼杂双环[3,3,3]十一碳烷的合成及性质。化合物(1)的制备已有报导,而化合物(2),(3)则为新的化合物。我们研究了它们的成环条件,制备的最佳条件及化学稳定性。     

SYNTHESIS OF 1-(O,O-DIALKYLPHOSPHORYLAMIDO)PROPYL-5-AZA-2,8,9-TRIOXA-1 SILATRICYCLO-[3,3,3,01,5] UNDECANES

Ten 1-(O,O-dialkyl phosphorylamido)propyl-5-aza-2,8,9-trioxa-1-silatricyclo [3,3,3,0^1,5] undecanes were synthesized by the reaction of dialkoxy phosphoryl chlorides with aminopropyl silatrane and their structures were established by elemental analysis, IR, ¹HNMR, and MS measurement. The suitable reaction conditions are discussed based on the related reaction mechanism.     

STRUCTURE OF 1-CHLOROMETHYL-2,8,9-TRIOXA-5-AZA-3,4-BENZO-7,10- DIMETHYL-l-SILATRICYCLO-(3,3.3.O~(1,5))-UNDECANE

<正> Mr=299.8, triclinic, Pl, a=10.395(2), b=11.191(2), c=14.051(3)A, α=81.80(2), β=89.42(2), r=66.47(1)°, v=1481.4(5)A3, Z=4, μ(MoKα)=3.37 cm-1, F(000)=632, Dx=1.34 g/cm3, room temperature. The final R=0.058, with unit weights and s=1.33 for 2900 independent reflexions with |Fo| ≥2.5σ(|Fo|). There are two molecules in an asymmetric unit and the lengths of dative N→ Si bond for the two molecules are 2.185(4) and 2.177(4)A, respectively. The different conformations were observed due to the rotation of the chloro-methyl groups.     

1-杂环芳酰氧基-2,8,9-三氧杂-5-氮杂-1-硅杂三环[3.3.3.0~(1,5)]十一碳烷的研究

本文合成了六个1-杂环芳酰氧基杂氮硅三环和三个1-杂环芳酰氧甲基杂氮硅三环,这些化合物均未见文献报道。通过1~H NMR、IR 和 X 射线衍射的方法,确证上述化台物为五配位结构,分子内的 N→Si 配键强度较大。这是一类低毒或中毒化合物。     

CRYSTAL AND MOLECULAR STRUCTURE OF 1-PHENYLAMINOMETHYL-3,7,10-TRIMETHYL-2,8,9-TRIOXA-5-AZA-1-SILITRICYCLO(3,3,3,0~(1,5)) UNDECANE

<正> The transparent colourless crystal of the title compound crystallized in monoclinic system with space group P21/c and cell dimensions a=9.857(7), b=11.128(4), c=16.036(7) A, β=103.31(5)°, V=1711.7A3, Z=4, Dc= 1.25 g.cm-3, λ =-1.5418 A, μ= 13.067 cm-1. The structure was solved by direct methods and refined by full matrix least-squares, the final discrepancy factor R=0.061 and Rw=0.060. The skeleton of the molecule is composed of three five-membered rings with a common edge N(l)-Si(l), and the dihedral angles between each two of the three rings are 110.5°, 107.9° and 105.0° respectively. The N(l)-Si(l) coordination bond length is 2.143(3) A. In comparison with the structures of other related compounds, it was found the N-Si bond length varies with the electronegativities of the substitute groups R at Si atom.     

1-(4级苯氧基)-3,3-二甲基-1-(1,2,4-三氮唑-1基)-丁醉2右旋A体的晶体结构和绝对构型

三唑醇(Triadimenol)是一种优良内吸性的广谱杀菌剂,用于处理各类作物种子时,防病效果显著。该化合物的分子式为C_(14)H_(18)N_3OCl,化学结构式如右。其中含有两个手性碳原子,应其有四种光学异构体。据文献报导,其中的两个非对映体之间的药效有明显的差别,有效体称为A体。A体的二个对映体之间的药效以(-)-A体为最佳有效体。鉴于了解A体的一对对映体的构型,对探讨其生物活性的作用机理及共与立体构型关系方面有重要意     

STRUCTURE OF 1-CHLOHOMETHYI-3,4,6,7,10,11-TRIBENZO-2,8,9-TRIOXA-5-AZA- 1-SILATRICYCLO-(3.3.3. O1,5)-UNDECANE C_(19)H_(14)ClNO_3Si

<正> Mr=367.88, Monoclinic, C2/c, a=17.758(7), b=ll.838(3), c= 16.793(7)A, β=103.79(3)°,V=3428(2)A3, Z=8,μ(MoKα)=3.10cm-1, F(000)=1520, Dx=1.43g/cm3, room temperature. The final R=0.074, Rw=0.073 with wt=[c2 (|Fo|) +0.0006|Fo| 2]-1, s=1.26 for 1465 independent reflections with |Fo|> 2.5(|Fo)). The length of dative N-Si bond is 2.256A, the Cl atom in -CH2Cl group is disordered.     

STRUCTURE OF 1-PHENYL-3,4-BENZO-7,10-DIMETHYL-2,8,9-TRIOXA-5-A2A- SILATRICYCLO(3.3.3.0~(1,5))UNDECANE

<正> Mr=327.49, monoclinic,C2/c,a=17.211(11), b=12.300(7),c=17.079(10)A,β=99.41(5)°,V=3567(4)A3,Z=8,μ(MoKα)=1.5cm-1,F(000)=1392,Dx=1.22g/cm3, room temperature.The final R=0.085,Rw=0.077 and s=1.27 for 1471 independent reflections with |Fo|>2.5σ(|Fo|).The length of the dative bond N→Si is 2.193(5)A.The structure Is disordered at C(7),C(13),C(10), C(12)positions.     

碘掺杂的3-乙基-5-[2-(3-乙基-2苯并噻唑啉基)亚乙基]罗丹宁的结构与电性能

标题化合物是一种商品名为Agfa-10的份菁染料,是一种光导性能较好的有机光导体。我们已对它的蒸发膜、溶液膜、单晶的培养与结构,晶型的转变及其电子性能进行了系统地研究与报导.它具有如下的分子结构:     

3-乙基-5-[2-(3-乙基-2-苯骈亚噻唑啉基)亚乙基]罗丹宁蒸发膜的一些研究

本文报道3-乙基-5-[2-(3-乙基-2-苯骈亚噻唑啉基)亚乙基]罗丹宁在室温导电玻璃上沉积得到的非晶态薄膜在室温放置逐渐转变为多晶膜的过程.在转变过程中薄膜的光电导也随之增高,最后达一稳定值.还报道用直流及交流方法研究此类蒸发膜光电导的一系列结果.并在高分子溶液中生长出染料的单晶.从单晶的X射线分析结果证明单晶中分子沿a轴方向成层状排列,有助于解释多晶薄膜的导电机理.     

3-取代-5(3-乙基-4,5-二苯基噻唑叉)洛丹宁的增感性能

简单份菁(或称零甲川份菁)是一种可以用作卤化银感光乳剂层感蓝增感的染料。彩色正性材料的发展,要求感蓝乳剂层使用氯溴化银乳剂,并配合使用感蓝增感染料以符合感蓝区域的光谱要求。以氩离子激光为光源的电子分色片乳剂要求对波长488nm附近有较高的敏感,此种乳剂本身感色范围偏离氩离子激光发射峰。寻找增感效率高、光谱增感峰适合的感蓝染料很有必要。本文用2-甲硫基-3-乙基-4,5二苯基噻唑对甲苯磺酸盐(1)分别与3-取代洛丹宁(2)在无水乙醇存在下反应,制得六个未见文献报导的3-取代-5-(3-乙基-     

ELECTROCHEMICAL LUMINESCENCE WITH N(5)-ETHYL-4a-HYDROXY-3-METHYL-4a, 5-DIHYDROLUMIFLAVIN. THE MECHANISM OF BACTERIAL LUCIFERASE

It has been proposed in the literature that the chemiluminescence of the flavoenzyme of bacterial luciferase is caused by a chemically initiated electron-exchange luminescence mechanism which provides an excited 4a-hydroxy-4a,5-dihydroflavin ([4a-FlHOH]*) as product of 1e- reduction of the radical 4a-FlHOH+.. Electrochemical/photon counting experiments were performed to assess the feasibility of this proposal. Potentials for step-wise oxidation of N(5)-ethyl-4a-hydroxy-4a,5-dihydroluminflavin (4a-FlEtOH) have been determined in dry N,N-dimethylformamide (DMF). Photon counting was carried out during the 1e- reduction of 4a-FlEtOH+.in both DMF and acetonitrile by use of an apparatus consisting of a photocell mounted below a Pt ring-disk electrode. By use of the ring-disk electrode a steady state concentration of [4a-FlEtOH]* could be maintained by continuous 1e- oxidation of 4a-FlEtOH----4a-FlEtOH+.and 1e- reduction of 4a-FlEtOH+.----4a-FlEtOH. A maximum of 14% collection (theoretical maximum is 18%) of FlEtOH.+ at the ring electrode was obtained below 5000 rotations per minute. Calibration of the apparatus using 9,10-diphenylanthracene allowed approximation of the quantum yield for 1e- reductive capture of 4a-FlEtOH+.as 10(-6) to 10(-4) in DMF and 10(-7) to 10(-5) in acetonitrile. No fluorescence for 4a-FlEtOH in DMF could be observed; if fluorescent, the efficiency of 4a-FlEtOH can be no greater than approximately 3 x 10(-5). No electrogenerated chemiluminescence is observed on the electrochemical recycling of FlEt+----FlEt2+ and FlEt2+----FlEt+.     

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.     

3-氰基-5-[2-(3-乙基-2-苯并噻唑啉基)亚乙基] 4-苯基-2(5H)-呋喃酮蒸发膜的结构与光、电导性能的关系

众所周知, 部花著染料已作为照相材料的光学增感剂, 并可能作为太阳能电池及光导器件材料, 本工作就是为了探索这种材料进行了标题化合物的合成, 单晶的培养, 蒸发膜的研制及其性能的研究, 并探讨了结构与性能的关系及其导电机制。     

S-（＋）-（E）-1-（2-furfuryl）-5-substituted-1,3,5-hexahydrotriazine-2-N-nitroimines：Synthesis,Crystal Structure and DFT Calculations

A novel neonicotinoid analogue(C13H19N5O5,3a)had been synthesized,the structure was characterized by elemental analysis,IR and 1H NMR spectra,and the S-(+)-(E)-configuration was confirmed by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21 with a = 8.7076(17),b = 8.3211(17),c = 10.642(2),β = 92.370(3)o,V = 770.4(3)3,Z = 2,Dc = 1.402 g/cm3,μ = 0.110 mm-1,Mr = 325.33,F(000)= 344,S = 1.027,R = 0.0543 and wR = 0.1229 for 3601 unique reflections with 2919 observed ones(I > 2σ(I)).Compound 3a is stabilized by intramolecular hydrogen bonds and intermolecular force.In addition,the structure of compound 3a was optimized by the B3LYP/6-31G(d,p).DFT/B3LYP optimizations were performed based on X-ray geometries applying 6-31G(d,p)basis set.The optimized structure of compound 3a by the B3LYP/6-31G(d,p)method is more bent than in the crystal.IR spectrum of the solid compound is consistent with the X-ray structure.The HOMO-LUMO gap in 3a(5.3 eV)indicates high kinetic stabilities of compound 3a.The preliminary bioassay test showed that 3a exhibited good activities against Nilaparvata legen,Pseudaletia separate Walker and Aphis medicagini at 500 mg/L.     

Synthesis of (−)-(4R,5R)- and (+)-(4S,5S)-1-alkyl-4-(4′-nitrophenyl)-1-azonium-3,7-dioxabicyclo[3.3.0]octane halides

A preparative method has been proposed for the synthesis of bicyclic quaternary ammonium salts via sequential treatment of (–)-(1R,2R)- and (+)-(1S,2S)-1-(4-nitrophenyl)-2-amino-1,3-propanediol with paraform followed by an alkyl halide.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1394–1395, October, 1990.     

Crystal Structure of 5-(l-Menthyloxy)-3-Bromo-4-(R)-(+)-Methylbenzylamino-2(5H)-Furanone

１ＩＮＴＲＯＤＵＣＴＩＯＮＳｅｖｅｒａｌｉｍｐｏｒｔａｎｔａｐｐｒｏａｃｈｅｓｔｏｔｈｅｓｙｎｔｈｅｓｉｓａｎｄｐｒｏｐｅｒｔｉｅｓｏｆｃｈｉｒａｌγ ａｌｋｙｌｏｘｙｂｕｔｅｎｏｌｉｄｅｓｈａｖｅａｔｒａｃｔｅｄｍｕｃｈａｔｅｎｔｉｏｎｏｗｉｎｇｔ...     

1-酰氧(胺)-2,8,9-三氧杂-5-氮杂-1-锡杂三环[3.3.3.01.5]十一烷的合成和结构研究

合成了１４个新化合物：１－酰氧（胺）基－２，８，９－三氧杂－５－氮杂－１－锡杂三环［３．３．３．０１．５］十一烷．由ＩＲ、１ＨＮＭＲ、１３ＣＮＭＲ和１１９ＳｎＮＭＲ及元素分析确定其结构．该类化合物在ＣＤＣｌ３中可能形成六配位化合物，而在ＤＭＳＯ中，溶剂分子参与Ｓｎ原子配位，聚合体解聚为六配位化合物．     

1-Trimethoxysilylmethyl-and 1-(2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3]undecan-1-ylmethyl)-1,1-dimethyl-2-(3-alkoxy-3-oxopropyl)hydrazinium halides

Previously unknown 1,1-dimethyl-1-trimethoxysilylmethyl-2-(3-alkoxy-3-oxopropyl)hydrazinium and 1,1-dimethyl-1-(2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3]undecan-1-ylmethyl)-2-(3-alkoxy-3-oxopropyl)-hydrazinium halides were synthesized, and physiological activity of 2-(3-ethoxy-3-oxopropyl)-1,1-dimethyl-1-(2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3]undecan-1-ylmethyl)hydrazinium chloride and bromide was studied.