12H-双苯并[1,3,2]-二氧磷杂八环的合成与波谱分析

通过双（2-羟基-3,5-二氯苯基）甲烷（1）与ROPXCl_2 （X = O，S）的关环 反应，合成了6-烃氧基-6-氧（硫）-2,4,8,10-四氯-12H-双苯并[1,3,2]-二氧磷杂 八环（3），3（X = 0）的收率为62%-85%，并测试了3的~1H NMR，~(13)C NMR，~ (31)P NMR以及MS。详细报道了3的~(13)C NMR中存在的远程偶合现象，并探讨了3 的质谱裂解方式。     

卤代双酚与PXCl3关环反应的研究

根据溶剂效应,选择合适的溶剂,合成了2,4,8,10－四氯－12H－双苯并[d,g][1,3,2]－二氧磷杂（硫代）磷酰氯,首次合成并纯化得到了2,4,8,10－四氯－12H－双苯并[d,g][1,3,2]－二氧磷杂（硫代）磷酰氯。     

6－烷氧基－6－硫－12H双苯并[1,3,2]二氧磷杂八环与DMSO反应研究

通过6－烷氧基－6－硫－2，4，8，10－四氯代－12H－双苯并[d,g][1,3,2]二 氧磷杂八环92）与DMSO在130℃反应，得到了相应的6－羟基－6－氧－双苯并[1， 3，2]二氧磷杂八环与DMSO（1：1）的分子复合物3。通过^31P NMR监视反应证实， 2与DMSO反应生成3的过程是先水解，后氧化，再形成复合物。     

卤代双酚及其环合物 6 _ 取代 _ 12H _ 双苯并 [d,g][1,3,2]二氧磷杂八环的质谱研究

对双（2－羟基－溴、氯代苯基）甲烷及其环化的衍生物6－取代－12H－双苯并[d,g][1,3,2]二氧磷杂八环－6－硫化合物进行了质谱分析并探讨了其裂解规律。母体化合物主要在苯基及亚甲基处开裂,环合后的衍生物主要以硫和氮原子为中心进行反应。溴、氯代双氧环离子（m/z422)为环合衍生物的特征离子。     

2-β-二酮-1,3,2-二苯并[d,f]和二萘并(α,β)[d,f]-二氧硼杂环庚二烯的合成与结构

本文报道1,3,2-二苯并[d,f]二氧硼杂环庚二烯和1,3,2-二萘并(α,β)[d,f]二氧硼杂环庚二烯的制备及其β-二酮衍生物—以硼为螺原子的螺环[6,5]化合物的合成与性质. 8个标题化合物均为新化合物, 具有与10-β-二酮-10, 9-硼氧杂菲类似的结构.     

新型磷杂三环化合物的结构研究

用X射线衍射方法测定了6,12-二氧代-1-对氯苯亚胺基-11-乙基-1,4,3-硫氮磷杂环已烷并[3,4-b]-1,3,2-苯并二氮磷杂环已烷(1)和6,12-二氧代-1-N-苄亚胺基-11-乙氧甲酰甲基-1,4,3-硫氮磷杂环已烷并[3,4-b]-1,3,2-苯并二氮磷杂环已烷(2)的晶体结构。1的晶体属P2~1/n空间群, a=11.276(1), b=10.109(1),c=15.750(2)A; β=94.37(1)^°; Z=4, D~m=1.50, D~c=1.51g/cm^3。对于2569个可观测反射点。最终的R=0.033。2的晶体属Pcab空间群, a=10.596(1),b=19.117(2), c=20.744(2)A; Z=8; D~m=1.39, D~c=1.40g/cm^3。对于1809个可观测反射点, 最终的R=0.031。对这两种新型的磷杂三环化合物的构象进行了分析,并指出了影响磷杂环构象的原因。     

新型螺环树状化合物的合成

利用环己二酮单腙芳构化反应, 得到9H, 9H, 11H, 11H, 12H, 12H-六氢化苯并[9,10]-(1H, 1H, 3H, 3H, 4H, 4H, 5H, 5H, 7H, 7H, 8H, 8H-十二氢)菲-2, 6, 10-三酮腙, 然后与季戊四醇反应, 得到9H, 9H, 11H, 11H, 12H, 12H-六氢化苯并[9,10]-(1H, 1H, 3H, 3H, 4H, 4H, 5H,5H, 7H, 7H, 8H, 8H-十二氢)菲-2,6,10-三酮缩三(2,2-二羟甲基-1,3-丙二醇), 再与9-[4-(2,6-二硫杂环己基)苯基]-3-[4-(二甲酯基甲基)苯基]-2,4,8,10-四氧杂螺[5.5]十一烷反应, 制成标题化合物. 中间体和标题化合物经过IR, 1H NMR, MS和元素分析表征.     

含磷杂环化合物研究(Ⅵ)——2-硫逐(或无取代)-2-酯基取代氧乙烯基(或肟、胺、烷硫基)1,3,2-苯并二氧磷杂戊环化合物

合成了4个1,3,2-苯并二氧磷杂戊环的三价磷化合物Ⅰ_1-4,7个2-硫逐1,3,2-苯并二氧磷杂戊环的五价磷化合物Ⅱ_1-7,研究了其波谱特性,认为当p(Ⅲ)存在时可影响乙烯基类反应的的E、Z体比例。观察到Ⅱ_1-3化合物可能产生红移现象。     

含硫环状膦酸酯衍生物的合成及其热性能

以三氯化磷、苯和硫粉为原料,用离子液体法绿色合成了硫代苯基膦酰二氯(3);3与季戊四醇或新戊二醇反应合成了两种新型含硫磷系阻燃剂--2,4,8,10-四氧杂-3,9-二磷杂螺环[5.5]十一烷-3,9-二硫-3,9-二苯(1)或5,5-二甲基-2-苯基-2-硫代-1,3-二氧-2-磷杂环己烷(2).用~1H NMR,IR,DSC和TG对其结构和性能进行了表征.结果表明,1具有良好的成炭性和热稳定性.     

螺环三代树形大分子化合物的合成

以对苯二甲醛单缩醛与季戊四醇反应得到了2,4,8,10-四氧杂-2,9-二(4-二氰基乙烯基苯基)螺[5.5]十一烷(1), 经水解, 再与丙二腈反应, 制备了中间体2,4,8,10-四氧杂-2-(4-二氰基乙烯基苯基)-9-(4-甲酰基苯基)螺[5.5]十一烷(3). 8-(4-氧代环己烷基)-1,4-二氧杂螺[4.5]癸烷经芳构化形成2,6,10-三-(4-氧代环己烷基)-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(4), 再与甲醛进行羟醛缩合, 制成了2,6,10-三-(4-羟基-3,3,5,5-四羟甲基环己烷基)-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(5), 将5与过量的3反应, 得到了目标树形大分子化合物2,6,10-三-{15-(3,11-二(-4-(3-((9-(4-二氰基乙烯基)苯基)2,4,8,10-四氧杂螺[5.5]十一烷基)))-7-羟基-二螺[5.1.5.3]十六烷基)}-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(6), 收率为18.1%. 产品结构经IR, 1H NMR, MS和元素分析进行了表征. 对影响反应的因素进行讨论.     

New N6‐substituted 8‐alkyl‐2‐phenylmethylsulfanyl‐adenines. II

Title compounds bearing substituents on C(2), C(6) and C(8) were prepared from a newly synthesized pyrimidine derivative 11. The new pyrimidine 11 was generated from compound 2 through two different synthetic schemes. In one pathway, compound 2 was nitrosated, reduced and alkylated to produce com pounds 9 , 10 and 11 respectively (Scheme). In an alternate route using compound 2 as the starting material, a coupling reaction using the diazonium salt derived from p‐methylaniline afforded the azo derivative 7 , which was subsequently alkylated and reductively cleaved to form compounds 8 and 11 respectively (See Scheme). Compound 11 was annulated to the corresponding hypoxanthine derivatives 12–14 ; compounds 12 and 13 were chlorinated with phosphorus oxychloride, then reacted with amines to yield compound 17 and 20 respectively. Compounds 21 , 22 and 23 were obtained by oxidation of the corresponding sulfide as depicted in Scheme. Alkylation of the thiol function of 1 gave a mixture of 3 and 4. Compound 3 was chlo rinated to 5. Nitration of 5 resulted in electrophilic aromatic substitution of the aryl ring and concomitant oxidation of the sulfide to the sulfoxide, producing 6.     

Condensation Reaction of 5,6-Dihydro-6-methyl-6-piperonyl-2H-pyran-2,4-dione,Ethyl Orthoformate and Substituted Anilines

Piperonyl methyl ketone was obtained by oxidizing isosafrole with hydrogen peroxide and formic acid.Dianion of ethyl acetoacetate reacted with piperonyl methyl ketone and 5,6-dihydro-6-methyl-6-piperonyl-2H-pyran-2,4-dione was prepared,which reacted with substituted anilines in the presence of ethyl orthoformate to obtain 3-anilinomethylene-5,6-dihydro-6-methyl-6-piperonyl-2H-pyran-2,4-diones.Their structure were confirmed by ^1HNMR and elemental analysis.     

萘并呋喃类化合物的染料化光氧化及其杂环衍生物的合成与表征

萘并呋喃类化合物1、7在四苯基卟啉存在与氧低温反应给出相应的二氧杂环丁烷类产物2、8，室温下分别全部分解成乙酰基乙酰氧基化合物4、9。2和盐酸作用可给出呋喃3-位甲基及所在萘半环β位的二氯代产物6。4与盐酸反应通过失去萘α位的酰基，形成羟基呋喃化合物3，1在三溴化硼酸解下亦可得同一产物。4在醋酸钠/酸酐中环构生成3-乙酰基吡喃酮(5)。     

Synthesis and reactivity of the phosphinoboranes R2PB(C6F5)2

The phosphinoboranes [R(2)PB(C(6)F(5))(2)](2) (R = Et 1, Ph 2) and R(2)PB(C(6)F(5))(2) (R = tBu 3, Cy 4, Mes 5) were synthesized from the reaction of (C(6)F(5))(2)BCl and the corresponding lithium phosphide. The relationships between B-P distance, P pyramidality, and the extent of BP multiple bonding were further explored computationally. Natural Bond Order (NBO) analyses of 3 and 4 showed that the π-bonding highest occupied molecular orbitals (HOMOs) were highly polarized. In addition the Lewis acid-base adducts, R(2)(H)P·B(H)(C(6)F(5))(2) (R = Et 6; Ph 7; tBu 8; Cy 9; Mes 10) were prepared via the reaction of the phosphines R(2)PH with the borane HB(C(6)F(5))(2). Compounds 1 and 2 showed no signs of reaction with H(2); however, reaction of compounds 3 and 4 with H(2) was observed to give 8 and 9. In a related set of reactions compounds 3 and 4 were reacted with H(3)NBH(3) or Me(2)(H)NBH(3) also led to the generation of 8 and 9, respectively. The reaction profile of the reaction of (CF(3))(2)BPR(2) with H(2) was examined computationally and shown to be exothermic. Efforts to effect the reverse reaction, that is, dehydrogenation of adducts 6-10 were unsuccessful. Compound 4 was also shown to react with 4-tert-butylpyridine to give Cy(2)PB(C(6)F(5))(2)(4-tBuC(5)H(4)N) 11 while reactions of 3 and 4 with the Lewis acid BCl(3) gave the dimers (R(2)PBCl(2))(2) (R = tBu 12, Cy 13) and the byproduct ClB(C(6)F(5))(2).     

6-烷氧基乙氧/硫基-6-氧/硫-双苯并[1,3,2]-二氧磷杂八环的合成与波谱特征

通过双(3,5-二氯-2-羟基-苯基)甲烷(1)分别与POCl₃或PSCl₃在三乙胺存在下关环, 再与单烷氧基乙醇钠作用, 得到了新化合物5或6; 以1与P₄S₁₀及三乙胺关环的产物4与烷氧基溴乙烷反应得到了7. 测试了5, 6和7的¹H, ¹³C和³¹P NMR及MS数据, 并讨论了其特征. 观察到了磷与C¹H (C¹¹H)或C³H (C⁹H)与P的⁵J_PH偶合常数(约为0.9 Hz). 在1与POCl₃关环产物与单甲氧基乙醇反应的产物中, 分离到了一个副产物8并确定了它的化学结构. 1与POCl₃按3∶2的物质的量比在三乙胺存在下反应, 得到收率75%的8.     

对苯醌-2,5-二羧酸酯的合成

氢醌-2,5-二羧酸酯(2a,b)用活性MnO~2氧化高产率地得到对苯醌-2,5-二羧酸酯(3a,b). 氢醌-2,5-二羧酸乙酯(2b)也能用PhI(O~2CCF~3)~2氧化成相应的对苯醌(3b). 在这个反应中,3b可以被环戊二烯捕获,并进一步与CF~3CO~2H反应. 当用2molPhI(O~2CCF~3)~2时, 得到3,6-二-三氟乙酰氧基氢醌-2,5-二羧酸乙酯(6),而在吡啶存在下, 得到6-吡啶基氢醌-2,5-二羧酸乙酯三氟乙酸盐.     

2-取代的6-溴甲基-4(3H)-喹唑啉酮的合成

2-取代的6-溴甲基-4(3H)-喹唑啉酮的合成;4(3H)-喹唑啉酮;苯并噁嗪酮;N-溴代琥珀酰亚胺; 合成     

Synthesis of Novel 1,2,3‐Triazole/Isoxazole‐Functionalized Imidazo[4,5‐b]pyridin‐2(3H)‐one Derivatives,Their Antimicrobial and Anticancer Activity

A series of novel 1,2,3‐triazole/isoxazole‐functionalized imidazo[4,5‐b]pyridine‐2(3H)‐one derivatives 7 and 8 were prepared starting from pyridin‐2(1H)‐one 1 in a series of steps. Initially, compound 1 was converted into imidazo[4,5‐b]pyridine‐2(3H)‐one 5 via formation of 2‐alkylamino/amino‐6‐phenyl‐4‐(trifluoromethyl)nicotinonitrile 3 followed by hydrolysis 4 and Hoffman type rearrangement 5 . Compound 5 was further reacted with propargyl bromide to form exclusively N‐propargylated derivatives 6 . Compounds 6 were cyclized with arylazides/aryloximes in the presence of CuI and sodium hypochlorite, respectively, and obtained title products 7 and 8 . All the final products 7 and 8 were screened for antimicrobial and anticancer activity.     

Diorganodiselenides and zinc(II) organoselenolates containing (imino)aryl groups of type 2-(RN=CH)C6H4

Several new diorganodiselenides containing (imino)aryl groups, [2-(RN[double bond, length as m-dash]CH)C(6)H(4)](2)Se(2) [R = Me(2)NCH(2)CH(2) (4), O(CH(2)CH(2))(2)NCH(2)CH(2) (5), PhCH(2) (6), 2',6'-(i)Pr(2)C(6)H(3) (7)] were obtained by reacting [2-{(O)CH}C(6)H(4)](2)Se(2) (3) with RNH(2). Treatment of the diselenides 6 and 7 with stoichiometric amounts of K-selectride or Na resulted in isolation of the selenolates K[SeC(6)H(4)(CH[double bond, length as m-dash]NCH(2)Ph)-2] (9) and Na[SeC(6)H(4)(CH[double bond, length as m-dash]NC(6)H(3)(i)Pr(2)-2',6')-2] (10), respectively. The reaction of potassium selenolates with anhydrous ZnCl(2) (2:1 molar ratio) gave Zn[SeC(6)H(4)(CH=NCH(2)Ph)-2](2) (11) and Zn[SeC(6)H(4)(CH[double bond, length as m-dash]NC(6)H(3)(i)Pr(2)-2',6')-2](2) (12). When the dark green solution obtained from diselenide 7 and an excess of Na (after removal of the unreacted metal) was reacted with anhydrous ZnCl(2) a carbon-carbon coupling reaction occurred and the 9,10-(2',6'-(i)Pr(2)C(6)H(3)NH)(2)C(14)H(10) (8) species was obtained. The compounds were investigated in solution by multinuclear NMR ((1)H, (13)C, (77)Se, including 2D and variable temperature experiments) and by mass spectrometry. The molecular structures of 6, 8, 11 and 12 were established by single-crystal X-ray diffraction. All compounds are monomeric in the solid state. In the diselenide 6 the (imino)aryl group acts as a (C,N)-ligand resulting in a distorted T-shaped coordination geometry of type (C,N)SeX (X = Se). For the zinc complexes 11 and 12 the (Se,N) chelate pattern of the selenolato ligands results in tetrahedral Zn(Se,N)(2) cores.     

Unusual structural types in polynuclear iron chemistry from the use of N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (edteH4): Fe5, Fe6, and Fe12 clusters

The syntheses, crystal structures, and magnetochemical characterization of five new iron clusters [Fe5O2(O2CPh)7(edte)(H2O)] (1), [Fe6O2(O2CBut)8(edteH)2] (2), [Fe12O4(OH)2(O2CMe)6(edte)4(H2O)2](ClO4)4 (3), [Fe12O4(OH)8(edte)4(H2O)2](ClO4)4 (4), and [Fe12O4(OH)8(edte)4(H2O)2](NO3)4 (5) (edteH4= N,N,N',N'-tetrakis(2-hydroxyethyl) ethylenediamine) are reported. The reaction of edteH4 with [Fe3O(O2CPh)6(H2O)3](NO3) and [Fe3O(O2CBut)6(H2O)3](OH) gave 1 and 2, respectively. Complex 3 was obtained from the reaction of edteH4 and NaO2CMe with Fe(ClO4)3, whereas 4 and 5 were obtained from the reaction of edteH4 with Fe(ClO4)3 and Fe(NO3)3, respectively. The core of 1 consists of a [Fe4(mu3-O)2]8+ butterfly unit to which is attached a fifth Fe atom by four bridging O atoms. The core of 2 consists of two triangular [Fe3(mu3-O)]7+ units linked together by six bridging O atoms. Finally, the cores of 3-5 consist of an [Fe12(mu4-O)4(mu-OH)2]26+ unit. Variable-temperature (T) and -field (H) solid-state direct and alternating current magnetization (M) studies were carried out on complexes 1-3 in the 1.8-300 K range. Analysis of the obtained data revealed that 1, 2, and 3-5 possess an S = 5/2, 5, and 0 ground-state spin, respectively. The fitting of the obtained M/N(muB) vs H/T data was carried out by matrix diagonalization, and this gave values for the axial zero-field splitting (ZFS) parameter D of -0.50 cm-1 for 1 and -0.28 cm-1 for 2.