(Z)-1-三苯基锡基-3-对氯苯基-1-丁烯-3-醇及其卤代物的合成、表征和晶体结构

在氮气保护下,3-对氯苯基-1-丁炔-3-醇与三苯基氢化锡进行游离基加成反应,获得加成物(Z)-1-三苯基锡基-3-对氯苯基-1-丁烯-3-醇(1).加成物(1)与卤素反应后,与锡原子相连的苯基被取代,得到一卤代、二卤代和混合二卤代物(2-8).通过元素分析、¹HNMR和IR表征了化合物1～8的结构,并测定了加成物(1)、一溴代物(3)和二溴代物(5)的晶体结构.在加成物(1)的晶体结构中存在一对对映体,由于分子内存在较弱的O→Sn配位作用,构成以锡原子为中心的扭曲四面体构型.在化合物3和5分子中,存在分子内O→Sn配位键,构成以锡为中心的扭曲三角双锥构型.该系列化合物分子内的O→Sn配位能力和Lewis酸性强弱的顺序为:二卤化物>一卤化物>加成物;氯代物>溴代物>碘代物.     

[Z]-2-(芳基锡基)-1-(9-芴醇)乙烯的合成、结构与性质

用三苯基氢化锡,三对甲苯基氢化锡作为锡氢化试剂与9-乙炔基-9-芴醇进行反应,合成了2个有机锡化合物:[Z]-2-(三苯基锡基)-1-(9-芴醇)乙烯(1)和[Z]-2-(三对甲苯基锡基)-1-(9-芴醇)乙烯(2)。化合物1和2分别与ICl,Br~2,I~2反应,得到6个有机锡一卤化物,6个有机锡二卤化物和2个有机锡混合卤化物(3-16)。有机锡一碘化物7,13和有机锡二碘化物8,14与KOH乙醇溶液反应,分别得到相应的有机锡氢氧化物17,18和有机锡氧化物19,20。有机锡二碘化物8,14分别与含氮双齿配体1,10-邻菲罗啉(Phen),2,2'-联吡啶(Bipy),8-羟基喹啉(Oxin)反应,得到6个相应的配合物21-26。26个新化合物通过元素分析,锡含量测定,IR,^1HNMR测定对其结构进行了表征。同时测定了化合物2的晶体结构,晶体属单斜晶系,空间群P2~1/c。化合物2是以Sn原子为中心扭曲的四面体构型。     

(Z)-1-[2-(三苯基锡基)乙烯基]-1-茚满醇及其酯和卤代物的合成与表征

在氮气保护下,1-乙炔茚满醇与三苯基氢化锡进行游离基加成反应,获得加成物(Z)-1-[2-(三苯基锡基)乙烯基]-1-茚满醇(1);将加成物(1)与苯酐反应,得到新型邻苯二甲酸单酯有机锡衍生物(2);衍生物(2)分别与二丁基氧化锡和三苯基氧化锡进行脱水反应,分别获得两个新型邻苯二甲酸酯的有机锡衍生物(3)和(4).将加成物(1)与卤素反应后,与锡原子直接相连的苯基被取代,得到一卤代和二卤代物(5～10).通过元素分析、¹HNMR和IR等手段对化合物1～10进行了结构表征,确定了该类邻苯二甲酸单酯和邻苯二甲酸酯的有机锡衍生物的结构.并测定了加成物(1)和一溴代物(6)的晶体结构,在加成物(1)中,由于分子内存在较弱的O→Sn[0.2778(8)nm]配位作用,锡原子呈扭曲三角双锥构型.在一溴代物(6)分子中,存在分子内O→Sn[0.2364(2)nm]配位键,锡原子呈扭曲的三角双锥构型.该系列化合物分子内的O→Sn配位能力和Lewis酸性强弱的顺序为:二卤化物>一卤化物>加成物;氯代物>溴代物>碘代物>加成物.     

[Z]-1-[2-(三芳基锡基)乙烯基]环辛醇的合成和性质

本文用三苯基氢化锡、三对甲苯基氢化锡作为锡氢化试剂与1-乙炔基环辛醇进行反应, 合成了两个有机锡化合物: [Z]-1-[2-(三苯基锡基)乙烯基]环辛醇(1)和[Z]-1-[2-(三对甲苯基锡基)乙烯基]环辛醇(2), 并测定了1的晶体结构。1和2分别与ICl, Br2, I~2反应, 得到六个有机锡一卤化物和三个有机锡二卤化物(3-11)。有机锡二卤化物6和一卤化物5与KOH乙醇溶液反应, 分别得到相应的锡氧化物和锡氢氧化物(12, 13)。有机锡二卤化物8分别与含氮双齿配体[2,2'-联吡啶(Bipy),5-硝基-1,10-邻菲罗啉(Nphen),8-羟基喹啉(Oxin)]反应, 得到三个相应的配合物(14-16)。十六个新化合物通过元素分析、锡含量测定、IR、^1H NMR测定对其结构进行了表征, 同时提出了1和2的生成反应历程。     

取代环戊二烯基三羰基合铬(钼)卤化物η5-RC5H4(CO)3MX的合成及结构

由η~5-RC_5H_4(CO)_3MNa(1)(R=MeCO,MeO_2C,EtO_2C;M=Cr,Mo)与 I_2、三卤化磷(PX(?),X=Cl,Br,I)、苯基二氯化膦或甲基二碘化胂反应,可得金属卤化物η~5-RCH_4(CO)_3MX(2a—21)(M=Cr,X=I;M=Mo,X=Cl,Br,I).鉴于1(R=MeO_2C,M=Mo)与 PCl_3反应的中间物η~5-MeO_2CC_5H_4(CO)_3MoPCl_2业已被析离,并可转变为相应氯化物η~5-MeO_2CC_5H_4(CO)_3MoCl(2g),因此1与三卤化磷、苯基二卤化膦或甲基二碘化胂生成金属卤化物的反应很可能经缩合及中间物分解两步简单反应.2f(R=MeCO,M=Mo,X=I)为单斜晶系,a=0.6663(2),b=1.2364(6),c=1.5464(5)nm;β=99.02(3)°;V=1.2581nm~3;D_o=2.186g/cm~3;Z=4;F(000)=776;空间群P2_1/c.     

取代环戊二烯基三羰基合铬(钼)卤化物η5-RC5H4(CO)3MX的合成及结构

由η^5^-RC5H4(CO)3MNa(1)(R=MeCO, MeO2C, EtO2C; M=Cr, Mo)与I3、三卤化磷(PX3, X=Cl, Br, I)、苯基二氯化膦或甲基二碘化胂反应, 可得金属卤化物η^5-RC6H4(CO)3MX(2a-2l)(M=Cr, X=I; M=Mo, X=Cl, Br, I)。鉴于1(R=MeO2C, M=Mo)与PCl3反应的中间物η^5-MeO2CC5H4(CO)3MoPCl2业已被析离, 并可转变为相应的氯化物η^5-MeO2CC5H4(CO)3MoCl(2g), 因此1与三卤化磷、苯基二卤化膦或甲基二碘化胂生成金属卤化物的反应很可能经缩合及中间物分解两步简单反应, 2f(R=MeCO, M=Mo, X=I)为单斜晶系, a=0.6663(2), b=1.2364(6), c=1.5464(5)nm; β=99.02(3)°;V=1.2581nm^3; Dc=2.186g/cm^3; Z=4; F(000)=776; 空间各P21/c。     

羰基铁-硫醇-三乙胺反应体系的研究, μ-酰基与μ-烯基铁硫配合物的合成系脱羰反应动力学

本文由反式巴豆酰氯与活性中间物[(μ-CO)(μ-R1S)Fe2(CO)6]ˉEt3N^+反应, 合成了两个新的μ-酰基铁硫配合物(μ-R1S)(μ-CH5CH=CHCO)Fe2(CO)6(R1=Et, Bu^t)和三个新的μ-烯基铁硫配合物(μ-R1S)(μ-CH3CH=CH)Fe2(CO)6(R1=Et, Bu^+, CH2=CHCH2), 此外还研究了μ-酰基配合物脱羰生成μ-烯基配合物的反应动力学, 证明为一级反应, 并求得在一定条件下的速率常数和半衰期。     

稀土与四甘醇醛缩苯丙氨酸Schiff碱配合物的合 成、性能与催化

合成了直链醚-氨基酸新型Schiff碱(四甘醇醛缩苯丙氨酸Schiff碱)及其与稀土新配合物,[Ln~3L~2(NO~3)~2]·(NO~3)~3·nH~2O(Ln=La,Nd,Sm,n=3;Ln=Gd,Dy,Er,Y,n=5),以元素分析、磁化率、红外光谱、^1HNMR等进行了表征,研究了的配位作用,根据预期设想,见到此类配合物在有机溶剂中的溶解性有明显改善。以EPR波谱探讨了配合物的晶体场强,并计算了晶体场参数。此外,发现在不加助催化剂条件下,此类配合物对MMA(甲基丙烯酸甲酯)聚合有一定的催化效果。     

两种新稀土双核配合物的合成、表征及其对磷酸二酯键模型物（BDNPP）和DNA的作用研究

合成和表征了两种新的双核配合物[Eu_2 (bbimp) (CH_3COO) (CH_3CH_2O)_2 (CH_3CH_2OH)] (ClO_4)_2 (A)和[Nd_2 (bbimp)-(CH_3COO) (CH_3CH_2O)_2 (CH_3CH_2OH)] (ClO_4)_2 (B)。用紫外光谱法分别研究了磷酸二酯键模型物双-（ 2，4-二硝基苯基）磷酸盐（BDNPP）与配合物（A，B）的水解动力学反应。当 BDNPP与A，B的浓度均为2.5 * 10~(-5) mol/L时，反应为二级反应；在25 ℃，pH 7.26时，二级水解速率常数分别为2479 (mol/L)~(-1)·min~(-1)，1678 (mol/L) ~(-1)·min~(-1)，半衰期分别为16.1 min和23.8 min，比单独的Eu~(3+)，Nd~ (3+)水解BDNPP的速率均快得多，37 ℃时反应更快；在25 ℃，pH 6.50～8.50时， 两个反应的水解速率常数的lgK与pH值均呈正的线性关系。两种配合物与小牛胸腺 （CT）DNA作用，使CT DNA最大吸收峰发生减色和红移，使溴化乙锭（EB）-DNA复 合物体系荧光强度减弱。两种配合物对超螺旋质粒pBR322 DNA的断裂在50 ℃，pH 8.0时，效果最好。     

{[（NH4）（18—冠—6）][Bi（NCS）Cl3]}n的合成及结构

用凝胶法合成了标题配合物,并进行了元素分析、红外光谱、质谱及差热-热重等物性表征;用四圆衍射仪测定了它的晶体结构。晶体属三斜晶系、空间群P1,晶胞参数α=9.097(2),ι=15.754(3),(?)=16.556(2),(?)=88.08(1)°,(?)=81.29(1)°,(?)=86.62(2)°Z=2。结构分析表明,该配合物中冠醚与铵离子形成配阳离子;铋(Ⅲ)由硫氰酸根和氯离子配位,并以配体桥联形成链状聚合的配合阴离子,配合阴、阳离子主要以静电吸引形成配合物。     

1-(Z)-[2-(三芳基锡基)乙烯基]环戊醇及其衍生物的合成及生物活性

合成了１４种新的（Ｚ）－［２－（三芳基锡基）乙烯基］环戊醇类有机锡化合物,通过元素分析,ＩＲ、＾１Ｈ ＮＭＲ 对所合成的化合物进行了表征,结果表明（Ｚ）－［２－（三芳基锡基）乙烯基］环戊醇类有机锡化合物中乙烯式双键为顺式构型,分子内羟基与锡原子发生配位,形成五元螯合环。生物活性测定结果表明,二卤化物在抗癌,免疫及受体作用等方面具有优良的活性。     

Determination of mono-, di- and tri-substituted butyltin,phenyltin and methyltin compounds as free halides using gas chromatography with flame photometric detection

A simple chromatographic procedure has been developed for the sensitive determination of mono-, di- and tri-substituted butyltin, phenyltin, and methyltin compounds as halides. The organotin compounds were separated on a DB-1 capillary column and detected by flame photometric detection (FPD) equipped with a 611.5 nm filter. Pretreatment of the capillary column with an ethyl acetate solution of hydrobromic acid, or doping of standard solutions with hydrobromic acid, was found to be necessary if reproducibly sharp peaks of organotin halides were to be obtained. Column treatment and acid doping did not cause any background problems or undesirable degradation of the organotin compounds. Three different standard solutions in ethyl acetate had to be Jrepared, because undesirable degradation of the organotin halides was observed when all the compounds were dissolved in the same solution. The first, standard solution I, contained tri-n-butyltin chloride (TBTCI) and trimethyltin chloride (TMTCI), the second, standard solution II, contained triphenyltin chloride (TPTCI), and the third, standard solution III, contained hydrogen bromide and the other organotin compounds: di-n-butyltin chloride (DBTCI), mono-n-butyltin chloride (MBTCI), dimethyltin chloride (DMTCI), monomethyltin chloride (MMTCI), diphenyltin chloride (DPTCI), and monophenyltin chloride (MPTCI). An ethyl acetate solution containing hydrobromic acid (20 × 10^?3 mol/I) was used for column treatment.     

Synthesis of 1-, 2-Methoxy-, 1,3-Dimethoxyadamantanes And 1-, 4-Methoxydiadamantanes by Reaction of Adamantyl and Diadamantyl Halides with Dimethyl Carbonate in the Presence of Zeolite Catalysts

Russian Journal of Organic Chemistry - 1-, 2-Methoxy-, 1,3-dimethoxyadamantane, and 1-, 4-methoxydiadamantane were prepared by the reaction of adamantyl and diadamantyl halides with dimethyl...     

Palladium-catalyzed highly regio- and stereoselective synthesis of (1E)- or (1Z)-1,2-dihalo-1,4-dienes via haloallylation of alkynyl halides

A highly efficient and selective synthesis of (1E)- or (1Z)-1,2-dihalo-1,4-dienes via Pd-catalyzed coupling of haloalkynes and allylic halides is described. The (1E)-1,2-dihalo-1,4-dienes were generated in good yields with excellent stereoselectivities (1E/1Z up to >98/2), while (1Z)-1,2-dihalo-1,4-dienes were produced in excellent yields and stereoselectivities (1Z/1E up to >98/2) by simply adding stoichiometric lithium halides.     

1,1-Dimethyl-1-(trialkoxysilylmethyl)hydrazinium and 1,1-Dimethyl-1-(silatranylmethyl)hydrazinium Halides

Formerly unknown 1,1-dimethyl-1-(trialkoxysilylmethyl)- and 1,1-dimethyl-1-(silatranylmethyl)hydrazinium halides were prepared by reaction of 1,1-dimethylhydrazine with (halomethyl)trialkoxysilanes XCH₂Si(OR)₃ (X = Cl, I; R=Me, Et) and 1-(halomethyl)silatranes XCH₂Si(OCH₂CH₂)₃N (X = Cl, Br). 1,1-Dimethyl-1-(silatranylmethyl)hydrazinium chloride and iodide were also obtained by transetherification of corresponding 1,1-dimethyl-1-(trimethoxysilylmethyl)hydrazinium halides with tris(2-hydroxyethyl)amine.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 915–919.Original Russian Text Copyright © 2005 by Sorokin, Voronkov.     

A novel mode of access to polyfunctional organotin compounds and their reactivity in Stille cross-coupling reaction

Mono-, di-, tri- and tetra-functional organotin compounds were easily prepared in a sonicated Barbier reaction using ultrasound technology via coupling reaction of organo halides with tin halides (Bu₃SnCl, Bu₂SnCl₂, BuSnCl₃, SnCl₄) mediated by magnesium metal. The di- and tri-functional organotin compounds were tested in a Stille cross-coupling reaction in order to ascertain how many groups were transferred.     

Tin(IV) cyanoximates: synthesis, characterization, and cytotoxicity

In recent years, numerous organotin(IV) derivatives have exhibited remarkable cytotoxicity against several types of cancer. However, the properties of the cyanoxime-containing organotin(IV) complexes are unknown. Previously, it has been shown that cyanoximes displayed an interesting spectrum of biological activity ranging from growth-regulation to antimicrobial and pesticide detoxification actions. The work presented here attempts to combine the useful properties of both groups of compounds and investigate the likely antiproliferating activity of the new substances. A series of 19 organotin(IV) complexes, with nine different cyanoxime ligands, were anaerobically prepared by means of the heterogeneous metathesis reaction between the respective organotin(IV) halides (Cl, Br) and ML (M=Ag, Tl; L=cyanoximate anion), using an ultrasound in the CH3CN at room temperature. The compounds were characterized using spectroscopic methods (UV-visible, IR, 1H,13C NMR, 119Sn M?ssbauer) and X-ray analysis. The crystal structures of the complexes revealed the formation of two types of tin(IV) cyanoximates: mononuclear five-coordinated compounds of R4-xSnLx composition (R=Me, Et, n-Bu, Ph; x=1, 2; L=cyanoximate anion), and the tetranuclear R8Sn4(OH)2O2L2 species (R=n-Bu, Ph). The latter complex contains a planar [Sn4(OH)2O2]2- core, consisting of three adjacent rhombs with bridging oxo and hydroxo groups. The tin(IV) atoms are five-coordinated and have distorted trigonal-pyramidal surrounding. This is the first instance when the organic anions were found to act as monodentate O-bound planar oxime ligands. All of the compounds were studied in vitro for antiproliferating activity, using human cervical cancer HeLa and WiDR colon cancer cell lines; cisplatin was used as a positive control substance. The two dibutyltin(IV) cyanoximates showed cytotoxicity similar and greater to that of cisplatin.     

(Z)-1-[2-(三苄基锡基)乙烯基]环庚醇及其衍生物的合成和性质

通过三苄基氢化锡与1-乙快基环庚醇发生加成反应，得到了一种有机锡化合物 ：(Z)-1-[2-(三苄基锡基)乙烯基]环庚醇(1)．化合物1与I2，Br2和IC1按1：1和1 ：2摩尔比投料进行卤化反应，得到6种构型保持的有机锡一卤化物2-4及二卤化物 5-7．有机锡一卤化物3与KOH乙醇溶液反应，得到了相应的有机锡氢氧化物8．以上 8种新化合物均通过熔点测定、元素分析、锡含量测定、红外光谱、核磁共振氢谱 对其结构进行了表征．并对其中的有机锡化合物1，3，4，6，7进行了体外抗P388 血癌活性测定，其中有机锡化合物4，6，7表现出强效．