1-[2′,4′-二氟-(1,1′-联苯)-4-基苯基甲基]-咪唑的合成

以2,4-二氟联苯为起始原料,经酰化反应制得2′,4′-二氟-(1,1′-联苯)-4-基苯基甲酮(2);2经NaBH4还原得2′,4′-二氟-(1,1′-联苯)-4-基苯基甲醇(3);3经氯代得2′,4′-二氟-(1,1′-联苯)-4-基苯基氯甲烷(4);4与咪唑发生亲核取代反应合成了1-[2′,4′-二氟-(1,1′-联苯)-4-基苯基甲基]-咪唑(5). 2～5为新化合物,其结构经1H NMR, IR, MS和元素分析确证.     

新型2,6-双(3,5-二取代吡唑基-1-羰基)吡啶的合成

报道了四种吡唑衍生物和它们四种新型的杂环酰胺衍生物的合成 ,它们是 3 ,5 二甲基吡唑 (1) ,5 甲基 3 苯基吡唑(2 ) ,3 ,5 二苯基吡唑 (3 ) ,5 甲基 3 二茂铁基吡唑 (4 ) ,2 ,6 双 (3 ,5 二甲基吡唑基 1 羰基 )吡啶 (5 ) ,2 ,6 双 (5 甲基 3 苯基吡唑基 1 羰基 )吡啶 (6) ,2 ,6 双 (3 ,5 二苯基吡唑基 1 羰基 )吡啶 (7)和 2 ,6 双 (5 甲基 3 二茂铁基吡唑基 1 羰基 )吡啶 (8) .并对它们进行了元素分析 ,FT IR ,1HNMR和13 CNMR等波谱分析 .     

新型2，6-双（3，5-二取代吡唑基-1-羰基）吡啶的合成

报道了四种吡唑衍生物和它们四种新型的杂环酰胺衍生物的合成，它们是3，5-二甲基吡唑(1)，5-甲基-3-苯基吡唑(2)，3，5-二苯基吡唑(3)，5-甲基-3-二茂铁基吡唑(4)，2，6-双(3，5-二甲基吡唑基-1-羰基)吡啶(5)，2，6-双(5-甲基-3-苯基吡唑基-1-羰基)吡啶(6)，2，6-双(3，5-二苯基吡唑基-1-羰基)吡啶(7)和2，6-双(5-甲基-3-二茂铁基吡唑基-1-羰基)吡啶(8)．并对它们进行了元素分析，FT-IR，^1H NMR和^13C NMR等波谱分析．     

1-羟基-2-(1-甲基咪唑-2-基)乙烷-1,1-双膦酸的合成

自从Fleisch等入[1]发现双膦酸盐类化合物的亲骨作用以来,双膦酸盐化合物逐渐成为治疗骨骼方面疾病的药物,包括骨质疏松症,肿瘤病并发的高钙血症和骨痛,变形性骨炎(Paget’s病)和多发性骨髓瘤[2-3]。目前以唑来膦酸[化学名为2-(2-甲基-咪唑-1-基)-1-羟基乙烷-1,1-双膦酸]综合疗     

E-、Z-2’-(1-咪唑基)-O-(α-甲基-二氯苄基)-2,4-二氯苯乙酮肟硝酸盐的合成与抑菌活性

以间二氯苯、氯乙酰氯和咪唑为原料 ,利用成肟和引入咪唑基顺序不同 ,首先合成了 E-,Z-2 -(1 -咪唑基 ) -2 ,4 -二氯苯乙酮肟 ( E、IZ) ,从二氯苯合成了 α-氯 -二氯取代乙苯 ( A、 B和 C) ,咪唑基 -二氯苯乙酮肟顺反异构体 ( Z、 E)分别与 α-氯 -二氯乙苯反应 ,生成 E-、Z-2 -(1 -咪唑基 ) -O-(α-甲基 -二氯苄基 ) -2 ,4 -二氯苯乙酮肟硝酸盐共 6种新化合物 ,产率为 5 7.5 %～ 64 .5 %,新化合物结构经元素分析、IR和 1H NMR表征 .初步实验表明 ,各化合物对水稻苗腐根有不同程度抑制活性 .     

1,3-二苄基-4-(4-甲氧羰基丁基)-噻吩并[3,4-d]-咪唑-2-酮的合成

1,3-二苄基-4-(4-甲氧羰基丁基)-噻吩并[3,4-d]-咪唑-2-酮(Ⅰ)是合成生物素的一个关键中间体.在超声波促进下,用低价钛试剂对(4 aR)-1,3-二苄基-4-(1-己二酸单甲酯酰基硫甲基)-咪唑-2,5-二酮(Ⅱ)进行还原偶联,即生成1,3-二苄基-4-(4-甲氧羰基丁基)-噻吩并[3,4-d]咪唑-2-酮(Ⅰ).超声反应1.5 h,收率71%.     

E-、Z-2＇-(1-咪唑基)-O-(α-甲基-二氯苄基)-2,4-二氯苯乙酮肟硝酸盐的合成与抑菌活性

E-、Z-2＇-(1-咪唑基)-O-(α-甲基-二氯苄基)-2;4-二氯苯乙酮肟硝酸盐的合成与抑菌活性     

[2,7,12,18-四甲基-13,17-双(-2甲氧基羰基乙基)]-次卟啉铜(Ⅱ)的合成

[2;7;12;18-四甲基-13;17-双(-2甲氧基羰基乙基)]-次卟啉铜(Ⅱ)的合成;氯化血红素;次氯化血红素;四甲基二氢卟啉二丙酸甲酯;［四甲基二（甲氧基羰基乙基）］卟啉铜（Ⅱ）;合成     

1-二茂铁基甲基-2-二茂铁基-3-烷基苯并咪唑盐的合成、晶体结构及性质研究

以二茂铁甲醛为原料,在对甲苯磺酸催化下,与邻苯二胺缩合得到1-二茂铁基甲基-2-二茂铁基苯并咪唑(2),化合物2与碘代烷进行烷基化反应得到1-二茂铁基甲基-2-二茂铁基-3-烷基苯并咪唑碘盐(3,4),并通过阴离子交换反应得到1-二茂铁基甲基-2-二茂铁基-3-烷基苯并咪唑六氟磷酸盐(5,6)及双三氟甲磺酰亚胺盐(7,8).利用1H NMR,13C NMR,IR,MS,HRMS及元素分析对所有产物进行结构表征.化合物5的单晶结构表明该化合物通过分子间氢键作用自组装成了沿c轴无限延伸的一条链状超分子结构.电化学分析表明化合物3～8中的Fe1与Fe2由原来的一组氧化还原峰分离成了两组氧化还原峰.UV-Vis吸收光谱曲线表明所有产物具有光致电荷迁移现象.DSC-TG(差示扫描量热-热重)曲线显示所得碘盐化合物对高氯酸铵(AP)热分解有较好的催化效果.     

2-(1H-咪唑-1基)-1-(2,3,4-三甲氧基苯)乙酮的和成

联苯三醚;制备;2-(1H-咪唑-1基)-1-(2;3;4-三甲氧基苯)乙酮的和成     

Reactions of Ru3(CO)12 with Ene-yne and Alkoxy-silyl Functionalized Compounds. The Crystal Structure of (μ-H)Ru3(CO)9[μ3-η2-HC=N(CH2)3Si(OEt)3]

Ru₃(CO)₁₂ has been reacted with the compounds hex-1-en-3-yne [EtC≡CCH=CH₂], 2-methyl-hex-1-en-3-yne [EtC≡CC(=CH₂)CH₃] and with 3(ethoxy-silyl)propyl isocyanate [(EtO)₃Si(CH₂)₃NCO] and the compound tb [(EtO)₃Si(CH₂)₃NHC(=O)OCH₂C≡CCH₂OC(=O)NH(CH₂)₃Si(OEt)₃] in hydrocarbon solution. Some reactions in CH₃OH/KOH solution (followed by acidification) have also been performed. The main products of the reactions with ene-ynes are the clusters Ru₃(CO)₆(μ-CO)₂L₂ (L = C₆H₈, C₇H₁₀) and their demolition products, the “ferrole” Ru₂(CO)₆L₂ complexes. One of the isomers of Ru₃(CO)₆(μ-CO)₂L₂, and Ru₂(CO)₆L₂ (L = C₇H₁₀) have been reacted with vinyl-triethoxysilane [(EtO)₃SiCH=CH₂]: these reactions did not afford complexes containing new carbon–carbon bonds or triethoxy-silyl groups. Only polymerization of vinyl-triethoxysilane occurred. The reactions of Ru₃(CO)₁₂ with triethoxysilyl-propyl-isocyanate and tb (in the presence of Me₃NO) lead to the same products, that is the isomeric complexes (μ-H)Ru₃(CO)₉[C=N(H)(CH₂)₃Si(OEt)₃] with a “perpendicular” ligand (complex 3, as proposed on the basis of spectroscopic results) and (μ-H)Ru₃(CO)₉[HC=N(CH₂)₃Si(OEt)₃] with a “parallel” ligand (complex 4, as confirmed by a X-ray analysis). The reaction pathways leading to these products are discussed. Complex 4 has been reacted with tetraethyl orthosilicate and the resulting material has been characterized. These reactions are part of a study on the synthesis of inorganic-organometallic materials through sol–gel techniques. This paper is dedicated to Prof. Gunther Schmid in the occasion of his 70th birthday.     

Syntheses and structural studies on two cycloruthenapentadienyl complexes: [(CO)3RuC4(CH2OH)4]Ru(CO)3·H2O and [(CO)3RuC4(CH2CH2OH)2(C2H5)2]Ru(CO)3

Syntheses and single-crystal X-ray diffraction studies have been completed on two cycloruthenapentadienyl (CO)₆Ru₂L₂ derivatives, with L = CH₂OHC = CCH₂OH and C₂H₅C=CCH₂CH₂OH respectively. Crystal data are as follows: for [(CO)₃RuC₄(CH₂OH)₄]Ru(CO)₃·H₂O, P2₁/c, a 13.72(1), b 9.501(4), c 14.86(1) Å, β 101.10(6)°, R_w = 0.052 for 1911 reflections; for [(CO)₃RuC₄(CH₂CH₂OH)₂(C₂H₅)₂]Ru(CO)₃, P2₁/c, a 9.191(3), b 16.732(4), c 14.903(3) Å, β 113.61(4)°, R_w = 0.042 for 2865 reflections. Both compounds are built up from binuclear units, each unit being regarded as a Ru(CO)₃ fragment π-bonded to a cycloruthenapentadienyl ring. The molecular parameters are compared with those of known cyclometallapentadienyl complexes of transition metals. The presence of a semi-bridging CO group is discussed.     

Reactions of the carbonyl complexes M(CO)3(L)3 (L = py,M = Mo,W; L = NH3, M = Mo) and M(CO)4(2-Mepy)2 (M = Mo,W) with HgX2 (X = Cl,CN, SCN)

The reactions of the substituted Group VI metal carbonyls of the type M(CO)₄(2-Mepy)₂ (M = Mo, w) and M(CO)₃(L)₃ (L = py, M = Mo, W; L = NH₃, M = Mo) with mercuric derivatives HgX₂ (X = Cl, CN, SCN) have given rise to three series of tricarbonyl complexes: M(CO)₃(py)HgCl₂ · 1/2HgCl₂ (M = Mo, W); 2[M(CO)₃(L)]Hg(CN)·nHg(CN)_x (L = py, M = Mo, W, n = $\text{1}\text{2}$, × = 2; L = 2- Mepy, × = 1; M = Mo, n = 3; M = W, n = 1); and [M(CO)₃(L)Hg(SCN)₂ · nHg(SCN)₂] (L = py, M = Mo,W, n = 0; L = 2-Mepy, M = Mo, W, n = $\text{1}\text{2}$; L = NH₃, M = Mo, n = 0) depending on which mercuric compound is employed. All the reactions with Hg(SCN)₂ give isolable products whereas those with Hg(CN)₂ and HgCl₂ did so far only the reactions with [M(CO)₄(2-Mepy)₂] and M(CO)₃(py)₃. The greater reactivity of Hg(SCN)₂ than of Hg(CN)₂ and HgCl₂ is consistent with the various acceptor capacities of the groups bonded to the mercury atom.The reactions studied always involve displacement of the N-donor ligand of the original complex and partial or total displacement of the halide or pseudohalide groups of the mercury compound to give in all cases compounds containing MHg bonds. In addition, elimination of a CO group in the tetracarbonyl complexes M(CO)₄(2-Mepy)₂occurs.     

Conjugate additions of functionalized carbanions to the vinylidene groups of [M(CO)4{(Ph2P)2CCH2}] (M = W,Mo or Cr)

Treatment of complexes of the type [M(CO)₄{(Ph₂P)₂CCH₂}] (M = W, Mo or Cr) with functionalized lithium reagents, LiR, followed by hydrolysis gives complexes of the type [M(CO)₄{PH₂P)₂CHCH₂R}] in high yields; R = C₆H₄Me-4, C₆H₄OMe-2, C₆H₃(OMe)₂-2,6, C₆H₄OH-2, C₆H₄(COOH)-2, CH₂COPh or CH₂COMe. IR, and ³¹P and ¹H NMR data are given.     

Electrochemical behaviour of [Ru(L)(CO)2Cl2] [Ru(L)(CO)Cl3][Me4N] and [Ru(L)(CO)2(CH3CN)2][CF3SO3]2 complexes (L = 2,2′- bipyridine or 4,4′-isopropoxycarbonyl-2,2′-bipyridine)

The clectrochemical behaviour of the complexes [Ru^II(L)(CO)₂Cl₂], [Ru^II(L)(CO)Cl₃][Me₄N] and [Ru^II(L)(CO)₂(CH₃CN)₂][CF₃SO₃]₂ (L = 2,2′-bipyridine or 4,4′-isopropoxycarbonyl-2,2′-bipyridine) has been investigated in CH₃CN. The oxidation of [Ru(L)(CO)₂Cl₂] produces new complexes [Ru^III(L)(CO)(CH₃CN)₂Cl]²⁺ as a consequence of the instability of the electrogenerated transient Ru^III species [Ru^III(L)(CO)₂Cl₂]⁺. In contrast, the oxidation of [Ru^II(L)(CO)Cl₃][Me₄N] produces the stable [Ru^III(L)(CO)Cl₃] complex. In contrast [Ru^II(L)(CO)₂(CH₃CN)₂][CF₃SO₃]₂ is not oxidized in the range up to the most positive potentials achievable. The reduction of [Ru^II(L)(CO)₂Cl₂] and [Ru^II(L)(CO)₂(CH₃CN)₂][CF₃SO₃]₂ results in the formation of identical dark blue strongly adherent electroactive films. These films exhibit the characteristics of a metal-metal bond dimer structure. No films are obtained on reduction of [Ru^II(L)(CO)Cl₃][Me₄N]. The effect of the substitution of the bipyridine ligand by electron-withdrawing carboxy ester groups on the electrochemical behaviour of all these complexes has also been investigated.     

The chemical oxidation and electronic spectra of the complexes trans-[M(CNR)2(Ph2PCH2CH2PPh2)2] (M = Mo or W)

Oxidation of the complexes $\text{trans}$-[M(CNR)₂(dppe)₂] (A) (M = Mo or W; R = Me, Bu^t or CH₃C₆H₄-$\text{4}$; dppe = Ph₂PCH₂CH₂PPh₂) with diiodine or silver (I) salts gives the paramagnetic cations $\text{trans}$-[M(CNR)₂(dppe)₂]⁺, (M = Mo, R = CH₃C₆H₄-$\text{4}$; M = W, R = Bu^t) and $\text{trans}$-[M(CNR)₂(dppe)₂]²⁺ (M = Mo, R = Me or CH₃C₆H₄-$\text{4}$; M = W, R = Me or Bu^t). Mixtures of products are generally produced when dichlorine or dibromine are the oxidising agents, however pure salts, the seven-coordinate complex cations [MX(CNC₆H₄CH₃-$\text{4}$)₂(dppe)₂]⁺ (B, X = Cl or Br) have been isolated. A simple molecular orbital scheme is proposed for complexes (A) and used to discuss their electronic spectra and their oxidation.     

Darstellung von mehrkernkomplexen aus As2Co2(CO)6

By reaction of As₂Co₂(CO)₆ with M(CO)₅THF (M = Cr, Mo, W), the heteronuclear complexes (CO)₅M · As₂Co₂(CO)₆ of low stability were obtained. Phosphine substitution increased the basicity of the As₂Co₂ cluster, into which up to two PMe₃ ligands and up to four P(OMe)₃ ligands could be introduced. Subsequently, two M(CO)₅ units (M = Cr, Mo, or W) could be attached to As₂Co₂(CO)₅ · PMe₃, As₂Co₂(CO)₄L₂ (L = PMe₃, P(OMe)₃), and As₂Co₂(CO)₃[P(OMe)₃]₃. The crystal structure of [(CO)₅W]₂As₂Co₂(CO)₄[P(OMe)₃]₂ was determined.     

Kinetics of nucleophilic attack on coordinated organic moieties : VI. Mechanism of addition of tri-n-butylphosphine to [(C7H7)M(CO)3]BF4 (M = Cr, Mo, W) and related cations

Phosphonium adduct formation via attack of tri-n-butylphosphine on the cations [(C₇H₇)M(CO)₃]⁺ (M = Cr, Mo, W) obeys the rate law, Rate = k [complex] [PBu₃]. The very similar rate constants for the Cr, Mo and W complexes confirm the similar electrophilicities of the tropylium rings in these cations, and also support the view that there is direct addition to the rings. The related complexes [(C₆H₇)Fe(CO)₃]BF₄ and [(C₆H₆)Mn(CO)₃]BF₄ also form adducts with PBu₃, and the quantitative reactivity order [(C₆H₇)Fe(CO)₃]⁺ > [(C₇H₇)Cr(CO)₃]⁺ » [(C₆H₆)Mn(CO)₃]⁺ (160:60:1) has been established.     

Synthesis and reactivity of [(RRN)2PH]Fe(CO)4 complexes. X-ray crystal structure of [(Ph2N)2PH]Fe(CO)4

KHFe(CO)₄ reacts with tris(amino)phosphines by substitution at phosphorus leading to [bis(amino)phosphine]tetracarbonyliron complexes [(R¹R²N)₂PH]Fe(CO)₄. The X-ray structure has been determined for R¹=R²=Ph. Deprotonation of these complexes with KH affords stable potassium phosphidotetracarbonylferrates which can be alkylated or acylated at phosphorus.     

Perfluormethyl-element-liganden : XXXI. Ligandeneigenschaften von Me2PP(CF3)2 und Me2AsP(CF3)2

The coordinating properties of the trifluoromethyl elemental compounds Me₂PP(CF₃)₂ and Me₂AsP(CF₃)₂ have been studied by the synthesis and spectroscopic investigations (IR, NMR, MS) of their complexes cis-M(CO)₄L₂ (A), [(CO)₄ML]₂ (B) and [(CO)₅M]₂L (C) (M = Cr, Mo, W). Complexes of type A with L = Me₂PP(CF₃)₂ are obtained in good yield by reaction with M(CO)₄NBD (NBD = norbornadiene), whereas with L = Me₂AsP(CF₃)₂ the homobinuclear compounds B are formed. The attempt to prepare the cis-M(CO)₄[Me₂AsP(CF₃)₂]₂ complexes by treating M(CO)₄(Me₂AsH)₂ with P₂(CF₃)₄ is successful only for M = W. Binuclear compounds of type B or C, in general, can be prepared by stepwise reaction of the ligands with either M(CO)₄NBD or M(CO)₅THF.