脯氨酰肼小分子催化的环己酮的直接α-硫代反应

研究了脯氨酰肼有机小分子催化环己酮的直接α-硫代反应. 考察了3种不同硫代试剂、9种溶剂、6种脯氨酰肼催化剂等对反应的活性和收率的影响. 结果表明, 硫代试剂、溶剂及催化剂的结构对反应的活性和反应收率均有较大的影响. 在优化条件下, 即以邻苯二甲酰亚胺为硫代试剂, 甲苯为溶剂, 脯氨酰肼1和4催化的环己酮的硫代反应活性比较高, 室温反应12 h, 收率达98%. 脯氨酰肼催化该类反应条件温和, 操作简单, 在药物合成中具有一定的应用潜力.     

一种简单、高效合成α-卤代甲基酮化合物的新方法

发展了一种简单、高效、温和的卤代炔烃水合反应体系.在阳离子金催化剂的催化作用下,以二氯乙烷为溶剂,室温下卤代炔烃发生水合反应,高收率、高区域选择性地得到单一的α-卤代甲基酮化合物(收率≥91%).该方法具有底物适用范围广、反应条件温和和环境友好等优点,为含α-卤代甲基酮结构单元的天然产物及复杂药物分子的合成提供了新方法.     

他氟前列素的合成工艺改进

以科立内酯为起始原料,经过Swern氧化反应、Hormer-Wadsworth-Emmons反应、氟代、水解、还原、Wittig反应、酯化等反应合成目标化合物,总收率为47.2%,目标化合物和关键中间体结构经MS和1H NMR确证。本工艺改进提高了反应收率,减少了过柱提纯的步骤,降低了生产成本,有利于工业化生产。     

离子液体中卤代哒嗪氟代新方法的研究

在离子液体和氟化钾反应体系中，研究了卤代哒嗪化合物的氟代反应，讨论了微波辐射条件下由卤代哒嗪化合物合成氟代哒嗪化合物的方法。用离子液体作为反应介质替代了传统的分子溶剂，提高了产物收率，简化了操作。用微波反应不仅获得了较好的收率，也缩短了反应时间。利用离子液体和微波辐射条件进行氟代反应是一种绿色化学方法。     

一种简单、 高效合成α-卤代甲基酮化合物的新方法

发展了一种简单、 高效、 温和的卤代炔烃水合反应体系. 在阳离子金催化剂的催化作用下, 以二氯乙烷为溶剂, 室温下卤代炔烃发生水合反应, 高收率、 高区域选择性地得到单一的α-卤代甲基酮化合物(收率≥91%). 该方法具有底物适用范围广、 反应条件温和和环境友好等优点, 为含α-卤代甲基酮结构单元的天然产物及复杂药物分子的合成提供了新方法.     

氟代芳香族化合物四甲基氟化铵氟代脱硝法的合成

以高活性无水四甲基氟化铵（TMAFanh.）为氟化试剂,优化反应的条件为：n(Substrate)∶n(TMAF_anh.)=1∶1.4、DMF用量为0.4 L/mol Substrate,由硝基芳烃化合物经低温氟代脱硝反应合成了含氟芳香族化合物,反应温度80~100 ℃,反应时间1~5 h,氟代产物收率19.4%~99.0%。 反应具有原料易得、工艺简单、条件温和、产物收率高和副反应少等优点。     

低温Suzuki反应合成联苯及三联苯化合物

发展了一个低温下无配体钯催化溴代芳烃与芳基硼酸的Suzuki反应体系。该体系以醋酸钯为催化剂,无水碳酸钾为碱,乙醇水溶液为溶剂,无需加入任何配体,在0oC下即可高效催化溴代芳烃与芳基硼酸的Suzuki反应;反应的底物容忍性好,产品分离收率最高达97%。以溴代芳基N-甲基亚氨基二乙酸硼酸酯为砌块分子,通过调控反应温度,实现了砌块分子选择性Suzuki反应,从而一锅合成了不对称三联苯化合物,产品收率最高为81%。     

1,1-二氘代-3,6,9,12-四氧代-1-二十四烷醇的合成

二缩三乙二醇在金属钠存在下与溴代十二烷反应生成3，6，9－三氧代－二十烷醇，收率86％；该醇与氯乙酸甲酯反应生成3，6，9，12－四氧化二十四烷酸甲酯，收率60％，3，6，9，12－四氧代二十四烷酸甲酯与氘代铝锂氢在乙醚中反应生成1，1－二氘代－3，6，9，12－四氧代－1－二十四烷醇，收率95％。     

离子液体中卤代炔烃高效水解制取α-卤代甲基酮的研究

在离子液体中,硫酸促进卤代炔烃水解生成α-卤代甲基酮,反应收率高达85%~94%.离子液体-硫酸反应体系可多次(5次以上)循环使用而不影响反应收率.同时,此反应体系底物适用性强,高效制得一系列芳环上不同取代基的(如甲基、甲氧基、羟基、硝基等)α-氯/溴/碘代苯乙酮及脂肪类卤代甲基酮.     

氘代阿戈美拉汀的合成

以苯酚为原料,氘代碘甲烷与氘代醋酸酐为氘代试剂.经过氘代甲基化、傅克酰基化、克脑文盖尔缩合、芳构化、还原及氘代乙酰化反应得到氘代标记的阿戈美拉汀(1).该合成路线简洁,原料易得、反应条件易于控制,总收率为15.2%,化学纯度为99.97%,氘代丰度大于98%.目标化合物结构经质谱、核磁共振等表征确定可用于其药代动力学研究.     

Hetero-Type Benzannulation Leading to Substituted Benzothio-Phenes

TiCl₄ (or SnCl₄)-promoted hetero-type benzannulation reactions using various (2,2-dichlorocyclopropyl)(thiophen-2-yl)methanols proceeded smoothly to produce uniquely substituted 4-chlorobenzothiophenes (five examples). The present approach involves the first distinctive thiophene formation from thiophene cores, in contrast to traditional methods of thiophene formation from benzene cores. The stereocongested (less reactive) Cl position in the obtained 4-chlorobenzothiophenes functioned successfully as the partners of three cross-coupling reactions: (i) a Suzuki–Miyaura cross-couplings using Pd(OAc)₂/SPhos/K₃PO₄ catalysis (seven examples; 63–91%), (ii) a hydroxylation using KOH/Pd(dba)₂/tBu-XPhos catalysis (85%), and (iii) a borylation using a B₂(pin)₂/Pd(dba)₂/XPhos/NaOAc catalysis-provided 4-(pin)B-benzothiophene (58%).     

Die Phosphide LiR2P7, Li2RP7 (R = Me3Si,Et, iPr,iBu) und alkyliert-silylierte Heptaphosphane(3)

The Phosphides LiR₂P₇, Li₂RP₇ (R = Me₃Si, Et, iPr, iBu) as well as Mixed Alkylated and Silylated Heptaphosphanes(3) Formation and properties of LiR₂P₇ and Li₂PR₇ (R = Me₃Si, Et, iPr, iBu) and their reactions with Me₃SiCl or alkylhalides yielding mixed alkylated and silylated heptaphosphanes(3) are reported. Reactions of (Me₃Si)₃P₇ and Li₃P₇. 3 DME produce mixtures of Li(Me₃Si)₃P₇, Li₂(Me₃Si)P₇ and Li₃P₇ from which pure Li(Me₃Si)₂P₇ (s, as) can be isolated by means of an extraction with toluene. Similarly, the isomers of LiR₂P₇ (R = Et, iPr, iBu) can be extracted from the mixtures obtained by reacting Li₃P₇ with alkylbromides. The (s) isomers of LiR₂P₇ in solution at about 20°C from the (as) isomers whereas the latter up to 70°C do not show any inversion. The (as) lithiumdialkylphosphides can be obtained as ether free products (red brown powder, isoluble in toluene, soluble in THF) by repeated addition of toluene and removal of the solvents; the (s) isomers decompose during the procure. In reactions of LiEt₂P₇. THF (s, as) in toluene at ?30°C with EtBr only the (s) isomer is substituted and gives Et₃P₇ (s), however on warming to 20°C by inversion of P^e a ratio of (s) : (as( = 1 : 3 is obtained. With Li(iBu)₂P₇, (s) reaction begins above ?20°C the giving both the (s) and the (as) isomer. (iBu)₃P₇ (s) is the prefered isomer at higher temperatures. Li(Me₃Si)₂P₇ (s, as) with Me₃SiCl exclusively yields (Me₃Si)₃P₇ (s). Li₂RP₇ (R = alkyl, Me₃SI) is not available. From mixtures with LiR₂P₇ and Li₃P₇, it can be isolated only after repeated cumbersome extraction of LiR₂P₇ as was shown with Li₂(iPr)P₇ as an example. Ether free LiEt₂P₇(s, as) with Me₃SiCl exclusively gives Et₂(Me₃Si)P₇ (s, as) whereas LiEt₂P₇ ? THF due to its THF content does not. Similarly, ether free Li(iBu)₂P₇ yields (iBu)₂(Me₃Si)P₇ (s, as). The compounds R(Me₃Si)₂P₇ (R = alkyl) cannot be selectively prepared neither starting from Li₂RP₇ with Me₃SiCI) nor from Li(Me₃Si)₂P₇ with RX. Such, the reaction of Li(Me₃Si)₂P₇ ? THF with EtBr in toluene at ?78°C yield a mixture of Et(Me₃Si)₂P₇ (42%), Et₂(Me₃Si)P₇ (27010), (Me₃Si)₃P₇ (29%) and Et₃P₇ (2%). (Me₃Si)₃P₇ with MeI in a molar ratio of 1 : 1 at 70°C quantitatively produces Me(Me₃Si)₂P₇ whereas already using a molar ratio of 1 : 2 also Me₃P₇ is obtained. With EtBr mixtures of Et(Me₃Si)₂P₇ and Et₃P₇ are formed. iBuBr gives iBu₃P₇, but tBuBr does not yield any tBu₃P₇.     

Einfache Trithio- und Perthiocarbonatokomplexe mit interessanter Koordinationschemie: [E(CS3)2]2− (E = Sn,Zn, Cd), [E(CS3)3]3− (E = As,Sb, Bi,Co), {Cu(CS3)−}∞ und [Zn(CS4)2]2−

Simple Trithio- and Perthiocarbonato Complexes with Interesting Bond Properties: [E(CS₃)₂]^2? (E = Sn, Zn, Cd), [E(CS₃)₃]^3? (E = As, Sb, Bi, Co), {Cu(CS₃)^?}_∞ and [Zn(CS₄)₂]^2? By reactions of potassium trithiocarbonate ( 1 ) with solutions of zinc(II)- acetylacetonate, cadmium(II)-chloride, tin(II)-chloride, arsenic(III)-sulfide (suspension), antimony(III)-chloride, bismuth(III)-chloride and copper(II)-chloride in dimethyl sulfoxide, as well as of trisodium hexanitrito cobaltate(III) in water, and the precipitation of the complexes with an aqueous solution of tetraphenylphosphonium chloride the compounds (PPh₄)₂[Zn(CS₃)₂] ( 2 ), (PPh₄)₂[Cd(CS₃)₂] ( 3 ), (PPh₄)₂[Sn(CS₃)₂] ( 4 ), (PPh₄)₃[As(CS₃)₃] ( 5 ), (PPh₄)₃[Sb(CS₃)₃] ( 6 ), (PPh₄)₃[Bi(CS₃)₃] ( 7 ), (PPh₄)₃[Co(CS₃)₃] ( 8 ) and (PPh₄)Cu(CS₃) ( 9 ) have been isolated. (PPh₄)₂[Zn(CS₄)₂] · CH₃NO₂ ( 10 ) has been prepared by heating a solution of 2 in nitromethane to 60--70°C in presence of air. The reaction of 1 in dimethyl sulfoxide with an aqueous tetraphenylphosphonium chloride solution in presence of oxygen leads to (PPh₄)₂[C₂S₆] ( 11 ). The compounds have been characterized by spectroscopical studies (IR, Raman, UV/Vis, ¹¹³Cd/⁵⁹Co-NMR), magnetic susceptibility measurements, powder diffractometry, elemental analyses and single crystal X-ray structure analysis ( 4 – 7 , 10 and 11 ). The difficult growing of single crystals has been reported in detail. For crystal data see Inhaltsübersicht.     

Phosphaniminato-Komplexe des Zinks mit Hydrido-, Alkinylo-, Alkenylo- und Amido-Liganden

Phosphoraneiminato Complexes of Zinc with Hydrido, Alkynylo, Alkenylo, and Amido Ligands Synthesis and properties of the phosphoraneiminato complexes [ZnCl(NPMe₃)]₄ ( 1 ), [ZnH(NPMe₃)]₄ ( 2 ) as well as of the alkynylo derivatives [Zn(C≡C–SiMe₃)(NPMe₃)]₄ ( 3 ), [Zn(C≡C–C≡C–SiMe₃)(NPR₃)]₄ [R = Me ( 4 a ), R = Et ( 4 b )], [Zn(C≡C–Ph)(NPMe₃)]₄ ( 5 ) and of the alkenylozinc complexes [Zn(CH=CHMe)(NPR₃)]₄ [R = Me ( 6 a ), R = Et ( 6 b )] are described. According to crystal structure analyses of 1 , 3 , and 4 b these complexes possess heterocubane structures with only slightly distorted Zn₄N₄ cubic skeletons. Experiments to substitute the terminal ligands at the zinc atoms by bis(trimethylsilyl)amido groups lead to disintegration of the heterocubanes and formation of the dimeric complex [Zn(μ₂-NPEt₃){N(SiMe₃)₂}]₂ ( 7 ) and of the trinuclear derivative [Zn₃(μ₂-NPMe₃)₄{N(SiMe₃)₂}₂] ( 8 ), in which the central zinc atom is surrounded by the four N atoms of the NPEt₃^– groups in a spiro-cyclic fashion. 7 and 8 are also characterized by crystal structure analyses.     

Eu3+ und Eu2+ in Oxometallaten der Zusammensetzung MBeLn2O5: SrBeEu2O5 und EuBeNd2O5

Eu³⁺ and Eu²⁺ in Oxides of the Composition MBeLn₂O₅: SrBeEu₂O₅ and EuBeNd₂O₅ Single crystals of (I): SrBeEu₂O₅ and (II): EuBeNd₂O₅ were prepared by CO₂-LASER (I) in air and plasma torch (II) technique in H₂ atmosphere. X-ray investigations led to orthorhombic symmetry, space group D-Pnma; (I): a = 9.488, b = 7.156, c = 6.495 Å; (II): a = 9.534, b = 7.225, c = 6.544 Å, Z = 4. Sr²⁺ and Eu³⁺ as well as Eu²⁺ and Nd³⁺ are in statistical distribution within a Kagomé framework. Both compounds are discussed with respect to the monoclinic form of MBeLn₂O₅.     

ChemInform Abstract: The New Misfit Compound (BiSe)1.15(TiSe2)2 and the Role of Dimensionality in the Cux(BiSe)1+δ(TiSe2)n Series.

Single crystals of (BiSe)_1.15(TiSe₂)₂ and (BiSe)_1.13(TiSe₂) are prepared from Bi, Ti, and Se in the molar ratio1:1:3 by vapor transport with TeCl₄ as transport agent (750—680 °C, 7 d).     

钳形酰腙类阴离子受体的合成及识别性质研究

设计合成了基于吲哚酰腙单元的钳形阴离子受体(1),UV-Vis滴定实验表明,它在含1%DMSO的CH3CN溶液中能选择性识别具有重要生物学意义的F-、Ac O-和H2PO4-(结合比均为1∶1且Ka104L/mol),但对Cl-、Br-、I-、NO3-、N3-、HSO4-和Cl O4-无识别作用。与它相比,端基为苯并呋喃的参照化合物2在同样溶剂中对上述3种阴离子的亲和性减弱,尤其是对H2PO4-。核磁滴定实验表明,受体1中的吲哚环NH和酰胺NH能产生协同效应,从而对阴离子产生了强效键合作用。     

Electrochemical and Chemical Syntheses of Trifluoromethylating Reagents and Trifluoromethyl Substituted Compounds

The electroreduction of the halofluoromethanes CF₃Br, CF₂Br₂ and CF₂BrCl has been studied in high‐pressure stainless steel autoclaves at different cathodes [Pt, steel (V2A, V4A), glassy carbon (GC)] and in various solvent‐supporting electrolyte systems (SSE), e.g. DMF/[Bu₄N]Br, NMP/[Bu₄N]BF₄ etc. The reduction potentials for CF₃Br increase from Pt (–1.6 V) < V2A (–1.8 V) < GC (–2.1 V) and are lower for CF₂Br₂ and CF₂BrCl suggesting a reductive cleavage of C‐X bonds as the first step. CF₂Br₂ and CF₂BrCl show a two‐step reduction in accord with the C–X bond energies (C–F > C–Cl > C–Br) and the “Perfluoro‐effect”. The electrolysis of CF₃Br in different SSE‐systems with sacrificial zinc or cadmium anodes has been reinvestigated with our experimental set‐up to elucidate the influence of the experimental conditions on the type and ratio of the products. The observed products CF₃MBr·42L and (CF₃)₂M·42L (M = Zn, Cd; L = DMF or AN) are the same as in the previous investigations, but are obtained in different ratios, as a rule caused by a parallel chemical corrosion of the respective anodes. By using aluminium as sacrificial anode no CF₃Al compounds are formed. The CF₃ species generated by electroreduction of CF₃Br react with the solvents via hydrogen abstraction and formation of CF₃H. The current yield with respect to the dissolution of the Al anode reaches 120 % indicating a considerable chemical corrosion in addition to the anodic oxidation. This result enabled a one‐pot trifluoromethylation reaction of NMP as organic carbonyl substrate and solvent with CF₃Br and aluminium powder (ratio 3 : 2) at higher temperatures (> 70 °C). The complete reaction of CF₃Br to give CF₃H and 1‐methyl‐2‐trifluoromethyl‐4,5‐dihydropyrrol allowed the isolation of the latter by vacuum condensation and distillation in 45 % yield, rel. to the CF₃Br used. Gallium and indium were also applied as sacrificial anodes in combination with CF₃Br as substrate. In both cases, anodic current yields of about 280 % indicated an extreme chemical corrosion together with cathodic metal depositions corresponding to the cathodic current yield. These deposits – in contrast to those of Zn and Cd – do not react with CF₃Br in Grignard‐type conversions to CF₃Ga and CF₃In compounds. So, the observed products (CF₃)_nMBr_3–n·L (M = Ga, In; n 1‐3; L = DMF, NMP) are obviously formed by chemical corrosion of the electro‐activated anodes. Finally, electrochemical and chemical trifluoromethylations were successfully carried out, using R₃SiCl (R = Me, Vi, Ph), Me₃M′Cl (M′ = Ge, Sn) and aluminium anodes or Al‐powder. The products were characterized either after isolation or in the product solutions by NMR‐spectroscopic investigations.     

The Influence of the Preparation Method on the Physico-Chemical Properties and Catalytic Activities of Ce-Modified LDH Structures Used as Catalysts in Condensation Reactions

Mechanical activation and mechanochemical reactions are the subjects of mechanochemistry, a special branch of chemistry studied intensively since the 19th century. Herein, we comparably describe two synthesis methods used to obtain the following layered double hydroxide doped with cerium, Mg₃Al_0.75Ce_0.25(OH)₈(CO₃)_0.5·2H₂O: the mechanochemical route and the co-precipitation method, respectively. The influence of the preparation method on the physico-chemical properties as determined by multiple techniques such as XRD, SEM, EDS, XPS, DRIFT, RAMAN, DR-UV-VIS, basicity, acidity, real/bulk densities, and BET measurements was also analyzed. The obtained samples, abbreviated HTCe-PP (prepared by co-precipitation) and HTCe-MC (prepared by mechanochemical method), and their corresponding mixed oxides, Ce-PP (resulting from HTCe-PP) and Ce-MC (resulting from HTCe-MC), were used as base catalysts in the self-condensation reaction of cyclohexanone and two Claisen–Schmidt condensations, which involve the reaction between an aromatic aldehyde and a ketone, at different molar ratios to synthesize compounds with significant biologic activity from the flavonoid family, namely chalcone (1,3-diphenyl-2-propen-1-one) and flavone (2-phenyl-4H-1benzoxiran-4-one). The mechanochemical route was shown to have indisputable advantages over the co-precipitation method for both the catalytic activity of the solids and the costs.     

Zur kristallchemischen Ähnlichkeit von Aurid- und Halogenid-Ionen

On the Crystal Chemical Similarity of Auride and Halide Anions The crystallographic properties of the aurides M₃AuO and the alkalimetal halide oxides M₃XO (M = K, Rb, Cs; × = Br, I) are compared. Rb₃BrO, Rb₃IO, Cs₃BrO, and Cs₃IO have been prepared and characterized for the first time: Rb₃BrO (a = 5.465(1) Å) crystallizes as a cubic anti perovskite, Cs₃BrO (a = 7.800(6), c = 7.122(6) Å) and Cs₃IO (a = 8.056(3), c = 7.168(3) Å) as hexagonal anti perovskites, Rb₃IO (a = 7.889(1), c = 19.640(1) Å) as a hexagonal anti BaTiO₃ type. The analysis of bond lengths, molar volumes and the systematic of the crystal structures leeds to the conclusion, that the crystallographic properties of auride- and bromide anions are similar. The radius of the Au^? has been found to be 2.2 Å (KZ 12).