Zur Darstellung von η5-Cyclopentadienyl(dicarbonyl)-[η2-diethylamino(methylthio)carben]wolfram durch Thiomethylierung von η5-Cyclopentadienyl(dicarbonyl)diethylaminocarbinwolfram

Dicarbonyl(η⁵-cyclopentadienyl)(diethylaminocarbyne)(tungsten reacts with dimethyl(methylthio)sulfonium tetrafluoroborate to form dicarbonyl(η⁵-cyclopentadienyl)[η²-diethylamino(methylthio)carbene]tungsten in high yields.     

Darstellung und Röntgenstrukturuntersuchung von [1-Carbonyl-1-(η5-cyclopentadienyl)-2,3-dimethyl-1-trimethylphosphin-3-trimethylphosphoranyliden-1-wolframa-2-thiacyclopropan]-tetrafluoroborat

Dicarbonyl(η⁵-cyclopentadienyl)[η²-(methylthio)methylcarbene] tungsten tetrafluoroborate reacts with an excess of trimethylphosphine under carbonyl substitution and addition of trimethylphosphine at the carbene carbon to yield a ‘wolframa-thiacyclopropane’ complex with a trimethylphosphoranylidene unit. Synthesis, spectroscopic investigation and the X-ray structure are reported.     

New Heteropolytungstates Incorporating Dioxouranium(VI). Derivatives of α-[SiW9O34]10−, α-[AsW9O33]9−, γ-[SiW10O36]8−, and [As4W40O140]28−

Reaction of uranium salts with several lacunary polyoxotungstate anions yields four new heteropolyanion assemblies in which the uranium atoms occupy pentagonal bipyramidal coordination polyhedra. Treatment of A,-[SiW₉O₃₄]^10– with UO₂(NO₃)₂ leads to Na₁₄[Na₂(UO₂)₂(SiW₉O₃₄)₂]38H₂O (1, Monoclinic, P2₁/c, a=16.5719(8) Å, b=14.1689(7) Å, c=21.2528(10) Å, =111.6670(10)°, V=4786.6(4) ų, Z=2) which proves to be isostructural with the analogous derivative of [PW₉O₃₄]^9– reported previously. Solutions of 1 exhibit the 5-line W-NMR spectrum expected for the structure of C _i point symmetry. The salt (NH₄)₁₇[(UO₂)₃(H₂O)₄As₃W₂₆O₉₄]16H₂O (2, Orthorhombic, Pnma, a=40.1747(2) Å, b=18.25840(10) Å, c=18.0817(2) Å, V=13263.4(2) ų, Z=4) was isolated in 64% yield from a reaction of UO₂(NO₃)₂ with B,-[AsW₉O₃₃]^9–. The structure of the anion in 2 has C _s symmetry and contains one -AsW₉O₃₃ and two novel -AsW₈O₃₀ units linked by the UO²⁺ ₂ groups; an additional WO₆ links the two AsW₈ fragments. Spectrophotometric titration of UCl₄ with the sodium salt of [As₄W₄₀O₁₄₀]^28– indicated the formation of a 4:1 U:As₄W₄₀ complex. During attempts to isolate a crystalline product from this reaction the uranium became oxidized and a guanidinium salt of [Na(UO₂)₃(OH)(H₂O)₆As₄W₄₀O₁₄₀(WO)]^18– (3, Orthorhombic, Fdd2, a=54.848(3) Å, b=80.809(4) Å, c=20.2874(2) Å, V=89919(7), Z=16) was isolated. The partially disordered structure of 3 shows the S₂ and adjacent sites of the lacunary As₄W₄₀ anion to be occupied by three UO₅ and one WO₅ polyhedra. A tetrameric assembly of -SiW₁₀ units linked by UO²⁺ ₂ groups occurs in [{M(OH₂)}₄(UO₂)₄(OH)₂(SiW₁₀O₃₆)₄]^22– (lithium salt, M=Na, 4a, tetragonal, P4₂/nmc, a=b=26.5285(2) Å, c=15.0463(2) Å, V=10589.0(2) ų, Z=2; sodium-potassium salt, M=K, 4b, orthorhombic, Fddd, a=24.180(5) Å, b=31.696(6) Å, c=58.012(12) Å, V=44460(15) ų, Z=8). Tungsten-183 NMR spectra show the slow transformation of the expected 5-line (1:1:1:1:1) spectrum of 4a to a new species giving a 6-line spectrum (2:2:2:1:2:1). The latter complex has not been successfully isolated.     

Gram-scale synthesis of anti-pancreatic flavonoids (±)-8-[1-(4′-hydroxy-3′-methoxyphenyl)prop-2-en-1-yl]-chrysin and -galangin

Gram-scale total synthesis of (±)-8-[1-(4′-hydroxy-3′-methoxyphenyl)prop-2-en-1-yl]-galangin (1) and -chrysin (2) has been accomplished in eight steps from commercially available phloroglucinol and three steps from commercially available chrysin, respectively, featuring an efficient introduction of C(8) (1-prop-2-en-1-yl)phenyl moiety in the natural products through chemo- and regioselective cinnamylation and regioselective aromatic Claisen rearrangement.     

Synthesis and structural studies of (1R,2R,5R)-chloro{o-[β-(2-hydroxy-2,6,6-trimethylbicyclo[3.1.1]hept-3-ylidenamino)ethyliminomethyl]phenoxy-O,N,N}palladium(II)

The reaction of (1R,2R,5R)-3-[{2-[(2-hydroxybenzylidene)amino]ethyl}imino]-2,6,6-trimethylbicyclo[3.1.1]heptan-2-ol with lithium tetrachloropalladate was studied. A chiral palladium(II) complex was thus obtained and its structure was confirmed by NMR spectroscopy and X-ray diffraction analysis.     

Synthesis and Crystal Structure of Spiro[1-bromo(S)-4-(R)-hydroxy-5-oxa-6-oxo-bicyclo[3.1.0]hexane-2,2''''-(3''''-diethyl-α-(S)-4''''''''-Cl-benzyloxyphosphonyl-4''''-(1R,2S,5R)-menthyloxybutyrolactone)]

1 INTRODUCTION In recent years, phosphorus compounds havebeen playing an important role in the new “high-tech” areas including life science and industrial te-chnology[1, .At the same time, the asymmetric syn- 2]thesis of various natural compounds containing cyc-lopropane components and organophosphorus grouphas attracted much attention due to their special bio-logical functions and antibiological activities[3～5].Despite the great advances in these areas, no novelapproach to the efficien…     

(6R,7R)-7-氨基-3-[2-(4-甲基-5-噻唑)乙烯基]-8-氧代-5-硫-1-氮杂双环[4.2.0]辛-2-烯-2-羧酸的合成

以1-磺丁基-3-甲基咪唑硫酸氢盐离子液体(b)为反应介质,7-氨基头孢烷酸(7-ACA,2)为原料,与4-甲基-5-甲酰基噻唑经缩合反应制得(6R,7R)-7-氨基-3-[2-(4-甲基-5-噻唑)乙烯基]-8-氧代-5-硫-1-氮杂双环[4.2.0]辛-2-烯-2-羧酸(7-ATCA,1),其结构经1H NMR,13C NMR和IR表征。考察了离子液体及其用量,原料摩尔比r[n(4-甲基-5-甲酰基噻唑)∶n(2)],反应温度和反应时间对1收率的影响。在最佳反应条件[b为反应介质,b用量为20 m L,r=1.3,于65℃反应5 h]下,1收率可达90%以上。     

(1R,2S,5R,8S,9R,10S)-8-甲基-4-氮杂-5-苯基-7-氧杂四环[8.2.1.0~(2,9).0(~4,8)]十三-11-烯-3-酮的合成和晶体结构

为确定内型降冰片烯酰亚胺与甲基格氏试剂反应所得加成产物的结构,合成了标题化合物(C18H19NO2)。其结构通过单晶X-射线衍射分析确定,该晶体属正交晶系,空间群为P212121,a = 6.293(1),b = 14.342(3),c = 16.357(3) 牛琕 = 1476.2(5) ?,Z = 4,Dc = 1.266 g/cm3, (MoKa) = 0.082mm-1,F(000) = 600。晶体结构用直接法解出,最终的偏离因子为R = 0.0535,wR = 0.988。由此晶体结构可确定加成产物为标题化合物,并由1H-NMR数据推测另一加成产物的结构。     

剪刀分子(2S, 8S)-双(2-萘甲酰氨基甲基)-1,5,9-三氮杂双环[4.4.0]癸-5-烯氯化物的合成和核磁共振研究

本文报道新的剪刀分子(2S, 8S)-双-(2-萘甲酰氨基甲基)-1,5,9-三氮杂双环[4.4.0]癸-5-烯氯化物的合成和核磁共振研究。新的剪刀分子和对硝基苯甲酸盐配合效应的研究表明, 它们通过氢键和芳环夹心π-π Stacking作用而自动缔合。     

剪刀分子(2S, 8S)-双(2-萘甲酰氨基甲基)-1,5,9-三氮杂双环[4.4.0]癸-5-烯氯化物的合成和核磁共振研究

本文报道新的剪刀分子(2S,8S)-双-(2-禁甲酸氨基甲基)-1,5,9-三氮杂双环[4.4.0]癸-5-烯氯化物的合成和核磁共振研究.新的剪刀分子和对硝基苯甲酸盐配合效应的研究表明,它们通过氢键和芳环夹心π-πStacking作用而自动缔合.     

Synthesis and Structure of 9-Aryl-8-aryl(fur-2-yl)-4,9-dihydrotetrazolo[1′,5′:1,2]pyrimido[4,5-d]pyridazin-5(6H)-ones

Russian Journal of General Chemistry - A method for the synthesis of new 9-aryl-8-aryl(fur-2-yl)-4,9-dihydrotetrazolo[1′,5′:1,2]pyrimido[4,5-d]pyridazine-5(6H)-ones by the reaction of...     

(R)-乙基-2-吡啶亚砜与(4R,5R)-TADDOL包结晶体 [C7H9NOS·C31H30O4]的晶体结构分析

（Ｒ）－乙基－２－吡啶亚砜与（４Ｒ，５Ｒ）－二（羟基－二苯基－甲基）－２，２－二甲基－１，３－二氧戊环（ＴＡＤ－ＤＯＬ）可以形成物质的量比为１∶１的手性包结晶体，Ｘ射线衍射分析确定该晶体属单钭晶系，Ｐ２１空间群，ａ＝０．９７０１（２）ｎｍ，ｂ＝０．９９５３（２）ｎｍ，ｃ＝１．７３９２（２）ｎｍ；β＝９２．０７９°（１４），Ｖ＝１．６７８１（５）ｎｍ３，Ｚ＝２，Ｄｃ＝１．２３０ｇ／ｃｍ３，分子式Ｃ３８Ｈ３９ＮＯ５Ｓ，Ｍｒ＝６２１．７６，最终偏离因子Ｒ＝０．０３５１，ＲＷ２＝０．０７７２，Ｆｌａｃｋ值为０．１（２）．结构分析表明，主客体存在分子间氢键．光学纯的ＴＡＤＤＯＬ与消旋的乙基吡啶亚砜（１）作用时，ＴＡＤＤＯＬ对１具有很好的手性识别能力，选择性地与１的一个对映体形成氢键，长成晶体．参照晶体结构确定了１的两个对映体的绝对构型     

π-complexes of monoanionic carborane ligand [9-(Me2S)-7,8-C2B9H10]− with [η-C5R5Fe]+ (R=H, Me) and [η-C4Me4Co]+ cationic fragments

Compounds (η-C₅R₅)Fe[η-9-(Me₂S)-7,8-C₂B₉H₁₀] (R=H, Me) and (η-C₄Me₄)Co[η-9-(Me₂S)-7,8-C₂B₉H₁₀] were synthesized by the reactions of Na[9-(Me₂S)-7,8-C₂B₉H₁₀] with complexes [(η-C₅H₅)Fe(MeCN)₃]PF₆, [(η-C₅Me₅)Fe(MeCN)₃]BF₄, and [(η-C₄Me₄)Co(MeCN)₃]PF₆, respectively. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 177–179, January, 1999.     

Organophosphoryl polyoxotungstates α-[R2PW9O34]5− [R = PhP(S), C6H11P(O), H2NCH(n-Pr)P(O)]

Tetrabutylammonium salts of organophosphoryl derivatives of tungstophosphate of formula α-[R₂PW₉O₃₄]⁵⁻ [R = PhP(S), C₆H₁₁P(O), H₂NCH(n-Pr)P(O)] have been prepared, purified and characterized by elemental analysis, i.r., ³¹P- and ¹⁸³W-n.m.r. spectroscopy. These anions consist of an α-[PW₉O₃₄]⁹⁻ framework on to which are grafted two equivalent organophosphoryl groups through P–O–W bridges; these new species still retain the ‘unsaturated’ Keggin structure. The five-line ¹⁸³W spectra indicates that the hybrid anions possess C _s symmetry in acetonitrile. This revised version was published online in June 2006 with corrections to the Cover Date.     

Koordinationschemie tripodaler Triisocyanid-Liganden: Synthese von Komplexen des Typs CH3C[CH2NC-M(CO)x]3 (M = Cr,W, χ = 5; M = Fe, χ = 4) und Kristallstruktur von CH3C[CH2NC-W(CO)5]3

The triisocyanide ligand CH₃C(CH₂NC)₃, time, reacts with metal carbonyls M(CO)_x (M = Cr, W, χ = 6; M = Fe, χ = 5) to give the triply metal carbonyl substituted complexes CH₃C[CH₂NCM(CO)_x]₃ (M = Cr, W, χ = 5; M = Fe, χ = 4). CH₃C[CH₂NCW(CO)₅]₃ was characterized by an X-ray structure determination.