三有机锡（4R）-3-[[（2S）-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯的合成、结构和体外抗癌活性

利用三有机锡氢氧化物和手性配体（4R）-3-[[（2S）-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸（HL）反应合成了3个三有机锡（4R）-3-[[（2S）-5-氧-2-吡咯烷基]羰基]-4-噻唑烷甲酸酯R₃SnL[1,R=c-C₆H₁₁（a）,C₆H₅（b）,C₆H₅C（CH₃）₂CH₂（c）],通过元素分析、IR、¹H NMR和X-射线单晶衍射表征了其结构。化合物1a属正交晶系,P2₁2₁2₁空间群;化合物1b属单斜晶系,P2₁空间群。二者均为由羧基氧和内酰胺羰基氧桥联配位形成的右螺旋链状有机锡配位聚合物,锡原子具有五配位[SnC₃O₂]畸变三角双锥构型。化合物1a和1b对体外2种人癌细胞Colo205和Bcap37增殖均有强的抑制作用,其活性为1b >1a。     

β-烷氧羰基乙基三氯化锡配合物的合成、结构表征及酯交换反应

合成了13个标题化合物ROCOCH2CH2SnCl3.L (R=C1-5烷基;L=DBSO, HMPA), 通过元素分析、IR和1H NMR进行了表征。n-PrOCOCH2CH2SnCl3.DBSO的晶体结构分析表明, 该晶体属正交晶系; 空间群P212121; a=1.062, b=1.427, c=1.635; Z=4。该化合物为含有分子内羰基配位和Lewis碱配位的具有畸变八面体构型的单分子有机锡化合物。研究了CH3OCOCH2CH2SnCl3.L和醇的酯交换反应, 提出了分子内Lewis酸催化的反应机理。     

(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。     

稠合四环噻嗪烷-4-酮衍生物的合成及其抗肿瘤活性

以叔丁氧羰基(Boc)保护的脯氨醛1、氨基酸酯盐酸盐2a～2d和巯基水杨酸3a～3b为原料,三组分一锅法得到苯并噻嗪烷-4-酮中间体.酸性条件下脱除Boc,分子内酰胺缩合制备稠合四环噻嗪烷-4-酮衍生物6～11.新生成手性碳(1-C)的构型通过H-1和H-2的偶合常数及X-ray单晶衍射确定.测试了化合物抗Hela和A549的肿瘤细胞增殖活性.结果表明,部分化合物具有中等的抗Hela细胞活性,其中(13a R,13b R)-1,2,3,13b-四氢苯并[e]吡咯并[2',1':3,4]吡嗪并[2,1-b][1,3]噻嗪-5,8(6H,13a H)-二酮(6b)的IC_(50)值为9.50μmol/L.所有化合物对A549的细胞没有抑制活性.     

利用断裂反应合成1,3-二(2-羟基-3,5-二叔丁基苄基)咪唑鎓氯盐

4,6-tBu2-1-(HO)C6H2CH2Cl与1,1'-羰基二咪唑反应成功地合成双阴离子芳氧功能化的氮杂环卡宾前体[[2-HO-3,5-tBu2-C6H2CH2]2{CH(NCHCHN)}]CI(I),结果表明在反应过程中发生了断裂反应。化合物I通过元素分析,1HNMR和X-ray衍射进行表征。晶体结构表明其晶体属三斜晶系,空间群为P-1,化学式为C33H49ClN2O2,晶胞参数为a=12.014(3),b=16.757(3),c=19.191(4),α=94.836(4)deg,β=92.658(4)deg,γ=92.631(4)deg,V=3840.8(14)3,Z=2,最终R=0.092,wR=0.291。     

3-[N-(4-甲基苯基)氨基羰基]-5-[4-(4-甲酸基苯甲氧基)苯亚甲基]-2,4-噻唑烷二酮的合成

以对甲苯胺和对甲基苯甲酸甲酯为起始原料,经NBS溴化、亲核取代、酸水解和Knoevenagel缩合等6步反应合成了抗细菌生物膜化合物—3-[N-(4-甲基苯基)氨基羰基]-5-[4-(4-甲酸基苯甲氧基)苯亚甲基]-2,4-噻唑烷二酮,总收率57.3％,其结构经1H NMR,ESI-MS和元素分析确证.     

S-[2-(叔丁氧羰基氨基)乙基]-3-苯基丙酸硫酯类化合物脱除Boc保护基的反应研究

报道了取代苯丙酸类化合物1a～1d与N-叔丁氧羰基-L-半胱氨酸甲酯(2)在双(2-氧代-3-噁唑烷基)次磷酰氯(BOP-C1)作用下,以79%～92%收率得到缩合产物S-[2-(叔丁氧羰基氨基)乙基]-3-苯基丙酸硫酯类化合物3a～3d;3a～3d在三氟乙酸(TFA)作用下脱除Boc保护基时,结果不仅得到了正常的脱保护基产物4a～4d,还生成了2-取代噻唑啉类化合物5a～5d,研究表明5a～5d是由4a～4d分子内脱水环合而成.通过优化三氟乙酸用量、反应温度以及反应时间等条件,能够以较高收率分别得到4a～4d和5a～5d(收率85%～91%和86%～89%).而S-[2-(叔丁氧羰基氨基)乙基]-3-苯基丙烯酸硫酯类化合物3e～3f由于双键结构,在三氟乙酸作用下仅生成脱除Boc保护基产物4e～4f.该反应的研究为2-取代噻唑啉类化合物的合成提供了一种简便有效的方法.     

一维链状配位聚合物乙醇合二丁基锡-3,5-二硝基-2-氧苯甲酸酯的合成、结构和性质

利用二丁基氧化锡和3,5-二硝基水杨酸在苯-乙醇中反应合成了新配合物乙醇合二丁基锡3,5-二硝基-2-氧苯甲酸酯(n-C4H9)2Sn(2-O-3,5-(NO2)2C6H2COO)(C2H5OH)(1),通过元素分析、IR、1H NMR和X-射线单晶衍射表征了其结构。化合物1属单斜晶系,P21/c空间群,a=1.363 33(10)nm,b=1.861 90(14)nm,c=0.841 51(6)nm,β=93.311(1)°,Z=4,V=2.132 5(3)nm3,R1=0.033 6,wR2=0.090 0。该化合物为由羧基桥联配位和分子间氢键形成的新型一维链状有机锡配合物,锡原子具有六配位[SnC2O4]畸变八面体构型。化合物1对2种人癌细胞A549和CoLo205增殖均有强的抑制作用,对乙酰乙酸乙酯与醇的酯交换反应具有高选择性和良好的催化活性。     

海兔毒素10关键合成子Dap的立体专一性合成

以N-丙酰基-(3R,4S)-3-甲基-4-苯基-2-羰基噁唑啉与N-(叔丁氧羰基)-S-脯氨醛为原料,经羟醛缩合反应合成了高立体专一性、具有三个手性中心的(4S,5S,2'R,3'R,2"S)-3-[3'-(N-叔丁氧羰基-2"-吡咯烷基)-3'-羟基-2'-甲基丙基)]-4-甲基-5-苯基-2-羰基噁唑烷酮(6);6脱去手性辅基,甲基化3'-羟基合成了抗肿瘤活性肽海兔毒索10的关键合成子--(2S,3S,2's)-3-(N-叔丁氧羰基-2'-吡咯烷基)-3-甲氧基-2-甲酸丙酸,其结构经1H NMR,13C NMR,m和MS表征.     

2-[[(4-吡啶)甲基]硫]-1H-苯并咪唑Ni(Ⅱ)配合物的合成、晶体结构及热稳定性

本文报道了[NiL2(NCS)2(CH3OH)2](L=2-[[(4-吡啶)甲基]硫]-1H-苯并咪唑)配合物的合成,并通过IR、X-射线单晶衍射、热稳定性进行了表征。晶体结构测试表明:该配合物属于单斜晶系,空间群P21/n,晶胞参数:a=0.94420(12)nm,b=1.35733(17)nm,c=1.341 64(17)nm,β=97.983 0(10)°,V=1.702 8(4)nm3,Z=2,F(000)=748,Dc=1.407 g.cm-3,Final GooF=1.027,R1=0.046 8,wR2=0.107 1。中心Ni(Ⅱ)原子采用六配位,分别与2个2-[[(4-吡啶)甲基]硫]-1H-苯并咪唑上的2个N原子,2个硫氰酸根的2个N原子和2个甲醇分子上的2个O原子进行配位。在Ni(Ⅱ)基本配位单元之间存在N…H-O氢键,形成一维双链堆积结构。     

Synthesis of tricyclic isoindoles and thiazolo[3,2-c][1,3]benzoxazines

The thermolysis of (3R,9bS)-5-oxo-2,3,5,9b-tetrahydrothiazolo[2,3-a]isoindole-3-carboxylic acids in Ac₂O led to novel 3-methylene-2,5-dioxo-3H,9bH-oxazolo[2,3-a]isoindoles and chiral (9bS)-5-oxo-2,3,5,9b-tetrahydrothiazolo[2,3-a]isoindoles were obtained on FVP. Starting from l-cysteine methyl ester (3R,10bR)-5-oxo-2,3-dihydro-10bH-[1.3]thiazolo[3,2-c][1,3]benzoxazines were obtained as single stereoisomers. The thermolysis of (3R,10bR)-5-oxo-2,3-dihydro-10bH-[1.3]thiazolo[3,2-c][1,3]benzoxazine-3-carboxylic acid in Ac₂O gave 5-acetyl-2-phenyl-2,3-dihydrothiazole. The structures of methyl (3R,9bS)-5-oxo-2,3,5,9b-tetrahydrothiazolo[2,3-a]isoindole-3-carboxylate 1a and methyl (2R,4R)-N-chlorocarbonyl-2-(2-hydroxyphenyl)thiazolidine-4-carboxylate 9 were determined by X-ray crystallography.     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

The crystal structures ofbis-{(2-benzotrifluoride)-[(2-oxo-3H-naphth-3-ylidene)-methyl]-aminato} Copper(II) andbis-{(3-benzotrifluoride)-[(2-oxo-3H-naphth-3-ylidene)-methyl]-aminato} Copper(II)

Summary TheSchiff base ligands 3-[(2-benzotrifluoride)-2-hydroxy-3H-naphth-3-ylidene)-methyl] aldamine (1) and 3-[(3-benzotrifluoride)-2-hydroxy-3H-naphth-3-ylidene)-methyl] aldamine (2) and their corresponding Cu(II) complexes (I, II) were synthesized. The crystal structures ofbis-{(2-benzotrifluoride)-[(2-oxo-3H-naphth-3-ylidene)]-methyl]-aminato} Copper(II) (I) andbis-{(3-benzotrifluoride)-[(2-oxo-3H-naphth-3-ylidene)-methyl]-aminato} Copper(II) (II) were determined. CompoundI crystallizes in the triclinic crystal system (a=12.561(3),b=16.211(4),c=8.007(2) Å, =96.29(2), =101.42(2), =97.10(2)°, space group ,Z=2); compoundII crystallizes in the monoclinic crystal system (a=5.064(2),b=19.172(4),c=15.111(3) Å, =95.05(2)°, space group P2₁/c,Z=2). The X-ray diffraction study shows that the geometry around the metal atom is square planar for both copper complexes.

---

Kristallstruktur vonbis-{(2-Benzotrifluorid)-[(2-oxo-3H-naphth-3-yliden)-methyl]-aminato}-Kupfer(II) undbis-{(3-Benzotrifluorid)-[(2-oxo-3H-naphth-3-yliden)-methyl]-aminato}-Kupfer(II)

Zusammenfassung DieSchiffschen Basen 3-[(2-Benzotrifluorid)-2-hydroxy-3H-naphth-3-yliden)-methyl]-aldamin (1) und 3-[(3-Benzotrifluorid)-2-hydroxy-3H-naphth-3-yliden)-methyl]-aldamin (2) sowie ihre entsprechenden Cu(II)-Komplexe (I,II) wurden synthetisiert und ihre Struktur im Kristall bestimmt. VerbindungI kristallisiert triklin (a=15.561(3),b=16.211(4),c=8.007(2) Å, =96.29(2), =101.42(2), =97.10(2)°, Raumgruppe ,Z=2); VerbindungII kristallisiert monoklin (a=5.064(2),b=19.172(4),c=15.111(3) Å, =95.05(2)°, Raumgruppe P2₁/c,Z=2). Aus der Röntgenstrukturanalyse ergibt sich eine quadratisch planare Geometrie der Komplexe.

     

Molecular Structure of Methyl 1-Isopropenyl- 5a,5b,8,8,11a-Pentamethyl-9-OXO-10-[(E)-1-Phenylmethylidene] Perhydrocyclopent [a]Chrysene-3a-Carboxylate

The molecular structure of methyl 1-isopropenyl-5a,5b,8,8,11a-pentamethyl-9-oxo-10-[(E)-1phenylmethylidene]perhydrocyclopent[a]chrysene-3a-carboxylate II is determined. Compound II C₃₈H₅₂O₃ crystallizes in the non-centrosymmetric P2₁ space group with the cell parameters: a= 11.4450(8) ?, b = 11.1995(8) ?, c = 12.5179(9) ?, β = 93.984(2)°.     

Zur Struktur der Tetrahydro-4-phenylspiro([1]benzopyran-2,4′(1′H)-pyrimidin)-2′(3′H)-one bzw.-thione über Heterocyclen, 49. Mitt

The structures of tetrahydro-4-phenylspiro([1]benzopyran-2,4(1H)-pyrimidin)-2(3H)-ones and-thiones4 a, b resp., are proved by synthesis. 3-(2-methoxy-3,5-dimethylphenyl)-3-phenylpropionic acid11 b is prepared from 3,4-dihydro-6,8-dimethyl-4-phenylcoumarin10. The lithium salt of11 b reacts with isobutenyl-lithium to 1-(2-methoxy-3,5-dimethylphenyl)-5-methyl-1-phenyl-4-hexen-3-on12 a. 12 a is transferred with urea in acid medium and NH₄CNS resp. in a mixture of dihydro-6-[2-(2-methoxy-3,5-dimethylphenyl)-2-phenyläthyl]-4,4-dimethyl-2(1H)-pyrimidinone and-thione13 a, b and tetrahydro-6-[2-(2-methoxy-3,5-dimethylphenyl)-2-phenyläthyliden]-4,4-dimethyl-2(1H)-pyrimidinone and-thione14 a, b resp.14 b leads to13 a, b with H₂O₂. Heating of13 a, 14 a and14 b resp. with pyridin-HCl leads to the spiro compounds4 a, b.     

Synthesis and DFT calculations of oxido and phenylimido-rhenium(V) complexes incorporating the N,O donor ligand 2-[(2-hydroxyethylimino)methyl]phenol

The reactions of equimolar amounts of trans-[ReOC1₃(PPh₃)₂] or trans-[Re(NPh)(PPh₃)₂Cl₃] with a Schiff base formed by condensation of 2-hydroxy-4-methoxybenzaldehyde and ethanolamine (H₂L) result in the formation of cis-[ReO(HL)PPh₃Cl₂] (1a) and trans-[Re(NPh)(HL)(PPh₃)Cl₂] (2b), respectively, in good yields. 1a and 2b have been characterized by a range of spectroscopic and analytical techniques. The X-ray crystal structures of 1a and 2b reveal that 1a is an octahedral cis-Cl,Cl oxorhenium(V) complex, while 2b is a trans-Cl,Cl phenylimidorhenium(V) complex. The complexes are weakly emissive at room temperature with quantum yields of 10^?4. Density functional theory calculations of the electronic properties of the complexes were performed and are in agreement with the experimental results. The complexes display quasi-reversible Re(V)/Re(VI) redox couples in acetonitrile. There is reasonable agreement between the experimental and calculated redox potentials of 1a and 2b.     

Crystal and molecular structure of methyl(±)-2-((1R,3R)-3-{ 2-[(3S)-1-ethyl-3-hydroxy-2-oxo-2,3-dihydro-1H-3-indolyl]acetyl}-2,2-dimethylcyclobutyl) acetate

The structure of methyl (±)-2-((1R,3R)-3-{ 2-[(3S)-1-ethyl-3-hydroxy-2-oxo-2,3-dihydro-1H-3-indolyl]acetyl}-2,2-dimethylcyclobutyl) acetate has been determined by single crystal X-ray diffraction. The crystal belongs to triclinic system; parameters of the unit cell are: a = 6.551(1) Å, b = 11.506(1) Å, c = 14.334(1) Å, α = 101.41(1)°, β = 97.57(1)°, γ = 104.72(1)°; space group P-1, Z = 2, composition C₂₁H₂₇NO₅. The structure of N-ethyloxindole fragment is usual for the present class of compounds. The configuration of the formed asymmetric carbon atom C(3) of the pyrrole ring along with the configuration of C(12) and C(14) atoms of 2,2-dimethylcyclobutane ring form the side chain of the molecule were determined. There is observed the generation of centrosymmetrical dimers in the crystal structure due to realized intermolecular hydrogen bond of O-H...O type, 2.808(2) Å.     

Structural and bonding investigation of the donor—acceptor complex 1-Sn(phenanthroline)-2, 3-[Si(CH3)]3]2-2,3-C2B4H4: A comparative study of the group 14 metallacarborane-Lewis base complexes

Closo-1-Sn-2,3-[Si(CH₃)₃]₂-2,3-C₂B₄H₄ (1) reacts with 1,10-phenanthroline to form the complex 1-(C₁₂H₈N₂)Sn-2, 3-[Si(CH₃)₃]₂-2,3-C₂B₄H₄. When crystals of this complex were grown slowly from benzene, a crystalline modification (2) was obtained in which the unit cell consisted of four identical molecules of the base-stannacarborane and six benzene molecules of solvation. When the complex was sublimed, a second crystalline modification (3) was obtained whose unit cell consisted of two crystaliographically different molecules (3-1 and3-2). In all three forms the tin was not symmetrically bonded to the carborane but was slipped toward the boron side of the C₂B₃ face, and the phenanthroline molecules were oriented opposite to the cage carbons so that the plane of the base and the carborane faces gave acute dihedral angles. However, the three forms showed a great deal of variation in the extent of slippage and the magnitudes of the base-carborane dihedral angles. Since these distortions are common structural features of base-group 14-carborane and cyclopentadienyl systems, MNDO-SCF molecular orbital calculations were carried out on the model compounds 1-(C₁₂H₈N₂)Sn-2,3-C₂B₄H₆, 1-[C₁₀H₈N₂)Sn-2, 3-C₂B₉H₁₁, and [(C₁₀H₈N₂)-SnC₅(CH₃)₅]⁺ to determine what factors dictate the structures of these complexes. The results showed that competing bonding interactions give rise to a very broad minimum in energy as a function of slippage and base orientation. Small energy variations, such as those produced by crystal packing forces, could produce large structural changes. Complex2 crystallizes in the monoclinic space group P2₁/n witha=11.096 (9) Å,b=26.51(2) Å,c=11.729 (7) Å,=107.43 (6) ,U=3291 (4) ų, andZ=4. Full-matrix least-squares analysis converged atR=0.044 andR _w=0.055. Complex3 crystallizes in the triclinic space group P¯1 witha=10.251 (3) Å,b= 13.845(9) Å;c=19.168 (9) Å,=71.12 (5) ,=89.29 (3) ,=84.62 (4) ,U=2562 (2) ų, andZ=4. The structure refined atR=0.079 andR _w=0.125.     

Synthesis,characterization and luminescence of the tetranuclear gold cluster: [Au4{7,8-(PPh2)2-7,8-C2B9H10}2(PPh3)2]

A tetranuclear gold cluster has been synthesized by the reaction of [Au(PPh₃)NO₃] with the closo carborane diphosphine 1,2-(PPh₂)₂-1,2-C₂B₁₀H₁₀ in THF, and characterized by elemental analysis, FT-IR, ¹H and ¹³C?NMR spectroscopy and X-ray structure determination. The cluster crystallizes in the triclinic Pī, a?=?15.118(8)?Å, b?=?16.057(9)?Å, c?=?24.284(13)?Å, α?=?80.822(9)°, β?=?79.624(8)°, γ?=?81.938(8)°, Z?=?2, R ₁?=?0.0626, wR ₂?=?0.1894. A single crystal structure determination showed that four gold atoms form a tetrahedral framework. Among these four gold atoms, two were chelated by two nido carborane diphosphine [7,8-(PPh₂)₂-7,8-C₂B₉H₁₀]^? anions coming from the degradation of the initial closo ligand 1,2-(PPh₂)₂-1,2-C₂B₁₀H₁₀, while the other two were ligated to two PPh₃ groups. The luminescence of this cluster was also investigated in dichloromethane solution at room temperature.