Synthesis,antitumor activity and crystal structure of the triphenyltin derivative of exo‐7‐oxa‐bicyclo[2,2,1]hept‐5‐ene‐3‐N‐p‐tolylamide‐2‐acid

The synthesis and crystal structure of­Ph₃SnO₂CCHCHCH:CHCH(O)CHCONHC₆H₄­CH₃·CH₂Cl₂ are reported. The monomer units­are bridged by the carbonyl oxygen of the amide group, thus forming a polymer in which each tin atom is best described as having a distorted five‐coordinate geometry. There is a relatively strong intramolecular hydrogen bond between the amide hydrogen and the ether oxygen. The in vitro antitumor activities of the title compound against HL‐60, BGC‐823, Bel‐7402, SKOV3, KB and Hela tumor lines are reported. The title compound shows a distinct advantage when the metal (tin) is introduced into the acid.Copyright © 2001 John Wiley & Sons, Ltd.     

Synthesis,characterization and cytotoxicity of some triarylbismuth(V) di(N‐p‐toluenesulfonyl) aminoacetates and the crystal structure of (4‐CH3C6H4SO2NHCH2CO2)2Bi(C6H4Cl‐4)3

A series of triarylbismuth(V) di(N‐p‐toluenesulfonyl)aminoacetates with the formula (4‐CH₃C₆H₄SO₂NHCH₂CO₂)₂BiAr₃ (Ar?C₆H₅, 4‐CH₃C₆H₄, 4‐ClC₆H₄, 4‐BrC₆H₄) were synthesized and characterized by elemental analysis, IR, ¹H NMR and mass spectra. The crystal structure of (4‐CH₃C₆H₄SO₂NHCH₂CO₂)₂Bi(C₆H₄Cl‐4)₃ was determined and shows the bismuth to exist in a distorted trigonal bipyramidal geometry. Four human neoplastic cell lines (HL‐60, PC‐3MIE8, BGC‐823 and MDA‐MB‐435) were used to screen these compounds. The results indicate that these compounds at 10 μM show cytotoxicity. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis,structure and antitumor activity of dibutyltin oxide complex with 5‐fluorouracil derivatives

The dibutyltin(IV) oxide complex reacts with 5‐fluorouracil‐l‐propanonic or5‐fluorouracil‐1‐acetic acid to give the potential antitumor activity complexes [(5‐fluorouracil)‐1‐(CH₂)_mCOOSn(Bu‐n)₂]₄O₂[m = 1, (1); m = 2, (2)] which were determined by IR and ¹H NMR. The crystal structure determination shows that complex 2 is a dimmer, in which two [(5‐fluorouracil)‐1‐CH₂CH₂COOSn(Bu‐n)₂]₂O units are linked by bridging oxygen atom, and the tin atoms adopt distorted trigonal bipyramids via two carbons from dibutyl group and three oxygen atoms from 5‐fluorouracil and bridging oxygen. In vitro test shows complexes 1 and 2 exhibit high cytotoxicity against OVCAR‐3 and PC‐14.     

Synthesis,characterization and in vitro antitumor activity of some arylantimony ferrocenecarboxylates and crystal structures of C5H5FeC5H4CO2SbPh4 and (C5H5FeC5H4CO2)2Sb(4‐CH3C6H4)3

A series of arylantimony ferrocenecarboxylates with the formula (C₅H₅FeC₅H₄CO₂)_nSbAr_(5?n) (n = 1, 2; Ar = C₆H₅, 4‐CH₃C₆H₄, 3‐CH₃C₆H₄, 2‐CH₃C₆H₄, 4‐ClC₆H₄, 4‐FC₆H₄) were synthesized and characterized by elemental analysis, IR, ¹H NMR and mass spectra. The crystal structures of (C₅H₅FeC₅H₄CO₂)₂Sb(4‐CH₃C₆H₄)₃ and C₅H₅FeC₅H₄CO₂SbPh₄ were determined by X‐ray diffraction. Four human neoplastic cell lines (HL‐60, Bel‐7402, KB and Hela) were used to screen these compounds. The results indicate that these compounds at 10 µM show certain in vitro antitumor activities. Copyright © 2003 John Wiley & Sons, Ltd.     

Solid‐state 119Sn NMR and antitumor activity of bis [1,3‐bis (3‐oxapentamethylenecarbamoylthioacetato)‐1,1,3,3‐tetrabutyl‐1,3‐distannoxare], and the crystal structure of its bis‐ethanol solvate

The ¹¹⁹Sn cross polarization‐magic angle spinning NMR spectrum of bis[1,3‐bis(3‐oxapentamethylenecarbamoylthioacetato)‐1,1,3,3‐tetrabutyl‐1,3‐distannoxane], {[(C₄H₉)₂SnO₂CCH₂SC(O)N(CH₂CH₂)₂O]₂O}₂, which consists of two resonances of similar chemical shifts and symmetry (δ_iso = −152, −202 ppm; asymmetry, κ = 0.38), implies the existence of two five‐coordinate tin sites in the centrosymmetric dimer. The assignment has been corroborated by X‐ray diffraction analysis on the compound that has been crystallized from ethanol; the crystal structure shows two tin atoms in cis‐C₂SnO₃ trigonal‐bipyramidal coordination [C‐Sn‐C = 131.5(1), 131.3(2) °]. The analysis also reveals the presence of two lattice ethanol molecules that are hydrogen‐bonded to the dimer [OO = 2.779(5) Å]. When exposed to air, the distannoxane loses ethanol. The unsolvated distannoxane is more active than cis‐platin when screened against MCF‐7 (mammary cancer), EVSA‐T (mammary cancer), WiDr (colon cancer), IGROV (ovarian cancer), M19 MEL (melanoma), A498 (renal cancer) and H226 (lung cancer) cell lines. Copyright © 2000 John Wiley & Sons, Ltd.     

氮芥苯甲酸氧化二丁基锡复合物的合成、晶体结构及其体外抗癌活性研究

Di-n-butyltin oxide reacted with p-[N,N-bis（2-chloroethyl）amino]benzoic acid to yield the compounds {{4-[（ClCH2CH2）2N]C6H4COOSnBu2}2O}2 （1） and {4-[（ClCH2CH2）2N]C6H4COO}2SnBu2 （2）, which have been characterized by IR and ^1H NMR spectra. The X-ray diffractional studies of 1 reveal the structure of the molecule to be a dimer, in which the two Bu2Sn groups were linked via two bridging oxygen atoms to form a central Bu4Sn2O2 unit. And the tin atom adopts two carbons from two n-butyl groups and three oxygen atoms from the acid and the bridging oxygen. In vitro test showed compound 1 to exhibit high cytotoxicity against P388 and HL-60 cell lines.     

Synthesis,Structure and in vitro Antitumor Activity of a Multinuclear Diorganotin(IV) Complex [(n‐Bu)4Sn2{2,5‐F2C6H3C(O)NHO}2{2,5‐F2C6H3C(NO)O}]2

A new multinuclear dibutyltin(IV) complex [(n‐Bu)₄Sn₂{2,5‐F₂C₆H₃C(?O)NHO}₂{2,5‐F₂C₆H₃C(?NO)O}]₂ 1 , was synthesized and structurally characterized by melting point measurement, elemental analysis, FT‐IR, ¹H, ¹³C, ¹¹⁹Sn NMR spectroscopies, and X‐ray diffraction analysis. The complex exhibited in vitro antitumor activity against a murine sarcoma carcinoma cell line (S‐180), which was higher than that of 5‐fluorouracil (5‐Fu), currently used clinically as an antitumor agent.     

Synthesis,characterization and cytotoxic activity of 5,10,15,20‐tetrakis[4‐(triorganostannyloxy)phenyl]porphyrins

5,10,15,20‐Tetrakis[4‐(triorganostannyloxy)phenyl]porphyrins, (R₃SnO)₄TPP [2, R = Cy (a), Ph (b), PhC(CH₃)₂CH₂ (c)], have been synthesized by the condensation of 4‐(triorganostannyloxy)benzaldehyde, 4‐(R₃SnO)C₆H₄CHO (1), with pyrrole in the presence of BF₃ followed by oxidation by p‐chloranil and characterized by means of elemental analysis, IR, UV–visible and NMR (¹H, ¹³C and ¹¹⁹Sn) spectra. The results of X‐ray single‐crystal diffraction show that 1a and 1b possess a trans‐C₃SnO₂ trigonal bipyramidal geometry with the axial positions occupied by the phenolate oxygen and formyl group oxygen of an adjacent molecule and form a one‐dimensional zigzag chain. In 2a, the macrocyclic core of the porphyrin is coplanar and each tin atom possesses a distorted tetrahedral geometry. These compounds (1 and 2) have potent in vitro cytotoxic activity against two human tumor cell lines – CoLo205 and MCF‐7 – and the activity decreases in the order Ph > Cy > PhC(CH₃)₂CH₂ for the R group bound to tin. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis,structure and in vitro cytotoxicity testing of some 1,3,4‐oxadiazoline derivatives from 2‐hydroxy‐5‐iodobenzoic acid

The syntheses of nine new 5‐iodosalicylic acid‐based 1,3,4‐oxadiazoline derivatives starting from methyl salicylate are described. These compounds are 2‐[4‐acetyl‐5‐methyl‐5‐(3‐nitrophenyl)‐4,5‐dihydro‐1,3,4‐oxadiazol‐2‐yl]‐4‐iodophenyl acetate ( 6a ), 2‐[4‐acetyl‐5‐methyl‐5‐(4‐nitrophenyl)‐4,5‐dihydro‐1,3,4‐oxadiazol‐2‐yl]‐4‐iodophenyl acetate ( 6b ), 2‐(4‐acetyl‐5‐methyl‐5‐phenyl‐4,5‐dihydro‐1,3,4‐oxadiazol‐2‐yl)‐4‐iodophenyl acetate, C₁₉H₁₇IN₂O₄ ( 6c ), 2‐[4‐acetyl‐5‐(4‐fluorophenyl)‐5‐methyl‐4,5‐dihydro‐1,3,4‐oxadiazol‐2‐yl]‐4‐iodophenyl acetate, C₁₉H₁₆FIN₂O₄ ( 6d ), 2‐[4‐acetyl‐5‐(4‐chlorophenyl)‐5‐methyl‐4,5‐dihydro‐1,3,4‐oxadiazol‐2‐yl]‐4‐iodophenyl acetate, C₁₉H₁₆ClIN₂O₄ ( 6e ), 2‐[4‐acetyl‐5‐(3‐bromophenyl)‐5‐methyl‐4,5‐dihydro‐1,3,4‐oxadiazol‐2‐yl]‐4‐iodophenyl acetate ( 6f ), 2‐[4‐acetyl‐5‐(4‐bromophenyl)‐5‐methyl‐4,5‐dihydro‐1,3,4‐oxadiazol‐2‐yl]‐4‐iodophenyl acetate ( 6g ), 2‐[4‐acetyl‐5‐methyl‐5‐(4‐methylphenyl)‐4,5‐dihydro‐1,3,4‐oxadiazol‐2‐yl]‐4‐iodophenyl acetate ( 6h ) and 2‐[5‐(4‐acetamidophenyl)‐4‐acetyl‐5‐methyl‐4,5‐dihydro‐1,3,4‐oxadiazol‐2‐yl]‐4‐iodophenyl acetate ( 6i ). The compounds were characterized by mass, ¹H NMR and ¹³C NMR spectroscopies. Single‐crystal X‐ray diffraction studies were also carried out for 6c , 6d and 6e . Compounds 6c and 6d are isomorphous, with the 1,3,4‐oxadiazoline ring having an envelope conformation, where the disubstituted C atom is the flap. The packing is determined by C—H…O, C—H…π and I…π interactions. For 6e , the 1,3,4‐oxadiazoline ring is almost planar. In the packing, Cl…π interactions are observed, while the I atom is not involved in short interactions. Compounds 6d , 6e , 6f and 6h show good inhibiting abilities on the human cancer cell lines KB and Hep‐G2, with IC₅₀ values of 0.9–4.5 µM.     

Tetrakis(bicyclo[2.2.2]oct‐2‐ene)‐Fused Calix[4]pyrrole

Tetrakis(bicyclo[2.2.2]oct‐2‐ene)‐fused calix[4]pyrrole, 5 , was obtained starting from (E)‐1,2‐bis(phenylsulfonyl)ethylene. This new calixpyrrole derivative is the prospective precursor of tetrabenzocalix[4]pyrrole, a potential ion‐pair receptor and an attractive species as a possible deep‐walled ‘molecular container’.     

Synthesis, crystal structure and in vitro antitumor activity of di-n-butyltin 4′-(7-oxabicyclo [2,2,1]-5-heptane-2,3-dicarboximide) benzoates

Dibutyltin(IV) oxide reacts with the cantharidin analogue, 4′-(7-oxabicyclo [2,2,1]-5-heptane-2,3-dicarboximide) benzoic acid, A, to give the complexes [(p-C₈H₈NO₃-C₆H₄-COOBu₂Sn)₂O]₂ (1) and (p-C₈H₈NO₃-C₆H₄-COO)₂SnBu₂ (2) which had been characterized by IR and ¹H, ¹³C, ¹¹⁹Sn NMR. Single X-ray crystal structure analysis has been determined for compound (1), which was analogue to most other [(RCOOBu₂Sn)₂O]₂. The dimer features central of Bu₄Sn₂O₂ unit with the two Bu₂Sn groups being linked via bridging oxygen atom. Each tin atom adopts distorted trigonal bipyramidal structures via two carbons from a dibutyl moiety and three oxygen atoms from cantharidin derivative and bridging oxygen atom. In vitro tests show compounds 1 and 2 exhibit high cytotoxicity against P388 and HL-60.     

Crystal Structure and Antitumor Activity of Tri[2- [N-(4''''-methyl-benzylsulfonyl)amino]ethyl]-amine

1 INTRODUCTION The supramolecular architectures of tripodal ligands with special cavities have attracted much attention of chemists and biochemists because of their interesting structures and possible properties such as ion and molecular recognition, selective inclusion and important biological function[1～5]. However, their potential applications in supra- molecular and biological chemistry for constructing various complexes have not been clearly realized until recent years. Few crystal…     

Di‐n‐butyltin aminoarylcarboxylates: structure,properties and in vitro antitumor activity

The properties and structures of the tetranuclear dibutyltin complexes [Sn₄(µ₃‐O)₂(C₄H₉‐n)₈­{OOCC₆H₃(NH₂)₂‐3,4}₄] (1), [Sn₄(µ₃‐O)₂(C₄H₉‐n)₈{OOCC₆H₃(NH₂)₂‐3,5}₄] (2), [Sn₄(µ₃‐O)₂(C₄H₉‐n)₈­{OOC‐2‐C₆H₄N?NC₆H₄N(CH₃)₂‐4}₄] (3) are described. Complex 3 adopts a structure with a tetranuclear Sn₄(µ₃‐O)₂ core. All tin atoms are five‐coordinate and form bonds with three oxygen atoms and two butyl ligands. Two carboxylates are bridging and two are terminal ligands. IR and NMR spectra indicate that the same structure is adopted by complexes 1 and 2. The molecular and electronic structures of complex 1 of C _i symmetry have been studied using the semi‐empirical PM3 formalism. The calculated structure and bond distances agree with X‐ray data. All complexes are effective antitumor agents. Copyright © 2002 John Wiley & Sons, Ltd.     

Crystal Structure and Antitumor Activity of Tri[2-[N-（4′-methyl-benzylsulfonyl）amino]ethyl]-amine

The crystal structure of the title compound (C27H38N4O7S3, Mr = 626.79) has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pīwith a = 9.411(1), b = 11.645(2), c = 14.672(2) (A。), α = 91.80(1), β = 95.36(1), γ =104.56(1)o, V = 1547.0 (A。)3, Z = 2, Dc = 1.346 g/cm3, λ = 0.71073 (A。), μ(MoKα) = 0.289 mm－1 and F(000) = 664. The structure was refined to R = 0.0406 and wR = 0.1177 for 4103 observed reflections with I > 2σ(I). X-ray diffraction analysis reveals that the title compound is a practically distorted tetrahedron and each molecule contains one lattice H2O by hydrogen bond. The antitumor activity of the title compound against HL-60 human leukemia cells has also been studied by MTT method.     

Synthesis of 7‐azabicyclo[2.2.1]heptane derivatives by transformation of tropinone

The bromination (CuBr₂, AcOEt/CHCI₃) plus Favorskii rearrangement (EtONa, EtOH) of N‐carbethoxytropinone ( 4 ), readily available from tropinone ( 3 ), affords mixtures of exo‐ and endo‐isomers of 2,7‐dicarbethoxy‐7‐azabicyclo[2.2.1]heptane ( 1b ) in variable and moderate chemical yield (maximum 37%). The bromination (Br₂, HBr/AcOH) reaction of compound 4 gives ethyl trans‐2,4‐dibromo‐3‐oxo‐8‐azabicyclo[3.2.1]octane‐8‐carboxylate ( 5 ) in 99% yield, a product that on Favorskii rearrangement (EtONa/EtOH) affords ethyl 2,2‐diethoxy‐3‐oxo‐8‐azabicyclo[3.2.1]octane‐8‐carboxylate in moderate yield ( 6 ) (52%).     

Synthesis,characterization, X‐ray crystal structure and in vitro antitumour activity of sodium bis(2‐(3′,6′,9′‐trioxadecyl)‐1,2‐dicarba‐closo‐dodecaborane‐1‐carboxylato)triphenylstannate

Sodium bis[2‐(3′,6′,9′‐trioxadecyl)‐1,2‐dicarba‐closo‐dodecaborane‐1‐carboxylato]triphenylstannate, [(CH₃OCH₂CH₂OCH₂CH₂OCH₂CH₂)‐1,2‐C₂B₁₀H₁₀‐9‐COO)₂SnPh₃]^? Na⁺, compound 1, was synthesized by the 1:1 condensation of triphenyltin(IV) hydroxide with 2‐(3′,6′,9′‐trioxadecyl)‐1,2‐dicarba‐closo‐dodecaborane‐1‐carboxylic acid and crystallized in the presence of sodium bicarbonate. Its structure was determined by spectroscopy, elemental analysis and X‐ray diffraction. The structure of 1 consists of trigonal bipyramidal [Sn(Ph)₃(L)₂]^? anions and Na⁺ cations coordinated by oxygen atoms of polyoxaalkyl chains of different stannate anions, forming cation–anion chains elongated along the c axis. Compound 1 is significantly more active in vitro against seven tumour cell lines of human origin than 5‐fluorouracil, cis‐platin, carboplatin, and previously reported organotin carboranecarboxylates, but is less active than organotin polyoxaalkylcarboxylates. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis and Characterization of Antimony(III) Complexes of Thioamides,and Crystal Structure of {[Sb(Imt)2Cl2]2((2‐Imt)}Cl2(Imt=Imidazolidine‐2‐thione)

Antimony(III) complexes of thioamides [thioamides=thiourea (Tu), N,N′‐dimethylthiourea (Dmtu), tetramethylthiourea (Tmtu), imidazolidine‐2‐thione (Imt) and diazinane‐2‐thione (Diaz)] with the general formulae, Sb(thione)_nCl₃ (n=1, 2, 2.5, 3) were prepared and characterized by elemental analysis, IR and NMR (¹H, ¹³C) spectroscopic methods. The spectral data of the complexes are consistent with the coordination of the thiones to antimony(III). The crystal structure of one of them, {[Sb(Imt)₂Cl₂]₂(μ₂‐Imt)}Cl₂ ( 1 ), was determined by X‐ray crystallography, which shows that the complex is dinuclear consisting of two [Sb(Imt)₂Cl₂] units bridged by an Imt molecule. In 1 , the antimony atom is bonded to two chlorine atoms, two sulfur atoms of coordinated Imt molecules and one sulfur atom of a bridging Imt molecule. The antimony environment can be considered to be distorted octahedral with one Cl^? ion weakly bound to antimony.     

(Z)-1[2-(苯基二溴化锡基)乙烯基]-1-环己醇的合成及晶体结构

报道了标题化合物〔C14H18Br2OSn〕的合成及晶体结构。该晶体属于单斜晶系，空间点群为P21/c，晶胞参数a=11.711(2)，b=9．114（2），c=16．864（3）A，β=102.94（1）°，V=1604.55（0）A3，Mr=480．78，Z=4，Dc=1．99g／cm3，u=65．20cm－1，F（000）=919，R=0．050，Rw=0．050．晶体结构由直接法解出。标题化合物分子中的锡原子被配体的2个碳、2个溴和1个氧原子配位，配位原子呈畸变的三角双锥构型，环已基为椅式构象，五员杂环为信封构象。     

Crystallographic report: Dimeric tetraphenyl‐1‐hydroxo‐3‐trifluoromethanesulfonatodistannoxane, [Ph2(HO)SnOSn(O3SCF3)Ph2]2

The molecular structure of the title compound, obtained by an adventitious phenyl group cleavage of Ph₃SnOSnPh₃ with triflic acid, reveals discrete centrosymmetric units of [Ph₂(HO)SnOSn(O₃SCF₃)Ph₂]₂ that are loosely associated via hydrogen bonding. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis,crystal structures and anti‐inflammatory activity of fluorine‐substituted 1,4,5,6‐tetrahydrobenzo[h]quinazolin‐2‐amine derivatives

Two fluorine‐substituted 1,4,5,6‐tetrahydrobenzo[h]quinazolin‐2‐amine (BQA) derivatives, namely 2‐amino‐4‐(2‐fluorophenyl)‐9‐methoxy‐1,4,5,6‐tetrahydrobenzo[h]quinazolin‐3‐ium chloride, ( 8 ), and 2‐amino‐4‐(4‐fluorophenyl)‐9‐methoxy‐1,4,5,6‐tetrahydrobenzo[h]quinazolin‐3‐ium chloride, ( 9 ), both C₁₉H₁₉FN₃O⁺·Cl^?, were generated by Michael addition reactions between guanidine hydrochloride and the α,β‐unsaturated ketones (E)‐2‐(2‐fluorobenzylidene)‐7‐methoxy‐3,4‐dihydronaphthalen‐1(2H)‐one, C₁₈H₁₅FO₂, ( 6 ), and (E)‐2‐(4‐fluorobenzylidene)‐7‐methoxy‐3,4‐dihydronaphthalen‐1(2H)‐one, ( 7 ). Because both sides of α,β‐unsaturated ketones ( 6 ) or ( 7 ) can be attacked by guanidine, we obtained a pair of isomers in ( 8 ) and ( 9 ). Single‐crystal X‐ray diffraction indicates that each isomer has a chiral C atom and both ( 8 ) and ( 9 ) crystallize in the achiral space group P2₁/c. The chloride ion, as a hydrogen‐bond acceptor, plays an important role in the formation of multiple hydrogen bonds. Thus, adjacent molecules are connected through intermolecular hydrogen bonds to generate a banded structure. Furthermore, these bands are linked into an interesting 3D network via hydrogen bonds and π–π interactions. Fortunately, the solubilities of ( 8 ) and ( 9 ) were distinctly improved and can exceed 50 mg ml^?1 in water or PBS buffer system (pH 7.4) at room temperature. In addition, the results of an investigation of anti‐inflammatory activity show that ( 8 ) and ( 9 ), with o‐ and p‐fluoro substituents, respectively, display more potential for inhibitory effects on LPS‐induced NO secretion than starting ketones ( 6 ) and ( 7 ).