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1.
In this study, we assessed the effects of tibolone and its metabolites on the production of a progesterone sensitive parameter, prolactin, in human endometrium stroma cells in vitro. In addition, the metabolism of the compounds by isolated stromal and epithelial cells was evaluated. The reference compounds, progesterone, Org 2058, and DHT all induced prolactin production. Oestradiol also slightly induced prolactin production and enhanced the response to Org 2058. Tibolone and Δ4-tibolone were similar with regard to potency to induce prolactin levels in the culture supernatant. Their potency was lower than that of Org 2058, similar to that of progesterone and higher than that of DHT. The efficacies of tibolone, Δ4-tibolone and Org 2058 were similar (200-fold induction). The estrogenic tibolone metabolites 3- and 3β-OH tibolone also significantly stimulated prolactin production. Their potency, however, was low since significance was reached only at the highest concentrations tested. The PR antagonist Org 31710 inhibited both tibolone- and Δ4-tibolone-induced prolactin production. The responses of tibolone and Δ4-tibolone were not affected by co-incubation with the androgen receptor antagonist OH-flutamide. The effect of tibolone, but not Δ4-tibolone, was antagonized approximately 50% in combination with the highest dose (1 μM) estrogen receptor antagonist, ICI 164384. The induction of prolactin by 3- and 3β-OH tibolone was antagonized most potently by Org 31710, but also by ICI 164384 and OH-flutamide. Tibolone is metabolized differently in epithelial and stromal cells of the human endometrium. The epithelial cells mostly produce the progestagenic/androgenic Δ4-tibolone. The stromal cells produce predominantly the 3β-OH tibolone, and some Δ4-tibolone, but the net effect observed with regard to prolactin production is progestagenic. When the metabolites 3-OH, 3β-OH, and Δ4-tibolone were added to the cultures no conversions were observed. The HPLC analyses showed no evidence for the production of sulfated metabolites. In conclusion, the net effects on endometrial stromal cells are predominantly progestagenic. Tibolone is converted by epithelial cells into Δ4-tibolone which displays progestagenic and androgenic activities, whereas in stromal cells also the estrogenic metabolites 3- and 3β-OH tibolone are formed. 相似文献
2.
From the cyclohexane extract of the leaves of Murraya exotica, five novel phytosterols: (23 S)-23-ethyl-24-methyl-cycloart-24(24 1)-en-3β-ol; 3β-methoxy-(23 S)-23-ethyl-24-methyl-cycloart-24(24 1)-en-3β-ol; (23 S)-23-ethyl-24-methyl-cycloart-24(24 1)-3β-yl acetate; (23ξ)-23-isopropyl-24-methyl-cycloart-25-en-3β-ol and (23ξ)-23-isopropyl-24-methyl-cycloart-25-en-3β-yl acetate have been isolated. Structural elucidation of the isolated compounds is based on physical, chemical and spectral analysis including IR, 1H and 13CNMR and mass spectrometry. 相似文献
3.
Reaction of RuCl(η 5-C 5H 5( pTol-DAB) with AgOTf (OTf = CF 3SO 3) in CH 2Cl 2 or THF and subsequent addition of L′ (L′ = ethene (a), dimethyl fumarate (b), fumaronitrile (c) or CO (d) led to the ionic complexes [Ru(η 5-C 5H 5)( pTol-DAB)(L′)][OTf] 2a, 2b and 2d and [Ru(η 5-C 5H 5)( pTol-DAB)(fumarontrile- N)][OTf] 5c. With the use of resonance Raman spectroscopy, the intense absorption bands of the complexes have been assigned to MLCT transitions to the iPr-DAB ligand. The X-ray structure determination of [Ru(η 5-C 5H 5)( pTol-DAB)(η 2-ethene)][CF 3SO 3] (2a) has been carried out. Crystal data for 2a: monoclinic, space group P2 1/ n with A = 10.840(1), b = 16.639(1), C = 14.463(2) Å, β = 109.6(1)°, V = 2465.6(5) Å 3, Z = 4. Complex 2a has a piano stool structure, with the Cp ring η 5-bonded, the pTol-DAB ligand σN, σN′ bonded (Ru-N distances 2.052(4) and 2.055(4) Å), and the ethene η 2-bonded to the ruthenium center (Ru-C distances 2.217(9) and 2.206(8) Å). The C = C bond of the ethene is almost coplanar with the plane of the Cp ring, and the angle between the plane of the Cp ring and the double of the ethene is 1.8(0.2)°. The reaction of [RuCl(η 5-C 5H 5)(PPh) 3 with AgOTf and ligands L′ = a and d led to [Ru(η 5-C 5H 5)(PPh 3) 2(L′)]OTf] (3a) and (3d), respectively. By variable temperature NMR spectroscopy the rottional barrier of ethene (a), dimethyl fumarate (b and fumaronitrile (c) in complexes [Ru(η 5-C 5H 5)(L 2)(η 2-alkene][OTf] with L 2 = iPr-DAB (a, 1b, 1c), pTol-DAB (2a, 2b) and L = PPh 3 (3a) was determined. For 1a, 1b and 2b the barrier is 41.5±0.5, 62±1 and 59±1 kJ mol −1, respectively. The intermediate exchange could not be reached for 1c, and the Δ G# was estimated to be at least 61 kJ mol −. For 2a and 3a the slow exchange could not be reached. The rotational barrier for 2a was estimated to be 40 kJ mol −. The rotational barier for methyl propiolate (HC≡CC(O)OCH 3) (k) in complex [Ru(η 5-C 5H 5)(iPr-DAB) η 2-HC≡CC(O)OCH 3)][OTf] (1 k) is 45.3±0.2 kJ mol −1. The collected data show that the barrier of rotational of the alkene in complexes 1a, 2a, 1b, 2b and 1c does not correlate with the strength of the metal-alkene interaction in the ground state. 相似文献
4.
The methanothermal reactions of M(CO) 6 (M = Mo, W) with Na 2S 2 gave a series of homonuclear clusters [{M(CO) 4} n(MS 4)] 2− (M=Mo, W; N=1, 2), i.e. (Ph 4P) 2[(CO) 4Mo(MoS 4)] (I), (Ph 4P) 2[(CO) 4W(WS 4)] (II), (Ph 4P) 2[(CO) 4Mo(MoS 4)Mo(CO) 4] (III) and (Ph 4P) 2[(CO) 4W(WS 4)W(CO) 4] (IV). The two dimers, I and II, as well as the two trimers, III and IV, are isostructural to each other, respectively. All compounds crystallize in the triclinic space group
with Z=2. The cell dimensions are: a=12.393(8), b=19.303(9), c=11.909(6) Å, =102.39(5), β=111.54(5), γ=73.61(5)°, V=2522(3) Å 3 at T=23 °C for I; a=12.390(3), b=19.314(4), c=11.866(2) Å, =102.66(2), β=111.49(1), γ=73.40(2)°, V=2511(1) Å 3 at T=23 °C for II; a=11.416(3), b=22.524(4), c=10.815(4) Å, =91.03(2), β=100.57(3), γ=88.96(2)°, V=2733(1) Å 3 at T=−100 °C for III, a=11.498(1), b=22.600(4), c=10.864(3) Å, =90.92(2), β=100.85(1), γ=88.58(1)°, V=2771(2) Å 3 at T=23 °C for IV. The dimers are each formed by the coordination of the tetrathiometalate as a bidentate chelating ligand to an M(CO) 4 fragment while addition of another M(CO) 4 fragment to the dimers results in the trimers. All compounds contain both tetrahedral and octahedral metal centers with the formal 6+ and 0 oxidation states, respectively. 相似文献
5.
Kinetic results are reported for intramolecular PPh 3 substitution reactions of Mo(CO) 2(η 1-L)(PPh 3) 2(SO 2) to form Mo(CO) 2(η 2-L)(PPh 3)(SO 2) (L = DMPE = (Me) 2PC 2H 4P(Me) 2 and dppe=Ph 2PC 2H 4PPh 2) in THF solvent, and for intermolecular SO 2 substitutions in Mo(CO) 3(η 2-L)(η 2-SO 2) (L = 2,2′-bipyridine, dppe) with phosphorus ligands in CH 2Cl 2 solvent. Activation parameters for intramolecular PPh 3 substitution reactions: Δ H≠ values are 12.3 kcal/mol for dmpe and 16.7 kcal/mol for dppe; Δ S≠ values are −30.3 cal/mol K for dmpe and −16.4 cal/mol K for dppe. These results are consistent with an intramolecular associative mechanism. Substitutions of SO 2 in MO(CO) 3(η 2-L)(η 2-SO 2) complexes proceed by both dissociative and associative mechanisms. The facile associative pathways for the reactions are discussed in terms of the ability of SO 2 to accept a pair of electrons from the metal, with its bonding transformations of η 2-SO 2 to η 1-pyramidal SO 2, maintaining a stable 18-e count for the complex in its reaction transition state. The structure of Mo(CO) 2(dmpe)(PPh 3)(SO 2) was determined crystallographically: P2 1/ c, A=9.311(1), B = 16.344(2), C = 18.830(2) Å, ß=91.04(1)°, V=2865.1(7) Å 3, Z=4, R( F)=3.49%. 相似文献
6.
The reaction of RuCl 3(H 2O), with C 5Me 4CF 3J in refluxing EtOH gives [Ru 2(η 5-C 5Me 1CF 2) 2 (μ-Cl 2] (20 in 44% yield. Dimer 2 antiferromagnetic (−2 J=200 cm 1). The crystal structures of 2 (rhombohedral system, R3 space group, Z=9, R=0.0589) and [Rh 2(η 5-C 5Me 4CF 3( 2Cl 2(μ-Cl) 2] (3) (rhombohedral system.
space group, Z = 9, R = 0.0641) were solved; both complexes have dimeric structures with a trans arrangement of the η 5-C 5Me 4CF 4 rings. Comparison of the geometry of 2 and 3 with those of the corresponding η 5-C 5Me 5 complexes shows that lowering the ring symmetry causes significant distortion of the M 2(μ-Cl) 2 moiety. The analysis of the MCl 3 fragment conformations in 2 and 3 and in the η 5-C 5ME 5 analogues shows that they are correlated with the M---M distances. The Cl atoms are displaced by Br on reaction of 2 with KBr in MeOH to give the diamagnetic dimer [Ru 2(η 5-C 5Me 4CF 3) 2Br 2 (μ-Br 2] (4). Complex 2 reacts with O 2 in CH 2Cl 2 solution at ambient temperature to form a mixture of isomeric η 6-fulvene dimers [Ru 2(η 6-C 5Me 3CF 3 = CH 2) 2Cl 2(μ-Cl) 2] (5). Reactions of 5 with CO and allyl chloride give Ru(η 5-C 5Me 3CF 3CH 2Cl)(CO) 2Cl (6) and Ru(η 5-C 5Me 3CF 3CF 3CH 2Cl)(η 3-C 3H 5)Cl 2 (7) respectively. 相似文献
7.
Recent studies from our laboratory resolved two subtypes of the κ 2 binding site, termed κ 2a and κ 2b, using guinea pig, rat, and human brain membranes depleted of μ and δ receptors by pretreatment with the site-directed acylating agents BIT (μ-selective) and FIT (δ-selective). 6β-Iodo-3,14-dihydroxy-17-cyclopropylmethyl-4,5-epoxymorphinan (IOXY), an opioid antagonist that has high affinity for κ 2 sites, was radioiodinated to maximum specific activity (2200 Ci/mmol) and purified by high pressure liquid chromotography and used to characterize multiple κ 2 binding sites. The results indicated that [ 125I]IOXY, like [ 3H]bremazocine, selectively labels κ 2 binding sites in rat brain membranes pretreated with BIT and FIT. Using 100 n M [
-Ala 2-MePhe 4,Gly-ol 5]enkephalin to block [ 125I]IOXY binding to the κ 2b site, two subtypes of the κ 2a binding site were resolved, both in the absence and presence of 50 μ M 5′-guanylyimidodiphosphate. Viewed collectively, these results provide further evidence for heterogeneity of the κ opioid receptor, which may provide new targets for drug design, synthesis, and therapeutics. 相似文献
8.
Reaction of (NEt 4) 2MS 4 (M = Mo, W) with CuCl and KSCN (or NH 4SCN) in acetone or acetonitrile affords a new set of mixed metal–sulfur compounds: infinite anionic chains Cu 4(NCS) 5MS 43− (1,2), (CuNCS) 3WS 42− (3) and two dimensional polymeric dianions (CuNCS) 4MS 42− (4,5). Crystal of 1 (M = W) and 3 are triclinic, space group P1(1: a = 10.356(2), b = 15.039(1), c = 17.356(2)Å, = 78.27(1)°, β = 88.89(2)° and γ = 88.60(1)°, Z = 2, R = 0.04 for 3915 independent data;3: a = 8.449(2), b = 14.622(4), c = 15.809(8)Å, = 61.84(3)°, β = 73.67(3)° and γ = 78.23(2)°, Z = 2, R = 0.029 for 6585 independent data). Crystals of 4 (M = W) and 5 (M = Mo) are monoclinic, space group P2 1/ m, Z = 2 (4: a = 12.296(4), b = 14.794(4), c = 10.260(3)Åand β = 101.88(3)°, R = 0.034 for 4450 independent data;5: a = 12.306(2), b = 14.809(3), c = 10.257(2)Åand β = 101.99(3)°, R = 0.043 for 3078 independent data). The crystal structure determinations of 4 and 5 show that four edges of the tetrahedral MS 42− core are coordinated by copper atoms forming WS 4Cu 4 aggregates linked by eight-membered Cu(NCS) 2Cu rings. A two-dimensional network is thus formed in the diagonal (101) plane. The space between the anionic two-dimensional networks is filled with the NEt 4+ cations. Additional NCS groups lead to the [Cu 4(NCS) 5WS 4] 3− (1) trianion connected by NCS bridges forming pseudo-dimers. These latter are held together by weak CuS(NCS) interactions giving rise to infinite chains along a direction parallel to [100]. In contrast complex3 develops infinite chains from WS 4Cu 3 aggregates with the same Cu(NCS) 2Cu bridges as in 4 and 5. These chains are running along a direction parallel to [010]. The structural data of the different types of polymeric compounds containing MS 42− and CuNCS have been used to interpret vibrational spectroscopic data of the thiocyanate groups. 相似文献
9.
The ligand 1,4,7-triazacyclononane-1,4,7-tris[2′( R)-2′-propionate](-3)(( R)-tacntp 3−), binds stereospecifically to transition metal ions. The structures of the complexes [Cr(( R)-tacntp)]·NaBr and [Fe(( R)-tacntp)]·H 2O have been determined by X-ray crystallography. Both complexes have the Λ-configuration but the conformation of the chelate rings in Λ-[Cr(( R)-tacntp)] is (λ,λ,λ) with a geometry close to octahedral while in Λ-[Fe(( R)-tacntp)] it is (δ,δ,δ) and the geometry is closer to that of a trigonal prism. Chiral induction in the electron transfer reactions of Λ-[Co(( R)-tacntp)], Λ-[Fe(( R)-tacntp)] and Λ-[Mn(( R)-tacntp)] with [Co(( RR,SS)-chxn) 3] 2+ has been investigated. All three reactions are outer-sphere and four isomeric [Co(( RR,SS)-chxn) 3] 3+ products are identified in each case. The oxidants Λ-[Fe(( R)-tacntp)] and Λ-[Mn(( R)-tacntp)] show very similar selectivities, quite different from those of Λ-[Co(( R)-tacntp)]. Reasons for this behavior are discussed. 相似文献
10.
A series of cationic nickel complexes [(η 3-methally)Ni(PP(O))]SbF 6 (1–4) [PP(O) = Ph 2P(CH 2)P(O)Ph 2 (dppmO) (1), Ph 2P(CH 2) 2P(O)Ph 2 (dppeO) (2), Ph 2P(CH 2) 3P(O)Ph 2 (dpppO) (3), pTol 2P(CH 2)P(O) pTol 2 (dtolpmO) (4)] has been synthesized in good yields by treatment of [(η 3-methally)NiBr] 2 with biphosphine monoxides and AgSbF 6. The ligands are coordinated in a bidentate way. Starting from [(η 3-all)PdI] 2 the cationic complexes [(η 3-all)PP(O))]Y (8–14). [PP(O) = dppmO, dppeO, dpppO, dtolpmO;Y = BF 4, SbF 6, CF 3SO 3, pTolSO 3] were synthesized in good yields. The coordination mode of the ligand is dependent on the backbone and the anion, revealing a monodentate coordination with dppmO for stronger coordinating anions. The intermediates [(η 3-all)Pd(I)(PP(O)-κ 1- P)] (5–7) [PP(O) = dppmO (5), dppeO (6), dtolpmO (7)] were isolated and characterized. Neutral methyl complexes [(Cl)(Me)Pd(PP(O))] (15–18). [PP(O) = dppmO (15), dppeO (16), dpppO (17), dtolpmO (18)] can easily be obtained in high yields starting from [(cod)PdCl 2]. For dppmO two different routes are presented. The structure of [(Me)(Cl)Pd{;Ph 2P(CH 2-P(O)Ph 2-κ 2- P, O};] · CH 2Cl 2 (15) with the chlorine atom trans to phosphorus was determined by X-ray diffraction. 相似文献
11.
The reaction of [Re(NMe)Cl 3(PPh 3) 2] with the pentadentate [N 3S 2] ligand pyN 2H 2S 2---H 2 [2,6-bis(2-mercaptophenylamino)dimethylpyridine] (1) in the presence of triethylamine did not yield the anticipated six-coordinate complex [Re(NMe)(η 5-pyN 2HS 2)] (2), but rather resulted in cleavage of the Re(V)=NMe bond. A novel six-coordinate Re(IV) [N 3S]/[NS] complex [Re(η 4-SC 6H 4---2-NCH 2---C 5H 3N---C=NC 6H 4---2-S)(η 2-NHC 6H 4---2-S)] (4) was thus obtained with the simultaneous coordination of 2-aminothiophenol, a dianionic bidentate [NS] donor resulting from the decomposition of the parent ligand and ligand 3, a dianionic tetradentate [N 3S] donor formed by partial self-condensation and subsequent oxidation of the parent ligand 1. Crystal data for 4: C 25H 18N 4S 3Re·CH 2Cl 2, monoclinic, space group P2 1/ n, a=9.255(2) Å, b=11.181(2) Å, c=25.316(4) Å, β=97.434(3)°, V=2587.8(7) Å 3 and Z=4. 相似文献
12.
The Pt 2 (II) isomeric terminal hydrides [(CO)(H)Pt(μ-PBu t 2) 2Pt(PBu t 2H)]CF 3SO 3 (1a), and [(CO)Pt(μ-PBu t 2) 2Pt(PBu t 2H)(H)]CF 3SO 3 (1b), react rapidly with 1 atm of carbon monoxide to give the same mixture of two isomers of the Pt 2 (I) dicarbonyl [Pt 2(μ-PBu t 2)(CO) 2(PBu t 2H) 2]CF 3SO 3 (3-Pt); the solid state structure of the isomer bearing the carbonyl ligands pseudo- trans to the bridging phosphide was solved by X-ray diffraction. A remarkable difference was instead found between the reactivity of 1a and 1b towards carbon disulfide or isoprene. In both cases 1b reacts slowly to afford [Pt 2(μ-PBu t 2)(μ,η 2,η 2-CS 2)(PBu t 2H) 2]CF 3SO 3 (4-Pt), and [Pt 2(μ-PBu t 2)(μ,η 2,η 2-isoprene) (PBu t 2H) 2]CF 3SO 3 (6-Pt), respectively. In the same experimental conditions, 1a is totally inert. A common mechanism, proceeding through the preassociation of the incoming ligand followed by the P---H bond formation between one of the bridging P atoms and the hydride ligand, has been suggested for these reactions. 相似文献
13.
The phosphinoalkenes Ph 2P(CH 2) nCH=CH 2 ( n= 1, 2, 3) and phosphinoalkynes Ph 2P(CH 2) n C≡CR (R = H, N = 2, 3; R = CH 3, N = 1) have been prepared and reacted with the dirhodium complex (η−C 5H 5) 2Rh 2(μ−CO) (μ−η 2−CF 3C 2CF 3). Six new complexes of the type (ν−C 5H 5) 2(Rh 2(CO) (μ−η 1:η 1−CF 3C 2CF 3)L, where L is a P-coordinated phosphinoalkene, or phosphinoalkyne have been isolated and fully characterized; the carbonyl and phosphine ligands are predominantly trans on the Rh---Rh bond, but there is spectroscopic evidence that a small amount of the cis-isomer is formed also. Treatment of the dirhodium-phosphinoalkene complexes with (η−CH 3C 5H 4)Mn(CO) 2thf resulted in coordination of the manganese to the alkene function. The Rh 2---Mn complex [(η−C 5H 5) 2Rh 2(CO) (μ−η 1:η 1−CF 3C 2CF 3) {Ph 2P(CH 2) 3CH=CH 2} (η−CH 3C 5H 4)Mn(CO) 2] was fully characterized. Simi treatment of the dirhodium-phosphinoalkyne complexes with Co 2(CO) 8 resulted in the coordination of Co 2(CO) 6 to the alkyne function. The Rh 2---Co 2 complex [(η−C 5H 5) 2Rh 2(CO) (μ−η 1:η 1−CF 3C 2CF 3) {Ph 2PCH 2C≡CCH 3}Co 2(CO) 2], C 37H 25Co 2F 6O 7PRh 2, was fully characteriz spectroscopically, and the molecular structure of this complex was determined by a single crystal X-ray diffraction study. It is triclinic, space group
( Ci1, No. 2) with a = 18.454(6), B = 11.418(3), C = 10.124(3) Å, = 112.16(2), β = 102.34(3), γ = 91.62(3)°, Z = 2. Conventional R on | F| was 0.052 fo observed ( I > 3σ( I)) reflections. The Rh 2 and Co 2 parts of the molecule are distinct, the carbonyl and phosphine are mutually trans on the Rh---Rh bond, and the orientations of the alkynes are parallel for Rh 2 and perpendicular for Co 2. Attempts to induce Rh 2Co 2 cluster formation were unsuccessful. 相似文献
14.
In on-going studies of ‘classical’ and ring B-unsaturated oestrogens in equine pregnancy, the products of metabolism of [2,2,4,6,6- 2H 5]-testosterone and [16,16,17- 2H 3]-5,7-androstadiene-3β,17β-diol with equine placental subcellular preparations and allantochorionic villi have been identified. Using mixtures of unlabelled and [ 2H]-labelled steroid substrates has allowed the unequivocal identification of metabolites by twin-ion monitoring in gas chromatography–mass spectrometry (GC–MS). Two types of incubation were used: (i) static in vitro and (ii) dynamic in vitro. The latter involved the use of the Oxycell™ cartridge (Integra Bioscience Systems, St Albans, UK) whereby the tissue preparation was continuously supplied with supporting medium plus appropriate cofactors in the presence of uniform oxygenation. [ 2H 5]-Testosterone was converted into [ 2H 4]-oestradiol-17β, [ 2H 4]-oestrone and [ 2H 3]-6-dehydro-oestradiol-17 in both placental and chorionic villi preparations, but to a greater extent in the latter, confirming the importance of the chorionic villi in oestrogen production in the horse. On the basis of GC–MS characteristics (M+ m/z 477/482 (as O-methyl oxime-trimethyl silyl ether), evidence for 19-hydroxylation of testosterone was found in static incubations, while the presence of a 6-hydroxy-oestradiol-17 was recorded in dynamic incubations (twin peaks in the mass spectrum at m/z 504/507, the molecular ion M+). It was not possible to determine the configuration at C-6. The formation of small, but significant, quantities of [2H4]-17β-dihydroequilin was also shown, and a biosynthetic pathway is proposed. In static incubations of placental microsomal fractions, the 17β-dihydro forms of both equilin and equilenin were shown to be major metabolites of [2H3]-5,7-androstadiene-3,17-diol. Using static incubations of chorionic villi, the deuterated substrate was converted into the 17β-dihydro forms of both equilin and equilenin, together with an unidentified metabolite (base peak, m/z 504/506). The isomeric 17-dihydroequilins were also obtained using the dynamic in vitro incubation of equine chorionic villi, together with the 17β-isomer of dihydroequilenin. Confirmation of the identity of 17β-dihydroequilin and 17β-dihydroequilenin was obtained by co-injection of the authentic unlabelled steroids with the phenolic fraction obtained from various incubations. Increases in the peak areas for the non-deuterated steroids (ions at m/z 414 (17β-dihydroequilin) and 412 (17β-dihydroequilenin) (both as bis-trimethyl silyl ether derivatives) were observed. Biosynthetic pathways for formation of the ring B-unsaturated oestrogens from 5,7-androstadiene-3β,17β-diol are proposed. 相似文献
15.
New mixed metal complexes SrCu 2(O 2CR) 3(bdmap) 3 (R = CF 3 (1a), CH 3 (1b)) and a new dinuclear bismuth complex Bi 2(O 2CCH 3) 4(bdmap) 2(H 2O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF 2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi 2O 3 at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2 J = 34.0(8) cm −1. Crystal data for 1a: C 27H 51N 6O 9F 9Cu 2Sr/THF, monoclinic space group P2 1/ m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) Å 3, Z = 2; for 1b: C 27H 60N 6O 9Cu 2Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) Å 3, Z = 8; for 2: C 22H 48O 11N 4Bi 2, monoclinic space group P2 1/ c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) Å 3, Z = 4. 相似文献
16.
Biotransformation of the phytoestrogen [ 14C]genistein was investigated in male and female rats by application of narrow-bore radio-HPLC-MS n (LCQ, Finnigan) to determine intermediates in metabolism. Urine contained five metabolites, Gm1–Gm5, 24 h after dosing by gavage with [ 14C]genistein (4 mg kg −1). Structural analysis following ESI revealed molecular ions [M+H] + of m/z 447, 449, 273, and 271 for metabolites Gm2, Gm3, Gm5 and genistein, respectively and an [M–H] − of m/z 349 for Gm4. Metabolite structure was deduced by evaluation of product ion spectra derived from unlabelled and [ 14C]-labelled ions and sensitivity to treatment with β-glucuronidase. These studies indicated identity of metabolites with genistein glucuronide (Gm2), dihydrogenistein glucuronide (Gm3), genistein sulphate (Gm4) and dihydrogenistein (Gm5). Detection of the β-glucuronidase resistant major metabolite Gm1 by ESI was poor and so was analysed by negative ion APCI; this revealed a deprotonated molecular ion of m/z 165 which had chromatographic and mass spectral properties consistent with authentic 4-hydroxyphenyl-2-propionic acid, a novel metabolite of genistein. In vitro metabolism studies with anaerobic caecal cultures derived from male and female rats revealed metabolism of genistein to Gm1 via Gm5 and an additional metabolite (Gm6) which was identified from product ion spectra as 6′-hydroxy- O-desmethylangolensin. Biotransformation of genistein by both isolated hepatocytes and precision-cut liver slices was limited to glucuronidation of parent compound. Commonality of genistein metabolites found in rats with those reported in man suggest similar pathways of biotransformation, primarily involving gut micro-flora. 相似文献
17.
Three seriesof Rh(I) complexes of the type Tp 3R,5RRh(LL), with LL = 2 CO (1), norbornadiene (NBD) (2) and 1,5-cyclooctadiene (COD) (3) and the tris (pyrazolyl)borate (Tp) ligands 3R=5R=Me (a), 3R=CF 35R=Me (b); and 3R=5R=CF 3 (c) were synthesized and fully characterized by IR and multinuclear NMR spectroscopy. Three isomeric forms were identified in solutions of these complexes: two square-planar isomers with a κ 2-Tp 3R,5R ligand, the uncoordinated pyrazolyl ring occupying either an equatorial position (type A), or an axial position (type B), and a five-coordinate species with a κ 3, Tp 3R,5R ligand (type C). In the carbonyl complexes 1 the dynamic equilibria between these isomers are solvent dependent. Interestingly, solutions of complex 1c contained all three isomers simultaneously. 103Rh and 13C NMR spectral studies indicate that the NBD compounds, 2, preferentially form square-planar complexes when Tp CF3,Me and Tp CF3,CF3 are present, while for the COD complexes, 3, square-planar complexes are preferred for all three Tp-type ligands. The X-ray structure of Tp CF3,MeRh(CO) 2 (1b) was determined (spacce group C2/ c, a = 21.271(9), B = 11.004(3), C = 21.563(9) Å, β = 114.93(3)°, V=4577(3) Å 3, Z = 8, R = 3.41, Rw = 4.70). Its structure is of type B, with the third pyrazolyl ring axially placed, the N(4) being almost directly above the Rh atom but exerting only a weak Rh-N interaction. 相似文献
18.
The X-ray structure is reported for the complex Cu 2(medpco-2H)Cl 2, (medpco = N, N′-bis- N, N-dimethylaminoethyl)pyridine-2,6-dicarboxamide 1-oxide. The complex is triclinic,
, a=8.313(4), B=11.403(5), C=11.611(3) Å, =91.66(3), β=108.99(4), γ=109.60(3)° and Z=2. The deprotonated ligand (medpco-2H) 2− acts as a binulceating ligand, producing an N-oxide-bridged complex. Each copper in Cu 2(medpco-2H)Cl 2 is five-coordinate, being coordinated by a bridging N-oxide oxygen, a deprotonated amide nitrogen, a tertiary amine nitrogen and two bridging chlorides. The complex does not exhibit significant magnetic interaction, and this may be the result of distortion of the bridging geometry from planarity. A range of other, apparently N-oxide-bridged, complexes of the type Cu 2(medpco-2H)X 2 is reported. The complex Cu 2(medpco-2H)Br 2·H 2O is strongly antiferromagnetic, with magnetic data closely fitting the expected binuclear structure. 相似文献
19.
Two new sesquiterpene polyol esters with β-dihydroagarofuran skeleton were isolated from the root bark of Celastrus rosthornianus. Their structures were elucidated, mainly on the basis of spectral analyses, as 1 β-acetoxy-8β,9-dibenzoyloxy-6-hydroxy-2β(-methylbutanoyloxy)-β-dihydroagarofuran and 1β-acetoxy-9-benzoyloxy-8β-(β-furanocarbonyloxy)-6-hydroxy-2β(-methylbutanoyloxy)-β-dihydroagarofuran. The complete assignments of 13C NMR chemical shifts for both compounds on the basis of 1H- 13C chemical-shift correlation spectrum were also carried out. 相似文献
20.
The first 1:2 metal complexes of 2-(2′-pyridyl)quinoxaline (L) have been isolated. The physical and spectroscopic characteristics of the compounds [MCl 2L 2] (M = Ni, Cu, Cd) and [Cu IL 2](PF 6) are described. The structure of the copper(I) complex has been determined by X-ray diffraction methods. Crystals are orthorhombic, space group Pcnb with A = 11.014(2), B = 12.886(2), C = 17.806(4) Å, V = 2527.1(9) Å 3 and Z = 4. Refinement of the structure gave a final R factor of 0.046 ( Rw = 0.041) for 814 unique reflections having I > 2.0σ( I). The ligand L acts as a bidentate chelate, the ligated atoms being the pyridine nitrogen and the nearest quinoxaline nitrogen. The structure of [CuL 2] + consists of a distorted tetrahedral arrangement around the copper(I) atom with Cu---N bond lengths of 2.023(6) and 2.059(5) Å and the N---Cu---N angle of the chelating ligand equal to 80.6(2)°. A monomeric trans pseudo-octahedral stereochemistry is assigned for the [MCl 2L 2] complexes. 相似文献
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