With the aim of discovering new molecules with K+ channel modulating properties, we have synthesized analogues of cromakalim, an important molecule which shows specific affinity toward the K+ channels, by replacing the benzopyrane ring with a benzoxazine moiety. As a part of this study, we have synthesized and characterized, in solution and in the solid state as well, the compound ethyl [2,2-dimethyl-6-(2-thiazolin-2-yl)-4H-l,4-benzoxazin-3-one-4-yl]butyrate (V). This compound exhibits in the solid state the following parameters: molecular formula C19H24N2O4S, triclinic, space group
, Mw = 376.5, a = 12.581(3) Å, b = 5.485(4) Å, c = 14.612(2) Å, = 91.85(2), = 108.9(3), = 82.04(4), V = 944.7 Å3, Z = 2, d = 1.323 g·cm–3. We describe here the synthesis and discuss the solid-state conformation of this new molecule; when tested on rat aorta ring precontracted with phenylephrine, the compound showed a concentration-dependent relaxation comparable to that measured for cromakalin taken as reference drug. 相似文献
Furans with side-chains at C(2) of various lengths terminating in diazomethyl keto groups are shown to undergo Rh2(OAc)4-catalyzed furan unravelling with the production of 2-cyclopentenone, 2-cyclohexenone, and 2-cycloheptenone to each of whose olefinic C(β) is attached an acrylaldehyde unit. Interposition of a cyclohexane or a methylaminomethylene moiety between the furan and diazoketo functions leads to the formation of a hydroindenone and pyrrolone, respectively. Replacement of the diazomethylketo terminus by an α-diazoethylketo system or a α-diazo-β-keto-ester function produces 2-substituted 2-cycloalkenones. A furan with a C4, diazo-methylketo-terminating side-chain at C(3) is described to be transformed into a 4-formylmethylidene-2-cyclohe-xenone. 相似文献
The 1H NMR spectra of the 2-trifluoroacetyl derivatives of benzo[b]furan and benzo[b]thiophene were recorded at 200MHz in two solvents, chloroform and acetone. A long-range coupling constant, 5J(HF), between the fluorine nuclei of the trifluoroacetyl group and H-3, of a value higher than 1 Hz, was measured. From the comparison of the 1H chemical shifts of, and the solvent effects on, the trifluoroacetyl compounds and those of the corresponding 2-acetyl derivatives, and on the basis of an empirical interpretation of the 5J(HF) coupling constant, a predominant Z conformation was tentatively assigned to these derivatives. 相似文献
Given a finite ordered set of items and an unknown distinguished subset P of up to p positive elements, identify the items in P by asking the least number of queries of the type ‘‘does the subset Q intersect P?”, where Q is a subset of consecutive elements of {1,2,…,n}. This problem arises, e.g., in computational biology, in a particular method for determining splice sites in genes. We consider time-efficient algorithms where queries are arranged in a fixed number s of stages: In each stage, queries are performed in parallel. In a recent bioinformatics paper, we proved optimality (subject to lower-order terms) with respect to the number of queries, of some strategies for the special cases p=1 or s=2. Exploiting new ideas, we are now able to provide improved lower bounds for any p?2 and s?3 and improved upper bounds for larger s. Most notably, our new bounds converge as s grows. Our new query scheme uses overlapping query intervals within a stage, which is effective for large enough s. This contrasts with our previous results for s?2 where optimal strategies were implemented by disjoint queries. The main open problem is whether overlaps help already in the case of small s?3. Anyway, the remaining gaps between the current upper and lower bounds for any fixed s?3 amount to small constant factors in the main term. The paper ends with a discussion of practical implications in the case that the positive elements are well separated. 相似文献
The results obtained using different semi-empirical approaches, namely EHMO, IEHMO, CNDO/2 and INDO, in the calculation of spin–spin coupling constants within the framework of the one-electron MO approximation are systematically compared in the case of several classes of organic molecules. While, at a semi-empirical level SCF methods normally provide satisfactory wave function, the use of the simple EHMO seems better able to satisfy the problem connected with the calculation of spin–spin coupling constants, expecially when an appropriate set of AO's is chosen, in order to avoid parametrisation of Dirac monocentric integrals. Charge iteration (IEHMO) seems to improve the results slightly only when heteroatoms are present, but the complexity introduced into the calculations and the greatly increased computer time do not justify the slight improvement achieved, particularly as the method is applied to large molecules and organometallic compounds. 相似文献
Under solvent-free conditions, thiosalicylic acid (2) efficiently self-promotes the thiolysis of 1,2-epoxides 1, anti-stereoselectively and generally totally beta-regioselectively. The resulting beta-hydroxysulfide products 3 have been obtained in very good yields. Benzo[e]1,4-oxathiepin-5-ones 4 have been easily prepared in a regio- and diasteroselective manner and in satisfactory yields under SFC by a one-pot protocol including nucleophilic ring opening of 1,2-epoxides 1 by thiosalicylic acid (2) and thermally induced lactonization of beta-hydroxy arylsulfides 3. Solvent-free condition and the absence of any catalyst make this procedure atom-economical and environmentally friendly. 相似文献
Environmentally benign synthesis of novel pegylated polyphenolics, by combining the extraordinary selectivities of a lipase and an oxidase to develop polymeric electrolytes for applications in dye sensitised solar cells. 相似文献
Self‐doped sulfonated polyaniline (PSA) has been synthesized on the surface of micellar nanoparticles made from positively charged surfactants by biocatalysis. The conformation forced by the electrostatic charge interactions between the positively charged micelle and the negatively charged PSA increases the conductivity of the PSA by three orders of magnitude. The pure PSA recovered from ion exchange, however, shows quite similar electrical properties compared with sulfonated polyanilines reported earlier. The increased conductivity of PSA complexes is as a result of the increased charge carrier concentration caused by a certain conformational locking.