（E） -α- （ Methoxyimi no ） -2 - [ 1-（aryloxy） methyl ]-benzeneacetates, the analogues of Kresoxim-methyl, were ste- rcoselectively synthesized with the coupling reaction of 2-methylphenyldiazonium chloride and methyl 2-hydroxyiminoacetate in the presence of CuSO4/Na2SO3 as a key step, and it was first found that the coupling reaction could give the key intermediate material（ E）- and（Z）-methyl 2-（hydroxyimino）-2-o-tolylacetate with a molar ratio of 14： 1. The （E）-configurations of all these compounds were assigned on the basis of their 2D-NOESY spectra of ^1H NMR. The preliminary bioassays indicate that most of the compounds show an activity against a wide variety of fungi.
LI YanLIU JieZHOU Ye-bingZHANG Hong-quanCHEN Zu-xinLIU Zhao-jie
The title compound (C25H20FN5OS) has been synthesized and its crystal structure was determined by X-ray analysis. The crystal belongs to the orthorhombic system, space group Pbca with a = 10.327(4), b = 20.307(7), c = 21.234(9) ? α = 90, β = 90, γ = 90, V = 4453(3) 3, Z = 8, Dc = 1.365 g/cm3, Mr = 457.52, μ = 0.182 mm-1, F(000) = 1904, the final R = 0.0600 and wR = 0.0932 for 3911obsered reflections with I≥2σ(I). In the title compound, the S(1), C(1), C(2), C(3), C(4), C(5), N(1), N(2), N(3), N(4), O(1) and N(5) atoms form a mean planeⅠroughly within the average deviation of 0.0207 ? The dihedral angles between planesⅠandⅡ(C(19)C(20) C(21)C(22)C(23)C(24)),Ⅲ(C(6)C(7)C(8)C(9)C(10)C(11)) and Ⅳ(C(12)C(13)C(14) C(15)C(16)C(17)C(18)F(1)) are 21.40, 84.00 and 75.88, respectively.
Intestinal absorption of two oxovanadium complexes, vanadyl acetylacetonate (VO(acac)2) and bis (maltolato)-oxovanadium (VO(ma)2), has been compared using Caco-2 monolayers as a model system. The two compounds are similar in chemical structures but different in glucose-lowering effects. Our experimental results show that they are both transported via passive diffusion with apparent permeabilty coefficients (apical→basolateral) of (82.0 ± 6.7)× 10-7 and (14.6 ± 0.7)× 10-7 cm· s-1, respec-tively. This suggests that absorptivity of VO(acac)2 is much higher than that of VO(ma)2. This difference may be related to the metabolism of either compound, or its ligand, or both in the course of the transport. However, This difference in absorption will cause the great difference in bioavailability,which might account for better efficacy of VO(acac)2 than VO(ma)2 as the insulin-mimic agent.
