Thermolysis of a benzocyclobutene derivative () prepared from norcamphor produced stereoselectively a tetracyclic compound (), which was converted to a lactone () having correct stereochemistry at C7, C8, C9, C11, C13, and C14 positions of (±)-klaineanone. 相似文献
Six 20,24-dimethylscalarane derivatives (, , , , , and ) have been isolated from the Neo Guinean sponge Carteriospongia foliascens. Compound is identical with a C27 tetracyclic terpene previously isolated from an Australian specimen of the same sponge. The five other derivatives are new and their structures have been established on the basis of their spectral data. The structure of was confirmed by single-crystal X-ray diffraction and that of by chemical correlation with . The configuration at C-4 for all these compounds has been determined through 13C NMR data. Evidence leading to reverse the configuration at this centre in previously reported C27 tetracyclic terpenes is discussed. An ecological function is suggested for these molecules. 相似文献
The 1H and 13C nmr spectra of , -9-oxobicyclo[3.3.1]nonane-2,4-dicarboxylic acid, 3, in DMSO-d6 or alkaline D2O, clearly show that it exists in a --conformation with carboxyl groups, thus being the first case of - preference of a bicyclo[3.3.1] nonan-9-one due to the presence of ,-2,4- substituents. 相似文献
Incorporations of [1-13C]?, [2-13C]?, [1,2-13C2]-acetates and [13C]-methionine into anditomin, a metabolite of , indicate its formation by a mixed polyketide-terpenoid biosynthetic pathway similar to that elucidated for andibenin; observations are made on the possible biosynthetic relationship of the metabolites with austin and terretonin, mycotoxins recently isolated from and respectively. 相似文献
Comparative study on the proton and carbon NMR spectra for a series of - and -acyl substituted monohydroxypyridines (C5H4NO: =-H, -CHO, -COCH3, -COC(CH3)3, -COCF3, -COC6H5, -SO2CH3, -SO2C6H4CH3 is reported. p]Characteristic 1H, 13 NMR and IR spectral features allow simple and unambiguous distinction between the isomeric - and/or -acyl-derivatives of 2-, 3- and 4-hydroxypyridines, so that both forms can clearly be identified when tautomeric equilibria occur, since the tautomerism rate is slow on the NMR time scale 相似文献
Vincadifformine and its 10-substituted analogs give in good yields 16-nitro indolenines of which the reactivity has been studied. By a two step process (demethoxycarbonylation and chloration on C16) nitro-indolenine leads to gem-chloro-nitro . By an other two step sequence (NaBH3CN, NaH) nitro-indo-lenine yields compound via a 16 → 1 COOCH3 migration. By heating compounds and in CF3COOH, rearranged products are obtained : vincamione from and azahomoaspidospermane from . Mechanisms of formation of , and are discussed. 相似文献
For 12-- locked retinal analogues, thermal equilibria are established between 11-, 13--1c and 13--2c and between 9-, 11-, 13--1d and 9-, 13--2d; a photoisomerization occurs to transform 2c to --2a and 2d to 9--2b 相似文献
The structure of sarothamnoside (genistein 7,4′-di-O-[4-O-β-D-glucopyranosyl-β-D-apiofuranoside]), a new isoflavone glycoside from and , patens, has been established by spectral analysis, mainly 13C NMR. 相似文献
Single crystals of the title compounds have been grown by the Czochralski technique. Pb4P2O9 crystallizes in the space group with the parameters a = 9.4812 Å, b = 7.1303 Å, c = 14.390 Å, β = 104.51° and Pb8P2O13 in with a = 10.641 Å, b = 10.206Å c = 14.342 Å, β = 98.34°. 相似文献
The 6-phenyl-dihydro-α-pyrone moiety of psilotin is formed from [2′,3′-13C2,1′-14C,-4-3H]phenylalanine in the plant with retention of all the isotopes. 相似文献
tert-Butyl azidoformate () reacts with the conjugate bases of , , (R1 = R2 = CH3), and (R1 = CH3, R2 = H) to give products [, , , and , respectively] in addition to the expected N-(tert-butoxycarbonyl)indole derivatives. 相似文献
The C4erythro and threo diols (7) and (8) are converted either into the chiral epoxides (13) and (15) or into the enantiomers (14) and (16); the epoxide (13) is used as chiral synthon for the preparation of (3,4) 4-methyl-3-heptanol (21). 相似文献
The Sharpless asymmetric epoxidation was used for the synthesis of D--dihydrosphingosine triacetate and (2, 3, 5)-2-acetamino-5,9-dimethyl-8-decene-1,3-diol, whose 13C-NMR study coupled with biogenetic consideration enabled us to propose (2, 3, 5,13, 14)-stereochemistry for aplidiasphingosine. 相似文献
Reaction of the amines (CF3)2NX (X=Cl,Br) with norbornadiene either in solvent (CH2Cl2) at ?78 °C in the dark or in the vapour phase at 20 °C in daylight gives a mixture of 3-halogeno-5-(-bistrifluoromethylamino)nortricyclene (, -and , -isomers) and -5-(-bistrifluoromethylamino)- -7-halogenonorbornene in quantitative yield formed halonium ion addition to the diene. The reaction of the amine (CF3)2NBr in solvent Me2O or Et2O at ?78 °C in the dark gives the same products in low yield, together with 3-bromo-5-alkoxynortricyclene (, - and , -isomers) and the amine (CF3)2NR (R=Me, Et) in high yield. 相似文献
The lithium polyfluorobenzenesulphinates, Li O2SR (R = C6F5, -HC6F4, -HC6F4, or -HC6F4), and the dilithium tetrafluorobenzenedisulphinates, - and -(LiO2S)2C6F4, have been prepared by reaction of the appropriate polyfluoroaryllithium compounds with sulphur dioxide. All compounds were isolated as hydrates and gave the corresponding -benzylthiouronium salts on treatment with -benzylthiouronium chloride. From reactions of the lithium sulphinates with suitable mercuric salts in water, generally at room temperature, the derivatives RHgX (R = C6F5, X = Cl, Br, CH3CO2, or PhSO2; R = -HC6F4, X = Cl, Br, or CH3CO2; R = -HC6F4, X = Cl or Br; R = -HC6F4, X = Cl), -(XHg)2C6F4 (X = Cl, Br, or CH3CO2), and -(XHg)2C6X4 (X = Cl or Br) have been prepared. Similarly, the bispolyfluorophenylmercurials R2Hg (R = C6F5, -HC6F4, or -HC6F4) have been prepared from the corresponding lithium sulphinates and either mercuric salts or polyfluorophenylmercuric halides in aqueous -butanol. A possible mechanism for the sulphur dioxide elimination reactions is discussed. 相似文献
N.m.r. parameters for nine (I-IX) -chloropolyfluorocyclohexa-2,5-dienylideneamines are reported and discussed; the magnitudes of the FF-coupling constants fall into the following ranges: 12 0-2.8; 13, 35 6.0-6.8; 14 <1; 15 0-2.6; 23, 34 25.5-27.2; 24 0-6.0; 25 0-1.2; 45 5.4-9.8 Hz (I) X = Y = Z = F; (II) X = OMe, Y = Z = F; (III) X - CF3, Y = Z = F; (IV) X = Ph, Y = Z = F; (V) X = Cl, Y = Z = F; (VI) X = Br, Y = Z = F; (VII) X = Y = F, Z = Cl; (VIII) X = Y = F, Z = Br; (IX) X = Z = F, Y = H. The spectra of -methyl-4-chloropentafluorocyclohexa-2,5-dienyldeneamine have also been analysed. All the imines examined are configurationally stable at the nitrogen atom. 相似文献
The - and -2-amino-4-cyclohexene-1-carboxylic acids and react with imidates to give the condensed-skeleton, bicyclic - and -pyrimidin-4-ones and . The amino acids and were reduced to the -and -1, 3-aminoalcohoIs and , which were cyclized by means of imidates to the bicyclic tetrahydro-4-3,1-benzoxazines and , or were converted, the corresponding carbamates and into the tetrahydro-4-3,1-benzoxazin-2(1)-ones and . The 2-thioxo analogues and were prepared by cyclization of the dithiocarbamates obtained from the aminoalcohols and by treatment with carbon disulphide. The -aminoalcohol and its saturated analogue reacted with -chlorobenzaldehyde to furnish the hexahydro and octahydro-4-3,1-benzoxazine , respectively. 1H and 13C NMR studies showed that, similarly to the earlier-investigated analogues containing oxygen or unsubstituted nitrogen at position 1, the synthesized isomrs , , and occurred as the preferred conformer in the heterocyclic twist inverse form of -inside type ( C6-N bond) (B). In the isomers containing a saturated C-2 atom ( and ), H-2 and H-6 are in relative positions. 相似文献
Optical absorption and emission spectra are reported for single crystals of the cubic elpasolite Cs2NaSmCl6. The variable temperature spectra obtained at high resolution are assigned using energies and relative intensities. Transitions from the ground level, 6H to cystal fi levels of 6H-, 6F-, 4G-, 4F,, 4I, and 6P, are located and characterized. Intensity calculations are reported for magnetic dipole allowed transitions. The dominance of vibronic intensity in 6H→6F - and 6P, transitions is accounted for qualitatively through the ligand polarization model involving quadrupole metal (Sm3+)-ligand (Cl?) interaction mechanisms. The Eu″(6H)→E′(6H) Eu′(6F) no-phonon transition is postulated to be pure electric quadrupole allowed. The ground state magnetic moment is determined to be very small from magnetic circular dichroism (MCD) spectra.This study has led to the assignment of nearly all of the crystal field levels in the visible and IR region for Cs2NaSmCl6. A total of 27 such levels were identified, 17 from no-phonon transitions and the rest from vibronic transitions. The magnetic dipole intensity calculated using intermediate coupling Oh wavefunctions along with a crystal field analysis of the splitting pattern was used in the assignment of the levels. Vibronic bands were observed for all transitions and their vibrational symmetries were tentatively assigned. MCD data were used to determine the magnet moment of the ground state. 相似文献
A methoxy group on a styrene double bond directs O2 attack , giving 1,4 addition if the phenyl is , or ene reaction if a CH3 is . If no substituent is , 1,4 attack on the phenyl occurs at a slower rate. 相似文献
Subsolidus phase relations of ternary oxide systems containing divalent Fe, Mg, or Ni, trivalent Al, Cr, or Fe, and tetravalent Ti are characterized by solid solutions at metal/oxygen ratios , , and . At low temperatures only compounds with cubic or hexagonal close-packed oxygen and uniform oxygen coordination remain stable in the crystal structures NaCl, spinel, ilmenite-α-Al2O3, TiO2. The pseudobrookite phases FeTi2O5, MgTi2O5, Al2TiO5, Fe2TiO5, the V3O5 structure phase Cr2TiO5, and the Andersson phases Cr2Tin?2O2n?1 (n = 4,6,7,8,9) decompose. Additional phases with close-packed oxygen as predicted by a simple structure model for metal/oxygen ratios , , and do not form but presumably are important for nonstoichiometric solid solutions. Most differences between systems containing transition metals and the MgOAl2O3TiO2 system can be attributed to crystal field effects. 相似文献