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51.
[reaction: see text] The properties of the self-assembling aziadamantane inclusion complex with two alpha-cyclodextrin molecules have been exploited to perform a chemospecific monofunctionalization of alpha-cyclodextrin. The insertion of the photochemically generated carbenes takes place chemospecifically into the cyclodextrin's C-3-OH and C-2-OH bonds in 39 and 18% yield, respectively. This model reaction surpasses conventional methods in terms of yield as well as selectivity. 相似文献
52.
Preparation and Crystal Structure of LnAl3Br12 (Ln = La, Ce, Pr, Nd, Sm, Gd) and Thermal Decomposition to LnBr3 LnAl3Br12 (Ln = La, Ce, Pr, Nd, Sm, Gd) was prepared in crystalline form for the first time. The crystal structures of LaAl3Br12, PrAl3Br12, and NdAl3Br12 were determined on single crystals by X-ray methods. The isotypic compounds crystallize with trigonal symmetry, space group P 3112, Z = 3. A structural comparison to lanthanoide chloroaluminates of equal composition is given and thermal decomposition of LnAl3Br12 (Ln = Nd) to the corresponding lanthanoide tribromide is described. 相似文献
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The novel benzoxathiepinopyrimidines 6a-d were synthesized by ring transformations of 3-chloromethylsulfonylchromone ( 2 ) with amidines 3a-d . 相似文献
57.
Kozikowski AP Tückmantel W Böttcher G Romanczyk LJ 《The Journal of organic chemistry》2003,68(5):1641-1658
We report an improved synthesis of bis(5,7,3',4'-tetra-O-benzyl)epicatechin 4beta,8-dimer (3) from 5,7,3',4'-tetra-O-benzylepicatechin (1) and 5,7,3',4'-tetra-O-benzyl-4-(2-hydroxyethoxy)epicatechin (2) by replacing the previously employed Lewis acid, titanium tetrachloride, with the clay mineral Bentonite K-10. Under the same conditions, the benzyl-protected all-4beta,8-trimer, -tetramer, and -pentamer were obtained regioselectively from their lower homologues, albeit in rapidly decreasing yields. Reaction of 2 with an organoaluminum thiolate generated from 2-mercaptobenzothiazole and trimethylaluminum followed by acetylation produced 3-O-acetyl-4-[(2-benzothiazolyl)thio]-5,7,3',4'-tetra-O-benzylepicatechin (12). Medium-sized protected oligomers with 4beta,8-interflavan linkages are obtained in improved yields by using this compound as the electrophile and silver tetrafluoroborate as activator and are isolated by reversed-phase HPLC. Their deprotection by ester saponification followed by hydrogenolysis yielded the free procyanidins, which were characterized as their peracetates. The synthetic procyanidins are identical by normal-phase HPLC with fractions isolated from cocoa. The principle of chain extension by two members was demonstrated using a dimeric electrophile obtained by self-condensation of compound 12. Both the synthetic and natural pentamer 32 inhibit the growth of several breast cancer cell lines. Using the MDA MB 231 line, it was established that this outcome is based on the induction of cell cycle arrest in the G0/G1 phase. Subsequent cell death is more likely necrotic rather than apoptotic. Control experiments demonstrate that the polyphenol itself, rather than hydrogen peroxide potentially formed by its autoxidation, is the causative agent. 相似文献
58.
Werner Korsatko Christian Knopp Alfred Fuchsgruber Gustav Zigeuner 《Monatshefte für Chemie / Chemical Monthly》1976,35(2):745-755
The structures of tetrahydro-4-phenylspiro([1]benzopyran-2,4(1H)-pyrimidin)-2(3H)-ones and-thiones4 a, b resp., are proved by synthesis. 3-(2-methoxy-3,5-dimethylphenyl)-3-phenylpropionic acid11 b is prepared from 3,4-dihydro-6,8-dimethyl-4-phenylcoumarin10. The lithium salt of11 b reacts with isobutenyl-lithium to 1-(2-methoxy-3,5-dimethylphenyl)-5-methyl-1-phenyl-4-hexen-3-on12 a. 12 a is transferred with urea in acid medium and NH4CNS resp. in a mixture of dihydro-6-[2-(2-methoxy-3,5-dimethylphenyl)-2-phenyläthyl]-4,4-dimethyl-2(1H)-pyrimidinone and-thione13 a, b and tetrahydro-6-[2-(2-methoxy-3,5-dimethylphenyl)-2-phenyläthyliden]-4,4-dimethyl-2(1H)-pyrimidinone and-thione14 a, b resp.14 b leads to13 a, b with H2O2. Heating of13 a, 14 a and14 b resp. with pyridin-HCl leads to the spiro compounds4 a, b. 相似文献
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Winfried Mientus Hans-Georg Bartel Werner Haberditzl Hans-Joachim Spitzer 《Monatshefte für Chemie / Chemical Monthly》1980,111(3):597-606
A normalization of the wave functions by means of the theoretical exact Multiple-Scattering-(MS)-formalism is discussed within the framework of the SCF-X-SW-method. For the atomic and extramolecular regions the integrals of normalization can be easily determined and the results can be described by the corresponding electronic charges. The calculation of the integral of the interatomic region is problematic. The needful volume integration is only necessary to theGreen's functions of the wave functions and can be solved by means of the residual theory. The further analytical calculation of the surface integrals leads to a complicated formalism which can be numerically evaluated. 相似文献