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71.
S. Bhattacharya A.N. Mandal S.R. Ray Chaudhuri A. Chatterjee 《Tetrahedron letters》1984,25(28):3007-3010
An efficient ring contraction of stereoisomeric 1,2-benzo-4-bromo-3-hydroxycyclohept-1-ene and their derivatives (1a-e) to (2a-c) is reported, and a probable mechanism for this ring contraction has been suggested. 相似文献
72.
Floating spherical Gaussian orbital model is used to discuss the average electric polarisabilities and magnetic susceptibilities
of a series of hydrocarbons. It has been noticed that the core contributions are negligibly small and these quantities (average
electric polarisabilities and magnetic susceptibilities) can be well estimated from contributions localised on bond Gaussians. 相似文献
73.
Tripathi SK Patel U Roy D Sunoj RB Singh HB Wolmershäuser G Butcher RJ 《The Journal of organic chemistry》2005,70(23):9237-9247
[Structure: see text]. The synthesis and characterization of a series of organochalcogen (Se, Te) compounds derived from benzyl alcohol 13 are described. The synthesis of the key precursor dichalcogenides 15, 22, and 29 was achieved by the ortho-lithiation route. Selenide 18 was obtained by the reaction of the dilithiated derivative 14 with Se(dtc)2. Oxidation of 15 and 22 with H2O2 afforded the corresponding cyclic ester derivatives 17 and 24, respectively. Oxidation of selenide 18 with H2O2 affords the spirocyclic compound 19. The presence of intramolecular interactions in dichalcogenides 15 and 22 has been proven by single-crystal X-ray studies. The cyclic compounds 17 and 19 have also been characterized by single-crystal X-ray studies. GP(X)-like antioxidant activity of selenium compounds has been evaluated by the coupled bioassay method. Density functional theory calculations at the mPW1PW91 level on ditelluride 22 have identified a fairly strong nonbonding interaction between the hydroxy oxygen and tellurium atom. The second-order perturbation energy obtained through NBO analysis conveys the involvement of n(O) --> sigma(Te-Te) orbital overlap in nonbonding interaction. Post wave function analysis with the Atoms in Molecules (AIM) method identified distinct bond critical point in 15 and 22 and also indicated that the nonbonding interaction is predominantly covalent. Comparison between diselenide 15 and ditelluride 22 using the extent of orbital interaction as well as the value of electron density at the bond critical points unequivocally established that a ditelluride could be a better acceptor in nonbonding interaction, when the hydroxy group acts as the donor. 相似文献
74.
A new method for the preparation of the synthon (±)-2,6,7,7a-tetrahydro-1β-hydroxy-4-formyl-7aβ-methylindene (1,a) for the
total synthesis of steroids in both (±) and (+) forms, starting from the known β-ketoester, (±)-methyl 1β-t-butoxy-5,6,7,7a-tetrahydro-7aβ-methyl-5-keto-4-indancarboxylate (2,a) has been described. An alternative route to (1,a) has
been investigated. Although the compound, (±)-1β-hydroxy-5,6,7,7a-tetrahydro-7aβ-methyl-5-keto-4-methoxymethylindan (2,b)
could not be prepared, interesting pathways leading to two unexpected products, (±)-5,6,7,7a-tetrahydro-4,7a-dimethyl-5H-indene-1,5-dione
and (±)-2,6-diketo-3-methyltricyclo-(5,2,1,0)decan-8-ol (3 and 4), were encountered during an attempted annelation reaction
of the ketone, N-diethylamino-5-methoxypentan-3-one (6), with 2-methylcyclopentan-1,3-dione (5). Trapping of the intermediate,
(±)-3a,4,5,6,7,7a-hexahydro-3a-hydroxy-4-methylene-7a-methylindene-1,5-dione (7), through the formation of the adduct, (±)-3a,4,5,6,7,7a-hexahydro-3a-hydroxy-4-(1′,
3′-diketo-2′-methylcyclopentano-2′-methylene)-7a-methylindene-1,5-dione (8), established the mechanism of the formation of
the products (3 and 4). 相似文献
75.
Garner P Anderson JT Cox PB Klippenstein SJ Leslie R Scardovi N 《The Journal of organic chemistry》2002,67(17):6195-6209
The development of an effective chiral auxiliary for hydroxyalkyl radicals is delineated. Both the 2-tetrahydropyranyl (THP) and tri-O-benzyl-2-deoxy-alpha-D-glucopyranosyl (GLU) auxiliaries resulted in diastereoselective radical additions to methyl acrylate at -78 degrees C (ds = 6/1 and 11/1, respectively). The developing stereochemistry at the radical center was completely under auxiliary control. Correlation experiments showed that the D-GLU auxiliary led to attack on the radical Si-face. The selectivity of these radical additions dropped-off considerably when the more reactive 2-nitropropene trap was employed. Computational studies suggested that the observed facial selectivity was due primarily to entropic factors in the transition state but that a smaller temperature-dependent enthalpic contribution was also involved. It was hypothesized that incorporation of a quaternary center at C-6 (THP numbering) would restore the facial selectivity with more reactive radical traps by restricting the orientations available to the incoming alkene. In the event, the trans-6-tert-butyltetrahydropyranyl (tBu-THP) auxiliary resulted in very good diastereoselection with 2-nitropropene (ds = 35/1 at -78 degrees C, 15/1 at 0 degrees C, and 8/1 at RT) as did the tri-O-benzyl-6,6-dimethyl-2-alpha-D-deoxyglucopyranosyl (diMe-GLU) auxiliary during additions to ethyl alpha-trifluoroacetoxyacrylate (ds = 10/1 at 0 degrees C). A protocol for recovery of the sugar-derived chiral auxiliaries was also established. This work sets the stage for the development of a novel approach to 1, 3, 5.(2n + 1) polyols based on iterative radical homologation as well as the application of these pyranosidic auxiliaries to other synthetically important reactions. 相似文献
76.
Rupendranath Banerjee 《Transition Metal Chemistry》1985,10(4):147-148
Summary In low acid (0.02 M HClO4) media, Pb2+ ion strongly catalyses the aquation of Cr(ox)
3
3–
to givecis-Cr(ox)2(OH2)
2
–
ion. The catalytic efficiency of Pb2+ as represented by the second order rate constant, kpb (3.76 × 10–4 M–1 s–1 at 25 °C; I, 1.0 M perchlorate), for the Pb2+ catalysed path is remarkably higher than might be expected on the basis of Kpb-ox, the first formation constant for the lead-oxalate complex. This catalytic superiority of Pb2+ has been found to result mainly from a comparatively much lower H (65.2 ±0.8 kJ mol–1) value which more than compensates for the relatively unfavourable S value (–93.2 ±2.4 JK–1mol–1) for this catalysed path. This low S value is, however, in line with the entropy of hydration of Pb2+ ion. These facts, together with the different LFER plots, have been utilised to propose a plausible mechanism for such catalysed reactions. 相似文献
77.
A gaussian based model potential is used within the FSGO formalism to study a series of open-shell systems (e.g. LiH+, NaH+, Li+2 and LiNa+). Results for calculated equilibrium geometries and dissociation energies are compared to the corresponding quantities from available all-electron ab initio studies and other more elaborate theoretical estimates. The overall agreement is quite satisfactory. 相似文献
78.
Peter LeemingColin A Ray Stephen J SimpsonTimothy W Wallace Richard A Ward 《Tetrahedron》2003,59(3):341-352
Heterodiene [4π+2π] cycloadditions of (S,S)-4,5-diaryl-2-methylene-1,3-dioxolanes 1 to a series of β-amido-α,β-unsaturated carbonyl compounds are diastereoselective (d.r.≥4:1). The products can be purified by trituration or crystallisation and hydrolysed with acid to generate the corresponding β-amido carbonyl compounds, the overall sequence effecting an auxiliary-based enantioselective conjugate addition of an acetate enolate, leading to β-aminoacid derivatives. 相似文献
79.
A chemical flux of sulfur hexafluoride (SF6) in conjunction with low-energy Ar-ion bombardment has been used for chemically assisted ion beam etching (CAIBE) of silicon and silicon dioxide. The study has shown a large degree of independent control over the selectivity and anisotropy in dry etching. The total etch rate could be controlled by varying either the Ar-ion milling parameters or the chemical flux of SF6. Etch rate enhancement of 7–8 for silicon and 3–4 for silicon dioxide have been obtained over pure physical etching. 相似文献
80.
Spiro [3H-indole-3,2′-[4H] pyrido [3,2-e]-1,3-thiazine]-2,4′ (1H) diones, a class of previously unknown compound which does not form under conventional conditions, can be prepared by treatment of ‘in situ’ generated 3-indolylimine derivatives with 2-mercaptonicotinic acid under microwave irradiation in absence of any solvent or solid support in 85-92% yields in 3-8 min. The facile one pot reaction is generalized for a variety of ketones and amines to give pure pyrido [3,2-e] thiazine derivatives, which do not require further purification processes. 相似文献