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951.
Contributions to the Chemistry of Phosphorus. 221. Stannyl-Substituted Bicyclo[1.1.0]tetraphosphanes: Formation and properties of R3Sn(H)P4 (R ? CH3, C6H5, c-C6H11, o-C7H7) The unsymmetrically substituted bicyclo[1.1.0]tetraphosphanes Me3Sn(H)P4 ( 1 ), Ph3Sn(H)P4 ( 2 ), (c-Hex)3Sn(H)P4 ( 3 ) and (o-Tol)3Sn(H)P4 ( 4 ) have been obtained by reaction of a solution of (Na/K) HP4 with R3 SnCl (R ? Me, Ph, c-Hex, o-Tol) under proper conditions. The structure of the compounds 1 – 4 , which are only stable in solution, has been elucidated by means of 31P-NMR-spectroscopy. Whereas 3 exists at ?60°C as the exo,endo isomer, 1, 2 and 4 are fluctuating molecules at room temperature and probably invert between the three possible configurational isomers (exo,exo-, exo,endo- and endo,endo-form). 相似文献
952.
Suzuki-Miyaura coupling was achieved on a variety of aryl chlorides by using di(2,6-dimethylmorpholino)phenylphosphine (L1) as a bulky electron-rich monoaryl phosphine ligand. We report the couplings of various chlorobenzenes and heteroaryl chlorides. 相似文献
953.
The potential energy surface (PES) for the CF3CFHO2+HO2 reaction has been theoretically investigated using the DFT [B3LYP/6‐311G(d,p)] and B3LYP/6‐311++G(3df,3pd)//B3LYP/6‐311G(d,p) levels of theory. Both singlet and triplet PESs are investigated. The reaction mechanism on the triplet surface is simple. It is revealed that the formation of CF3CFHOOH+3O2 is the dominant channel on the triplet surface. On the basis of the ab initio data, the total rate constants for the reaction CF3CFHO2+HO2 in the T = 210–500 K range have been computed using conventional transition state theory with Wigner's tunneling correction and have been fitted by a rate constant expression as k = 1.04 ×10?12(cm3 molecule?1 s?1) exp (700.33/T). Calculated transition state rate constants with Wigner's tunneling correction for the reaction CF3CFHO2+HO2 are in good agreement with the available experimental values. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
954.
3-[(E)-Arylmethylidene]-3,9-dihydropyrrolo[2,1-b]quinazolin-1(2H)-ones were prepared by reaction of quinazolyl-2-propionic acid
hydrochloride with aromatic aldehydes in acetic anhydride in the presence of Et3N. 3-[(E)-Arylmethylidene]-1,2,3,9-tetrahydropyrrolo[2,1-b]quinazolin-1-ols were formed by reduction of the 3-arylidene derivatives
with sodium borohydride in methanol, readily lost water when heated with acids, and were converted into 3-[(E)-arylmethylidene]-3,9-dihydropyrrolo[2,1-b]quinazolines.
__________
Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 463–467, September–October, 2006. 相似文献
955.
J. Horn H. -Ch. Semmelhack H. Börner F. Schlenkrich 《Journal of Thermal Analysis and Calorimetry》1994,41(5):995-1005
We propose a reaction model for the synthesis of YBa2Cu4O8 under normal pressure conditions, which contains 4 partial reaction steps. In a first step bariumnitrate and copperoxide react to Ba2Cu3O5+δ. This substance will be formed for each mixtures Ba:Cu=2∶3...3∶2. The following two partial reaction steps are connected to Ba2Cu3O5+δ, which reacts with Y2O3 and CuO to YBa2Cu4O8 or decomposes to BaCuO2 and CuO. In a last step parts of BaCuO2 reacts with Y2O3 and CuO to YBa2Cu4O8. 相似文献
956.
V. V. Gritsenko O. A. D'yachenko P. Cassoux A. I. Kotov E. E. Laukhina C. Faulmann E. B. Yagubskii 《Russian Chemical Bulletin》1993,42(7):1149-1151
A neutral metal complex, [Pt(dddt)2]° (1), has been obtained by oxidation of the [Pt(dddt)2]– anion with excess (Bu4N)AuBr4 in nitrobenzene. Crystallographic data for 1a=17.854(9) Å,b=18.409(9) Å,c=4.717(5) Å, =68.83(2)°, space group P21/n,Z=4,d
calc=2.55 g/cm3. In1 two independent centrosymmetric [Pt(dddt)2]° molecules are packed in stacks that form layers parallel to the (110) plane. The molecules of1 in the layers have shortened S...S contacts 3.491(9) Å, and 3.594(10) Å. The average bond lengths Pt-S 2.242(7) Å, S-C 1.71(2) Å and C=C 1.40(3) Å, together with the square-planar coordination of Pt in PtS4, suggest considerable conjugation in the metal cycles.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1207–1209, July, 1993. 相似文献
957.
A. V. Varlamov D. G. Grudinin A. I. Chernyshev A. N. Levov I. Yu. Lobanov R. S. Borisov F. I. Zubkov 《Russian Chemical Bulletin》2004,53(8):1711-1716
5-Methyl-4,5-dihydro-3H-spiro[benzo-2-azepine-3,1-cyclohexane] N-oxide was rear- ranged into 5-methyl-1-oxo-1,2,4,5-tetrahydro-3H-spiro[benzo-2-azepine-3,1-cyclohexane]. The latter was used for the synthesis of spiro{triazolo[3,4-a]- and-tetrazolo[5,1-a]benzo-2- azepinecyclohexanes}.Published in Russian in Izvestiya Akademii Nauk.
Seriya Khimicheskaya, No. 8, pp. 1647–1651, August, 2004. 相似文献
958.
Epoxidation of ethyl 3-(6-hydroxycyclohex-1-en-1-yl)propanoate (11) provided the syn epoxide 12. By invoking chelation controlled epoxide opening the triol derivatives 13 and 14 or the spiro lactone 25 could be obtained. Elimination of HBr from the bromides 26 and 27 produced the spiro cyclohexenones 28 and 29. Epoxidation of the double bond occurred in a diastereoselective manner to give epoxides 30 and 31, respectively. Treatment of the epoxide 31 with LiBr/AcOH gave the bromo hydrin 38. In a ‘merry go round’ fashion 38 was further functionalized on the cyclohexane ring by elimination, epoxidation, and epoxide opening resulting in the bromo hydrin 43. Other cyclohexane derivatives that were produced during these studies include the cyclohexenone 19 and the cyclohexanediol 23. In addition, enolate azidation of the spiro lactone 29 proceeded in a diastereoselective manner providing the α-azido lactone 32. 相似文献
959.
Ab initio SCF computations on the intrinsic preferences of the H+, CH
3
+
and C2H
5
+
cations towards the two principal sites of protonation or alkylation on cytosine, N3 or O2, show that this preference undergoes a continuous modification with the increase in size and complexity of the cation. N3 is the preferred site of fixation of H+, O2 the preferred site of C2H
5
+
, while CH
3
+
has no marked preference. The exchange repulsion term of the binding energy appears responsible for the preference of C2H
5
+
for O2.This work was supported by the Ligue Francaise contre le Cancer and the National Foundation for Cancer Research (USA) 相似文献
960.
Lorenzo MalavasiPaolo Ghigna Gaetano ChiodelliGiorgio Maggi Giorgio Flor 《Journal of solid state chemistry》2002,166(1):171-176
The synthesis and structural properties of Mg1−xMn2+xO4, for 0≤x≤1 are described. Complete miscibility in the solid state exists for this system. For the material with the correct stoichiometry, i.e. MgMn2O4, the effect of temperature on the cation distribution was investigated= above 600°C the inversion degree (m) starts increasing. The electrical conductivity shows a small dependence on P(O2) which is consistent with the small oxygen non-stoichiometry determined by means of thermogravimetry. The main contribution to the transport properties arises from the inversion equilibrium. Two distinct conductivity regimes, below and above the inversion threshold, can be assumed to explain the electrical conductivity and thermoelectric power results. 相似文献