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991.
G.K. Surya Prakash 《Journal of fluorine chemistry》2002,117(2):103-105
1,3-Dehydroadamantane undergoes a facile reaction with tetrafluorohydrazine to give 1,3-bis(N,N-difluoroamino)adamantane, the product of 1,3-NF2 radical addition. 相似文献
992.
The reliability of the two-layer own N-layered integrated molecular orbital and molecular mechanics (ONIOM) method was examined for the SN2 reaction CH(4–n)Cln+OH–. In the ONIOM calculation, only the methyl chloride and OH–were treated at a high level and the effect of polychlorination was taken into account only at a low level. The ONIOM results were compared with the target CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ results obtained by Borisov etal. [(2001) J. Phys. Chem. A 105:7724]. The ONIOM[MP2/aug-cc-pVDZ:B3LYP/6-31+G(d)] was found to reproduce well the target geometry and energy at the MP2/aug-cc-pVDZ level. The single-point improved energetics at the ONIOM[CCSD(T)/aug-cc-pVDZ:MP2/6-31+G(d)] is found to give results nearly as accurate as the target CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ results. The substantially reduced cost, 20% for optimization and 5% for single-point improved energy of the target cost for n=4, as well as small errors suggest that ONIOM is a powerful tool for accurate potential-energy surfaces of the reaction of large polyhalohydrocarbons. 相似文献
993.
V. A. Yanchenko A. M. Demchenko M. O. Lozinskii 《Chemistry of Heterocyclic Compounds》2004,40(4):516-518
We propose a method for obtaining derivatives of 7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine by alkylation of 4-amino-5-methyl-4H-1,2,4-triazole-3-thiol by substituted -chloroacetanilides, followed by cyclization of the intermediate by phosphorus oxychloride. 相似文献
994.
Flow injection spectrofluorimetry with in-line Winklers procedure was developed for the dissolved oxygen (DO) determination. 2-Thionaphthol reacted with iodine produced by Winkler’s method to form fluorescence inactive disulfide compound. To automate the process completely, a 5-channel flow system with a newly designed 16-way valve was assembled. The system consisted of a dispersion coil (DC), a precipitate formation coil (PFC), a precipitate dissolving coil (PDC), and extraction coil (EC). A calibration can be constructed by using a standard iodine solution for dissolved oxygen. The calibration graph was linear over the range 1.2×10−4∼6.0×10−4 mol l−1 iodine (1.96∼9.80 mg O l−1)). The relative standard deviation (n=6) was below 0.3% for the 4×10−4 mol l−1 iodine (6.27 mg O l−1) determination. The sample throughput was 12/h. 相似文献
995.
The binary phase diagram of KNO3-KClO3 is studied by means of differential scanning calorimetry (DSC) and high-temperature X-ray diffraction. The limited solid solutions, K(NO3)1−x(ClO3)x (0<x<0.20) and K(NO3)1−x(ClO3)x (0.90<x<1.0), were formed in the KNO3-based solid solutions and KClO3-based solid solutions phase, respectively. For KNO3-based solid solutions, KNO3 ferroelectric phase can be stable from 423 to 223 K as a result of substituting of NO3 by ClO3-radicals. The temperatures for solidus and liquidus have been determined based on limited solid solutions. Two models, Henrian solution and regular solution theory for KNO3-based (α) phase and KClO3-based (β) phase, respectively, are employed to reproduce solidus and liquidus of the phase diagram. The results are in good agreement with the DSC data. The thermodynamic properties for α and β solid solutions have been derived from an optimization procedure using the experimental data. The calculated phase diagram and optimized thermodynamic parameters are thermodynamically self-consistent. 相似文献
996.
2'-azido-2'-deoxyribonucleoside 5'-diphosphates are mechanism-based inhibitors of Ribonucleotide Reductase. Considerable effort has been made to elucidate their mechanism of inhibition, which is still controversial and not fully understood. Previous studies have detected the formation of a radical intermediate when the inhibitors interact with the enzyme, and several authors have proposed possible structures for this radical. We have conducted a theoretical study of the possible reactions involved, which allowed us to identify the structure of the new radical among the several proposals. A new reactional path is also proposed that is the most kinetically favored to yield this radical and ultimately inactivate the enzyme. The energetic involved in this mechanism, both for radical formation and radical decay, as well as the calculated Hyperfine Coupling Constants for the radical intermediate, are in agreement with the correspondent experimental values. This mechanistic alternative is fully coherent with remaining experimental data. 相似文献
997.
M. SAADIOUI Z. ASFARI J. VICENS N. REYNIER J. F. DOZOL 《Journal of inclusion phenomena and macrocyclic chemistry》1997,28(3):223-244
This article describes the synthesis, structure andUV properties of azocalixcrowns in which the photoresponsivetrans-cis azo benzene unit has been introduced in the glycolicchains of the calix[4]crowns. The synthesis proceeded via the selective-1,3O-dialkylation of calix[4]arene with glycolic chains terminated bynitrophenyl residues. After reduction of thenitro groups into amino functions,intramolecular oxidative coupling produced thecapping of the calixarene. Thesynthetic approaches and the cis-transstructure of these new ligandsare discussed and full details on synthesesand structural data are given. Apreliminary example of cesium complexation byone of the ligands is proposed. 相似文献
998.
The reaction of 2,3-dihydro-2,3-benzo[b]furandione with the triphenylphosphazines of diazo compounds leads to substituted
2-methylenehydrazono-2,3-dihydro-3-benzo[b]furanones, which are hydrolyzed in an acidic medium to the substituted methylenehydrazides
of o-hydroxyphenylglyoxalic acid and react with amines to form the products of addition at the activated CH=N bond of the
side chain or 2-hydrazono-2,3-dihydro-3-benzo[b]furanone respectively.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 817–822, June, 2007. 相似文献
999.
A. V. Kazakova N. D. Kushch L. I. Buravov E. B. Yagubskii S. V. Simonov L. V. Zorina S. S. Khasanov R. P. Shibaeva E. Canadell J. Yamada M. Umemiya 《Russian Chemical Bulletin》2007,56(1):49-55
New radical cation salts based on 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions, β-(BDA-TTP)4Cu2Cl6 and (BDA-TTP)2CuCl4, were synthesized and structurally characterized. Single crystals were prepared by electrochemical oxidation of BDA-TTP under
galvanostatic conditions. X-ray diffraction study demonstrated that the salts have a layered structure, in which the conducting
BDA-TTP layers alternate with the [Cu2Cl6]2− or [CuCl4]2− anions. Both salts show the semiconductor-type temperature dependence of the conductivity.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 48–54, January, 2007. 相似文献
1000.
以(S)-2-氨基丙醇为手性源与α-溴-3-氯苯丙酮反应, (R)-2-氨基丙醇为手性源与6-甲氧基-2-(2-溴丙酰基)萘反应, 分别合成了手性纯化合物(2R,3R,5S)-3,5-二甲基-2-(3-氯苯基)-2-吗啉醇盐酸盐(4a)和(2S,3S,5R)-3,5-二甲基-2-(6-甲氧基-2-萘基)-2-吗啉醇盐酸盐(4b), 利用X射线单晶衍射仪测定了两化合物的晶体结构和两化合物的空间结构, 并初步分析两化合物空间结构, 化合物4a晶体属正交晶系, 空间群为P21212, 晶胞参数为: a=0.8718(2) nm, b=0.7883(2) nm, c=2.0247(6) nm, Z=4, V=1.3915(7) nm3, Dc=1.328 g/cm3, F(000)=584, R1=0.0399, wR2=0.0797, S=1.042. 化合物4b晶体属正交晶系, 空间群为P212121, 晶胞参数为: a=0.71035 (9) nm, b=0.77703(10) nm, c=2.9820(4) nm, Z=4, V=1.6318(4) nm3, Dc=1.318 g/cm3, F(000)=688, R1=0.0520, wR2=0.1108, S=0.994. 相似文献