Environmental Effect of Macrocyclic Molecules on the Oxidation of Triethylamine by Ferricyanide Ion in Aqueous Solution

The effect of 18-crown-6 and kryptofix (2,2,1) on the oxidation of triethylamine byaqueous ferricyanide ion has been studied at pH 4, 7, and 9.The macrocycle retarded the normal oxidation process at all pH values,the effect depending on the macrocyclic ligand concentration Kryptofix (2,2,1) had a greater effect than 18-crown-6 at all pHvalues in this study. For 18-crown-6, retardation decreases in the order pH 9 > 4 > 7 while forkryptofix it follows the order pH 9 > 7 > 4.     

Convenient preparative method for synthesis of methyl (Z)-3-aryl-2-(carbobenzoxyamino)acrylates by Wittig—Horner reaction with the use of Et3N as a base

The Wittig—Horner reaction of CbzNHCH(CO₂Me)P(O)(OMe)₂ (1) with ArCHO (2) in the presence of Et₃N as a base affords methyl (Z)-3-aryl-2-(carbobenzoxyamino)acrylates (3) with high degrees of diastereoselectivity (Z)/(E) > 101. One recrystallization of the crude product is sufficient to obtain isomerically and chemically pure (Z)-3.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2218-2220, November, 1995.The authors are grateful to the Dupont company (USA) for financing this study     

Easily synthesized antimalarial ferrocene triazacyclononane quinoline conjugates

Starting from triazacyclononane, easily accessible ferrocenic quinoline derivatives were synthesized. Their antiplasmodial properties were investigated against chloroquine sensitive (HB3) and chloroquine-resistant (Dd2) Plasmodium falciparum. One of them, 7-chloro-4-[4-(7-chloro-4-quinolyl)-7-ferrocenylmethyl-1,4,7- triazacyclononan-1-yl]quinoline (4) showed potent antimalarial activity in vitro against the chloroquine-resistant strain Dd2 and therefore revealed to be the most promising lead from the present work for new organometallic antimalarial agents.     

钯催化全氟及多氟碘化物与三乙胺的反应

Pullin等人曾对全氟碘代烷与三级胺的相互作用进行了研究,发现R_(?)I与NR_3能形成电荷转移络合物,即:R_(?)…I…NR_3。但此后却未见到有关反应的报道。我们发现在钯催化剂存在下,全氟碘化物与三乙胺能发生反应,反应条件较为温和,产物为氟代烷基烯基二乙基胺1。反应可能是在三乙胺中先产生一个双键,然后β碳原子接上一个全氟烷基。1的IR和NMR与Blanc报道的一致。化合物1经水解可得胺基烯酮2。在酸溶液中水解时,速度明显加快,而在碱溶液中,不仅不能加快水解速度,而且还有副反应发生。我们对化合物2进     

α-酮酯和α-酮酰胺的Henry反应

用三乙胺催化环状α-酮酯和α-酮酰胺同硝基甲烷的Henry反应, 首次合成了12个多官能团的β-硝基醇, 它们的结构用元素分析、红外光谱和核磁共振进行了表征. 这一反应速度较快, 室温下进行, 条件温和, 产率较好, 是合成多官能团硝基醇的有效方法.     

N-丙基-N-[2-(2,4,6-三氯苯氧基)乙基]-1H-咪唑-1-甲酰胺的合成

以2，4，6-三氯苯酚和1，2-二氯乙烷为初始原料，在相转移催化剂十六烷基三甲基溴化胺和弱碱性助剂三乙胺存在下合成了N-丙基-N-[2-(2，4，6-三氯苯氧基)乙基]-1H-咪唑-1-甲酰胺，其结构经元素分析,IR，^1H NMR分析证实。并对该合成路线的反应机理进行了讨论。     

Solubility of Triethylamine in Tetraethylammonium Chloride Aqueous Solutions from 20 to 35°C

Solubilities of triethylamine in aqueous tetraethylammonium chloride solutions were measured at 20, 25, and 35°C. The molalities in Et₄NCl of the aqueous solvents ranged from 0.03 to 1 mol-kg^–1. The data were evaluated from density measurements using a vibrating-tube densimeter. At each temperature, least-squares method was used to fit experimental density data points to double polynomial equations of various degrees. Triethylamine molalities of the saturated aqueous phases were estimated by extrapolation from those equations. Experimental data were interpreted in terms of hydrophobic and electrostatic perturbed domains in the hydration shells of the noneleceory and of the cation of the salt, as a function of temperature and salt concentration. The conclusions obtained are consistent with previous volumetric studies.     

Optimized POCl3-assisted synthesis of 2-amino-1,3,4-thiadiazole/1,3,4-oxadiazole derivatives as anti-influenza agents

Although recent decades have witnessed the synthesis of 1,3,4-thiadiazoles via phosphorus POCl₃-promoted cyclization reaction, simultaneous access to 2-amino-1,3,4-thiadiazole and 2-amino-1,3,4-oxadiazole analogs remains unexpected and elusive. Herein, a detailed regiocontrolled synthesis of 2-amino-1,3,4-thiadiazoles in good to high yields with good regioselectivities from readily available thiosemicarbazides using POCl₃ was disclosed. Meantime, to establish a comprehensive structure–activity relationship, 2-amino-1,3,4-oxadiazole derivatives as single regioisomers were prepared via EDCI·HCl-triggered cyclization of the thiosemicarbazide intermediates. The in vitro anti-influenza assays proved that the selected compounds with the pyrazine/pyridine ring exhibited certain inhibitory activities against influenza A virus strains A/HK/68 (H3N2) and A/PR/8/34 (H1N1) in MDCK cells. Among them, N-(adamantan-1-yl)-5-(5-(azepan-1-yl)pyrazin-2-yl)-1,3,4-thiadiazol-2-amine (4j) was the most active compound, and exhibited favorable activity with EC₅₀ values of 3.5 μM and 7.5 μM, respectively. In addition, the molecular docking results explained the reason why compound 4j had dual inhibitory activity and revealed the reasonable binding mode of this compound with the M2-S31N and M2-WT ion channels. This compound had the potential to be further developed as an anti-influenza drug.     

Spectroscopic characterization and preparation of low molecular,water‐soluble chitosan with free‐amine group by novel method

Low molecular, water‐soluble chitosan (LMWSC) with a free amine group was prepared by the novel salts‐removal method described in this study. A weight‐average molecular weight and degree of deacetylation (DDA) of LMWSC were determined by viscometry and Kina titration, resulting in 18,579 Da and 93% DDA, respectively. In the Fourier transform infrared spectroscopic, ¹H NMR, and ¹³C NMR spectra the absorption band by the carboxyl group derived from lactic acid and the impurities formed in the enzymatic process disappeared or were significantly lower than that of the control chitosan. Also, from the ¹H NMR and ¹³C NMR spectra the empirical value for the area ratio of the proton and carbon corresponds nearly to its theoretical values. The matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrum identified the difference in the two adjacent peaks as 161. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3796–3803, 2002