Synthesis,photophysical and NMR evaluations of thiourea-based anion receptors possessing an acetamide moiety

The synthesis and photophysical evaluation of three diaryl thiourea-based anion receptors (4–6) for comparison with their urea counterparts (1–3) is outlined. These anion receptors posses an acetamide functionality on one of the aryl groups and an electron-withdrawing CF₃ group on the other. By varying the position of the acetamide group, in the o-, m- and p-positions of 4–6, respectively, the anion binding ability was both tuneable and found to be, in some cases, significantly different from that seen for the urea analogues 1–3. The binding affinities of the receptors 4–6, as well as the binding stoichiometries, were evaluated using UV–vis absorption spectroscopy in MeCN. However, these receptors were not sufficiently emissive to quantify the anion recognition using fluorescence. The results confirmed strong binding of these receptors to anions such as fluoride, acetate, phosphate, pyrophosphate and chloride. Nevertheless, the overall results obtained did not conform to the anticipated trends seen for 1–3, which is most likely due to the enhanced binding affinity of the thiourea analogues 4–6. The binding interactions were also investigated by using ¹H NMR which confirmed that these receptors interacted with the anions in a stepwise manner, where the primary anion binding interaction occurred at the thiourea side, which led to an activation of the acetamide moiety towards the second anion binding interaction, an example of an allosteric activation mode.     

硫脲壳聚糖-银配合物的制备及其结构和抑菌性能

合成了一系列不同银含量的硫脲壳聚糖-银配合物;利用傅立叶变换红外光谱分析了合成产物的结构,并测定了壳聚糖、硫脲壳聚糖及4种硫脲壳聚糖-Ag配合物对细菌和植物病原菌的抑菌性能.结果表明:硫脲壳聚糖-Ag配合物的抑菌性能优于单一的壳聚糖和硫脲壳聚糖;随着硫脲壳聚糖-Ag配合物中银含量的增大,抑菌效果明显增强.     

One Facile Preparation of N‐Aroyl‐N′‐arylsulfonylhydrazines by Oxidation of Aromatic Aldehyde N‐Arylsulfonylhydrazones with bis(Trifluoroacetoxy)iodobenzene

N‐aroyl‐N′‐arylsulfonylhydrazines can be obtained by oxidation of aromatic aldehyde N‐arylsulfonylhydrazones with bis(trifluoroacetoxy)iodobenzene in acetone at room temperature in mild to good yields.     

Unexpected Isolation of 4‐Isothiocyanatomethylene‐4H‐pyridine‐1‐carboxylic Acid Ethyl Ester as Potential Template in Organic Synthesis

The synthesis of 4‐isothiocyanatomethyl‐pyridine 4 in 36% yield by Hasegawa and Kotani (Japanese patent 49088878, 1974) has spurred us to investigate this preparation in detail. In addition to this compound, 4‐isothiocyanatomethylene‐4H‐pyridine‐1‐carboxylic acid ethyl ester 3 can be isolated. The synthesis of both compounds 3 and 4 were optimized to 75% and 50% yield respectively. Reaction of compound 3 with methylamine gave thiourea derivatives 5, the same product obtained on reacting 4‐isothiocyanatomethyl‐pyridine 4 with methylamine. We succeed in adjusting the reaction conditions to obtain high yield either from compound 3 or isothiocyanate derivatives 4.     

Brønsted Acidic Ionic Liquids: New,Efficient, and Green Promoter System for the Synthesis of 4(3H)-Quinazolinones

A simple, inexpensive, and efficient new synthesis of 4(3H)-quinazolinones from the reaction of 2-aminobenzamide with aroyl chlorides in the presence of two new halogen-free Brønsted acidic ionic liquids, 3-methyl-1-(4-sulfonic acid)butylimidazolium hydrogen sulfate [(CH₂)₄SO₃HMIM][HSO₄] and 1-(4-sulfonic acid) butylpyridinium hydrogen sulfate [(CH₂)₄SO₃HPY][HSO₄], green and reusable catalysts, with excellent product yields under solvent-free conditions is reported. The products could be separated simply from the catalyst, and the catalyst could be recycled without noticeably decreasing the catalytic activity.     

Synthesis and Antioxidant Activity of New Thiazole Analogues Possessing Urea,Thiourea, and Selenourea Functionality

A new series of urea, thiourea, and selenourea derivatives with thiazole moieties were synthesized by the nucleophilic addition reaction of (2-amino-4-(3-chlorophenyl)thiazol-5-yl)(2-chlorophenyl)methanone with various substituted isocyanates/ isothiocyanates/isoselenocynates in acetone having a catalytic amount of sodium hydroxide at room temperature with good yields. All the synthesized compounds were fully characterized by spectroscopic data and screened for their in vitro antioxidant activity using 1,1-diphenylpicrylhydrazyl (DPPH), nitric oxide (NO), and hydrogen peroxide (H₂O₂) radical scavenging methods. A preliminary study of the structure–activity relationship revealed that the compounds containing selenourea functionality along with halogen group have exhibited potent activity (IC₅₀ ≤ 0.0309 µmol/mL) compared to the standards (IC₅₀ ≤ 0.0814 µmol/mL). Thus the title compounds are a new class of potent antioxidant agents and worthy of further investigation.     

Diastereoselective Synthesis of Functionalized Tetrahydropyrimidin‐2‐thiones via ZnCl2 Promoted One‐pot Reactions

In the presence of zinc chloride, the in situ generated β‐enamino ester from the reaction of morpholine, piperidine and pyrrolidine with methyl propiolate reacted, with aromatic aldehydes and thiourea in ethanol resulting in the functionalized tetrahydropyrimidin‐2‐thiones in satisfactory yields and with good diastereoselectivity. When aromatic aldehydes bearing electron‐withdrawing group were used in the reaction, the 4‐hydroxytetrahydropyrimidin‐2‐thione derivatives were obtained as the main product.     

硫脲络合–火焰原子吸收光谱法测定低硅铝合金中的银含量

采用硫脲络合–火焰原子吸收光谱法测定低硅铝合金中的银元素含量。实验探讨了酸度及硫脲用量对银测定的影响及铝合金中基体元素与共存元素对银元素分析线的干扰情况。结果表明:选用9%的盐酸和3%的硝酸溶解试样最好,加入5 mL 50 g/L硫脲溶液可消除氯离子对试验结果的影响,基体铝元素和其它共存元素不干扰银的测定。根据低硅铝合金中银元素的含量范围,合成系列标准溶液,建立工作曲线,工作曲线的线性范围为0.05%~0.50%。银元素含量为0.30%的样品测定结果的相对标准偏差为0.15%(n=8),标准加入回收率为96.8%~98.5%。该方法操作简便、重现性好、测量结果准确可靠。     

5,5-二苯基-2-硫代海因及其S-取代衍生物的绿色合成

以苯偶酰和硫脲为起始原料,在氢氧化钠水溶液中,合成了5,5-二苯基-2-硫代海因;再以5,5-二苯基-2-硫代海因为起始原料,与氯乙酸钠反应,在水相中合成了S-羧甲基-5,5-二苯基-2-硫代海因,考察了硫脲、氢氧化钠和水用量对合成5,5-二苯基-2-硫代海因产率的影响。考察了5,5-二苯基-2-硫代海因用量对合成S-羧甲基-5,5-二苯基-2-硫代海因产率的影响。确定了较佳工艺路线。产品结构经IR、1H NMR、13C NMR及质谱进行了表征。     

One-pot synthesis of 2-amino- 5-aryl -5H-thiazolo[4,3-b]-1,3,4-thiadiazoles

Equimolar mixtures of aromatic aldehydes with thioglycolic acid and thiosemicarbazide in H₂SO₄ transform into 2-amino-5-aryl-5H-thiazolo[4,3-b]-1,3,4-thiadiazoles.Translated fromIzvestiya Akademioi Nauk. Seriya Khimicheskaya, No. 3, pp. 763–764, March, 1996.