2-氯吡啶与硫脲缩合反应的特性。电化学镀镍过程中形成产物的结构及其对镀层性能的影响

V. A. Grabelnykh, I. N. Bogdanova, N. Sosnovskaya, N. V. Istomina, N. V. Russavskaya, E. Kondrashov, R. Butrik, N. A. Korchevin, I. B. Rozentsveig
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引用次数: 0

摘要

通过调节2-氯吡啶在巯基脲溶液中的进料速率,保证其在反应区内的低浓度,合成了2-吡啶基异硫脲氯铵并进行了光谱表征。根据核磁共振波谱(1H,13С,15N)的数据,得到的化合物是两个互变异构体的近似等摩尔混合物:预期的异硫脲盐和氯化吡啶,在第2位有异硫脲取代基。异硫脲盐向吡啶盐互变异构过渡的能力是由两个主要中心的存在决定的,包括异硫脲单元的氮原子和吡啶环的氮原子。使用DFT方法进行的量子化学分析表明,互变异构体的自由能值相似,与吡啶盐相比,在氮亚胺原子上质子化的互变异构体为2.9(气相)和4.7千卡/摩尔(考虑到PCM水平的二甲基亚砜溶剂DMSO)更有利。互变异构体能量的微小差异决定了它们以近似等摩尔的量形成。在反应区迅速向硫脲溶液中加入2-氯吡啶(5-10 mL/min)会产生多余的试剂,充当碱并引起异硫脲盐的分裂。这导致在反应介质中额外形成双(2-吡啶基)硫化物,代表获得配位化合物的有价值的配体。合成的互变异构体混合物作为标准镀镍电解质的添加剂进行了测试。在0.3 ~ 0.5 g/L的浓度下,该添加剂可保证在5 ~ 10 a /dm2的电流密度和98 ~ 99%的电流收率下获得光亮的低孔镍镀层。
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Characteristics of 2-chloropyridine and thiourea condensation. Structure of the as-formed products and their effect on coating properties during electrochemical nickel plating
The synthesis and spectral characterisation of 2-pyridylisothiuronium chloride were performed by regulating the rate of feeding 2-chloropyridine into a thiourea solution in ethyl alcohol for ensuring its low concentration in the reaction zone. According to the data of NMR spectroscopy (1H,13С,15N), the obtained compound represents an approximately equimolar mixture of two tautomers: the expected isothiuronium salt and pyridinium chloride with an isothiocarbamide substituting group in the 2nd position. The ability of isothiuronium salt to transit tautomerically to pyridinium salt is determined by the presence of two main centres, including nitrogen atoms of the isothiourea unit and a nitrogen atom of the pyridine ring. A quantum chemical analysis performed using the DFT method showed that the free energy values of the tautomers were similar, with the tautomer protonated on the nitrogen imido-atom being 2.9 (in the gas phase) and 4.7 kcal/mole (taking into account the dimethyl sulphoxide solvent DMSO at the PCM level) more advantageous as compared to the pyridinium salt. A small difference in the tautomer energies determines their formation in an approximately equimolar quantity. A rapid addition (5–10 mL/min) of 2-chloropyridine to the thiourea solution in the reaction zone creates the surplus of the reagent, acting as a base and causing splitting of the isotiuronium salt. This leads to an additional formation of bis(2-pyridyl)sulphide in the reaction medium, representing a valuable ligand for obtaining coordination compounds. The synthesised mixture of tautomers was examined as an additive to the standard nickel-plating electrolyte. In the concentration of 0.3–0.5 g/L, this additive ensured the production of bright low-porous nickel coatings at a sufficiently high current density of 5–10 A/dm2 and a current yield of 98–99 %.
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