Abstract

The one-pot reaction of 5,6,7,8-tetrahydronaphthalen-1-amine, mercaptoacetic acid, and arenealdehydes having strong and weak electron-withdrawing groups gave the corresponding 1,3-thiazolidin-4-ones (47–70%). When arenealdehydes bearing strong and weak electron-donating groups were used as precursors, the 1,4-benzothiazepin-2-ones were obtained (30–72%) by p-TsOH catalysis. All compounds are unknown and were characterized by GC-MS and NMR techniques, and available crystals by X-ray diffraction studies. The atropisomerism phenomenon was observed in several 1,3-thiazolidin-4-ones as confirmed by VTNMR method. The Tc was established as 332 K and the energy required for the interconversion of one atrop­isomer into another is around 16.8 kcal·mol^–1. Chemical quantum calculation and NOESY displayed that more stable isomer has the tetrahydro­naphthalene portion below the five-ring plane. Only a small difference between isomers (–0.21 to –0.84 kcal·mol^–1) was observed by calculated energy.

The one-pot reaction of 5,6,7,8-tetrahydronaphthalen-1-amine, mercaptoacetic acid, and arenealdehydes having strong and weak electron-withdrawing groups gave the corresponding 1,3-thiazolidin-4-ones (47–70%). When arenealdehydes bearing strong and weak electron-donating groups were used as precursors, the 1,4-benzothiazepin-2-ones were obtained (30–72%) by p-TsOH catalysis. All compounds are unknown and were characterized by GC-MS and NMR techniques, and available crystals by X-ray diffraction studies. The atropisomerism phenomenon was observed in several 1,3-thiazolidin-4-ones as confirmed by VTNMR method. The Tc was established as 332 K and the energy required for the interconversion of one atrop­isomer into another is around 16.8 kcal·mol^–1. Chemical quantum calculation and NOESY displayed that more stable isomer has the tetrahydro­naphthalene portion below the five-ring plane. Only a small difference between isomers (–0.21 to –0.84 kcal·mol^–1) was observed by calculated energy.

中文翻译：

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5,6,7,8-四氢萘-1-胺作为噻唑烷酮和苯并噻嗪酮的前体：合成与阻转异构关系

摘要

具有强和弱吸电子基团的5,6,7,8-四氢萘-1-胺，巯基乙酸和芳醛的一锅反应得到相应的1,3-噻唑烷丁-4-酮（47-70％ ）。当带有强电子给体基团和弱电子给体基团的戊二醛用作前体时，通过对-TsOH催化可制得1,4-苯并噻唑啉-2-酮（30-72％）。所有化合物均未知，并已通过GC-MS和NMR技术进行了表征，并通过X射线衍射研究获得了可用的晶体。如通过VTNMR方法所证实的，在几个1，3-噻唑烷酮-4-酮中观察到阻转异构现象。Tc被确定为332 K，一种阻转异构体相互转化为另一种所需的能量约为16.8 kcal·mol ^–1。化学量子计算和NOESY表明，更稳定的异构体在五环平面以下具有四氢萘部分。通过计算得出的能量，仅观察到异构体之间的微小差异（–0.21至–0.84 kcal·mol ^–1）。

具有强和弱吸电子基团的5,6,7,8-四氢萘-1-胺，巯基乙酸和芳醛的一锅反应得到相应的1,3-噻唑烷丁-4-酮（47-70％ ）。当带有强电子给体基团和弱电子给体基团的戊二醛用作前体时，通过对-TsOH催化可制得1,4-苯并噻唑啉-2-酮（30-72％）。所有化合物均未知，并已通过GC-MS和NMR技术进行了表征，并通过X射线衍射研究获得了可用的晶体。如通过VTNMR方法所证实的，在几个1，3-噻唑烷酮-4-酮中观察到阻转异构现象。Tc被确定为332 K，一种阻转异构体相互转化为另一种所需的能量约为16.8 kcal·mol ^–1。化学量子计算和NOESY表明，更稳定的异构体在五环平面以下具有四氢萘部分。通过计算得出的能量，仅观察到异构体之间的微小差异（–0.21至–0.84 kcal·mol ^–1）。