Complexities of chromato-mass spectrometric identification of products of free radical chlorination of indane

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Abstract

Using the example of the products of free radical chlorination of indane (with data for tetralin mentioned for comparison), it is shown that chromato-mass spectrometric analysis can only establish their molecular formulas, and based on this, the reaction mechanism is detailed. Refining the structure of the components requires interpreting their gas chromatographic retention indices in the form of localized additive schemes created to solve the specific task at hand. If such schemes are formed based on data from objects containing all the structural elements of the characterized compounds, they are fairly reliable. However, if this condition is not met (as in the case under consideration), the possibility of interpreting the retention indices is fundamentally preserved, but the accuracy of the estimates is significantly reduced, and the amount of preliminary calculations increases substantially. A key structural fragment of chlorinated indane derivatives, practically absent among previously characterized compounds, is the chlorine atom in the alicyclic fragment of the structure at the α-position relative to the aromatic system. Secondary chlorinated derivatives are formed as a result of dehydrochlorination of the primary reaction products, followed by chlorine addition to C=C double bonds.

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About the authors

I. G. Zenkevich

St. Petersburg State University

Author for correspondence.
Email: izenkevich@yandex.ru
Russian Federation, St. Petersburg

E. V. Eliseenkov

St. Petersburg State University

Email: izenkevich@yandex.ru
Russian Federation, St. Petersburg

A. I. Ukolov

Research Institute of Hygiene, Occupational Diseases, and Human Ecology Federal Medical and Biological Agency of Russia

Email: izenkevich@yandex.ru
Russian Federation, Kuzmolovsky settlement

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8. Схема 1. Образование продуктов последовательного хлорирования тетралина.

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9. Схема 2. Фрагментация молекулярных ионов тетралинов по типу ретрореакции Дильса–Альдера.

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10. Схема 3. Схематическое изображение структурного фрагмента, хуже всего представленного среди соединений, охарактеризованных газохроматографическими индексами удерживания.

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11. Схема 4. “Сборка” индановых структур из ароматического и ациклических фрагментов.

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