Synthesis and Characterization of Secondary Nitrosamines from Secondary Amines Using Sodium Nitrite and p‐Toluenesulfonic Acid. Issue 3 (12th January 2015)

• Record Type: Journal Article
• Authors: Miró Sabaté, Carles; Delalu, Henri
• Is Part Of: Chemistry, an Asian journal. Volume 10:Issue 3(2015:Mar.)
• Page Start: 674
• Page End: 678
• Publication Date: 2015-01-12
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201403182
• Languages: English
• ISSNs: 1861-4728

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>We synthesized nitrosamines (R<sub>2</sub>NNO) with R=<italic>i</italic>Pr (<bold>1</bold>), <italic>n</italic>Pr (<bold>2</bold>), <italic>n</italic>Bu (<bold>3</bold>), and hydroxyethyl (<bold>4</bold>) from the amine using sodium nitrite/<italic>p</italic>‐toluenesulfonic acid in CH<sub>2</sub>Cl<sub>2</sub>. The rate of formation of <bold>1</bold>–<bold>4</bold> increases in the direction <italic>i</italic>Pr<<italic>n</italic>Pr<<italic>n</italic>Bu<CH<sub>2</sub>CH<sub>2</sub>OH. Compounds <bold>1</bold>–<bold>3</bold> were obtained as colorless solids, whereas <bold>4</bold> is a bright yellow liquid. Compounds <bold>1</bold>–<bold>4</bold> were characterized by elemental analysis, MS, IR, and multinuclear NMR (<sup>1</sup>H, <sup>13</sup>C, and <sup>15</sup>N) spectroscopies. Additionally, we measured the UV/Vis spectra of all compounds, which show maxima of absorption at approximately 221 nm and molar extinction coefficients between 3043 and 4859 L mol<sup>−1</sup> cm<sup>−1</sup>. We calculated the optimized structures of <bold>1</bold>–<bold>4</bold> (B3LYP/6‐311+G(d, p)) and computed the NMR spectroscopic chemical shifts and infrared frequencies. Furthermore, we carried out a natural bond orbital (NBO) analysis of the nitrosamine moiety. Lastly, the compounds described in this work are valuable starting materials for the synthesis of 2‐tetrazenes with potential interest to replace highly toxic hydrazines in rocket propulsion.</p> </abstract>