1. The distinct behavior of 1º, 2º & 3º-aliphatic amines is an instructive challenge to our understanding of their chemistry, but is of little importance as a synthetic tool. After completion, the reaction mixture was quenched with H2O and extracted with EtOAc. [180 mg, 70%], [Patent Reference: WO2014149164, page 290, (23.7 MB)], A suspension of the aryl chloride (A) (0.5 g, 2.00 mmol) and the amine (B) (0.390 mL, 2.99 mmol) in EtOH (3 mL) was heated in a microwave reactor at 140 C for 45 min. Depending on ring substitution, 3º-Aryl amines may undergo aromatic ring nitrosation at sites ortho or para to the amine substituent. For more information contact us at info@libretexts.org or check out our status page at https://status.libretexts.org. The LibreTexts libraries are Powered by MindTouch® and are supported by the Department of Education Open Textbook Pilot Project, the UC Davis Office of the Provost, the UC Davis Library, the California State University Affordable Learning Solutions Program, and Merlot. Amines can be classified according to the nature and number of substituents on nitrogen. Once nitrosated, the activating character of the amine nitrogen is greatly diminished; and N-nitrosoaniline derivatives, or indeed any amide derivatives, do not undergo ring nitrosation. The org layer was dried (Na2SO4) and concentrated in vacuo to provide the product as a white solid. The N-nitrosamines formed from 2º-amines are carcinogenic, and are not generally useful as intermediates for subsequent reactions. In the common naming system, we name aliphatic amines by prefixing an alkyl group to a mine, i.e. Example 2. The commonest name at this level is methylamine and, similarly, the second compound drawn above is usually called ethylamine. Given below are some common primary amines. The S N 1 product mixtures from 1º-amines are difficult to control, and rearrangement is common when branched primary alkyl groups are involved. Nitrous acid reactions of 1º-aryl amines generate relatively stable diazonium species that serve as intermediates for a variety of aromatic substitution reactions. The nitrosonium cation is not sufficiently electrophilic to react with benzene itself, or even toluene, but highly activated aromatic rings such as amines and phenols are capable of substitution. For example, if a methyl group is present in a primary amine, the compound is named as methylamine or methenamine (preferred IUPAC name). Of course, the rate of reaction of NO(+) directly at nitrogen is greater than that of ring substitution, as shown in the previous example. The crude product was filtered and purified by HPLC (H2O/ACN with AcOH). The org layer was washed with brine and dried (Na2SO4). Nitrous acid (\(HNO_2\) or \(HONO\)) reacts with aliphatic amines in a fashion that provides a useful test for distinguishing primary, secondary and tertiary amines. The reaction mixture was stirred at 80 C for 10 h. After completion, the reaction mixture was concentrated in vacuo and partitioned between EtOAc (100 mL) and H2O (50 mL). A primary (1º) amine is an amine that has the following general structural formula.. R= alkyl, aryl. [160 mg, 26%], [Patent Reference: WO2010038081, page 89, (33.8 MB)]. For example: 1. For example: Primary Amines. The resulting solids were filtered and the filter cake was rinsed with H2O (2 x 300 mL). Watch the recordings here on Youtube! The crude was purified by column chromatography (2% MeOH/CHCl3) to provide the product. A mixture of the aryl chloride (A) (1 Kg, 7.72 mol), the amine (B) (1.5 Kg, 10.03 mol), TEA (3.23 L, 23.2 mol), and n-BuOH (8 L) were stirred at reflux for 36 h. Upon completion, the reaction mixture was cooled to RT, diluted with H2O (8 L), and extracted with EtOAc (2 x 10 L). [1.3 g, 87%], [Patent Reference: WO2014149164, page 296, (23.7 MB)], A mixture of the aryl chloride (A) (16 g, 73.1 mmol), the amine (B) (10 g, 73.1 mmol), and TEA (15.2 g, 146 mmol) in DMSO (150 mL) was stirred at RT overnight. The resulting residue was diluted with H2O, treated with saturated aq NaHCO3, and extracted with EtOAc. Missed the LibreFest? The resulting mixture was stirred at 80 C for 16 h, after which time it was cooled to 30 C and transferred into H2O (5 L) at RT. Thus, although isopropylamine looks similar to isopropyl alcohol, the former is a primary amine, while the latter is a secondary alcohol. The mixture was concentrated in vacuo.