Amine primary aliphatic amines

Table 8 Acidities of Fischer carbene complexes and intrinsic rate constants for their deprotonation by secondary alicyclic amines, primary aliphatic amines and hydroxide ion in 50% MeCN-50% water (v/v) at 25°C... 

When the electron-deficient atom is the nitrogen atom of nitrous acid or nitrosyl chloride, the products will depend on whether the amine is a primary or secondary amine. Primary aliphatic amines give rise to dia-zonium salts (RNj X) which readily decompose, sometimes with rearrangement. Aromatic diazonium salts (ArNj X ) are very important in aromatic transformations, and are discussed later. Secondary amines, on the other hand, give rise to nitrosamines... 

The test is best used to distinguish primary aromatic and primary aliphatic amines from secondary and tertiary amines. It also differentiates aromatic and aliphatic primary amines. It cannot distinguish between secondary and tertiary amines. You will need to use infrared spectroscopy to make the distinction between secondary and tertiary amines. Primary aliphatic amines lose nitrogen gas at low temperatures under the conditions of this test. Aromatic amines yield a more stable diazonium salt and do not lose nitrogen until the temperature is elevated. In addition, aromatic diazonium salts produce a red azo dye when -naphthol is added. Secondary and tertiary amines produce yellow nitroso compounds, which may be soluble or may be oils or solids. Many nitroso compounds have been shown to be carcinogenic. Avoid contact and immediately dispose of all such solutions in an appropriate waste container. 

Note. PRIMARY ALIPHATIC AMINES. The lower amines are gases or low-boiling liquids (b.ps. CHjNH, 7 CiHjNH, 17 CH,(CH2,>,NH 49 (CHg)jCHNHa, 34 ) but may be encountered in aqueous or alcoholic solution, or as their crystalline salts. They are best identified as their benzoyl, or toluene-/>-sulphonyl derivatives (c/. (C) above), and as their picrates when these are not too soluble. This applies also to benzylamine, CjHsCHjNH, b.p. 185 also to ethylenediamine, usually encountered as the hydrate, NHj (CHj)j NH2,HjO, b.p. 116 , for which a moderate excess of the reagent should be used to obtain the di-acyl derivative. (M.ps., pp. 55 55 )... 

They are readily hydrolysed by boiling dilute hydrochloric acid and the original amine can be recovered by neutralisation with alkali and steam distillation. Primary aliphatic amines liberate nitrogen with nitrous acid whilst tertiary amines are unaffected. 

The glycidyl adducts are skin irritants similar in behaviour in this respeet to the parent amines. The skin sensitisation effects in the primary aliphatic amine may be reduced by addition of groups at the nitrogen atom. The hydroxyethyl group and its alkyl and aryl derivatives are the most effective found so far. 

Until recently, no synthetically useful procedures for replacement of primary aliphatic amines by fluorine had been developed... 

Diazobenzene Sulphate.—Whereas nitrous acid immediately decomposes the primary aliphatic amines wdth et olution of nitiogen,... 

The resulting diazo reagents undergo a wide variety of reactions including those of interest in the manufacture of azo dyes and pharmaceuticals. With primary aliphatic amines the course of the reaction is different N2 is quantitatively evolved and alcohols usually result ... 

Instead of a diazonium salt, a diazo compound is obtained from reaction of a primary aliphatic amine 8 that has an electron-withdrawing substituent at the a-carbon (e.g. Z = COOR, CN, CHO, COR) as well as an a-hydrogen ... 

Catalysts show remarkable product variation in hydrogenation of simple nitriles. Propionitrile, in neutral, nonreactive media, gives on hydrogenation over rhodium-on-carbon high yields of dipropylamine, whereas high yields of tripropylamine arise from palladium or platinum-catalyzed reductions (71). Parallel results were later found for butyronitrile (2S) and valeronitrile (74) but not for long-chain nitriles. Good yields of primary aliphatic amines can be obtained by use of cobalt, nickel, nickel boride, rhodium, or ruthenium in the presence of ammonia (4J 1,67,68,69). 

Several articles [7,8] have reported that a persulfate-amine system, particularly persulfate-triethanol amine and persulfate-tetramethylethylenediamine (TMEDA) can be used as redox initiators in aqueous solution polymerization of vinyl monomers. Recently, we studied the effect of various amines on the AAM aqueous solution polymerization and found that not only tertiary amine but also secondary and even primary aliphatic amine and their polyamines can promote the vinyl polymerization as shown in Table 6 [40-42]. 

The ethoxycarbonyl derivative 11 is converted into derivatives 12 of 2-pyrimidone by the action of primary aliphatic amines.291 The products 12cyclize to the 5-aminopyrimido[4,5-/>][l,5]ben-zodiazepinones 13 on heating with ethanolic triethylamine.292... 

Reaction of a-isocyano-a, / -unsaturated sulfones with primary aliphatic amines affords 1,5-disubstituted imidazoles 59 (equation 56)48. The reaction of aromatic amines such as aniline is too slow to be of practical use. Results of the preparation of 59 are listed in Table 5. 

This method gives better yields than other methods of preparation of 2-bromoallylamine, and it is the most convenient method for the preparation of large quantities of the compound. The procedure illustrates a reaction, the so-called Delepine reaction, that has been used for the preparation of many primary aliphatic amines.8-12 A number of primary aliphatic amines have been prepared by this method without isolation of the intermediate hexaminium salt.11 Several preparations of aliphatic aldehydes via the hexaminium salt have been described in earlier volumes of this series.13... 

The reaction of diazo compounds with amines is similar to 10-15. The acidity of amines is not great enough for the reaction to proceed without a catalyst, but BF3, which converts the amine to the F3B-NHR2 complex, enables the reaction to take place. Cuprous cyanide can also be used as a catalyst. The most common substrate is diazomethane, in which case this is a method for the methylation of amines. Ammonia has been used as the amine but, as in the case of 10-44, mixtures of primary, secondary, and tertiary amines are obtained. Primary aliphatic amines give mixtures of secondary and tertiary amines. Secondary amines give successful alkylation. Primary aromatic amines also give the reaction, but diaryl or arylalkyl-amines react very poorly. 

Primary (R = H) and secondary aromatic amines react with alkenes in the presence of thallium(III) acetate to give vie- diamines in good yields. " The reaction is not successful for primary aliphatic amines. In another procedure, alkenes can be diaminated by treatment with the osmium compounds R2NOSO2 and R3NOSO (R = t-Bu)," analogous to the osmium compound mentioned at 15-51. The palladium-promoted method of 15-51 has also been extended to diamination. " Alkenes can also be diaminated indirectly by treatment of the aminomercurial compound mentioned in 15-51 with a primary or secondary aromatic amine. 

Primary aliphatic amines can be oxidized to aldehydes or ketones. Other reagents... 

A number of drawbacks in the application of the 0PA/2-ME reagent system include the instability of the fluorescent isoindole derivative (5-7) the use of the noisome reagent 2-mercaptoethanol the low and solvent-dependent fluorescence efficiencies (8,9) of the isoindole and—perhaps the most limiting—the effective restriction of the OPA assay to primary aliphatic amines and to amino acids. 

The initial discoveries of the extension of the aromatic ring of the ortho-phthalaldehyde (OPA) to a naphthalene-2,3-dicarboxaldehyde (NBA) and the substitution of cyanide (CN ) for 2-ME as the nucleophile have provided the Center with a much more versatile reagent system (5,11), which maintains the sensitivity for primary aliphatic amines and amino acids, and now is known to form fluorescent products with oligopeptides, proteins, and other related analytes that possess a primary amine function (Equation 1). 

The reaction of EPM-g-MA with primary aliphatic amines results in amide acids, which at elevated temperature convert to imides [12] (Figure 13.6). The reaction of EPM-g-MA with alcohols yields... 

Rummey et al. [223] searched replacements for the pyrrolidine present in their DPP-IV inhibitor searching a 10,000-molecule subset of small primary aliphatic amines extracted from the available chemical directory and visually inspected the top 500 of them. Four were selected for testing and two of them were novel hits. 

Primary aliphatic amines and piperidine react even at room temperature, whereas secondary aliphatic amines require reflux temperature. Primary and secondary aromatic amines also require reflux temperature and A -methylimidazole as catalyst. 

Woodbum HM, Morehead BA, Chih CM (1950) The reaction of cyanogens with organic compounds. II. Primary aliphatic amines. J Org Chem 15(3) 535-540... 

Recently, the oxidation of primary aliphatic amines to the corresponding nitro compounds has also been achieved using the catalyst system based on zirconium tetra tert-butoxide and tert-butyl hydroperoxide in a molecular sieve (50-98% yield) (Eqs. 2.56 and 2.57 and Table... 

A number of palladium-catalysed reactions of the triflate 61 have been reported but the nucleophilic displacement with primary aliphatic amines was, surprisingly, very slow in refluxing THF (24-92h). However, under microwave irradiation the reactions were very rapid and gave high yields, although even with microwaves, secondary amines and anilines failed to... 

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