Amines preparation from

The SEM derivative of a secondaiy aromatic amine, prepared from SEMCl (NaH, DMF, 0°, 100% yield), can be cleaved with HCl (EtOH, >88% yield). ... 

Originally, a C-20 amine (prepared from a bisnorcholanic acid) was converted into its 7V-chloro derivative, dehydrohalogenated to the imine, converted into the A-acetylenanime, reacted with perbenzoic acid, then hydrolyzed to the 17a-hydroxy-20-ketone ... 

Amines, preparation from isothiocyanates, 18, 5 from ketones, 17, 76 m-Aminobenzaldehyde, 13, 28... 

Few examples of the preparation of hydrazines or hydroxylamines on insoluble supports have been reported (Table 10.17). Hydrazines have been prepared by the reduction of aromatic diazonium salts or /V-nitroso amines (prepared from secondary amines by treatment with tert-butyl nitrite [340]), and by the N-amination of support-bound amines (Entry 3, Table 10.17). The direct reduction of hydrazones with borane to yield hydrazines on solid phase has not been reported, and appears to be difficult because of the ease with which the N-N bond of hydrazines is cleaved by reducing agents [340]. 

Exercise 23-24 Show how a mixture of amines prepared from 1-bromobutane and an excess of butanamine may be resolved into its components by reaction with the anhydride of 1,4-butanedioic acid, (CH2)2(CO)20, separation of the products through advantage of their solubility properties in acid or base, and regeneration of the corresponding amines (Section 18-10C). Write equations for the reactions involved. 

The ultraviolet spectra 27,28 exhibit, in agreement with the general postulate of Braude et al.2%-30 a bathoehromic shift to 225-235 m/j. caused by the auxochromic action of the nitrogen-free electron pair. This shift is approximately the same as that caused by introduction of a conjugated double bond, and is increased by further conjugation with other multiple bonds, e.g. in diene-amines prepared from A -3-oxosteroids.31,32 Spectral maxima (at 280-285 mfi, e 19,000-26,000) point to the conjugation of three mobile electron pairs but cannot decide the position of the double bonds the molecular extinction coefficient indicates a transoid (5) rather than cisoid arrangement (e.g. 6).33... 

Di-n-propylamine can be produced in industrial scale by the alkylation of ammonia with n-propanol on Ba(OH)2 modified Ni/Al203 catalyst [2], by the reductive amination of propionaldehyde over a cobalt-containing catalyst [3] or by the hydrogenation acrylonitrile in n-exane on Ni/Al203 catalyst [4,5]. However, only scare data is available about the alkylation of ammonia or i-butylamine with i-butanol [6-10]. Di-i-butylamine was prepared from i-butanol over alumina at 370-380 C with 28 % yield [7]. 20 wt% Co - 5 wt% Ni catalyst supported on alumina was used to prepare di-i-butylamine fi"om i-butanol and i-butylamine at 200 °C with a yield of 60. 6 [10]. Aliphatic mixed secondary amines prepared from a pimary amine and an alcohol were usually obtained on copper-containing catalysts at 190-200 C with 30-50 % yields [11-13]. 

The diamine (R=Ph) was also applied to the synthesis of optically active a-hydroxyaldehydes. Treatment of the aminal, prepared from the chiral diamine and phenylglyoxal, with Grignard... 

Platinum oxide (0.2 g) is suspended in water (10 ml) and reduced by hydrogen, then the ketone (0.3 mole), ammonium chloride (20 g, 0.37 mole), saturated methanolic ammonia solution (225 ml), and aqueous ammonia (25 ml) are added, and the mixture is hydrogenated at 1-3 atm. The following are among the amines prepared from the corresponding ketones, in the yields stated, by this method 4-methyl-2-pentanamine (57-65%), 4-heptanamine (40 to 60%), 2,4-dimethyl-3-pentanamine (55%), and (x-methylbenzylamine (69%).1002... 

Addition of ethylene oxide and propylene oxide to fatty amines prepared from naturally occurring fatty acids encounters no difficulties. The reaction results in surfactants of mainly nonionic character those are characterised by better compatibility with anionics and moderate toxicity in comparison to initial amines. The ethoxylated fatty amines found application in textile finishing, acidic cleaners and cosmetics. Commercial ethoxylated fatty amines are known, for example, as Ethomeen , Genamin C/O/S/T , Imbentin-CAM/OTM , Marlazin , and Rhodameen/Cemulcat series of Akzo Nobel, Clariant, Kolb, Condea, and Rhodia, respectively. 

Electrochemical oxidaticai of bicyclic amine prepared from (5)-prolinol and trifluoroace-taldehyde proceeded to afford enantiomerically pure methoxylated compound in excellent regioselectivity. This product was easily... 

Scheme 10.35. A representation of the Curtins rearrangement showing that the amine prepared from the corresponding carboxylic acid retains the absolute conhguration.

Scheme 10.37. A representation of the Lossen rearrangement showing that the amine prepared from the corresponding carboxylic acid retains the absolnte configuration (see Lossen, W. Liebigs Ann. Chem., 1872,161, 347 as well as Yale, H. L. Chem. Rev., 1943,33, 219).

Ethyl a-cyano-a-cyclohexylacetate dissolved in an ice-cold ethanolic soln. of slightly more than 1 mole of hydroxyl-amine prepared from the hydrochloride in ethanol and an equivalent amount of Na-ethoxide, then a soln. of Na in etha-... 

Protonated esteramines are claimed for use as low-cost, biodegradable fabric softener agents [88]. Quaternized amines prepared from fatty acids and methylethanolisopropanolamine show good softening and improved rewetting compared with the methyldiethanolamine-based products [89],... 

These are made by ethoxylation of amines prepared from naturally occuring fatty acids (5). 

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