Alkyl derivatives primary alkylamines

Alkylation of phthalimide The Gabriel synthesis (Section 22 8) The potassium salt of phthalimide reacts with alkyl hal ides to give N alkylphthalimide deriva fives Hydrolysis or hydrazinolysis of this derivative yields a primary alkylamine... 

We ve already seen in Sections 20.7 and 21.7 how amines can be prepared by reduction of nitriles and amides with LiAlH4. The two-step sequence of 5 2 displacement with C followed by reduction thus converts an alkyl halide into a primary alkylamine having one more carbon atom. Amide reduction converts carboxylic acids and their derivatives into amines with the same number of carbon atoms. 

Recently Mukaiyama and Ta chi [244] have reported a new method for the preparation of primary alkylamines which may offer advants es over the Gabriel synthesis (Section 2.1.2.1) for certain applications. Di(phenylsulphenyl)imide (39) readily yields an iV-lithio derivative which may be alkylated with halides orp-toluenesulphonates and subsequently hydrolyzed to give good yields of primary amines. 

Photoamination via Category III has been investigated in polycyclic arenes such as phenanthrene (la) and its derivatives (Ib-li), anthracene (Ij), and naphthalene derivatives (Ik-lv) [36-37], A typical example was photoamination of la with NHj, which was performed by the irradiation of an ammonia-saturated MeCN-H O solution containing la and m-DCB for 17 h to give the Type I aminated product, 9-amino-9,10-dihydrophenanthrene (10a), in 84% yield (Scheme 6.11). It was apphed to photoamination with primary amines such as alkylamines, ethanolamine, allylamine, and glycine ethyl ester and so on, which gave efficiently A-alkyl derivatives of 10a. But photoamination with secondary alkylamines such as dimethylamine and diethylamine were inefficient [38]. 

The preparation of fluorinated carbohydrates via nucleophilic displacement of the. sulfonate group of the corresponding sulfonates by fluoride is a well-known rcaction " however, potassium fluoride, which was used to prepare the first alkyl fluoride type of sugar derivative, has been progressively replaced by the alkylamine fluorides (.see Section 1.1.4.2.1.2.). The substitution of relatively unhindered primary mesylates or tosylates in cxocyclic positions of carbo-... 

Preparation of secondary amines by reductive alkylation of ammonia is not such a general reaction as that of primary amines. In the aliphatic series treating ammonia with 2 moles of a carbonyl compound usually affords a mixture of mono-, di-, and tri-alkylamines. However, 80-90% yields of the corresponding dibenzylamine are obtained from benzaldehyde or its o-chloro or o-methyl derivative.996... 

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