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Please login or sign up for a free trial to access the full content. Method 1: Reactions of Ammonia with Alcoholic Hydroxy Groups

DOI: 10.1055/sos-SD-140-00180

Scammells, P. J.Science of Synthesis Knowledge Updates, (20132445.

The direct amination of alcohols using ammonia and a heterogeneous catalyst has emerged as a useful method for the preparation of primary amines.[‌54‌‌56‌] For example, the conversion of primary alcohols into the corresponding primary amines 21 by treatment with ammonia in the presence of a pincer-type ruthenium(II) complex 20 has been reported.[‌54‌] Using this procedure, benzyl alcohol and ammonia (7.5 atm) react in the presence of complex 20 (0.1 mol%) to give benzylamine (21, R1 = Ph) in 75% isolated yield (Scheme 14). The scope of this reaction has been explored, with a range of aryl- and het­aryl-substituted methanols, as well as primary aliphatic alcohols, being converted into the corresponding primary amines in yields ranging from 61 to 96%. Interestingly, reactions of this type can be conducted in neat alcohol and even „on water“ in the case of insoluble or poorly water-soluble alcohols. However, water-soluble alcohols such as 2-pyridyl­methanol and 2-methoxyethanol undergo minimal conversion even after prolonged heating when the reaction is conducted in water. It is noteworthy that the ruthenium catalyst used in these reactions is readily prepared from 4,5-bis(bromomethyl)acridine in two high-yielding steps, and is found to be stable in air for several months.[‌54‌]

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Meeeeeeeeee 88

M8 Meeeeeeeeee (%) Meeeee,e (%) Mee
Me 88 88 (88) [‌88‌]
8-Mee 888 88 (88) [‌88‌]
8-MeMM8M8 888 88 [‌88‌]
8-MM8M8 888 88 [‌88‌]
8-eeeeeee 888 88 [‌88‌]
8-eeeee 888 88 [‌88‌]
Me 88 88 [‌88‌]
Me 888 88 [‌88‌]
MM8MMe 888 88 [‌88‌]
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Me 88 88 [‌88‌]
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Meeeee 88 Meeeeeeee Meeeee ee Meeeeeee ee Meeeeeeee Meeeeeee eeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeeeeeeeee (%) Meeeee (%) Mee
(MM8)8Me Me 88 88 [‌88‌]
(MM8)8Me Me 88 88 [‌88‌]
Me Me 88 88 [‌88‌]
Me Me 88 88 [‌88‌]
8-eeeee Me 88 88 [‌88‌]
MM8MMe8 Me 88 88 [‌88‌]
(MM8)8 888 88 [‌88‌]
(MM8)8 88 88 [‌88‌]
(MM8)8 888 88 [‌88‌]
(MM8)8M(MM8)8 88 88 [‌88‌]
88 88 (88)e [‌88‌]
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Meeeee 88 Meeeeee-Meeeeeeee Meeeeeeee ee Meeeeeee eeee Meeeeeee Meeee[‌88‌]

Meeeeeeeeee 88

M M8 M8MM (eeee) Meeeeeee 88 (eee%) Meeeeeeeee Meeee (%) Mee
88 88
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MM8 Me 88 8.8 888 °M, 88 e 88 e [‌88‌]

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Meeeeeeeeeee Meeeeeeee

Meeeeee Meeeee 88; Meeeeee Meeeeeeee:[‌88‌]

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Meeeeeeee-8-eeeee (88, M8,M8 = Meeeeee[8.8.8]eeeeee-8,8-eeee); Meeeeee Meeeeeeee:[‌88‌]

Me8(MM)88 (88.8 ee, 8.88 eeee), 8-(eeeeeeeeeeeeeeeeeeeee)-8-eeeeee-8M-eeeeeee (88; 88.8 ee, 8.88 eeee), eee eeeeeeeee-8-ee (888 ee, 8 eeee) eeee eeeeeeeee ee 8-eeeeeeeeeee-8-ee (8 eM) ee e eeeee eeeeeeee eeee (88 eM) eeeee ee eeeee eeeeeeeeee. Mee eeeeeeee eeee eee eeee eeeeee eee eeeeee ee eee eee ee eeeee ee eeeeeeeee MM8 (8 e) ee eeeeeeeeeeee. Mee eeeeeeeee eeeeeee eee eeeeeee ee 888 °M ee ee eee eeee eeeee eeeeee eeeeeeeeee eee 88 e, eee eeee eee eeeeeee eee eeeeeee eeeee eeeeee. Mee eeeeeee eee eeeeeeeee ee MeMM eee eee eeee eee eeeeeee ee ee Meeeeee MMM-8 eeeeee (8 e/88 eM, Meeeeee). Mee eeeee eee eeeeeeee ee eee MMM eeeeee eee eee eeeeeee eeeeee eeeeeee. Mee eeeeee eee eeee eeeeee eeee MeMM eee eee eeeeeee eee eeeeee eeeeeeee eeee e 8 M eeee ee MM8 ee MeMM. Mee MeMM eee eeee eeeeeee eeeee eeeeee ee eeee eee eeeeeee ee e eeee eeeeee eeeee; eeeee: 888 ee (88%).

Meeeeeeeeeeeee (88, M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

MM8MMe (888 ee, 8.88 eeee), eeeeeeee 88 [88 ee, 8.888 eeee, 8.8 eee% (8.8 eee% Me)], eee MeMMM8 (888 ee, 8.88 eeee, 88 eee%) eeee eeeee ee e 888-eM eeeee eeeee ee eeeeeeeeee ee eeeee. MeMM (8.888 e, 88.8 eeee) eee eeee eeeee ee eeeeeee, eee eee eeeee eee eeeeee eeee e eeeee eeeeeee. Mee eeeeeee eee eeeeeee ee ee eee 88 eee eee eeee ee 888 °M eee 88 e. Meee, 8 M ee MeMM (88 eM) eee eeeee ee eee eeeeeee eee eee eeeeeee eee eeeeeeeee eeee MM8Me8 (88 eM). Meeeeee ee eee eeeeeee eeeeeeee ee Meeeeeeee eeeeeeeeeeee (ee 888 °M/8.8 Meee) eeee eee eeeeeee eeeeeee; eeeee: 8.88 e (88%).