Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content.
40.1.1.5.4.5.2.1 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]

Meeeee 88 Meeeeee Meeeee ee Meeeeeee ee Meeeeee Meeeeeee eeee Meeeeee[‌88‌]

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]
e-Me 88 88 [‌88‌]
Me 88 88 [‌88‌]
88 88 [‌88‌]

e Meeeee eeeeeeeeee ee MM eeeeeeee.

e Meeeee ee eeeeeeeeeee eee eee eeeeeeee eeeeee.

Meee eeeeeee eeeeeeee eee eeee eeeeeeee ee eee eeeeeeee ee eeeeeeeee eeeeeeee eeee eeeeeee.[‌88‌] Mee eeeeeeee ee eeeeeeeeeeee eeee eeeeeee ee 888 °M ee eee eeeeeeee ee e eeeeeeeee eeeeeeee [Me8(MM)88] eeee eeeeeee eeeeeeeee eeeeeee eee eeeeeeeeeeee eeeeeeeee. Mee eeeeeeee ee eeeee eeeeeeeee eeeeeeeee ee eeee eeeee, eeeeeeee eee eeeeeeee eeeeeeeee 8-(eeeeeeeeeeeeeeeeeeeee)-8-eeeeee-8M-eeeeeee (88) eeeeee eeee eeeeeee, eeeeeeeee eeeeeeeeeeeeeee ee 88% eeeee. Meeeeee eeeeeeeeeeee ee eee eeeeeeee eeeeeeeeee eeeeeeeeeeeee eeeeeeee eeee eeeeeee eee, eeee eeeeeeeeeeee, eee eee ee 8-eeeeeeeeeee-8-ee ee eee eeeeeeee eeeeeee eeeeeeee eeee eee eeeeeeee ee eeeeeeeee eeeeee ee eeeeee eeeee eeeeeeeee eee eeeee ee eeeeeeeeeeeeeee ee 88%. Meee eeeeeeeeeee eee eeeeeeeeeeee eeee eeee ee eeeeeee e eeeee ee eeeeeeeee eeeeeeee eeee eee eeeeeeeeeeeee eeeeee 88 (Meeeee 88).[‌88‌] M eeeeeee eeeeeee eeeeeeeee eee eee eeeeeeeee ee eeeeeeeee eeeeeeee eeee eeeeeee eee eeee eeeeeeeeeee ee eeeeeeeee eeeeeeee eee eeeeee 88 eee eeee eeeeeeeee ee eeeeeeee eeee eeee eeee.[‌88‌]

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]
88 88 [‌88‌]

e Meeeee eeeeeeeeee ee MM eeeeeeee eeee eeeeeeeeee ee ee eeeeeeee eeeeeeee.

e Meeee ee eeeeeeeeeee ee eee ee eeeeeeee eeeee.

Me eeee eeeeeeee eee eeeeeee eeeeeeeee eeeeeeeee eeeeeeeeeeeeeee ee eeee ee eeeeeeee ee eeeeee, eeeeeeee ee eeeeeeee eeee eeeeeee ee eeee ee eeeee (Meeeee 88).[‌88‌] Meeeeeeeeeeee ee eeee eeeee eeeeeee eee eeeeeeeeeeeee eeeee ee eee eeeeeee. Mee eeeee-eeeeeeeee eeeeeeeeeeeeeee eeee eeeeeeeeee eeeeeeee eee eeeeeeee eee eee eeeeeeeeeeeee eeee, ee eeee eeeeeee eee eeee eeeeeeeee ee e „eeeeeeeee eeeeeeee“ ee „eeeeeeee eeeeeeeeeeee eeeeeeeee“.

Meeeee 88 Meeeeeeee ee Meeeeeee eeee Meeeeee[‌88‌]

Meeeeee-eeeeeeeee eeeeeeeeee eeee eeee eeee eeeeeeeee eee eee eeeeeeeee M-eeeeeeeeee ee eeeeeeee eeeee eeee eeeeeee eee eeeeeeeee eeeeeeee ee eee eeeeeee ee eeeeeee. Meeeeeeeeeeeee eeeeeeee eee eeee eeeeee eee eeeeeeee ee Meeeee 88.[‌88‌] Mee eeeee eeeeeee eeeeeeeeeeee eee eeeeeeeee eeeeeeeeeee ee e eeeeeeee eeeee, eeeeeeeeeeeeee (88, M8 = Me), eee eeeeeeeeeeeee ee eeeeeeee eeeeeee eeee eeeeee eeeeeee eeeee eeeeeee eeeeeeee 88. Me eeee eeeeeeee eeeeeeee eeeeeeee ee eeeeeeee ee eeeeeeee eee eeeeeeeee ee eeeeeeeeeeeee (88, M8 = Me). Mee eeeeee eeeeeee eeeee eee eeeeeeeee eeeeeeeeeee ee e eeeeeeeee eeeee, eeeeeeeeeeee [88, M8 = (MM8)8Me], eee eee eeeeeeeeeeee ee eeeeeeee eeeeeeeeeeeeeeeee eeee eeeeeee. Mee eeeeee ee eeeeeeee eeee eeeeee ee ee eeeeeeeee eee eee eeeeeeeee ee eeeeeeeee eeeeee ee eeee eeee. Mee eeeeeee, eee eeeeeeee ee eeeeeeee eeeeeee eeee eeeeeee (8.8 eeeee) eeeeeee eeee eeeee eeeeeee ee eeeeeeeeeeee, eeee eeeeeeeeeeeee [88, M8 = (MM8)8Me] eeeee eee eeeee eeeeeee (88%). Mee eeeee eeeeeee eeeeeeeeeee eee eeeeeeeee eeeeeeeeeee ee e eeeeeeeee eeeee, eeeeeeeeeeeeeeeee (88, M8 = Me), eee eee eeeeeeee ee eeeeeeee eeeeeeeeeeeeeeeee eeee eee eeeeeeeee eeeeeee eeeeeeeeeeee. Me eeeeeeeee eeeeeee eeeeeeee eeeeeeeeeeeeeeeee eee eeeeeeeee eeeeeeee, eee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeeee eeeee ee eee eeeeeeee, eeeeeeeeee eee ee eeeeee eeeeeee.

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
MMe Me 88 8.8 888 °M, 88 e eeeee 88 [‌88‌]
MM8 (MM8)8Me 88 8 888 °M, 88 e 88 8 [‌88‌]
MM8 Me 88 8.8 888 °M, 88 e 88 e [‌88‌]

e Meeeeee eee eeeeeeee.

Meeeeeeeeeee Meeeeeeee

Meeeeee Meeeee 88; Meeeeee Meeeeeeee:[‌88‌]

MeMeM(MM)(MMe8)8 (888 ee, 8.88 eeee), 8,8-eee[(eeeeeeeeeeeeeeeeeeee)eeeeee]eeeeeeee (888 ee, 8.88 eeee), eee eeeeeee (88 eM) eeee eeeee ee e Meeeeee eeeee eeeeee eeeee e M8 eeeeeeeeee. Mee eeeeeee eee eeeeee ee 88 °M eee 8 e, eee eeeeeee eee eeeeeee, eee eee eeeeee eeeee eeeeeeee eee eeeeee eeee eeeeeee eee eeeee eeeee eeeeee eeeeeeeee, eeeeeeeee ee eeee eeeeeee 88; eeeee: 888 ee (eeeee).

Meeeeee 88 (8.8 ee, 8.88 eeee), eee eeeeeee (88 eeee), eee eeeeeee (8 eM) eeee eeeee ee e 88-eM Meeeeee–Meeeee eeee eeeee ee eeeeeeeeee ee eeeeeeee M8 ee e eeeeeeee. Mee eeee eee eeeee eee ee eee eeeeeeee, MM8 (8.8 eee) eee eeeee, eee eee eeeeeee eee eeeeeeee ee ee eee eeee eeeeeee ee e eeeeeeeeee eeeeee eee eee eeeeeeeee eeee. Meeee eeeee eeeeeee ee eeee ee ee, eee eeeeeeee eeee eeeeeeee ee MM, eeee eeeeeee ee eeeeeeeeee ee ee eeeeeeee eeeeeeee [MM-8 eeeee-eeeeee 8% MM MM eeeeeeee eeeeee (88 e × 8.88 ee × 8.88 μe eeee eeeeeeeee)].

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%).

References


Cookie-Einstellungen