Reductive Amination of 2-Amino-2-methyl-1-propanol and Ammonia to Produce 2-Methyl-1,2-propanediamine over Raney Nickel Catalyst

Abstract

The selective synthesis of 2‐methyl‐1,2‐propyldiamine (MPDA) directly from 2‐amino‐2‐methyl‐1‐propanol (AMP) and ammonia via one‐pot reaction is reported for the first time. The effects of catalyst species and reaction variables on the synthetic performance of MPDA were systematically studied. In contrast to other catalysts, a high MPDA selectivity of 88.3% and AMP conversion of 45.6% were obtained over Raney Ni catalyst. The components of the final reaction mixtures were particularly dependent on the initial hydrogen pressure and stirring speed. Furthermore, a possible mechanism of the reaction was proposed on the basis of experimental results, which has great implications in the development of more efficient and higher selectivity catalysts.

Ni-Catalyzed reductive amination of phenols with ammonia or amines into cyclohexylamines

“…28 So far, no protocols relate to the substitution of these precious metals by more earthabundant metals such as Ni, even though the use of this metal is well established in the chemical industry. Based on related Nicatalyzed reactions, [29][30][31][32][33][34][35] we hypothesized that a sufficient amount of the cyclohexanone intermediate might be formed in the course of the reaction, which in turn could afford primary or N-substituted cyclohexylamines in the presence of ammonia or amines, respectively. Moreover, the effect of the acid-base properties of the supporting material remains unclear, as only commercially available Rh or Pd on carbon catalysts were used so far.…”

Identification of an Active NiCu Catalyst for Nitrile Synthesis from Alcohol

“…Ni-based catalysts − have been extensively investigated in the hydrogen-free conversion of alcohols to primary amines, based on a “hydrogen-borrowing” strategy. − In this case, the amination reaction follows a dehydrogenation–imination–hydrogenation pathway, where alcohols are dehydrogenated to aldehydes/ketones and then react with ammonia to afford imines and finally to amines via hydrogenation. Recently, a Ni/Al 2 O 3 catalyst was reported to convert a series of aliphatic and aromatic primary alcohols to nitriles under oxidant-free conditions .…”

Efficient Synthesis of 5-Amino-1-pentanol from Biomass-Derived Dihydropyran over Hydrotalcite-Based Ni–Mg3AlOx Catalysts

“…These findings indicate that high H 2 pressure favors not only the RA of 2-HTHP to the target 5-AP product, but also the direct hydrogenation of the highly reactive intermediate of 5-HP and 5-HPIP to 1,5-PD and DPA side-products, respectively. Previous studies in the RA of carbonyl compounds 29 and the direct amination of alcohols 6,31,34 also show that increase of H 2 pressure promoted both the desired and side reactions. Therefore, an appropriate H 2 pressure, i.e., 2 MPa is required for the efficient RA of 2-HTHP to produce 5-AP.…”

“…Clearly, the above findings indicate that the inexpensive Ni-LDO has the potential to be an alternative catalyst for the RA of 2-HTHP with high activity and selectivity. Previous studies also show that Ni is an active non-noble metal for the direct amination of alcohols by BH mechanism and the RA of aldehydes and ketones. ,,− …”

“…It has been reported that the reaction parameters of temperature, H 2 pressure, and ammonia amount significantly affect the catalytic performance of the RA of aldehydes and ketones. ,,, The effect of these reaction parameters on the RA of 2-HTHP over 30Ni-LDO prereduced at 750 °C was investigated and the results were compiled in Table . A high 2-HTHP conversion of 98.8% could be obtained even at low temperature of 40 °C (Table , entry 1), showing the high reactivity of 2-HTHP, as mentioned above.…”