RANEY® nickel-catalyzed reductive N-methylation of amines with paraformaldehyde: theoretical and experimental study

Abstract

RANEY® Ni-catalyzed reductive N-methylation of amines with paraformaldehyde has been investigated.

Reductive N-methylation of amines using dimethyl carbonate and molecular hydrogen: Mechanistic insights through kinetic modelling

“…Component generation rates in a batch reactor can be easily written (13) where CS is the concentration of side products.…”

“…The selective N-methylation of amines is a frequently used reaction in organic synthesis, affording valuable compounds used as drugs, agrochemicals or dyes [11][12][13]. From an industrial perspective, the preferred methylation agents are formaldehyde, using the Eschweiler-Clarke methodology [13] and methanol, employing zeolites as dehydration catalysts.…”

“…The selective N-methylation of amines is a frequently used reaction in organic synthesis, affording valuable compounds used as drugs, agrochemicals or dyes [11][12][13]. From an industrial perspective, the preferred methylation agents are formaldehyde, using the Eschweiler-Clarke methodology [13] and methanol, employing zeolites as dehydration catalysts. [14] An interesting alternative to these methodologies would be the use of dimethyl carbonate (DMC) in the presence of a reducing agent, as DMC is a non-toxic, safe and biodegradable compound which is currently used in the industry.…”

N-Methylation of amines with methanol in a hydrogen free system on a combined Al2O3–mordenite catalyst

“…[1][2][3] The Nmethylation reaction is an important way to synthesize Nmethyl amines, and N-methylation of amines with methanol is considered to be a green production technology because its byproduct is mainly water. [1][2][3] The Nmethylation reaction is an important way to synthesize Nmethyl amines, and N-methylation of amines with methanol is considered to be a green production technology because its byproduct is mainly water.…”

Efficient Cobalt‐Catalyzed Methylation of Amines Using Methanol

“…[2] General methods to introduce methyl group often involve the use of hazardous methylating agents, such as methyl iodide, dimethyl sulfate or diazomethane, accompanied with the drawbacks of low product selectivity, toxic byproduct generation, expensive and tedious downstream processing. [4] Hence, development of efficient methylation protocols utilizing safer methylating agents and cheaper catalytic systems is of paramount importance and highly desirable. [4] Hence, development of efficient methylation protocols utilizing safer methylating agents and cheaper catalytic systems is of paramount importance and highly desirable.…”