3218-01-7

Upstream product

• 201230-82-2 carbon monoxide 
• 110-83-8 cyclohexene 
• 100-49-2 cyclohexylmethyl alcohol 
• 2043-61-0 cyclohexanecarbaldehyde 
• 57-13-6 urea 
• 931-51-1 cyclohexylmagnesiumchloride 
• 121238-82-2 tris(benzotriazol-1-ylmethyl)amine 
• 766-05-2 cyclohexane carbonitrile 

Relevant academic research and scientific papers

Highly Selective Hydrogenative Conversion of Nitriles into Tertiary, Secondary, and Primary Amines under Flow Reaction Conditions

Flow reaction methods have been developed to selectively synthesize tertiary, secondary, and primary amines depending on heterogeneous platinum-group metal species under catalytic hydrogenation conditions using nitriles as starting materials. A 10 % Pd/C-packed catalyst cartridge affords symmetrically substituted tertiary amines in good to excellent yields. A 10 % Rh/C-packed catalyst cartridge enables the divergent synthesis of secondary and primary amines, with either cyclohexane or acetic acid as a solvent, respectively. Reaction parameters, such as the metal catalyst, solvent, and reaction temperature, and continuous-flow conditions, such as flow direction and second support of the catalyst in a catalyst cartridge, are quite important for controlling the reaction between the hydrogenation of nitriles and nucleophilic attack of in situ-generated amines to imine intermediates. A wide variety of aliphatic and aromatic nitriles could be highly selectively transformed into the corresponding tertiary, secondary, and primary amines by simply changing the metal species of the catalyst or flow parameters. Furthermore, the selective continuous-flow methodologies are applied over at least 72 h to afford three different types of amines in 80–99 % yield without decrease in catalytic activities.

One-Pot Synthesis of Symmetrical Tertiary and Secondary Amines from Carbonyl Compounds, Ammonium Carbonate and Carbon Monoxide as a Reductant

Rh-catalyzed one-step synthesis of tertiary and secondary amines from aldehydes and ketones, ammonium carbonate serving as nitrogen source, and carbon monoxide as a reducing agent has been developed. Aliphatic and aromatic aldehydes lead to the corresponding tertiary symmetrical amines in 69–83 % yields. Aromatic and aliphatic ketones lead to the corresponding secondary symmetrical amines which were obtained in 62–79 % yields.

Catalyst-Dependent Selective Hydrogenation of Nitriles: Selective Synthesis of Tertiary and Secondary Amines

In the presence of palladium on carbon (Pd/C) as a catalyst, hydrogenation of aliphatic nitriles in cyclohexane efficiently proceeded at 25-60 °C under ordinary hydrogen gas pressure to afford the corresponding tertiary amines. However, the use of rhodium on carbon (Rh/C) led to the highly selective generation of secondary amines. Hydrogenation of aromatic nitriles and cyclohexanecarbonitrile selectively produced secondary amines in the presence of either Pd/C or Rh/C.

Using aqueous ammonia in hydroaminomethylation reactions: Ruthenium-catalyzed synthesis of tertiary amines

The direct synthesis of tertiary amines from ammonia and olefins is presented. Using a combination of Ru3(CO)12 and 2-phosphino-substituted imidazole ligand as catalyst system allows for hydroaminomethylation reactions of bulk aliphatic and functionalized olefins. Tertiary amines are obtained in an atom-efficient domino process in moderate to good isolated yields (45-76%) with excellent regioselectivities (n/iso up to 99:1).

The "borrowing hydrogen strategy" by supported ruthenium hydroxide catalysts: Synthetic scope of symmetrically and unsymmetrically substituted amines

The N-alkylation of ammonia (or its surrogates, such as urea, NH 4HCO3, and (NH4)2CO3) and amines with alcohols, including primary and secondary alcohols, was efficiently promoted under anaerobic conditions by the easily prepared and inexpensive supported ruthenium hydroxide catalyst Ru(OH)x/TiO2. Various types of symmetrically and unsymmetrically substituted "tertiary" amines could be synthesized by the N-alkylation of ammonia (or its surrogates) and amines with "primary" alcohols. On the other hand, the N-alkylation of ammonia surrogates (i.e., urea and NH 2HCO3) with "secondary" alcohols selectively produced the corresponding symmetrically substituted "secondary" amines, even in the presence of excess amounts of alcohols, which is likely due to the steric hindrance of the secondary alcohols and/or secondary amines produced. Under aerobic conditions, nitriles could be synthesized directly from alcohols and ammonia surrogates . The observed catalysis for the present N-alkylation recations was intrinsically heterogeneous, and the retrieved catalyst could be reused without any significant loss of catalytic performance. The present catalytic transformation would proceed through consecutive N-alkylation reactions, in which alcohols act as alkylating reagents. On the basis of deuterium-labeling experiments, the formation of the ruthenium dihydride species is suggested during the N-alkylation reactions.

Synthesis of polyamines via hydroaminomethylation of alkenes with urea - A new, effective and versatile route to dendrons and dendritic core molecules

Polyamines, structurally related to putrescines and spermidines, are easily obtainable via hydroaminomethylation of methylallylphthalimide with primary or secondary amines. In addition, hydroaminomethylation of monoolefins with urea as a synthetic equivalent for ammonia, in contrast to other methods (e.g. the alkylation of ammonia or ammonium salts), allows selective synthesis of symmetric tertiary amines. By combining both methods dendrons and dendrimer cores are conveniently obtained. The Royal Society of Chemistry 2006.

HYDROAMINOMETHYLATION OF OLEFINS

The present invention relates to a method comprising the step of contacting under hydroaminomethylation conditions, an olefin, an amine, a rhodium-phosphorous ligand, and synthesis gas (syngas). In particular, it has been discovered that, under some circumstances, a neutral rhodium-monodentate phosphite ligand is prescribed. The invention provides a simple way of making, in high yields and regiospecificity, a variety of products, including pharmacologically active products such as ibutilide, terfenadine, and fexofenadine, and derivatives thereof.

The Chemistry of N-Substituted Benzotriazoles. Part 14. Novel Routes to Secondary and Tertiary Amines and to N,N-Disubstituted Hydroxylamines

Tertiary amines of types R4R3CHNR1R2 (2), (R2CH2)2NR1 (10) and 11, or (R2CH2)3N (12), secondary amines of type (R2CH2)2NH (8), and N,N-disubstituted hydroxylamines of type (R2CH2)2NOH (9), are prepared in high yield by the action of Grignard reagents or sodium borohydride on easily available N,N-dialkyl-N-amines (1) or tris(benzotriazolylmethyl)amine (7), on bis(benzotriazolylmethyl)amines (3), (5), and (6), and on N,N-bis(benzotriazolylmethyl)hydroxylamine (4), respectively.