20849-95-0

Upstream product

• 4360-51-4 cinnamylamine 
• 2687-12-9 cinnamyl chloride 
• 4360-47-8 cinnamonitrile 
• 104-54-1 3-Phenylpropenol 
• 111-26-2 hexan-1-amine 
• 100-46-9 benzylamine 
• 4393-06-0 1-Phenyl-2-propen-1-ol 

Downstream Products

• 20870-50-2 Chloressigsaeure-dicinnamylamid 

Relevant academic research and scientific papers

Chemoselective hydrogenation of unsaturated nitriles to unsaturated primary amines: Conversion of cinnamonitrile on metal-supported catalysts

The liquid-phase hydrogenation of cinnamonitrile to selectively obtain the unsaturated primary amine (cinnamylamine) was studied at 383 K and 13 bar on Ni, Co, Ru and Cu metals supported on a commercial silica. Ni/SiO2 and Co/SiO2 were the most active catalysts for cinnamonitrile conversion but formed only small amounts of cinnamylamine. In contrast, Cu/SiO2 and Ru/SiO2 presented low activity for cinnamonitrile hydrogenation but formed selectively cinnamylamine in the liquid phase; nevertheless, on both samples the carbon balance was only about 40%. In an attempt of promoting the rate and yield to cinnamylamine, additional catalytic runs were carried out at higher temperatures and H2 pressures on a highly dispersed Cu(11%)/SiO2 catalyst prepared by the chemisorption-hydrolysis method. Results showed that when cinnamonitrile hydrogenation was performed at 403 K and 40 bar on Cu(11%)/SiO2, the yield to cinnamylamine was 74% giving as by-product only the unsaturated secondary amine (dicinnamylamine).

Platinum-catalyzed direct amination of allylic alcohols with aqueous ammonia: Selective synthesis of primary allylamines

Direct amination of unactivated allylic alcohols with aqueous ammonia was catalyzed by a Pt/phosphine complex to give the corresponding allylamines along with water as the sole by-product. Under optimized reaction conditions, primary allylamines were obtained as major products with excellent monoallylation selectivity. cod=1,5-cyclooctadiene.

Why platinum catalysts involving ligands with large bite angle are so efficient in the allylation of amines: Design of a highly active catalyst and comprehensive experimental and DFT study

The platinum-catalyzed allylation of amines with allyl alcohols was studied experimentally and theoretically. The complexes [Pt(η3-allyl)- (dppe)]OTf (2) and [Pt(η3-allyl)(DPP-Xantphos)]PF6 (5) were synthesized and structurally characterized, and their reactivity toward amines was explored. The bicyclic aminopropyl complex [Pt(CH2CH 2CH2NHBn-κ-C,N)-(dppe)]OTf (3) was obtained from the reaction of complex 2 with an excess of benzylamine, and this complex was shown to be a deactivated form of catalyst 2. On the other hand, reaction of complex 5 with benzylamine and allyl alcohol led to formation of the 16-VE platinum(0) complex [P(η2-C3H3OH)-(DPP-Xantphos)] (7), which was structurally characterized and appears to be a catalytic intermediate. A DFT study showed that the mechanism of the platinum-catalyzed allylation of amines with allyl alcohols differs from the palladium-catalyzed process, since it involves an associative ligand-exchange step involving formation of a tetracoordinate 18-VE complex. This DFT study also revealed that ligands with large bite angles disfavor the formation of platinum hydride complexes and therefore the formation of a bicyclic aminopropyl complex, which is a thermodynamic sink. Finally, a combination of 5 and a proton source was shown to efficiently catalyze the allylation of a broad variety of amines with allyl alcohols under mild conditions.

METHOD FOR PRODUCING PRIMARY AMINE COMPOUND

Disclosed is a method for producing a primary amine compound represented by the formula (2) below, which is characterized in that a halogen compound represented by the formula (1) below, ammonia and formaldehyde are reacted with each other, and then the thus-obtained reaction product is [1] brought into contact with an aqueous solution of an acid or [2] reacted with a hydroxylamine under acidic conditions. By this method, a primary amine compound can be commercially advantageously produced by using a low-cost ammonia while suppressing production of a secondary amine as a by-product. (1) (In the formula, R1 and R2 independently represent a hydrogen atom, a C1-C5 alkyl group which may be substituted by a halogen atom or the like, a C1-C5 alkoxy group which may be substituted by a halogen atom, a cyano group, a C2-C11 alkenyl group or a phenyl group or the like; R3 represents a hydrogen atom, a linear or branched C1-C5 alkyl group or a cyano group; and X represents a halogen atom.) (2) (In the formula, R1, R2 and R3 are as defined above.)

Rapid reduction of nitriles to primary amines with nickel boride at ambient temperature

Reduction of a variety of nitriles to their corresponding primary amines can be achieved with nickel boride generated in situ in dry ethanol at ambient temperature. The reductions are very rapid and chemoselective.