21968-26-3

Basic information

• Product Name: N-FORMYL-4-PIPECOLINE
• Synonyms: N-FORMYL-4-PIPECOLINE;1-Piperidinecarboxaldehyde, 4-methyl-
• CAS NO: 21968-26-3
• Molecular Formula: C₇H₁₃NO
• Molecular Weight: 127.18
• Mol File: 21968-26-3.mol

Chemical Properties

• Appearance: /
• CAS DataBase Reference: N-FORMYL-4-PIPECOLINE(CAS DataBase Reference)
• NIST Chemistry Reference: N-FORMYL-4-PIPECOLINE(21968-26-3)
• EPA Substance Registry System: N-FORMYL-4-PIPECOLINE(21968-26-3)

Safety Data

• Hazardous Substances Data: 21968-26-3(Hazardous Substances Data)

Upstream product

• 626-58-4 4-methylpiperidin 
• 124-38-9 carbon dioxide 
• 108-89-4 picoline 
• 109-94-4 formic acid ethyl ester 
• 96-26-4 dihydroxyacetone 
• 56-81-5 glycerol 
• 201230-82-2 carbon monoxide 
• 50-00-0 formaldehyd 
• 18513-84-3 4-methyl-1-(2-methyl-propenyl)-piperidine 
• 73822-92-1 1,2-bis(4-methylpiperidin-1-yl)ethane 
• 67-66-3 chloroform 
• 64-18-6 formic acid 
• 75-87-6 chloral 

Downstream Products

• 637751-97-4 3-(2,3-dihydrobenzo[1,4]dioxan-6-yl)-7-hydroxy-8-(4-methylpiperidin-1-ylmethyl)-chromen-4-one 

Relevant articles and documents

Thioamides and selenoamides with chirality solely due to hindered rotation about the C-N bond: Enantioselective complexation with optically active hosts

Several thioformamides and selenoformamides, with chirality solely due to restricted rotation about the C-N bond, were resolved to enantiomers by inclusion crystallization with optically active diols (TADDOLs). The absolute configuration of the guest molecules was deduced from the X-ray crystal structures of the inclusion complexes. The optical activity of the resolved compounds is manifested by their CD spectra showing relatively strong Cotton effects in the region of thioamide or selenoamide n-π* transition. The optically active thioformamides and selenoformamides are configurationally labile compounds and gradually racemize in solution but are stable in the form of the inclusion complexes. The first-order kinetics of the racemization in solution allowed us to assign the C-N rotation barriers of thioformamides by spectropolarimetric measurements.

Amine formylation with CO2 and H2 catalyzed by heterogeneous Pd/PAL catalyst

For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at 100 °C, and good to excellent yields were obtained.

Selective synthesis of formamides, 1,2-bis(N-heterocyclic)ethanes and methylamines from cyclic amines and CO2/H2 catalyzed by an ionic liquid-Pd/C system

The reduction of CO2 with amines and H2 generally produces N-formylated or N-methylated compounds over different catalysts. Herein, we report the selective synthesis of formamides, 1,2-bis(N-heterocyclic)ethanes, and methylamines, which is achieved over an ionic liquid (IL, e.g., 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIm][BF4])-Pd/C catalytic system. By simply varying the reaction temperature, formamides and methylamines can be selectively produced, respectively, in high yields. Interestingly, 1,2-bis(N-heterocyclic)ethanes can also be obtained via the McMurry reaction of the formed formamide coupled with subsequent hydrogenation. It was found that [BMIm][BF4] can react with formamide to form a [BMIm]+-formamide adduct; thus combined with Pd/C it can catalyze McMurry coupling of formamide in the presence of H2 to afford 1,2-bis(N-heterocyclic)ethane. Moreover, Pd/C-[BMIm][BF4] can further catalyze the hydrogenolysis of 1,2-bis(N-heterocyclic)ethane to access methylamine. [BMIm][BF4]-Pd/C was tolerant to a wide substrate scope, giving the corresponding formamides, 1,2-bis(N-heterocyclic)ethanes or methylamines in moderate to high yields. This work develops a new route to produce N-methylamine and opens the way to produce 1,2-bis(N-heterocyclic)ethane from cyclic amine as well.

The synthesis of cyanoformamides via a CsF-promoted decyanation/oxidation cascade of 2-dialkylamino-malononitriles

A mild and efficient method for the synthesis of cyanoformamides from N,N-disubstituted aminomalononitriles with CsF as the promoter has been developed. This method features a wide substrate scope and high reaction efficiency, and will facilitate corresponding cyanoformamide-based biological studies and synthetic methodology development.

Method for preparing N-formylated amine compounds

The invention discloses a method for preparation N-formylated amine compounds. In the method, the amine compounds and 1,3-dihydroxy acetone are taken as reaction raw materials reacting in a reactor for 2-48 hours at the reaction temperature of 0-100DEG C in a reaction medium in the presence of composite catalysts and oxidants, and the N-formylated amine compounds are obtained. The method is simpleand moderate in reaction conditions, cost can be reduced, target products can be obtained with high yield, and the catalysts used have high catalytic activity and are easy to be separated from a reaction system and reuses; the method is environment friendly during the whole process, the reaction raw materials are easy to be converted from biodiesel by-product propylene glycol, and use of glycerolis facilitated.

Methanol Promoted Palladium-Catalyzed Amine Formylation with CO2 and H2 by the Formation of HCOOCH3

The N-formylation reaction of amines is one of the most effective measures to make the best use of CO2, since the formamides have widespread applications in industry. Herein, we performed the N-formylation reaction over Mg?Al layered double hydroxide (Mg?Al LDH) supported Pd catalyst (Pd/LDH) for the first time and studied the relation between the solvent and the mechanism. In this reaction, the methanol can greatly improve the yield of the desired product by forming the HCOOCH3. The catalytic system is effective for various amines including cyclic and alkyl secondary amines. Under the optimized reaction condition, we gained 88.5 %–97.4 % yields of the formamides for various substrates.

Synthesis of formamides containing unsaturated groups by: N -formylation of amines using CO2 with H2

Formamides have wide applications in the industry and have been synthesized using CO2 as a carbon source and H2 as a reducing agent. However, previous systems required a noble catalyst and high temperature to achieve high efficiency, and the substrate scope was mostly limited to saturated amines. The selective N-formylation of amines containing unsaturated groups using CO2 and H2 is challenging because the efficient catalysts for the N-formylation are usually very active for hydrogenation of the unsaturated groups. Herein, we achieved for the first time a selective and efficient N-formylation of amines containing unsaturated groups using CO2 and H2 with a Cu(OAc)2-4-dimethylaminopyridine (DMAP) catalytic system. The substrates were converted to the desired formamides, while the unsaturated groups, such as the carbonyl group, the CC bond, CN bond and the ester group remained. The main reason for the excellent selectivity of the Cu(OAc)2-DMAP catalytic system was that it was very active for the N-formylation reaction, but was not active for the hydrogenation of the unsaturated groups.

Glycerol as a Building Block for Prochiral Aminoketone, N-Formamide, and N-Methyl Amine Synthesis

Prochiral aminoketones are key intermediates for the synthesis of optically active amino alcohols, and glycerol is one of the main biomass-based alcohols available in industry. In this work, glycerol was catalytically activated and purposefully converted with amines to generate highly valuable prochiral aminoketones, as well as N-formamides and N-methyl amines, over CuNiAlOx catalyst. The catalyst structure can be anticipated as nano-Ni species on or in CuAlOx via the formation of nano- Cu?Ni alloy particles. This concept may present a novel and valuable methodology for glycerol utilization.

Supported nano-gold-catalyzed N-formylation of amines with paraformaldehyde in water under ambient conditions

A simple and efficient Au/Al2O3 catalyst was prepared by the co-precipitation method for the oxidative N-formylation of amines with paraformaldehyde. Under the optimized reaction conditions, excellent amine conversion and N-formamide selectivity can be obtained with up to 97% yield with water as the solvent under ambient conditions. This catalyst tolerated a wide range of primary amines and second amines, and it can be reused for at least five runs without obvious deactivation.

A Practical and General Base-Catalyzed Carbonylation of Amines for the Synthesis of N-Formamides

A highly practical and general base-catalyzed carbonylation of amines to the corresponding N-formamides has been realized. Cheap inorganic bases, including GroupIA and IIA metal hydroxides, alkoxides, carbonates, and phosphates, were effective catalysts for the transformation. In the presence of 10-40mol% of KOH or K2CO3, various amines were converted into the corresponding N-formamides in good-to-excellent yields using CO as the formylation reagents. Metal-free carbonylation: A simple and practical procedure for the catalytic carbonylation of amines has been developed (see scheme). In the presence of 10-40mol% of KOH or K2CO3, various amines have been converted into the corresponding N-formamides in good-to-excellent yields by using CO as the formylation reagent.