2591-86-8

Basic information

• Product Name: N-Formylpiperidine
• Synonyms: 1-formyl-piperidin;1-Piperidinecarbaldehyde;N-Formylpiperdine;N-Formylpiperidin;nfp;Piperidine, 1-formyl-;Piperidinoformamide;PIPERIDINE-1-CARBOXALDEHYDE
• CAS NO: 2591-86-8
• Molecular Formula: C₆H₁₁NO
• Molecular Weight: 113.16
• EINECS: 219-986-0
• Product Categories: Piperidine
• Mol File: 2591-86-8.mol

Chemical Properties

• Melting Point: -31 °C
• Boiling Point: 222 °C(lit.)
• Flash Point: 197 °F
• Appearance: Clear colorless to slightly yellow/Liquid
• Density: 1.019 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.1 mm Hg ( 25 °C)
• Refractive Index: n20/D 1.484(lit.)
• Storage Temp.: Store below +30°C.
• PKA: -0.44±0.20(Predicted)
• Water Solubility: freely soluble
• BRN: 107697
• CAS DataBase Reference: N-Formylpiperidine(CAS DataBase Reference)
• NIST Chemistry Reference: N-Formylpiperidine(2591-86-8)
• EPA Substance Registry System: N-Formylpiperidine(2591-86-8)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 21/22-36/37/38
• Safety Statements: 26-36/37-36
• RIDADR: UN 2810 6.1/PG 3
• WGK Germany: 3
• RTECS: TN0380000
• TSCA: Yes
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 2591-86-8(Hazardous Substances Data)

Usage

Uses

Used in Chemical Synthesis:
N-Formylpiperidine is used as a reactant for various chemical reactions, including direct amidation of azoles with formamides via metal-free C-H activation in the presence of tert-butyl perbenzoate, Vilsmeier-type reactions of pyrazoles with amides in the presence of phosphorous oxychloride, CO-free aminocarbonylation of N-substituted formamides with aryl iodides/bromides catalyzed by palladium acetate and Xantphos for the synthesis of arylamides, and one-pot double functionalization of π-deficient heterocyclic lithium reagents.
Used in Polymer Science:
N-Formylpiperidine is used as a solvent for polar and nonpolar compounds, as well as many high polymers. It is also used in the synthesis of alternating copolymers for organic photovoltaic applications.
Used in Gas Absorption:
N-Formylpiperidine is used in gas absorption processes due to its ability to interact with various gases.
Used in Plastics Modification:
N-Formylpiperidine is used as a plastic modifier to improve the properties of plastics, such as flexibility, durability, and resistance to environmental factors.
Used in the Synthesis of Thermally Stable Compounds:
N-Formylpiperidine is used in the synthesis of thermally stable piezofluorochromic aggregation-induced emission compounds, which have potential applications in various fields, including sensors and imaging.

Synthesis Reference(s)

Chemical and Pharmaceutical Bulletin, 42, p. 1655, 1994 DOI: 10.1248/cpb.42.1655Synthetic Communications, 20, p. 447, 1990 DOI: 10.1080/00397919008052787

References

Debrauwere, Verzale, Bull. Soc. Chim. Belg., 84, 167 (1975)

InChI:InChI=1/C6H11NO/c8-6-7-4-2-1-3-5-7/h6H,1-5H2

Upstream product

• 110-89-4 piperidine 
• 64-18-6 formic acid 
• 302-17-0 chloral hydrate 
• 64-17-5 ethanol 
• 107-31-3 Methyl formate 
• 74-90-8 hydrogen cyanide 
• 67-66-3 chloroform 
• 1493-02-3 formyl fluoride 
• 77287-34-4 formamide 
• 15719-64-9 methylammonium carbonate 
• 109-94-4 formic acid ethyl ester 
• 2981-10-4 1-(cyclohex-1-en-1-yl)piperidine 
• 60-29-7 diethyl ether 
• 4706-33-6 2-oxo-2-(piperidin-1-yl)acetic acid 

Downstream Products

• 104507-68-8 1-(1-cyclohexen-1-ylmethyl)-1-piperidine 
• 5005-72-1 1-(cyclohexylmethyl)piperidine 
• 20615-64-9 fluorene-9-carbaldehyde 
• 120-14-9 3,4-dimethoxy-benzaldehyde 
• 132567-84-1 1-(4-phenylbutan-2-yl)piperidine 
• 108984-17-4 2-[1-(4-chloro-phenyl)-3-piperidino-propyl]-pyridine 
• 590-86-3 isovaleraldehyde 
• 6220-95-7 N-4-Heptylpiperidine 
• 123-72-8 butyraldehyde 
• 27049-60-1 N²-tosyl-N¹,N¹-cyclopentyl formamide 
• 632-51-9 1,1,2,2-tetraphenylethylene 
• 10527-66-9 1-benzhydryl-piperidine 
• 100-52-7 benzaldehyde 
• 123-11-5 4-methoxy-benzaldehyde 

Relevant articles and documents

Reactions of diazomethylphosphonate: The first synthesis of a formylphosphonate hydrate

Formylphosphonate hydrate has been synthesised by the oxidation of diazomethylphosphonate with dimethyldioxirane (DMD) and its reactions, including the formation of imines, oximes, and Wittig olefination products, have been investigated. Formylphosphonate also acts as an efficient, selective formylating agent of secondary amines. β-Ketophosphonic acids derived from a range of amino acids have been prepared by the tin (II) chloride-catalysed reaction of diazomethylphosphonate with amino aldehydes and in certain cases shown to be potent inhibitors of leucine aminopeptidase.

Pyridine-functionalized organic porous polymers: applications in efficient CO2 adsorption and conversion

Pyridine-functionalized porous organic polymers showed excellent CO2 uptake capacity (up to 63 and 171 mg g-1 at 0.1 and 1 bar at 273 K), and performed well as supports for Ru(0) nanoparticles. The resultant CarPy-CMP@Ru served as an efficient catalyst for the formylation of amines with CO2/H2, together with high product yields (89-93%), high stability and easy recyclability.

Carbonylation of piperidine with carbon monoxide in the presence of CuNaA-zeolite catalyst

Zeolite CuNaA at 200-300° and a CO pressure of 100 atm is an active and stable catalyst for the carbonylation of piperidine to formylpiperidine (30-40% yield).

Mechanistic studies on the N-formylation of amines with CO2 and hydrosilane catalyzed by a Cu-diphosphine complex

The reaction mechanism, reaction intermediates, and catalytically active species of the Cu-diphosphinecatalyzed N-formylation of amines (R1R2NH) with CO2 and hydrosilane were investigated. The NMR and kinetic experiments show that the catalytically active species is a Cu-hydride-diphosphine complex, which was generated from the Cu precursor, diphosphine ligand, and hydrosilane. Isotopic experiments using 13CO2 and deuterated hydrosilane revealed the incorporation of the carbonyl group of CO2 and the H atom of Si-H moiety into the formamide (R1R2NCHO) product. The formation of a Cu-formate species as an intermediate of the reaction was clarified by in situ 1H and 13C NMR studies.

A Fortuitous, Mild Catalytic Carbon-Carbon Bond Hydrogenolysis by a Phosphine-Free Catalyst

The putative catalyst trans-[Ru((S,S)-skewphos)(H)2((R,R)-dpen)] (skewphos=2,4-bis(diphenylphosphino)pentane; dpen=1,2-diphenylethylenediamine) transforms the trifluoroacetyl amide 2,2,2-trifluoro-1-(piperidin-1-yl)ethanone under mild conditions (4 atm H2, room temperature, 4-24h, 1 mol-% Ru, 15 mol-% KOtBu in tetrahydrofuran) to generate the formylated amine 1-formylpiperidine and fluoroform via C-C bond hydrogenolysis. Catalysts are also prepared by reacting cis-[Ru(η3-C3H5)(MeCN)2(COD)]BF4 (COD=1,5-cyclooctadiene) with diamine ligands in situ. Lowerature NMR studies provided insight into this reaction.

Synthesis of 3-Amino-4-iodothiophenes through Iodocyclization of 1-(1,3-Dithian-2-yl)propargylamines

1-(1,3-Dithian-2-yl)propargylamines undergo iodo-cylization regioselectively to afford tetrasubstituted 3-amino-4-iodothiophenes in 30–87 % yields by iodide induced cleavage of dithiane ring in a bicyclic sulfonium intermediate. A mechanism for this unprecedented transformation was proposed and tentatively supported by the isolation of an intermediate structure. 1-(1,3-Dithian-2-yl)propargylamines were prepared in 30–94 % yields by Au-catalyzed one-pot, three-component reaction of 1,3-dithiane-2-carbaldehydes, amines, and alkynes so called A3-coupling reaction.

Amide Bond Formation via Aerobic Photooxidative Coupling of Aldehydes with Amines Catalyzed by a Riboflavin Derivative

We report an effective, operationally simple, and environmentally friendly system for the synthesis of tertiary amides by the oxidative coupling of aromatic or aliphatic aldehydes with amines mediated by riboflavin tetraacetate (RFTA), an inexpensive organic photocatalyst, and visible light using oxygen as the sole oxidant. The method is based on the oxidative power of an excited flavin catalyst and the relatively low oxidation potential of the hemiaminal formed by amine to aldehyde addition.

Germyliumylidene: A Versatile Low Valent Group 14 Catalyst

Bis-NHC stabilized germyliumylidenes [RGe(NHC)2]+ are typically Lewis basic (LB) in nature, owing to their lone pair and coordination of two NHCs to the vacant p-orbitals of the germanium center. However, they can also show Lewis acidity (LA) via Ge?CNHC σ* orbital. Utilizing this unique electronic feature, we report the first example of bis-NHC-stabilized germyliumylidene [MesTerGe(NHC)2]Cl (1), (MesTer=2,6-(2,4,6-Me3C6H2)2C6H3; NHC= IMe4=1,3,4,5-tetramethylimidazol-2-ylidene) catalyzed reduction of CO2 with amines and arylsilane, which proceeds via its Lewis basic nature. In contrast, the Lewis acid nature of 1 is utilized in the catalyzed hydroboration and cyanosilylation of carbonyls, thus highlighting the versatile ambiphilic nature of bis-NHC stabilized germyliumylidenes.

Selective N-formylation of amines catalysed by Ag NPs festooned over amine functionalized SBA-15 utilizing CO2 as C1 source

N-formylation of amines using CO2 as C1 source has been an uphill transformation in the catalysis research as it involves the utilization of abundant thermodyanamically stable and kinetically inert CO2 to form the N-formylated products, which are potential intermediates for the synthesis of valuable chemicals. Previously various noble as well as non-noble metal nanoparticles have been employed for N-formylation of amines. However, herein for the first time we explored N-formylation reaction under lenient conditions utilizing silver nanoparticles, which are decorated over amine functionalized periodically ordered 2D-hexagonal SBA-15 material, serving as a robust heterogeneous catalyst. The AgNPs@SBA-15-NH2 has been intensively characterized by powder XRD, Brunauer-Emmett-Teller (BET), FEG-TEM, SEM, XPS, TGA, CO2-TPD, FTIR and UV–vis spectroscopic analyses. This supported AgNPs material showed remarkable catalytic activity for N-formylation over a wide range of amines under 0.5 MPa CO2 pressure and at mild temperature (35 °C) conditions. In addition, this AgNPs@SBA-15-NH2 material exhibited high chemical stability and reusability, suggesting its promising future in the CO2 fixation reactions.

Mesoporous Sn(IV) Doping DFNS Supported BaMnO3 Nanoparticles for Formylation of Amines Using Carbon Dioxide

Abstract: In the present paper, Sn(IV) doping DFNS (SnD) supported nanoparticles of BaMnO3 (BaMnO3/SnD) and using as a catalyst for the N-formylation of amines by CO2 hydrogenation. In this catalyst, the SnD with the ratios of Si/Sn in the range of from 6 to 50 were obtained with method of direct hydrothermal synthesis (DHS) as well as the nanoparticles of BaMnO3 were on the surfaces of SnD in situ reduced. Scanning electron microscope (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray energy dispersive spectroscopy (EDS), and transmission electron microscopy (TEM) were utilized for characterizing the nanostructures BaMnO3/SnD. It is found that the nanostructures of BaMnO3/SnD can be a nominate due to its effective and novel catalytic behavior in N-formylation of amines through hydrogenation of CO2. Graphic Abstract: [Figure not available: see fulltext.]