2591-86-8

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 academic research and scientific papers

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.

Chromium-catalysed efficient: N -formylation of amines with a recyclable polyoxometalate-supported green catalyst

A simple and efficient protocol for the formylation of amines with formic acid, catalyzed by a polyoxometalate-based chromium catalyst, is described. Notably, this method shows excellent activity and chemoselectivity for the formylation of primary amines; diamines have also been successfully employed. Importantly, the chromium catalyst is potentially non-toxic, environmentally benign and safer than the widely used high valence chromium catalysts such as CrO3 and K2Cr2O7. The catalyst can be recycled several times with a negligible impact on activity. Finally, a plausible mechanism is provided based on the observation of intermediate and control experiments.

Nickel-Catalyzed Amination of Aryl Chlorides with Amides

A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been realized under mild conditions. A broad substrate scope with excellent functional group tolerance at a low catalyst loading makes the protocol powerful for synthesizing various aromatic amines. The aryl chlorides could selectively couple to the amino fragments rather than the carbonyl moieties of amides. Our protocol complements the conventional amination of aryl chlorides and expands the usage of inactive amides.

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.

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.