935-30-8

Usage

Uses

Used in Analytical Chemistry:
2-Azacyclononanone is used as an internal standard in liquid chromatography-ultraviolet detection methods for the determination of caprolactam in the aqueous food stimulant 3% acetic acid (w/v). It provides a reliable and accurate reference for the quantification of caprolactam, ensuring the accuracy of the analytical results.
Used in Complex Formation:
2-Azacyclononanone forms complexes with hydrated lanthanides trifluoroacetate in ethanol and reacts with mercury(II)acetate and erbium(III)nitrate in methanol to yield heterocyclic complexes. These complexes have potential applications in various fields, such as coordination chemistry, materials science, and catalysis, due to their unique properties and structures.

Purification Methods

Dissolve it in CHCl3, decolorise it with charcoal, evaporate to dryness and recrystallise it from CHCl3/hexane. Sublime it at high vacuum. The oxime has m 117o (from *C6H6 or pet ether). [Guggisberg Helv Chim Acta 61 1050 1978, Olah et al. Synthesis 538 1979, Behringer & Meier Justus Liebigs Ann Chem 607 67 1957, Beilstein 21 III/V 3260.]

InChI:InChI=1/C8H15NO/c10-8-6-4-2-1-3-5-7-9-8/h1-7H2,(H,9,10)

Upstream product

• 502-49-8 cycloactanone 
• 1311145-83-1 N-(hex-5-enyl)-2-iodoacetamide 
• 3931-72-4 cyclooctanone oxime ; hydrochloride 
• 208124-34-9 N-(3,5-Difluorophenylacetyl)-L-alanine 
• 75920-68-2 1,1-bis(methylthio)cyclooctane 
• 217180-76-2 8-azido octanoic acid 
• 1002-57-9 8-Aminooctanoic acid 
• 1074-51-7 cyclooctanone oxime 
• 946-89-4 cyclododecanone oxime 
• 613688-08-7 N₃(CH₂)7C(O)SCH₂P(C₆H₅)2BH₃ 
• 30100-16-4 8-tert-butoxycarbonylaminooctanoic acid 
• 46875-43-8 1-benzoyl-azonan-2-one 
• 111-86-4 n-Octylamine 

Downstream Products

• 21577-72-0 1-aza-2-cyclononanthione 
• 5661-71-2 azonane 
• 6932-49-6 1-methyl-azonan-2-one 
• 5048-29-3 oct-7-enenitrile 
• 29833-31-6 8-aminooctanoic acid ethyl ester hydrochloride 
• 55114-43-7 2-ethoxy-3,4,5,6,7,8-hexahydro-2H-azonine 
• 131043-42-0 N-(o-azidobenzoyl)-2-azacyclononanone 
• 2740-00-3 indolizidin-3-one 
• 32537-55-6 hexahydroindolizin-5(1H)-one 
• 1002-57-9 8-Aminooctanoic acid 
• 501131-78-8 N-acetyl-1-aza-2-cyclononanone 
• 943601-42-1 1-nosylazonan-2-one 
• 644-90-6 2-aminooctanoic acid 
• 183990-46-7 8-(N-[2-hydroxybenzoyl]amino)caprylic acid 

Relevant academic research and scientific papers

A novel synthetic route of fused tricyclic framework quinoline derivatives from readily available aliphatic amino carboxylic acid substrates

A novel and an efficient strategy of fused tricyclic quinoline heterocycle compounds from aliphatic amino carboxylic acid substrates was studied. The protocol here is proceed over main reaction processes including: cyclization, protection, amidine formation, further cyclization and finally coupling with boronic acid substrate through Suzuki reaction. These reactions afforded the corresponding products in high yields. Furthermore, all synthesized compounds were identified by spectral data.

Scope and mechanism of a true organocatalytic beckmann rearrangement with a boronic acid/perfluoropinacol system under ambient conditions

Catalytic activation of hydroxyl functionalities is of great interest for the production of pharmaceuticals and commodity chemicals. Here, 2-alkoxycarbonyl- and 2-phenoxycarbonyl-phenylboronic acid were identified as efficient catalysts for the direct and chemoselective activation of oxime N-OH bonds in the Beckmann rearrangement. This classical organic reaction provides a unique approach to prepare functionalized amide products that may be difficult to access using traditional amide coupling between carboxylic acids and amines. Using only 5 mol % of boronic acid catalyst and perfluoropinacol as an additive in a polar solvent mixture, the operationally simple protocol features mild conditions, a broad substrate scope, and a high functional group tolerance. A wide variety of diaryl, aryl-alkyl, heteroaryl-alkyl, and dialkyl oximes react under ambient conditions to afford high yields of amide products. Free alcohols, amides, carboxyesters, and many other functionalities are compatible with the reaction conditions. Investigations of the catalytic cycle revealed a novel boron-induced oxime transesterification providing an acyl oxime intermediate involved in a fully catalytic nonself-propagating Beckmann rearrangement mechanism. The acyl oxime intermediate was prepared independently and was subjected to the reaction conditions. It was found to be self-sufficient; it reacts rapidly, unimolecularly without the need for free oxime. A series of control experiments and 18O labeling studies support a true catalytic pathway involving an ionic transition structure with an active and essential role for the boronyl moiety in both steps of transesterification and rearrangement. According to 11B NMR spectroscopic studies, the additive perfluoropinacol provides a transient, electrophilic boronic ester that is thought to serve as an internal Lewis acid to activate the ortho-carboxyester and accelerate the initial, rate-limiting step of transesterification between the precatalyst and the oxime substrate.

Synthesis of Cyclic Peptide Mimetics by the Successive Ring Expansion of Lactams

A successive ring-expansion protocol is reported that enables the controlled insertion of natural and non-natural amino acid fragments into lactams. Amino acids can be installed into macrocycles via an operationally simple and scalable iterative procedure, without the need for high dilution. This method is expected to be of broad utility, especially for the synthesis of medicinally important cyclic peptide mimetics.

HIERARCHICAL ALUMINOPHOSPHATES AS CATALYSTS FOR THE BECKMANN REARRANGEMENT

Methods for producing lactams from oximes by performing a Beckmann rearrangement using a hierarchical porous aluminophosphate catalyst having interconnected microporous and mesoporous networks are provided. Exemplary catalysts include a plurality of weak Brnsted acid active sites, including silicon-containing aluminophosphates having the IZA framework code AFI, such as SAPO-5, CHA, such as SAPO-34, and FAU, such as SAPO-37.

Hierarchical silicalite-1 octahedra comprising highly-branched orthogonally-stacked nanoplates as efficient catalysts for vapor-phase Beckmann rearrangement

A triblock structure-directing agent was designed to synthesize hierarchical silicalite-1 octahedra comprising highly-branched, orthogonally-stacked and self-pillared nanoplates that exhibited excellent and stable activity for the vapor-phase Beckmann rearrangement of cyclic oximes and high lactam selectivity.

Establishment of an activated peroxide system for low-temperature cotton bleaching using N-[4-(triethylammoniomethyl)benzoyl]butyrolactam chloride

Cotton bleaching is traditionally carried out in strongly alkaline solution of hydrogen peroxide (H2O2) at temperatures close to the boil. Such harsh processing conditions can result in extensive water and energy consumptions as well as severe chemical damage to textiles. In this study, an activated peroxide system was established for low-temperature cotton bleaching by incorporating a bleach activator, namely N-[4-(triethylammoniomethyl)benzoyl]butyrolactam chloride (TBBC) into an aqueous H2O2 solution. Experimental results showed that the TBBC-activated peroxide system exhibited the most effective bleaching performance in a pH range of 6-8 which could be approximated by adding sodium bicarbonate (NaHCO3). The TBBC/H2O2/NaHCO3 system led to rapid bleaching of cotton at a temperature as low as 50°C. In comparison with the hot alkaline peroxide bleaching system, the TBBC/H2O2/NaHCO3 system provided cotton fabric with an equivalent degree of whiteness, higher degree of polymerization, and slightly lower water absorbency. The new activated peroxide system may provide a more environmentally benign approach to cotton bleaching.

Titanium cation-exchanged montmorillonite as an active heterogeneous catalyst for the Beckmann rearrangement under mild reaction conditions

Titanium cation-exchanged montmorillonite acts as an efficient heterogeneous catalyst for the Beckmann rearrangement of a wide range of ketoximes including aromatic, aliphatic, and alicyclic ketoximes under mild reaction conditions. After the rearrangement reaction, titanium cation-exchanged montmorillonite is easily separated by simple filtration, and can be reused with retention of high efficiency.

Efficient and regioselective 9-endo cyclization of α-carbamoyl radicals

With the promotion of Lewis acid BF3?OEt2, various N-(hex-5-enyl)-2-iodoalkanamides underwent efficient and regioselective 9-endo iodine-atom-transfer radical cyclization reactions at room temperature. The cyclized products were readily converted to the corresponding azonan-2-ones by reduction with Bu3SnH or to hexahydroindolizin-3(5H)-ones by treatment with aqueous Na2CO3 in a one-pot, two-stage manner.

METHOD FOR PRODUCING LACTAM COMPOUND

Disclosed is a method for industrially efficiently producing a lactam compound having 8 to 15 carbon atoms at low cost by allowing a rearrangement reaction of a cyclic oxime compound to proceed without causing large amounts of by-products such as ammonium sulfate. [Solving Means] Disclosed is a method for producing a lactam compound, which includes the step of rearranging a cyclic oxime compound in a nonpolar solvent B in the presence of an aromatic compound A to give the lactam compound, in which the aromatic compound A has a leaving group bonded to a carbon atom constituting its aromatic ring and contains, as an atom constituting the aromatic ring, a heteroatom, or a carbon atom bonded with an electron-withdrawing group, the cyclic oxime compound is represented by following Formula (1): wherein “m” denotes an integer of 7 to 14, and the lactam compound is represented by following Formula (2): wherein “m” is as defined above.

Cyclopropenium ion catalysed Beckmann rearrangement

1-Chloro-2,3-diphenylcyclopropenium ion was found to be a very efficient organocatalyst (3 mol% loading) for liquid phase Beckmann rearrangement of various ketoximes to the corresponding amides/lactams within 2 h in acetonitrile at reflux temperature. This is the first example of the application of the cyclopropenium ion as a catalyst, which opens up a new aspect of the synthetic utility of aromatic cation based catalysis.