22693-32-9

Upstream product

• 874-60-2 4-methyl-benzoyl chloride 
• 99-94-5 p-Toluic acid 
• 59046-28-5 p-toluoyl-1H-1,2,3-benzotriazole 
• 766-97-2 4-n-methylphenylacetylene 
• 4974-59-8 2,2-dichloro-4'-methylacetophenone 
• 25856-03-5 1-(4-methoxy-phenyl)-3-p-tolyl-propane-1,3-dione 
• 3594-36-3 1,3-bis(p-methylphenyl)-1,3-propanedione 
• 50-00-0 formaldehyd 
• 624-31-7 4-tolyl iodide 
• 201230-82-2 carbon monoxide 
• 14189-19-6 ethyl 4-methylbenzoyl carbonate 
• 36106-76-0 2,4-dinitrophenyl 4-methylbenzoate 
• 3619-22-5 p-toluic hydrazide 

Downstream Products

• 20553-99-5 N-(1-butyl-1λ⁵-phospholan-1-ylidene)-4-methyl-benzamide 
• 126802-30-0 C₁₆H₁₅N₅O₂ 
• 5602-96-0 methyl p-tolylcarbamate 
• 93628-72-9 5-Methoxy-4,4-dimethyl-2-p-tolyl-4,5-dihydro-oxazole 
• 622-58-2 p-Tolylisocyanate 
• 954412-94-3 C₂₈H₂₂NOP 
• 93628-73-0 2-(p-toluoylamino)-2-methylpropanal 
• 305862-64-0 C₁₄H₁₂N₄O 

Relevant academic research and scientific papers

Reactions of Primary Amines and Alcohols with 4-Toluoyl Azide

Primary amines 2 react with 4-toluoyl azide 1 in non-nucleophilic solvents in a clear second order reaction, which is strongly dependent on the size of the amine 2 and the solvent polarity (k2: 15.51 (2a), 0.83 (2b) and 0.19 (2c) l/mol*min; ΔH(excit.) = 22.1 kJ/mol, ΔS(excit.) = -170.5 J/mol*K ).Drastic changes occur in the presence of nucleophilic solvents.With nucleophilic amines 2 added to these in the solutions a concurrent reaction with alcohols 4 yielding 4-toluoyl ester 5 is observed.This is especially dominating with the "smallest" alcohol methanol (4a) and/or effectively promoted by "bulky" amines (2b, 2c; up to 99percent 5a).Compared with the pure alcoholysis a huge acceleration of the ester formation, proportional to the concentration of the nucleophilic amine 2, is observed.The reaction mechanism is discussed with special emphasis on steric effects in the competition of nucleophiles for the aroyl azide 1. - Keywords.Aroyl azide; 4-Toluoyl azide; Alcoholysis; Aminolysis; "Nucleophilic catalysis"; Kinetics; Steric effects.

The electronic absorption spectra of some acyl azides. Molecular orbital treatment

The electronic absorption spectra of benzoyl azide and its derivatives: p-methyl, p-methoxy, p-chloro and p-nitrobenzoyl azide were investigated in different solvents. The observed spectra differ basically from the electronic spectra of aryl azides or alkyl azides. Four intense π-π* transitions were observed in the accessible UV region of the spectrum of each of the studied compounds. The contribution of charge transfer configurations to the observed transitions is rather weak. Shift of band maximum with solvent polarity is minute. On the other hand, band intensity is highly dependent on the solvent used. The observed transitions are delocalized rather than localized ones as in the case with aryl and alkyl azides. The attachment of the C{double bond, long}O group to the azide group in acyl azides has a significant effect on the electronic structure of the molecule. The arrangements as well as energies of the molecular orbitals are different in acyl azides from those in aryl azides. The first electronic transition in phenyl azide is at 276 nm, whereas that of bezoyle azide is at 251 nm. Ab initio molecular orbital calculations using both RHF/6-311G* and B3LYP/6-31+G* levels were carried out on the ground states of the studied compounds. The wave functions of the excited states were calculated using the CIS and the AM1-CI procedures.

Deoxygenative Amination of Azine-N-oxides with Acyl Azides via [3 + 2] Cycloaddition

A transition-metal-free deoxygenative C-H amination reaction of azine-N-oxides with acyl azides is described. The initial formation of an isocyanate from the starting acyl azide via a Curtius rearrangement can trigger a [3 + 2] dipolar cycloaddition of polar N-oxide fragments to generate the aminated azine derivative. The applicability of this method is highlighted by the late-stage and sequential amination reactions of complex bioactive compounds, including quinidine and fasudil. Moreover, the direct transformation of aminated azines into various bioactive N-heterocycles illustrates the significance of this newly developed protocol.

Synthesis of: N -methylated amines from acyl azides using methanol

The transformation of acyl azide derivatives into N-methylamines was developed using methanol as the C1 source via the one-pot Curtius rearrangement and borrowing hydrogen methodology. Following this protocol, various functionalised N-methylated amines were synthesized using the (NNN)Ru(ii) complex from carboxylic acids via an acyl azide intermediate. Several kinetic studies and DFT calculations were carried out to support the mechanism and also to determine the role of the Ru(ii) complex and base in this transformation.

Visible Light-Induced Regioselective Cycloaddition of Benzoyl Azides and Alkenes to Yield Oxazolines

Visible light catalysis allows the regioselective synthesis of oxazolines in high yields. The mild photosensitized manifold leverages the intermolecular formation of oxazolines with a wide functional group tolerance on both benzoyl azides and alkenes part

Direct conversion of carboxylic acids to various nitrogen-containing compounds in the one-pot exploiting curtius rearrangement

Herein we report, a single-pot multistep conversion of inactivated carboxylic acids to various N-containing compounds using a common synthetic methodology. The developed methodology rendered the use of carboxylic acids as a direct surrogate of primary amines, for the synthesis of primary ureas, secondary/tertiary ureas, O/S-carbamates, benzoyl ureas, amides, and N-formyls, exploiting the Curtius reaction. This approach has a potential to provide a diversified library of N-containing compounds, starting from a single carboxylic acid, based on the selection of the nucleophile.

Synthesis of Acyl Azides from 1,3-Diketones via Oxidative Cleavage of Two C-C Bonds

A metal-free PhI(OAc)2-mediated method for the synthesis of acyl azides through oxidative cleavage of 1,3-diketones is described. This method is shown to have a broad substrate scope, providing a useful tool for multiproduct synthesis in a single procedure. A possible reaction pathway is proposed based on mechanistic studies.

Palladium-Catalyzed One-Pot Synthesis of N -Sulfonyl, N -Phosphoryl, and N -Acyl Guanidines

An efficient palladium-catalyzed cascade reaction of azides with isonitrile and amines is presented; it offers an alternative facile approach toward N -sulfonyl-, N -phosphoryl-, and N -acyl-functionalized guanidines in excellent yield. These series of substituted guanidines exhibit potential biological and pharmacological activities. In addition, the less reactive intermediate benzoyl carbodiimide could be isolated by silica gel column flash chromatography in moderate yield.

Iridium(III)-Catalyzed Selective and Mild C-H Amidation of Cyclic N-Sulfonyl Ketimines with Organic Azides

A general protocol for iridium catalyzed direct C?H amidation of cyclic N-sulfonyl ketimines using sulfonyl, acyl and aryl azides as nitrogen source is reported herein. The reaction takes place at room temperature with acyl and aryl azides, while an elevated temperature needed with sulfonyl azides to furnish aminated sultams in excellent yields with complete chemo and regioselectivity, thus providing a robust and environmentally benign process to the synthesis of aminosultams. (Figure presented.).

Pathways in the Degradation of Geminal Diazides

The degradation of geminal diazides is described. We show that diazido acetates are converted into tetrazoles through the treatment with bases. The reaction of dichloro ketones with azide anions provides acyl azides, through in situ formation of diazido ketones. We present experimental and theoretical evidence that both fragmentations may involve the generation of acyl cyanide intermediates. The controlled degradation of terminal alkynes into amides (by loss of one carbon) or ureas (by loss of two carbons) is also shown.