121004-44-2

Upstream product

• 70972-96-2 N-Chloro-N-methyl-m-nitrobenzylamin 
• 99-61-6 3-nitro-benzaldehyde 
• 74-89-5 methylamine 
• 65398-48-3 methylammonium N-methylcarbamate 
• 593-51-1 methylamine hydrochloride 
• 19499-61-7 methyl-(3-nitro-benzyl)-amine 
• 98760-23-7 C₈H₉BrN₂O₂ 

Downstream Products

• 99-61-6 3-nitro-benzaldehyde 
• 74-89-5 methylamine 
• 895024-22-3 C₁₂H₁₁N₃O₃ 
• 19499-61-7 methyl-(3-nitro-benzyl)-amine 

Relevant academic research and scientific papers

Assessment of a reductive amination route to methyl(3-nitrobenzyl)amine hydrochloride

During the development of a sodium borohydride mediated reductive animation of 3-nitrobenzaldehyde with methylamine, studies revealed that partial reduction of the nitro group occurred, and potentially dangerous azo- and azoxy-containing products were gen

Stable carbamate pathway towards organic-inorganic hybrid perovskites and aromatic imines

Methyl ammonium methyl carbamate (MAC), formulated as CH3NH3+CH3NHCO2-, was synthesized by reacting liquid methylamine with supercritical CO2, and its structure was refined by single-crystal X-ray diffraction. MAC is a white crystalline salt and is as reactive as methylamine, and is a very efficient alternative to toxic methylamine. We were able to produce hybrid perovskite MAPbI3 (MA = methyl ammonium) by grinding MAC with PbI2 and I2 at room temperature, followed by storing the mixed powder. Moreover, this one-pot method is easily scalable for the large-scale synthesis of MAPbI3 in a small vessel. We have also investigated the reactivity of MAC towards aromatic aldehydes in the absence of solvent. The solventless reactions afforded imines as exclusive products with over 97% yield, which show higher selectivity than the methylamine-based synthesis. Complete conversions were typically accomplished within 3 h at 25 °C. The results of this study emphasize the importance of solid carbamates such as MAC to develop an environmentally friendly process for the synthesis of various amine-based materials on the industrial scale.

Mechanosynthesis of N-methyl imines using recyclable imidazole-based acid-scavenger: In situ formed ionic liquid as catalyst and dehydrating agent

1,1′-(1,4-Butanediyl)bis(imidazole) was prepared by a modified method and its application as an efficient promoter was demonstrated for the mechanosynthesis of N-methyl imines using ball milling as a non-conventional process under solvent-free conditions. In this new protocol design, the bis-imidazole acted as a recyclable acid-scavenging agent. This efficient approach to the N-methyl imines displays a combination of the synthetic virtues of a non-conventional condensation reaction with ecological benefits and convenience of a facile mechanosynthetic process. The current method has advantages such as reduced waste by avoiding solvent, exclusion of hazardous materials during the reaction, elimination of handling an anhydrous gas in an evacuated container or a solution of methylamine in ethanol, good yields for relatively unreactive benzaldehydes containing electron-donating substituents, short reaction times, and metal- and acid-free conditions. Furthermore, the promoter was easily regenerated and reused several times with no significant loss of activity.

Mixed carboxylic-sulfonic anhydride in reaction with imines: A straightforward route to water-soluble β-lactams via a Staudinger-type reaction

The first example of employing a mixed carboxylic-sulfonic anhydride in reaction with imines is reported. Unlike its well-studied isostere homophthalic anhydride, benzo[c][1,2]oxathiin-3(4H)-one 1,1-dioxide gave no product of a formal [4 + 2] cycloaddition and only followed an alternative reaction pathway toward β-lactams, presumably, via a formal [2 + 2] cycloaddition (a Staudinger-type reaction). Optimized reaction conditions involve the use of triethylamine as a base promoter, which also allows isolating the product β-lactam benzene sulfonic acids as respective triethylammonium salts by conventional column chromatography. The reaction shows some preference to trans-isomer formation; pure diastereomers can be isolated in some cases.

Thiazolidinones derived from dynamic systemic resolution of complex reversible-reaction networks

A complex dynamic system based on a network of multiple reversible reactions has been established. The network was applied to a dynamic systemic resolution protocol based on kinetically controlled lipase-catalyzed transformations. This resulted in the formation of cyclized products, where two thiazolidinone compounds were efficiently produced from a range of potential transformations.

Asymmetric synthesis of tetrahydropyridines via an organocatalytic one-pot multicomponent Michael/aza-Henry/cyclization triple domino reaction

A low loading of a quinine-derived squaramide efficiently catalyzes the triple-domino Michael/aza-Henry/cyclization reaction between 1,3-dicarbonyl compounds, β-nitroolefins, and aldimines to provide tetrahydropyridines bearing three contiguous stereogeni

Simple and efficient one-pot solvent-free synthesis of N-methyl imines of aromatic aldehydes

A one-pot solvent-free synthesis of N-methyl imines in good to excellent yields was performed by grinding together aromatic aldehydes and methylamine hydrochloride in the presence of a base. The best yields were achieved when an excess of methylamine hydrochloride and inexpensive sodium hydrogen carbonate was used (usually in a molar ratio ArCHO/CH3NH2· HCl/NaHCO3 = 1:5:5), allowing the reaction to proceed for 1 h (in the case of aromatic aldehydes containing electron-withdrawing substituents) or overnight (in the case of electron-rich aldehydes). After a simple work-up (extraction with diethyl ether) the obtained products were mostly pure enough for spectral characterization. In this way, 31 N-methyl imines were prepared, among which eight were synthesized for the first time. Their structures were elucidated by spectral means (1H- and 13C-NMR, IR, MS) whenever it was possible. In the case of salicylaldehyde and 4-chlorobenzaldehyde, the synthesis of the corresponding imines was also conducted on a gram-scale with a 72% and 84% isolated yield, respectively. The present approach not only provides good to high yields, but also eliminates the disadvantages of the traditional synthesis of N-methyl imines, such as the use of hazardous solvents and more or less expensive catalysts and the necessity of work/handling with an anhydrous gas in pressurized containers.

Efficient synthesis of new 4-arylideneimidazolin-5-ones related to the GFP chromophore by 2+3 cyclocondensation of arylideneimines with imidate ylides

A 2+3 condensation of a wide assortment of Schiff bases, prepared from aromatic aldehydes and primary amines, with methyl (1-ethoxyethylideneamino) acetate allows convenient access to an extensive family of substituted 4-arylideneimidazolin-5-one analogues of the green fluorescent protein (GFP) chromophore. Georg Thieme Verlag Stuttgart · New York.

Reactions of N-Chloro-N-alkylbenzylamines with Amines in Acetonitrile. Origin of Steric Effect in Imine-Forming Elimination

Reaction of N-chloro-N-alkylbenzylamines in which the alkyl group is Me, Et, i-Pr, sec-Bu, and t-Bu with MeNH2 and Et2NH in MeCN have been studied kinetically.The eliminations are quantitative and regiospecific, producing only N-benzylidenealkylamines.The relative rates of elimination for Me/Et/i-Pr/sec-Bu/t-Bu alkyl substituents are 1/0.6/0.4/0.3/0.1 with MeNH2 and 1/0.5/0.3/0.2/0.03 with Et2NH, respectively.Comparison with published data reveals that Charton's value for the imine-forming elimination decreases with the variation of the base-solvent from MeONa-MeOH to MeNH2-MeCN but increases when the base is changed from MeNH2 to Et2NH.For a given base, Hammett ρ and kH/kD values decrease and the ΔH(excit.) and ΔS(excit.) values increase with bulkier alkyl substituents.From these results, the origin of the steric effect in imine-forming elimination is attributed to the repulsive interaction between the alkyl group and the base in the transition state.

Reactions of N-Halogenobenzylmethylamines with Triethylamine in Acetonitrile. Effect of Leaving Group upon the Imine-forming Transition State

Reactions of N-halogenobenzylmethylamines (1) and (2) with Et3N-MeCN have been investigated kinetically.Eliminations from (1) and (2) were quantitative and regiospecific, producing only benzylidenemethylamines.For the elimination reaction of (1) with Et3N, kH/kD 5.7, ρ 0.88, 9.1 kcal mol-1, and -42.4 cal mol-1 K-1 were determined.The transition-state structure is assessed as being highly symmetric with similar extents of Cβ-H and Nα-Cl bond cleavage, little carbanionic character, and significant ?-bond formation.The structure of the transition state changes only slightly with the change in the leaving group from Cl to Br.