Communications: Formylation of Aromatic Amines with Dimethylformamide

Pettit, George R.; Thomas, Evan G.

doi:10.1021/jo01088a633

Cited by 36 publications

(10 citation statements)

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“…Ionization constants (pK a ) were determined for the carboxyland hydroxyl-substituted formanilides using potentiometry (p-hydroxy (9.58)) and UV spectroscopy (pcarboxyl (4.02), m-carboxyl (3.86), o-carboxyl (3.37), m-hydroxyl (9.59), and o-hydroxyl(8.98)) [21,22]. The compounds had melting points and NMR spectra in good agreement with literature values [6,9,[23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39]. The spectra of the compounds not previously synthesized are reported below.…”

Section: Experimental Synthesissupporting

confidence: 61%

The Ortho Effect on the Acidic and Alkaline Hydrolysis of Substituted Formanilides

Desai

Kirsch

2015

Int J of Chemical Kinetics

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The kinetics of formanilides hydrolysis were determined under first-order conditions in hydrochloric acid (0.01-8 M, 20-60°C) and in hydroxide solutions (0.01-3 M, 25 and 40°C). Under acidic conditions, second-order specific acid catalytic constants were used to construct Hammett plots. The ortho effect was analyzed using the Fujita-Nishioka method. In alkaline solutions, hydrolysis displayed both first-and second-order dependence in the hydroxide concentration. The specific base catalytic constants were used to construct Hammett plots. Ortho effects were evaluated for the first-order dependence on the hydroxide concentration. Formanilide hydrolyzes in acidic solutions by specific acid catalysis, and the kinetic study results were consistent with the A AC 2 mechanism. Ortho substitution led to a decrease in the rates of reaction due to steric inhibition of resonance, retardation due to steric bulk, and through space interactions. The primary hydrolytic pathway in alkaline solutions was consistent with a modified B AC 2 mechanism. The Hammett plots for hydrolysis of meta-and para-substituted formanilides in 0.10 M sodium hydroxide solutions did not show substituent effects; however, ortho substitution led to a decrease in rate constants proportional to the steric bulk of the substituent. C 2015 Wiley Periodicals, Inc. Int J Chem Kinet 47: [471][472][473][474][475][476][477][478][479][480][481][482][483][484][485][486][487][488] 2015

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Section: Experimental Synthesissupporting

confidence: 61%

The Ortho Effect on the Acidic and Alkaline Hydrolysis of Substituted Formanilides

Desai

Kirsch

2015

Int J of Chemical Kinetics

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“…Formation of various by‐products was observed. On the other hand, the ethanethiol–sodium tert ‐butoxide couple in DMF yielded the formamide derivative 32 (78 %), which could be formed via a base‐catalyzed formylation of the intermediate 33 with DMF . Saponification of the formamide 32 gave the linear AAP 33 with a yield of 90 %.…”

Section: Resultsmentioning

confidence: 99%

Enantiopure cis‐ and trans‐2‐(2‐Aminocyclohexyl)phenols: Effective Preparation, Solid‐State Characterization, and Application in Asymmetric Organocatalysis

et al. 2018

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Effective synthesis of cis‐ and trans‐2‐(2‐methoxyphenyl)cyclohexylamine as well as their multigram‐scale optical resolution by diastereomeric salt formation with dibenzoyl tartaric acid have been described. Assignment of absolute configurations to the enantiomers has been made by X‐ray crystallography. Starting from the resolved precursor, diverse aminoalkylphenols (AAPs) having primary, secondary, and tertiary amine group as well as a quaternary ammonium phenol have been prepared as potential bifunctional organocatalysts based on the cyclohexane backbone. We furthermore report herein that AAPs carrying a primary amine and a phenolic hydroxyl group can catalyze the direct aldol reaction with high activity and setereoselectivity, and thus up to 97 % yield, 90:10 syn/anti diastereomeric ratio, and 80 % enantiomeric excess can be achieved.

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“…DMF has previously been reported to act as a source of the formyl group in a number of reactions, [33] including the N -formylation of halo and carboxyl anilines in DMF under reflux in the presence of sodium methoxide. [34] …”

Section: Resultsmentioning

confidence: 99%

Rapid Room‐Temperature ¹¹C‐Methylation of Arylamines with [¹¹C]Methyl Iodide Promoted by Solid Inorganic‐Bases in DMF

Cai

Guo

et al. 2012

Eur J Org Chem

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11[C]Methyl iodide is the most widely used reagent for labeling radiotracers with carbon-11 (t1/2 = 20.4 min) for molecular imaging with positron emission tomography. However, some substrates for labeling, especially primary arylamines and pyrroles, are sluggishly reactive towards [11C]methyl iodide. We found that insoluble inorganic bases, especially Li3N or Li2O, are effective in promoting rapid reactions (≤ 10 min) of such substrates with no-carrier-added [11C]methyl iodide in DMF at room temperature to give 11C-methylated products in useful radiochemical yields. In particular, we discovered that some primary arylamines in Li3N-DMF were converted into their formanilides, and that these were readily N-methylated with [11C]methyl iodide, preceding easy basic hydrolysis to the desired [11C]N-methyl secondary arylamines. Use of a solid base permitted selective reaction at an arylamino group and in some cases also avoided undesirable side reaction, such as ester group hydrolysis. An ultrasound device proved useful to provide remote and constant agitation of the radioactive heterogeneous reaction mixtures, but imparted no ‘ultrasound-specific’ chemical effect.

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Communications: Formylation of Aromatic Amines with Dimethylformamide

Cited by 36 publications

References 1 publication

The Ortho Effect on the Acidic and Alkaline Hydrolysis of Substituted Formanilides

The Ortho Effect on the Acidic and Alkaline Hydrolysis of Substituted Formanilides

Enantiopure cis‐ and trans‐2‐(2‐Aminocyclohexyl)phenols: Effective Preparation, Solid‐State Characterization, and Application in Asymmetric Organocatalysis

Rapid Room‐Temperature ¹¹C‐Methylation of Arylamines with [¹¹C]Methyl Iodide Promoted by Solid Inorganic‐Bases in DMF

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Communications: Formylation of Aromatic Amines with Dimethylformamide

Cited by 36 publications

References 1 publication

The Ortho Effect on the Acidic and Alkaline Hydrolysis of Substituted Formanilides

The Ortho Effect on the Acidic and Alkaline Hydrolysis of Substituted Formanilides

Enantiopure cis‐ and trans‐2‐(2‐Aminocyclohexyl)phenols: Effective Preparation, Solid‐State Characterization, and Application in Asymmetric Organocatalysis

Rapid Room‐Temperature 11C‐Methylation of Arylamines with [11C]Methyl Iodide Promoted by Solid Inorganic‐Bases in DMF

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Rapid Room‐Temperature ¹¹C‐Methylation of Arylamines with [¹¹C]Methyl Iodide Promoted by Solid Inorganic‐Bases in DMF