The alkali metal adducts of acetophenone anil

1967 ◽  
Vol 45 (15) ◽  
pp. 1785-1794 ◽  
Author(s):  
James G. Smith ◽  
C. Doreen Veach
Keyword(s):  
Nitrogen Atom ◽  
Alkali Metal ◽  
Alkyl Halide ◽  
Chemical Behavior ◽  
Methyl Group ◽  
Metal Adducts ◽  
Hydrolysis Of

Contrary to previous reports, the reaction between acetophenone anil and sodium produces a product containing one atom of sodium per mole of anil. In its chemical behavior, this adduct appears to consist of equal parts of N-sodio-N,1-diphenylethylamine and α-sodioacetophenone anil. Thus, treatment with an alkyl halide results in products derived by alkylation of the nitrogen atom of N,1-diphenylethylamine and alkylation of the methyl group of acetophenone anil.The behavior of acetophenone anil towards lithium is quite different and very solvent dependent. In ether, hydrolysis of the lithium adduct produces a dimer, N,N′,2,3-tetraphenyl-2,3-butanediamine. In tetrahydrofuran with either lithium or potassium, another dimer, N,N′,l,4-tetraphenyl-1,4-butanediamine, is formed by dimerization through the methyl group of acetophenone anil. The structure of this new dimer was established by separation of the diastereomers and cyclization of each to the corresponding 1,2,5-triphenylpyrrolidine.The mechanism by which these products are formed is discussed.

Dirhodium-Catalyzed Chemo- and Site-Selective C–H Amidation of N,N-Dialkylanilines

Synlett ◽  
2020 ◽  
Author(s):  
Yoshihiro Ueda ◽  
Gong Chen ◽  
Kenta Arai ◽  
Kazuhiro Morisaki ◽  
Takeo Kawabata
Keyword(s):  
Nitrogen Atom ◽  
Aromatic Ring ◽  
Methyl Group ◽  
Site Selective

AbstractA method for dirhodium-catalyzed C(sp3)–H amidation of N,N-dimethylanilines was developed. Chemoselective C(sp3)–H amidation of N-methyl group proceeded exclusively in the presence of C(sp2)–H bonds of the electron-rich aromatic ring. Site-selective C(sp3)–H amidation proceeded exclusively at the N-methyl group of N-methyl-N-alkylaniline derivatives with secondary, tertiary, and benzylic C(sp3)–H bonds α to a nitrogen atom.

scholarly journals Synthesis and spectral characterization of novel 1,5-benzodiazepine oxime derivatives

2019 ◽  
Vol 84 (4) ◽  
pp. 343-353
Author(s):  
Lina Rekovic ◽  
Lidija Kosychova ◽  
Irina Bratkovskaja ◽  
Regina Vidziunaite
Keyword(s):  
Nitrogen Atom ◽  
Fluorescence Spectroscopy ◽  
Organic Solvent ◽  
Elemental Analysis ◽  
13C Nmr ◽  
1H And 13C Nmr ◽  
Methyl Group ◽  
Oxime Derivatives ◽  
New Compounds

Three new 1,3,4,5-tetrahydro-2H-1,5-benzodiazepin-2-one oximes were synthesized and characterized by the methods of 1H- and 13C-NMR, IR and elemental analysis. Along with previously described compounds bearing one additional methyl group on the 5th nitrogen atom, the new compounds were characterized in bulk by UV?Vis and fluorescence spectroscopy in various solvents. The influence of the nature of the organic solvent on the spectra of the title compounds was investigated and is discussed.

scholarly journals Unexpected Resistance to Base-Catalyzed Hydrolysis of Nitrogen Pyramidal Amides Based on the 7-Azabicyclic[2.2.1]heptane Scaffold

Molecules ◽  
2018 ◽  
Vol 23 (9) ◽  
pp. 2363 ◽  
Author(s):  
Diego Ocampo Gutiérrez de Velasco ◽  
Aoze Su ◽  
Luhan Zhai ◽  
Satowa Kinoshita ◽  
Yuko Otani ◽  
...  
Keyword(s):  
Nitrogen Atom ◽  
Amide Bond ◽  
Free Energies ◽  
Amide Nitrogen ◽  
Bond Rotation ◽  
Entropy Term ◽  
And Inversion ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Amide Nitrogen Atom

Non-planar amides are usually transitional structures, that are involved in amide bond rotation and inversion of the nitrogen atom, but some ground-minimum non-planar amides have been reported. Non-planar amides are generally sensitive to water or other nucleophiles, so that the amide bond is readily cleaved. In this article, we examine the reactivity profile of the base-catalyzed hydrolysis of 7-azabicyclo[2.2.1]heptane amides, which show pyramidalization of the amide nitrogen atom, and we compare the kinetics of the base-catalyzed hydrolysis of the benzamides of 7-azabicyclo[2.2.1]heptane and related monocyclic compounds. Unexpectedly, non-planar amides based on the 7-azabicyclo[2.2.1]heptane scaffold were found to be resistant to base-catalyzed hydrolysis. The calculated Gibbs free energies were consistent with this experimental finding. The contribution of thermal corrections (entropy term, –TΔS‡) was large; the entropy term (ΔS‡) took a large negative value, indicating significant order in the transition structure, which includes solvating water molecules.

scholarly journals Use of a Hydrolytic Procedure and Spectrometric Methods in the Structure Elucidation of a Thiocarbonyl Analogue of Sildenafil Detected as an Adulterant in an Over-the-Counter Herbal Aphrodisiac

2009 ◽  
Vol 92 (5) ◽  
pp. 1336-1342 ◽  
Author(s):  
John C Reepmeyer ◽  
D Andr d'Avignon
Keyword(s):  
Dietary Supplement ◽  
Carbonyl Group ◽  
Minor Component ◽  
Pyrimidine Ring ◽  
Over The Counter ◽  
Methyl Group ◽  
Nmr Spectrometry ◽  
A Minor ◽  
Hydrolysis Of ◽  
Hydroxyethyl Group

Abstract A sildenafil-related compound was detected in an herbal dietary supplement marketed as an aphrodisiac. The compound was identified as an analogue of sildenafil in which the carbonyl group in the pyrimidine ring of sildenafil was substituted with a thiocarbonyl group, and the methyl group on the piperazine ring was substituted with a hydroxyethyl group. Based on this structure, the compound was named thiohydroxyhomosildenafil. The structure of the compound was established using HPLC/MS, UV spectrometry, electrospray ionization-MS/MS, NMR spectrometry, and a hydrolytic process. One key product of hydrolysis was 1-(2-hydroxyethyl)-piperazine; the identification of this product defined the amine portion of the compound. Another key product of hydrolysis was hydroxyhomosildenafil, generated by hydrolysis of the thiocarbonyl group to a carbonyl group (C S C O). Hydroxyhomosildenafil was detected as a minor component in the dietary supplement.

Gas-phase fragmentation of metal adducts of alkali-metal oxalate salts

2014 ◽  
Vol 49 (3) ◽  
pp. 195-200 ◽  
Author(s):  
Robert D. Hale ◽  
Chang-Ching Chan ◽  
Carl S. Weisbecker ◽  
Athula B. Attygalle
Keyword(s):  
Alkali Metal ◽  
Gas Phase ◽  
Metal Oxalate ◽  
Metal Adducts ◽  
Gas Phase Fragmentation

Purely Aliphatic Azoxy Compounds with a Methyl Group attached to the Nitrogen Atom

Nature ◽  
1951 ◽  
Vol 167 (4256) ◽  
pp. 863-864 ◽  
Author(s):  
J. G. ASTON ◽  
D. M. JENKINS
Keyword(s):  
Nitrogen Atom ◽  
Methyl Group ◽  
Azoxy Compounds

scholarly journals Isolation of two N-monosubstituted protoporphyrins, bearing either the whole drug or a methyl group on the pyrrole nitrogen atom, from liver of mice given griseofulvin

1991 ◽  
Vol 274 (3) ◽  
pp. 843-848 ◽  
Author(s):  
A E Holley ◽  
Y Frater ◽  
A H Gibbs ◽  
F De Matteis ◽  
J H Lamb ◽  
...  
Keyword(s):  
Nitrogen Atom ◽  
Protoporphyrin Ix ◽  
Secondary Product ◽  
Structural Isomers ◽  
Green Pigment ◽  
Methyl Group ◽  
Group 4 ◽  
Pyrrole Nitrogen

1. A hepatic green pigment with inhibitory properties towards the enzyme ferrochelatase has been isolated from the liver of mice treated with griseofulvin and identified as N-methylprotoporphyrin. 2. All four structural isomers of N-methylprotoporphyrin have been demonstrated to be present, NA, where ring A of protoporphyrin IX is N-methylated, being the predominant isomer. 3. In addition to N-methylprotoporphyrin, a second green pigment, present in far greater amounts, was also isolated from the liver of griseofulvin-treated mice. This second green pigment is also an N-monosubstituted protoporphyrin, but in this case the substituent on the pyrrole nitrogen atom appears to be intact griseofulvin rather than a methyl group. 4. The fragmentation of this adduct in tandem m.s. studies suggests that griseofulvin is bound to the pyrrole nitrogen through one of its carbon atoms and further suggests that N-methylprotoporphyrin may arise as a secondary product from the major griseofulvin pigment.

Micellar Catalysis of Organic Reactions. XVII. Hydrolysis of Nitrazepam and Some N-Alkylated Derivatives

1985 ◽  
Vol 38 (7) ◽  
pp. 1037 ◽  
Author(s):  
TJ Broxton ◽  
SR Morrison
Keyword(s):  
Aqueous Solution ◽  
Nitrogen Atom ◽  
Sodium Dodecyl Sulfate ◽  
Sodium Dodecyl ◽  
Initial Attack ◽  
Amide Nitrogen ◽  
High Acid ◽  
Alkyl Derivatives ◽  
Hydrolysis Of ◽  
Amide Nitrogen Atom

Product studies for the acid catalysed hydrolysis of nitrazepam and some N-alkyl derivatives in the presence of micelles of sodium dodecyl sulfate ( sds ) have been carried out by a U.V. spectrophotometric technique. Attack of water at C2 leading to initial amide cleavage is favoured by high acid concentrations, by micelles of sds and by small R groups attached to the amide nitrogen atom. For nitrazepam, a change of mechanism from water attack at C5 (leading to initial azomethine cleavage) to water attack at C2 (leading to initial amide cleavage) was observed on transfer from water to micelles of sds . For N-benzyl nitrazepam (1d), however, no change of mechanism was detected. Initial attack of water occurred at C5 (leading to initial azomethine cleavage), both in aqueous solution and in micelles of sds.

Kinetics of acid-catalyzed cyclization of substituted hydantoinamides to substituted hydantoins

1987 ◽  
Vol 52 (8) ◽  
pp. 1999-2004 ◽  
Author(s):  
Jaromír Kaválek ◽  
Vladimír Macháček ◽  
Gabriela Svobodová ◽  
Vojeslav Štěrba
Keyword(s):  
Hydrogen Atom ◽  
Nitrogen Atom ◽  
Hydrochloric Acid ◽  
Dissociation Constants ◽  
Amide Group ◽  
The Other ◽  
Methyl Group ◽  
Acid Catalyzed ◽  
Cyclization Rate ◽  
Kinetics Of

The kinetics of acid-catalyzed cyclization of the hydantoinamides type R3-N(5)H-CO-N(3)R2-CH2-CO-N(1)HR1 (R1, R2, R3 = H and/or CH3) has been studied in 0·5 to 5 mol l-1 hydrochloric acid. The cyclization rate is limited by the rate of the attack of nitrogen atom N(5) on the carbon atom of the protonated amide group. The dissociation constants of the protonated hydantoinamides and rate constants of their cyclizations have been determined. Replacement of hydrogen atom by methyl group at the N(5) nitrogen atom accelerates the cyclization about two times., the same substitution at N(3) accelerates about 50x, whereas at N(1) it results in a 300 fold retardation. With the hydantoinamides having R3 = CH3, the cyclization rate of the protonated hydantoinamide increases with increasing concentration of hydrochloric acid, whereas with the other derivatives this value is independent of the acid concentration.

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