scholarly journals A Comprehensive Extraction Study Using a Mono-alkylated Diglycolamic Acid Extractant: Comparison Between a Secondary Amide Group and a Tertiary Amide Group

2017 ◽  
Vol 24 (2) ◽  
pp. 61-69 ◽  
Author(s):  
Tsuyoshi SUGITA ◽  
Iori FUJIWARA ◽  
Hiroyuki OKAMURA ◽  
Tatsuya OSHIMA ◽  
Yoshinari BABA ◽  
...  
Keyword(s):  
Amide Group ◽  
Secondary Amide ◽  
Tertiary Amide ◽  
Extraction Study ◽  
Acid Extractant

scholarly journals Selective Extraction of Platinum(IV) from the Simulated Secondary Resources Using Simple Secondary Amide and Urea Extractants

Separations ◽  
2021 ◽  
Vol 8 (9) ◽  
pp. 139
Author(s):  
Yuki Ueda ◽  
Shintaro Morisada ◽  
Hidetaka Kawakita ◽  
Keisuke Ohto
Keyword(s):  
Electrical Equipment ◽  
Selective Extraction ◽  
Extraction Process ◽  
Secondary Amide ◽  
Separation And Purification ◽  
Secondary Resources ◽  
Tertiary Amide ◽  
Third Phase ◽  
Simulated Effluent ◽  
Secondary Amides

The recycling of rare metals such as platinum (Pt) from secondary resources, such as waste electronic and electrical equipment and automotive catalysts, is an urgent global issue. In this study, simple secondary amides and urea, N-(2-ethylhexyl)acetamide, N-(2-ethylhexyl)octanamide, and 1-butyl-3-(2-ethylhexyl)urea, which selectively extract Pt(IV) from a simulated effluent containing numerous metal ions, such as in an actual hydrometallurgical process, were synthesized and achieved efficient Pt(IV) stripping using only water. Comparison of Pt(IV) extraction behavior with a tertiary amide without N–H moieties suggests that the secondary amides and urea extractants effectively use hydrogen bonding to the hexachloroplatinate anion by N–H moieties. Examining the conditions for the third phase formation revealed that the secondary amide extractant with the longest alkyl chain can be used in the extraction process for a long time without forming any third phase, despite its lower Pt(IV) extraction capacity. The practical trial with simple compounds developed in this study should contribute to the development of Pt separation and purification processes.

scholarly journals The ozonolysis of primary aliphatic amines in fine particles

2008 ◽  
Vol 8 (5) ◽  
pp. 1181-1194 ◽  
Author(s):  
J. Zahardis ◽  
S. Geddes ◽  
G. A. Petrucci
Keyword(s):  
Fine Particles ◽  
Reaction System ◽  
Tropospheric Chemistry ◽  
Ozone Exposure ◽  
Surface Barrier ◽  
Secondary Amide ◽  
Tertiary Amide ◽  
Aerosol Mass ◽  
Criegee Intermediates ◽  
Species Specific

Abstract. The oxidative processing by ozone of the particulate amines octadecylamine (ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines resulted in strong NO2– and NO3– ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitroalkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO3– (HNO3). For ozonized mixed particles containing ODA or HDA + oleic acid (OL), with pO3≥3×10–7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines) and stabilized Criegee intermediates (SCI) or secondary ozonides (for amides) from the fatty acid. The routes to amides via SCI and/or secondary ozonides were shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10−3 atm for 17 s). This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g.~NO2, NO3), formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

Hydride Reductions of 1H-Pyrrolo[2,1-c][1,4]-benzodiazepine-5,11-diones: Selective Reduction of Secondary Amides to Carbinolamines

1998 ◽  
Vol 51 (12) ◽  
pp. 1121 ◽  
Author(s):  
Andrew G. Katsifis ◽  
Meredith E. McPhee ◽  
Damon D. Ridley
Keyword(s):  
Selective Reduction ◽  
Secondary Amide ◽  
Tertiary Amide ◽  
Secondary Amides

For the syntheses of radiolabelled pyrrolo[1,4]benzodiazepine antitumour antibiotics we required a method in which the unstable carbinolamine functionality was introduced prior to the radiolabel. In turn this required the selective reduction of a secondary amide in the presence of, inter alia, a tertiary amide. We report methods which can be used to achieve this outcome in a series of 1H-pyrrolo[2,1-c][1,4]benzodiazepine-5,11-diones.

A REMPI and ZEKE Spectroscopic Study of a Secondary Amide Group in Acetanilide

2002 ◽  
Vol 106 (40) ◽  
pp. 9181-9187 ◽  
Author(s):  
Susanne Ullrich ◽  
Klaus Müller-Dethlefs
Keyword(s):  
Spectroscopic Study ◽  
Amide Group ◽  
Secondary Amide

Effects of Internal Hydrogen Bonds between Amide Groups: Protonation of Alicyclic Diamides

2003 ◽  
Vol 9 (2) ◽  
pp. 81-95 ◽  
Author(s):  
Matthias Witt ◽  
Dirk Kreft ◽  
Hans-Friedrich Grützmacher
Keyword(s):  
Hydrogen Bonds ◽  
Major Part ◽  
Kinetic Method ◽  
Amide Group ◽  
Boat Conformation ◽  
Free Rotation ◽  
Tertiary Amide ◽  
Dipole Interactions ◽  
Amide Derivatives ◽  
Entropy Effects

The proton affinity ( PA) of cyclopentane carboxamide 1, cyclohexane carboxamide 2 and their secondary and tertiary amide derivatives S1, S2, T1 and T2, was determined by the thermokinetic method and the kinetic method [ PA(1) = 888 ± 5 kJ mol−1; PA(2) = 892 ± 5 kJ mol−1; PA(S1) = 920 ± 6 kJ mol−1; PA(S2) = 920 ± 6 kJ mol−1; PA(T1) = 938 ± 6 kJ mol−1; PA(T2) = 938 ± 6 kJ mol−1]. Special entropy effects are not observed. Additionally, the effects of protonation have been studied using an advanced kinetic method for all isomers 3–7 of cyclopentane dicarboxamides and cyclohexane dicarboxamides (with the exception of cis-cyclopentane-1,2-dicarboxamide) and their bis-tertiary derivatives T3–T7 by estimating the PA and the apparent entropy of protonation Δ(Δ Sapp). Finally, the study was extended to bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxamide 8 and its bis-tertiary derivative T8, to all stereoisomers of bicyclo[2.2.1]heptane-2,3-dicarboxamide 9, their secondary and tertiary amide derivatives S9 and T9, and to endo–endo–bicyclo[2.2.1]heptane-2,5-dicarboxamide 10 and the corresponding secondary and tertiary derivatives S10 and T10. Compared with 1 and 2, all alicyclic diamides exhibit a significant increase of the PA (ΔPA) and special entropy effects on protonation. For alicyclic diamides, which can not accommodate a conformation appropriate for building a proton bridge, the values of Δ PA and Δ(Δ Sapp) are small to moderate. This is explained by ion / dipole interactions between the protonated and neutral amide group which stabilize the protonated species but hinder the free rotation of the amide groups. If any of the conformations of the alicyclic diamide allows formation of a proton bridge, Δ PA and Δ(Δ Sapp) increase considerably. A spectacular case is cis-cyclohexane-1,4-dicarboxamide 7c which is the most basic monocyclic diamide, although generation of the proton bridge requires the unfavorable boat conformation with both amide substituents at a flagpole position. A pre-orientation of the two amide groups in such a 1,4-position in 10 results in a particularly large PA of < 1000 kJ mol−1. The observation of comparable values for Δ(Δ Sapp) for linear and monocyclic diamides indicates that a major part of the entropy effects originates from freezing the free rotation of the amide groups by formation of the proton bridge. This is corroborated by observing corresponding effects during the protonation of dicarboxamides containing the rigid bicyclo[2.2.1]heptane carbon skeleton, where the only internal movements of the molecules corresponds to rotation of the amide substituents.

scholarly journals Reverse Polarity Reductive Functionalization of Tertiary Amides via a Dual Iridium Catalyzed Hydrosilylation & SET Strategy

2020 ◽  
Author(s):  
Tatiana Rogova ◽  
Pablo Gabriel ◽  
Stamatia Zavitsanou ◽  
Jamie Leitch ◽  
Fernanda Duarte ◽  
...  
Keyword(s):  
Active Pharmaceutical Ingredient ◽  
Building Blocks ◽  
Chemical System ◽  
Secondary Amide ◽  
Reductive Activation ◽  
Tertiary Amide ◽  
New Strategy ◽  
Tandem Process ◽  
Electron Reduction ◽  
Tertiary Amides

A new strategy for the mild generation of synthetically valuable α-amino radicals from robust tertiary amide building blocks has been developed. By combining Vaska’s complex-catalyzed tertiary amide reductive activation and photochemical single electron reduction into a streamlined tandem process, metastable hemiaminal intermediates were successfully transformed into nucleophilic α-amino free radical species. This umpolung approach to such reactive intermediates was exemplified through coupling with an electrophilic dehydroalanine acceptor, resulting in the synthesis of an array of α-functionalized tertiary amine derivatives, previously inaccessible from the amide starting materials. The utility of the strategy was expanded to include secondary amide substrates, intramolecular variants and late stage functionalization of an active pharmaceutical ingredient. DFT analyses were used to establish the reaction mechanism and elements of the chemical system that were responsible for the reaction’s efficiency.

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