Aerobic oxidative N-dealkylation of tertiary amines in aqueous solution catalyzed by rhodium porphyrins

2013 ◽  
Vol 49 (39) ◽  
pp. 4214-4216 ◽  
Author(s):  
Zhen Ling ◽  
Lin Yun ◽  
Lianghui Liu ◽  
Bing Wu ◽  
Xuefeng Fu
Keyword(s):  
Aqueous Solution ◽  
Tertiary Amines ◽  
Rhodium Porphyrins

ChemInform Abstract: Aerobic Oxidative N-Dealkylation of Tertiary Amines in Aqueous Solution Catalyzed by Rhodium Porphyrins

ChemInform ◽  
2013 ◽  
Vol 44 (36) ◽  
pp. no-no
Author(s):  
Zhen Ling ◽  
Lin Yun ◽  
Lianghui Liu ◽  
Bing Wu ◽  
Xuefeng Fu
Keyword(s):  
Aqueous Solution ◽  
Tertiary Amines ◽  
Rhodium Porphyrins

The Extraction of Anionic Beryllium Complexes by Tri-iso-octylamine

1962 ◽  
Vol 15 (3) ◽  
pp. 457 ◽  
Author(s):  
HJ de Bruin ◽  
D Kairaitis ◽  
RB Temple
Keyword(s):  
Aqueous Solution ◽  
Stability Constants ◽  
Complexing Agents ◽  
Conditional Stability ◽  
Tertiary Amines ◽  
Ph Titration ◽  
Anionic Complexes ◽  
The Stability ◽  
Conditional Stability Constants ◽  
Beryllium Complexes

The extraction of beryllium from aqueous solution by long-chain tertiary amines has been observed in the presence of ligands giving rise to anionic complexes. The nature of the oxalate complex extracted by solutions of tri-iso-octylamine in chloroform has been studied in detail and the species formed in the organic phase were shown to have the composition Be(C2O4)2.{NH(i-C8H15)3}2. The complexes formed in aqueous solution between beryllium and several anionic complexing agents have been examined by the method of pH-titration. Conditional stability constants have been obtained for the complexes formed with oxalic, malonic, maleic, succinic, phthalic, and salicylic acids. Differences in their extractabilities can be explained semiquantitatively with the help of the stability constants and the acid association constants of the complexing agents.

Adsorption of alkylammonium cations by montmorillonite

Clay Minerals ◽  
1967 ◽  
Vol 7 (1) ◽  
pp. 1-17 ◽  
Author(s):  
B. K. G. Theng ◽  
D. J. Greenland ◽  
J. P. Quirk
Keyword(s):  
Aqueous Solution ◽  
Single Layer ◽  
Tertiary Amines ◽  
X Ray Diffraction ◽  
Ammonium Ions ◽  
X Ray ◽  
Inorganic Cations ◽  
Quaternary Ammonium Ions ◽  
Contact Distance ◽  
Alkyl Groups

AbstractThe adsorption of various alkylammonium cations from aqueous solution by sodium and calcium montmorillonite has been studied. Adsorption occurred through an exchange reaction between the inorganic cations on the clay and the alkylammonium ions in solution. The affinity of the clay for these cations was linearly related to molecular weight, with the exception of the smaller methyl-ammonium and the larger quaternary ammonium ions. Comparison of primary, secondary and tertiary amines containing the same alkyl groups showed that the affinity of the clay was greatest for the primary amine and least for the tertiary. This behaviour has been interpreted in terms of the size and shape of the cations. X-ray diffraction analysis showed that no more than a single layer of adsorbed cations was present in the inter-lamellar space at maximum adsorption. Comparison between Δ-values and the thickness of the adsorbed ions showed that there was a contraction in the apparent contact distance of these cations. The amount of contraction could be accounted for by ‘keying’ of the adsorbed ions into the montmorillonite surface.

Aerobic oxidative N-dealkylation of secondary amines in aqueous solution catalyzed by rhodium porphyrins

2014 ◽  
Vol 18 (10n11) ◽  
pp. 937-943 ◽  
Author(s):  
Lin Yun ◽  
Ling Zhen ◽  
Zikuan Wang ◽  
Xuefeng Fu
Keyword(s):  
Aqueous Solution ◽  
Oxidation Reaction ◽  
Catalyst Deactivation ◽  
Secondary Amines ◽  
First Order ◽  
Rate Determining Step ◽  
First Order Kinetics ◽  
Biochemical Oxidation ◽  
Iminium Ion ◽  
Rhodium Porphyrins

N-dealkylation demonstrates an important biochemical oxidation reaction by cytochrome P450 and other monooxygenases. In this article, catalytic oxidative N-dealkylation of secondary amines was achieved using rhodium(III) tetra (p-sulfonato-phenyl) porphyrin (( TSPP ) Rh III ) in aqueous solution with oxygen as the sole oxidant. Addition of benzaldehyde to trap primary amine product inhibited catalyst deactivation and dramatically increased reaction turnover numbers (TONs). Substrate scope examination suggested the reaction was performed with a preference for bulkier secondary amines. Kinetic study exhibited first-order kinetics with regard of ( TSPP ) Rh III catalyst. Results from the Hammett study gave a ρ value of -1.38, suggesting formation of an iminium ion intermediate in the rate determining step.

Determination of small amounts of long-chain aliphatic tertiary amines in aqueous solution

The Analyst ◽  
1963 ◽  
Vol 88 (1045) ◽  
pp. 322 ◽  
Author(s):  
M. W. Desai ◽  
T. K. S. Murthy
Keyword(s):  
Aqueous Solution ◽  
Tertiary Amines ◽  
Long Chain

scholarly journals Kinetics of Carbon Dioxide with tertiary Amines in aqueous solution

AIChE Journal ◽  
1990 ◽  
Vol 36 (11) ◽  
pp. 1633-1640 ◽  
Author(s):  
R. J. Littel ◽  
W. P. M. Van Swaaij ◽  
G. F. Versteeg
Keyword(s):  
Carbon Dioxide ◽  
Aqueous Solution ◽  
Tertiary Amines ◽  
Kinetics Of

Organic sulfur mechanisms. 24. Preparation and reactions of 2-hydroxyethanesulfonyl chloride, the first hydroxyalkanesulfonyl chloride

1983 ◽  
Vol 61 (7) ◽  
pp. 1583-1593 ◽  
Author(s):  
James Frederick King ◽  
John Henry Hillhouse
Keyword(s):  
Aqueous Solution ◽  
Hydroxy Group ◽  
Intramolecular Cyclization ◽  
Ring Opening ◽  
Sulfonyl Chloride ◽  
Tertiary Amines ◽  
Deuterium Labelling ◽  
Chlorination Process ◽  
Principal Reaction ◽  
A Minor

2-Hydroxyethanesulfonyl chloride (1a) is readily made by reaction of an aqueous solution of 2-mercaptoethanol (4a) with chlorine. This is the first clearly proved preparation of a compound which is both an alcohol and a sulfonyl chloride. Reactions of 1a with water and alcohols evidently proceed largely by intramolecular cyclization to the transient β-sultone (2a), which then undergoes nuclcophilic ring opening to form the products. In the presence of tertiary amines a minor but significant part of the reaction is shown by deuterium labelling to proceed via hydroxymethylsulfene (14). the principal reaction of which is simply to add the alcohol or water; only a small part, if any, of the sulfene (14) loses the hydroxy¡ group to give the ethenesulfonate derivatives (13 or 22). Aqueous chlorination of 3-mercapto-1-propanol gave 3-chloro-1-propanesulfonyl chloride (5a) and 1,3-propane sultone (2b) with no sign of any 3-hydroxy-1-propanesulfonyl chloride (1b). A mechanism for the aqueous chlorination process invoking a cyclic chlorooxasulfoxoniuin ion (27) is discussed.

The SN1CB Mechanism in Non-Aqueous Solution

1988 ◽  
Vol 41 (9) ◽  
pp. 1369 ◽  
Author(s):  
WG Jackson ◽  
RL Angel
Keyword(s):  
Aqueous Solution ◽  
Dimethyl Sulfoxide ◽  
Primary Amines ◽  
Tertiary Amines ◽  
Pka Values ◽  
First Order ◽  
Rate Laws ◽  
General Base ◽  
First Order Kinetics ◽  
Conjugate Base

The reaction between (NH3)5Co-NCMe3+ and dimethyl sulfoxide (Me2SO) to produce (NH3)5Co-OSMe23+ and MeCN in Me2SO solvent is general base-catalysed. The rates and rate laws have been determined for 10 substituted amines. First-order kinetics are observed, and the rates show a dependence which is less than first order on base (B) concentration. These facts are rationalized in terms of a common, reactive conjugate base (NH3)4(NH2)CoNCMe2+, the solvolysis of which occurs at a rate competitive with its rate of reprotonation by BH+. Alternative mechanisms are considered. The measured rates, which span two orders of magnitude, do not correlate with base nucleophilicity, steric features of the amines, nor pKa values as measured for aqueous solution. Primary amines are very effective catalysts; secondary and especially tertiary amines are poorer catalysts. There appears to be no reaction at the bound nitrile function as there is in aqueous solution.

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