scholarly journals Mechanism of color reaction of aromatic secondary and tertiary amines with quinonedichlorodiimide.

1979 ◽  
Vol 27 (3) ◽  
pp. 688-690
Author(s):  
MASAYASU YAMAMOTO ◽  
TOYOZO UNO
Keyword(s):  
Color Reaction ◽  
Tertiary Amines

scholarly journals The Color Reaction in Non-Aqueous Solvents. III. : The Color Reaction of Sulfonephthalein Dyes with Tertiary Amines and Solvent Effects on It

1971 ◽  
Vol 91 (12) ◽  
pp. 1286-1291
Author(s):  
KAZUO KIGASAWA ◽  
HIROAKI SHIMIZU ◽  
MITSUYO FUJINO ◽  
TOSHITAKA KOHAGIZAWA
Keyword(s):  
Solvent Effects ◽  
Color Reaction ◽  
Tertiary Amines

Mechanistic Insights into Fe Catalyzed α-C-H Oxidations of Tertiary Amines

2019 ◽  
Author(s):  
Christopher J. Legacy ◽  
Frederick T. Greenaway ◽  
Marion Emmert
Keyword(s):  
Free Radical ◽  
Catalytic Mechanism ◽  
Catalyst System ◽  
Oxidation Products ◽  
Tertiary Amines ◽  
Catalyst Activation ◽  
Rate Determining Step ◽  
Fe Catalyst ◽  
Ligand Coordination ◽  
Rate Kinetics

We report detailed mechanistic investigations of an iron-based catalyst system, which allows the α-C-H oxidation of a wide variety of amines, including acyclic tertiary aliphatic amines, to afford dealkylated or amide products. In contrast to other catalysts that affect α-C-H oxidations of tertiary amines, the system under investigation employs exclusively peroxy esters as oxidants. More common oxidants (e.g. tBuOOH) previously reported to affect amine oxidations via free radical pathways do not provide amine α-C-H oxidation products in combination with the herein described catalyst system. Motivated by this difference in reactivity to more common free radical systems, the investigations described herein employ initial rate kinetics, kinetic profiling, Eyring studies, kinetic isotope effect studies, Hammett studies, ligand coordination studies, and EPR studies to shed light on the Fe catalyst system. The obtained data suggest that the catalytic mechanism proceeds through C-H abstraction at a coordinated substrate molecule. This rate-determining step occurs either at an Fe(IV) oxo pathway or a 2-electron pathway at a Fe(II) intermediate with bound oxidant. We further show via kinetic profiling and EPR studies that catalyst activation follows a radical pathway, which is initiated by hydrolysis of PhCO3 tBu to tBuOOH in the reaction mixture. Overall, the obtained mechanistic data support a non-classical, Fe catalyzed pathway that requires substrate binding, thus inducing selectivity for α-C-H functionalization.<br>

Heterogeneous Bimetallic Pt-Sn/γ-Al2O3 Catalyzed N-Alkylation of Amines: Ef-ficient Synthesis of Secondary and Tertiary Amines

2013 ◽  
Vol 33 (4) ◽  
pp. 717-722 ◽  
Author(s):  
Wei HE ◽  
Songbo HE ◽  
Chenglin SUN ◽  
Kaikai WU ◽  
Liandi WANG ◽  
...  
Keyword(s):  
Tertiary Amines

New Cathepsin D Inhibitor Library Utilizing Hydroxyethyl Isosteres with Cyclic Tertiary Amines

2012 ◽  
Vol 8 (6) ◽  
pp. 1146-1154
Author(s):  
Rose M. McConnell ◽  
Kalyani Inapudi ◽  
Naveen Kadasala ◽  
Karthika Yarlagadda ◽  
Priya Velusamy ◽  
...  
Keyword(s):  
Cathepsin D ◽  
Tertiary Amines

Reaction of arylmethylenemalonaldehydes with some nucleophiles

1987 ◽  
Vol 52 (11) ◽  
pp. 2699-2709 ◽  
Author(s):  
Dalimil Dvořák ◽  
Zdeněk Arnold
Keyword(s):  
Inorganic Anions ◽  
Secondary Amines ◽  
Tertiary Amines ◽  
Primary And Secondary Amines ◽  
Dipolar Structure

Reaction of arylmethylenemalonaldehydes with tributylphosphine and tertiary amines affords compounds of dipolar structure whereas reaction with primary and secondary amines leads to 1,4-addition products. Salts of nucleophilic inorganic anions add to arylmethylenemalonaldehydes under formation of salts of substituted malonaldehydes.

Ionic dimerisation of trifluoropropenenitrile and its addition reactions with methyl trifluoropropenoate

1980 ◽  
Vol 45 (2) ◽  
pp. 406-414 ◽  
Author(s):  
Jiří Svoboda ◽  
Oldřich Paleta ◽  
Václav Dědek
Keyword(s):  
Reaction Mechanism ◽  
Proton Transfer ◽  
Substituent Effect ◽  
Solvent Molecule ◽  
Addition Product ◽  
Potassium Fluoride ◽  
Relative Reactivity ◽  
Addition Reactions ◽  
Tertiary Amines ◽  
Optimum Conditions

Dimerisation of trifluoropropenenitrile (I) in the presence of potassium fluoride and tertiary amines afforded a mixture of stereoisomeric perfluoro-4-methyl-pentenedinitriles (II), higher-boiling compounds, and 2,3,3,3-tetrafluoropropanenitrile (III) which arises by proton transfer from the solvent molecule. Under optimum conditions, product II was obtained in about 50% yield. Reaction of the nitrile I with methyl trifluoropropenoate (IV) gave, besides the dimers II and V, the product of addition of the nitrile I to the propenoate, IV, i.e. methyl 4-cyanoperfluoro-2-pentenoate (VI), and the addition product of the propenoate IV to the nitrile I, i.e. methyl 4-cyanoperfluoro-2-methyl-3-butenoate (VII). The relative reactivity if I and IV is discussed. The ratio of stereoisomers in II, V, VI and VII indicates that the magnitude of the steric substituent effect, operating in the reaction mechanism, decreases in the order -CFCF3.(COOCH3) > -CFCF3(CN) > -COOCH3 > -CN.

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