Reactions of Quinolizine- and Pyridino[1,2–a]pyrimidine-3-diazonium Tetrafluoroborates with Aliphatic Amines

2004 ◽  
Vol 59 (4) ◽  
pp. 380-385 ◽  
Author(s):  
Simon Rečnik ◽  
Jurij Svete ◽  
Branko Stanovnik
Keyword(s):  
Picolinic Acid ◽  
The Other ◽  
Aliphatic Amines ◽  
Secondary Amines ◽  
Primary Amines ◽  
Other Hand ◽  
High Yields

KeywordsReactions of 1-cyano-4-oxo-4H-quinolizine-3-diazonium tetrafluoroborate (1a) and 4-oxo-4Hpyridino[ 1,2-a]pyrimidine-3-diazonium tetrafluoroborate (1b) with aliphatic amines 2a - g were studied. Treatment of heteroaryldiazonium salts 1 with secondary amines 2a - d afforded the corresponding N-alkyl-N’-heteroaryltriazenes 3a - h in high yields. On the other hand, reactions of 1a with aliphatic primary amines 2e - g resulted in an unexpected rearrangements into the corresponding picolinic acid N-alkylcarboxamides 4a - c.

Acceptorless amine dehydrogenation and transamination using Pd-doped layered double hydroxides

2018 ◽  
Author(s):  
Diana Ainembabazi ◽  
Nan An ◽  
Jinesh Manayil ◽  
Kare Wilson ◽  
Adam Lee ◽  
...  
Keyword(s):  
Layered Double Hydroxides ◽  
Oxidation States ◽  
Secondary Amines ◽  
Primary Amines ◽  
Acid Dissolution ◽  
Oxidative Amination ◽  
Strong Function ◽  
Excellent Activity ◽  
High Yields ◽  
Double Hydroxides

<div> <p>The synthesis, characterization, and activity of Pd-doped layered double hydroxides (Pd-LDHs) for for acceptorless amine dehydrogenation is reported. These multifunctional catalysts comprise Brønsted basic and Lewis acidic surface sites that stabilize Pd species in 0, 2+, and 4+ oxidation states. Pd speciation and corresponding cataytic performance is a strong function of metal loading. Excellent activity is observed for the oxidative transamination of primary amines and acceptorless dehydrogenation of secondary amines to secondary imines using a low Pd loading (0.5 mol%), without the need for oxidants. N-heterocycles, such as indoline, 1,2,3,4-tetrahydroquinoline, and piperidine, are dehydrogenated to the corresponding aromatics with high yields. The relative yields of secondary imines are proportional to the calculated free energy of reaction, while yields for oxidative amination correlate with the electrophilicity of primary imine intermediates. Reversible amine dehydrogenation and imine hydrogenation determine the relative imine:amine selectivity. Poisoning tests evidence that Pd-LDHs operate heterogeneously, with negligible metal leaching; catalysts can be regenerated by acid dissolution and re-precipitation.</p> </div> <br>

Efficient Copper-Catalysed Synthesis of Carbazoles by Double N-Arylation of Primary Amines with 2,2′-Dibromobiphenyl in the Presence of Air

Synlett ◽  
2021 ◽  
Author(s):  
Tran Quang Hung ◽  
Tuan Thanh Dang ◽  
Peter Langer ◽  
Ha Nam Do ◽  
Nguyen Minh Quan ◽  
...  
Keyword(s):  
Aromatic Amines ◽  
Aliphatic Amines ◽  
Primary Amines ◽  
Coupling Reactions ◽  
Carbazole Derivatives ◽  
High Yields

AbstractAn efficient Cu-catalyzed synthesis of carbazole derivatives is reported, which proceeds by double C–N coupling reactions of 2,2′-dibromobiphenyl and amines in the presence of air. The reaction is robust, proceeds in high yields, and tolerates a series of amines including neutral, electron-rich, electron-deficient aromatic amines and aliphatic amines.

scholarly journals Synthesis of spiro[dihydropyridine-oxindoles] via three-component reaction of arylamine, isatin and cyclopentane-1,3-dione

2013 ◽  
Vol 9 ◽  
pp. 8-14 ◽  
Author(s):  
Yan Sun ◽  
Jing Sun ◽  
Chao-Guo Yan
Keyword(s):  
Acetic Acid ◽  
Reaction Mechanism ◽  
Room Temperature ◽  
The Other ◽  
Other Hand ◽  
Three Component Reaction ◽  
High Yields

A fast and convenient protocol for the synthesis of novel spiro[dihydropyridine-oxindole] derivatives in satisfactory yields was developed by the three-component reactions of arylamine, isatin and cyclopentane-1,3-dione in acetic acid at room temperature. On the other hand the condensation of isatin with two equivalents of cyclopentane-1,3-dione gave 3,3-bis(2-hydroxy-5-oxo-cyclopent-1-enyl)oxindole in high yields. The reaction mechanism and substrate scope of this novel reaction is briefly discussed.

scholarly journals Bifurcated synthesis of methylene-lactone- and methylene-lactam-fused spirolactams via electrophilic amide allylation of γ-phenylthio-functionalized γ-lactams

2020 ◽  
Vol 16 ◽  
pp. 2769-2775
Author(s):  
Tetsuya Sengoku ◽  
Koki Makino ◽  
Ayumi Iijima ◽  
Toshiyasu Inuzuka ◽  
Hidemi Yoda
Keyword(s):  
Hydroxy Group ◽  
The Other ◽  
Synthetic Methods ◽  
Other Hand ◽  
Acidic Conditions ◽  
High Yields

New synthetic methods for spirolactams bearing an α-methylene-γ-butyrolactone or its analogous methylene-lactam have been developed. The allylation of γ-phenylthio-functionalized γ-lactams with 2-(acetoxy)methyl acrylamides was accomplished by using 2.5 equivalents of NaH to give the corresponding adducts in excellent yields. The remaining phenylthio group was substituted with a hydroxy group by treatment with CuBr, and the resulting γ-hydroxyamides were cyclized under acidic conditions to afford the corresponding methylene-lactam-fused spirolactams in high yields. On the other hand, methylene-lactone-fused spirolactams could be delivered from the allyl adducts in high yields through a sequential N-Boc protection/desulfinative lactonization.

Acceptorless amine dehydrogenation and transamination using Pd-doped layered double hydroxides

2018 ◽  
Author(s):  
Diana Ainembabazi ◽  
Nan An ◽  
Jinesh Manayil ◽  
Adam Lee ◽  
Adelina Voutchkova-Kostal
Keyword(s):  
Layered Double Hydroxides ◽  
Oxidation States ◽  
Secondary Amines ◽  
Primary Amines ◽  
Acid Dissolution ◽  
Oxidative Amination ◽  
Strong Function ◽  
Excellent Activity ◽  
High Yields ◽  
Double Hydroxides

<div> <p>The synthesis, characterization, and activity of Pd-doped layered double hydroxides (Pd-LDHs) for for acceptorless amine dehydrogenation is reported. These multifunctional catalysts comprise Brønsted basic and Lewis acidic surface sites that stabilize Pd species in 0, 2+, and 4+ oxidation states. Pd speciation and corresponding cataytic performance is a strong function of metal loading. Excellent activity is observed for the oxidative transamination of primary amines and acceptorless dehydrogenation of secondary amines to secondary imines using a low Pd loading (0.5 mol%), without the need for oxidants. N-heterocycles, such as indoline, 1,2,3,4-tetrahydroquinoline, and piperidine, are dehydrogenated to the corresponding aromatics with high yields. The relative yields of secondary imines are proportional to the calculated free energy of reaction, while yields for oxidative amination correlate with the electrophilicity of primary imine intermediates. Reversible amine dehydrogenation and imine hydrogenation determine the relative imine:amine selectivity. Poisoning tests evidence that Pd-LDHs operate heterogeneously, with negligible metal leaching; catalysts can be regenerated by acid dissolution and re-precipitation.</p> </div> <br>

scholarly journals C–H bond activation of benzene and thiophene by photochemically generated rhenocene cation

1999 ◽  
Vol 1 (3) ◽  
pp. 157-160
Author(s):  
Hiroshi Ogino ◽  
Hiromi Tobita ◽  
Kouji Endo ◽  
Kiyonari Hashidzume
Keyword(s):  
Uv Irradiation ◽  
Bond Activation ◽  
The Other ◽  
Other Hand ◽  
Activation Products ◽  
Plausible Mechanism ◽  
Thiophene Derivatives ◽  
High Yields

A cationic rhenocene-acetonitrile adduct[Cp2Re(NCMe)](BF4)(1)reacted with an excess of benzene, thiophene, 2-methylthiophene, and pyrrole under UV irradiation to afford the C–H bond activation products[Cp2Re(H)R]BF4(R=phenyl, 2-thienyl, 2-(5-methylthienyl), 2-pyrrolyl) in high yields. In cases of thiophene derivatives and pyrrole,α-C–H bonds are selectively activated. A plausible mechanism involves the photodissociation of acetonitrile from 1 to generate a coordinatively unsaturated rhenocene cation[Cp2Re]+. When 2,5-dimethylthiophene and dibenzothiophene, having noα-C–H bonds, were used as substrates, products of the activation of other C–H bonds were formed first, but they isomerized to thermodynamically more stableη11-S-coordinated complexes in refluxing acetone. On the other hand, irradiation of theη1-S-coordinated complexes reproduced the original C–H bond activation products. Because of the cationic character,[Cp2Re(H)R]BF4were readily deprotonated by triethylamine to give neutral rhenocene derivativesCp2ReR. When R is thienyl or 2-(5-methylthienyl), treatment ofCp2ReRwithHBF4⋅Et2Oand MeI resulted in protonation and methylation to give[Cp2Re(H)R]BF4(R=and[Cp2Re(Me)R]I. Thermolysis of[Cp2Re(Me)R]Iin the presence ofPPh3unexpectedly resulted in migration of R to the Cp ring to give[(2 thienyl C5H4)CpRe(PPh3)]I.

Synthesis of new quinoxalinophenazinediones and tetrahydrobenzodipyrrolotetrones of biological interest

2008 ◽  
Vol 62 (2) ◽  
Author(s):  
Ahmed Hammam ◽  
Mohamed Youssef ◽  
Ferial Atta ◽  
Thana Mohamed
Keyword(s):  
Sodium Azide ◽  
Ethyl Acetoacetate ◽  
Diethyl Malonate ◽  
The Other ◽  
Primary Amines ◽  
Antibacterial Studies ◽  
Other Hand ◽  
Biological Interest

AbstractThe reaction of two equivalents of sodium azide with diarylaminodibromo-p-benzoquinone (I) in DMF for 15–24 h produced quinoxalinophenazinediones together with a byproduct identified as diarylaminodiaminobenzoquinone. On the other hand, the reaction of bromanil with active methylenes, such as diethyl malonate and ethyl acetoacetate, resulted in disubstitution products which, on treatment with primary amines, cyclized into benzodipyrroletetrones. Comparative antifungal and antibacterial studies were made.

Acceptorless amine dehydrogenation and transamination using Pd-doped layered double hydroxides

2018 ◽  
Author(s):  
Diana Ainembabazi ◽  
Nan An ◽  
Jinesh Manayil ◽  
Kare Wilson ◽  
Adam Lee ◽  
...  
Keyword(s):  
Layered Double Hydroxides ◽  
Oxidation States ◽  
Secondary Amines ◽  
Primary Amines ◽  
Acid Dissolution ◽  
Oxidative Amination ◽  
Strong Function ◽  
Excellent Activity ◽  
High Yields ◽  
Double Hydroxides

<div> <p>The synthesis, characterization, and activity of Pd-doped layered double hydroxides (Pd-LDHs) for for acceptorless amine dehydrogenation is reported. These multifunctional catalysts comprise Brønsted basic and Lewis acidic surface sites that stabilize Pd species in 0, 2+, and 4+ oxidation states. Pd speciation and corresponding cataytic performance is a strong function of metal loading. Excellent activity is observed for the oxidative transamination of primary amines and acceptorless dehydrogenation of secondary amines to secondary imines using a low Pd loading (0.5 mol%), without the need for oxidants. N-heterocycles, such as indoline, 1,2,3,4-tetrahydroquinoline, and piperidine, are dehydrogenated to the corresponding aromatics with high yields. The relative yields of secondary imines are proportional to the calculated free energy of reaction, while yields for oxidative amination correlate with the electrophilicity of primary imine intermediates. Reversible amine dehydrogenation and imine hydrogenation determine the relative imine:amine selectivity. Poisoning tests evidence that Pd-LDHs operate heterogeneously, with negligible metal leaching; catalysts can be regenerated by acid dissolution and re-precipitation.</p> </div> <br>

Derivatives of Khellinonequinone and their Aflatoxigenic Activity

1988 ◽  
Vol 43 (3) ◽  
pp. 343-346 ◽  
Author(s):  
O. H. Hishmat ◽  
S. S. Mabrouk ◽  
A. M. M. Nasef ◽  
N. M. A. Shayeb ◽  
S. A. Ismail
Keyword(s):  
Hydrazine Hydrate ◽  
Mycelial Growth ◽  
Main Product ◽  
The Other ◽  
Primary Amines ◽  
Weak Effect ◽  
Other Hand ◽  
Derivatives Of

Nitration of khellinone leads to the formation of a small amount of 3-nitrokhellinone and 5-acetyl-6-hydroxybenzofuran-4.7-dione (khellinonequinone) as a main product. The latter compound reacts with primary amines to give the corresponding imino compounds. Reaction of khellinone with o-phenylenediamine involves condensation followed by cyclisation. While on the other hand treating with phenyl hydrazines gives the phenyl hydrazone. The pyrazolobenzofuran derivative was obtained by the action of hydrazine hydrate on khellinonequinone. Finally the reaction with malononitrile leads to the formation of the ylidene derivative. Two quinone derivatives showed a weak effect on mycelial growth and aflatoxin formation.

Minimizing Nitrosamines Using Sterically Hindered Thiuram Disulfides/Dithiocarbamates

1994 ◽  
Vol 67 (2) ◽  
pp. 299-313 ◽  
Author(s):  
Robert W. Layer ◽  
Dwight W. Chasar
Keyword(s):  
The Other ◽  
Secondary Amines ◽  
Side Reactions ◽  
Other Hand ◽  
Steric Factors ◽  
Sterically Hindered

Abstract Sulfenamide accelerators and sulfur donors based on secondary amines must liberate all of their amine in order to function. Consequently, they are capable of producing relatively large amounts of nitrosamines. Thiuram disulfides and dithiocarbamates, on the other hand, only liberate their amines because of undesired side reactions. Accordingly, compared to sulfenamides, they produce significant, but much lower levels of nitrosamines during the cure. In an effort to reduce these side reactions, and thus the amount of nitrosamine which forms, we investigated the effect of steric factors on nitrosamine formation. We find that thiurams and dithiocarbamates made from sterically bulky amines, like diisobutylamine, produce orders of magnitude lower levels of nitrosamine than TMTD. At the same time, when used as a kicker for 2-benzothiazole sulfenamides, N,N,N′,N′-tetraisobutylthiuram disulfide has better scorch safety but cures at the same rate as TMTD. Uniquely, N,N,N′,N′-tetraisobutylthiuram monosulfide acts as a retarder as well as a kicker for 2-benzothiazole sulfenamides.

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