Synthesis of 1,1,3,3-Tetraalkylisoindolines Using a Microwave-Assisted Grignard Reaction

2008 ◽  
Vol 61 (3) ◽  
pp. 168 ◽  
Author(s):  
Richard C. Foitzik ◽  
Steven E. Bottle ◽  
Jonathan M. White ◽  
Peter J. Scammells
Keyword(s):  
Reaction Times ◽  
Magnesium Bromide ◽  
Grignard Reaction ◽  
Microwave Assisted ◽  
Limiting Step

1,1,3,3-Tetraalkylisoindolines are important intermediates in the preparation of stable nitroxides, such as 1,1,3,3-tetramethylisoindolin-2-oxyl, 1, and 1,1,3,3-tetraethylisoindolin-2-oxyl, 2. The limiting step in their preparation is the Grignard reaction between N-benzylphthalimide and the appropriate alkyl magnesium bromide, which typically proceeds in yields of ~28–40%. A microwave-assisted variation of this reaction has been optimized to give improved yields and reduced reaction times (45–60% and 2 h, respectively).

Microwave-Assisted Decarbonylation of Biomass-Derived Aldehydes Using Pd-Doped Hydrotalcites

2019 ◽  
Author(s):  
Nan An ◽  
Diana Ainembabazi ◽  
Kavya Samudrala ◽  
Christopher Reid ◽  
Kare Wilson ◽  
...  
Keyword(s):  
Heterogeneous Catalysts ◽  
Reaction Times ◽  
Inverse Correlation ◽  
Mulliken Charge ◽  
Metal Leaching ◽  
Carbonyl Carbon ◽  
Mild Conditions ◽  
Microwave Assisted ◽  
Biomass Processing ◽  
Alcohol Dehydrogenation

<p>Here we report the synthesis, characterization and activity of tunable Pd-doped hydrotalcites (Pd-HTs) for the decarbonylation of furfural, hydroxymethylfurfural (HMF), aromatic and aliphatic aldehydes under microwave conditions. The decarbonylation activity reported is a notable improvement over prior heterogeneous catalysts for this process. Furfural decarbonylation is optimized in a benign solvent compatible with biomass processing - ethanol, under relatively mild conditions and short reaction times. HMF selectively affords excellent yields of furfuryl alcohol with no humin formation, but longer reaction can also afford furan via tandem alcohol dehydrogenation and decarbonylation. Yields of substituted benzaldehydes are related to calculated Mulliken charge of the carbonyl carbon. The activity and selectivity differences can be traced to loading-dependent differences in Pd speciation on the catalysts. Poisoning studies show inverse correlation between Pd loading and metal leaching: Pd-HTs with lowest Pd loading, which consist of highly dispersed and oxidized Pd species, operate heterogeneously with negligible metal leaching. Recycling experiments are consistent with this trend, offering potential for further optimization to improve robustness.</p>

Regioselective Synthesis of Potent 4,5,6,7-Tetrahydroindazole Derivatives via Microwave-assisted Vilsmeier-Haack Reaction and their Antioxidant Activity Evaluation

2019 ◽  
Vol 16 (3) ◽  
pp. 194-201 ◽  
Author(s):  
Renu Bala ◽  
Vandana Devi ◽  
Pratibha Singh ◽  
Navjot Kaur ◽  
Pawandeep Kaur ◽  
...  
Keyword(s):  
Antioxidant Activity ◽  
Microwave Irradiation ◽  
Biological Activities ◽  
Reaction Times ◽  
Conventional Heating ◽  
High Chemical ◽  
Microwave Assisted ◽  
Work Up ◽  
Active Methylene ◽  
By Products

Background: Tetrahydroindazole, a member of the fused-pyrazole system, is a least studied class of heterocyclic compounds owing to its scarcity in nature. However, a large number of synthetically prepared tetrahydroindazoles are known to show a variety of biological activities such as interleukin- 2 inducible T-Cell kinase inhibitors, AMPA receptor positive allosteric modulators, antitumor, antituberculosis, anti-inflammatory and antimicrobial activities. Vilsmeier-Haack reaction is one of the most important chemical reactions used for formylation of electron rich arenes. Even though Vilsmeier- Haack reaction was studied on a wide variety of hydrazones derived from active methylene compounds, literature lacks the examples of the use of 4-substituted cyclohexanones as a substrate for the synthesis of 4,5,6,7-tetrahydroindazoles. The study of the reaction of Vilsmeier-Haack reagent with hydrazones derived from cyclic keto compounds having active methylene has been considered the interested topic of investigation. In the present study, ethyl cyclohexanone-4-carboxylate was treated with one equivalent of various hydrazines for two hours and the resulted hydrazones were further treated with an OPC-VH reagent (Vilsmeier-Haack reagent isolated from phthaloyl dichloride and N,Ndimethylformamide) afforded 4,5,6,7-tetrahydroindazoles in excellent yields. The synthesized compounds 4a-f and 5a-f were screened for their antioxidant activities using the DPPH radical scavenging assay. The target compounds were synthesized regioselectively using 4+1 approach in excellent yields. A number of experiments using both conventional heating as well as microwave irradiation methods were tried and on comparison, microwave irradiation method was found excellent in terms of easy work up, high chemical yields, shortened reaction times, clean and, no by-products formation. Some of the synthesized compounds showed significant antioxidant activity. The microwave assisted synthesis of 4,5,6,7-tetrahydroindazoles from ethyl cyclohexanone-4-carboxylate has been reported under mild conditions in excellent yield. Easy work up, high chemical yield, shortened reaction times, clean and no by-products formation are the major advantages of this protocol. These advantages may make this method useful for chemists who are interested in developing novel 4,5,6,7-tetrahydroindazole based drugs.

scholarly journals Microwave-Assisted Asinger Synthesis of Thiazolines

2020 ◽  
Vol 3 (1) ◽  
pp. 27
Author(s):  
Raúl Eduardo Gordillo-Cruz ◽  
Liliana Gonzalez-Reyes ◽  
Milton Coporo-Reyes ◽  
Nieves Zavala-Segovia ◽  
Bernardo A. Frontana-Uribe ◽  
...  
Keyword(s):  
Microwave Irradiation ◽  
Reaction Times ◽  
Reaction Conditions ◽  
Microwave Assisted

An array of 2,4-disubstituted thiazolines was obtained through Asinger reaction approach from the straightforward treatment of diverse aldehydes/ketones with 1-mercaptopropan-2-one, in the presence of NH3 assisted by microwave irradiation, displaying similar and sometimes higher yields, as well as shorter reaction times that traditional Asinger reaction conditions at room and lower temperatures.

scholarly journals Silica Supported Acids (SiO2-HClO4, SiO2-KHSO4) as Eco-friendly Reusable Catalysts for Bromination of Aromatic and Heteroaromatic Compoundsusing Kbr Under Solvothermal and Solvent-free Conditions

2021 ◽  
Author(s):  
Vijayshekar pulusu ◽  
Chinna Rajanna Rajanna Kamatala ◽  
Anil Kumar Mardhanpally ◽  
Hemanth Sriram Yel ◽  
Yaku Guguloth ◽  
...  
Keyword(s):  
Aromatic Compounds ◽  
Reaction Times ◽  
Solvent Free ◽  
Microwave Assisted ◽  
Rate Acceleration ◽  
Solvent Free Conditions ◽  
Ultrasonic Assisted

Abstract Silica supported nanogreenacids like Si-KHSO4, and Si-HClO4are explored as reusable catalysts for bromination of aromatic and hetero aromatic compounds using KBr under solvothermal, and solvent-free conditions. Reaction times reduced from Reacions under conventional solvothermal protocols conditions required (4 – 6) hours, while ultrasonic assisted reactions only (9 – 12) minutes for completion. But, solvent-free microwave assisted reactions required only (1-5) minutes exhibiting striking rate acceleration compared to the solvothermal and ultrasonic assisted protocols All the reaction protocols afforded fairly good yields of brominated products, which are comparable with existing protocols.

Microwave-assisted synthesis of zinc 5-(4-carboxyphenyl)-10,15,20-triphenylporphyrin and zinc 5-(4-carboxyphenyl)-10,15,20-triphenylchlorin

2015 ◽  
Vol 19 (04) ◽  
pp. 595-600 ◽  
Author(s):  
Rima Chouikrat ◽  
Aymeric Champion ◽  
Régis Vanderesse ◽  
Céline Frochot ◽  
Albert Moussaron
Keyword(s):  
Reaction Times ◽  
Microwave Assisted Synthesis ◽  
Spectroscopic Techniques ◽  
H Nmr ◽  
Microwave Assisted ◽  
Experimental Protocols ◽  
Time Of Reaction

The microwave-assisted synthesis of zinc 5-(4-carboxyphenyl)-10,15,20-triphenylporphyrin and zinc 5-(4-carboxyphenyl)-10,15,20-triphenylchlrorin are described and compared to classic conditions of synthesis in terms of time of reaction and yields obtained. The new experimental protocols are easy to implement required small amounts of reagents and solvents and lead to short reaction times. All compounds have been characterized by 1 H NMR, MS and spectroscopic techniques.

scholarly journals Syntheses of 3,4- and 1,4-dihydroquinazolines from 2-aminobenzylamine

2017 ◽  
Vol 13 ◽  
pp. 1470-1477 ◽  
Author(s):  
Jimena E Díaz ◽  
Silvia Ranieri ◽  
Nadia Gruber ◽  
Liliana R Orelli
Keyword(s):  
Reaction Times ◽  
Ring Closure ◽  
Cesium Carbonate ◽  
Amino Groups ◽  
Microwave Assisted ◽  
Common Precursor ◽  
Alkylation Reactions

A straightforward strategy for the synthesis of dihydroquinazolines is presented, which allows for the preparation of 3,4- and 1,4-dihydroquinazolines with different substitution patterns from 2-aminobenzylamine (2-ABA) as common precursor. The required functionalization of both amino groups present in 2-ABA was achieved by different routes involving selective N-acylation and cesium carbonate-mediated N-alkylation reactions, avoiding protection/deprotection steps. The heterocycles were efficiently synthesized in short reaction times by microwave-assisted ring closure of the corresponding aminoamides promoted by ethyl polyphosphate (PPE).

Grignard Reaction of 2-Substituted-3-Cyanoquinolines

1985 ◽  
Vol 40 (7) ◽  
pp. 990-995 ◽  
Author(s):  
◽  
Balkrishen Bhat ◽  
A. P. Bhaduri
Keyword(s):  
Cyano Group ◽  
The Other ◽  
Magnesium Bromide ◽  
Grignard Reaction ◽  
Reaction Products ◽  
Grignard Reactions ◽  
Magnesium Halide ◽  
Activated Surface

Abstract Grignard reactions of 2-morpholino and 2-methylthio-3-cyanoquinoline, 2-chloro-3-cyanoquinoline, 2-chloro-3-cyano-6-methoxyquinoline and 2-chloro-3-cyano-7-methylquinoline with alkyl or aryl magnesium halides have been studied. It was found that 2-morpholino and 2-methylthio- 3-cyanoquinolines gave 1,4-addition products followed by rapid aromatisation. 2-Chloro-3- cyanoquinoline with alkyl magnesium halides furnished 1,4-addition products but with aryl magnesium halides 1,4- and 1,2-addition products were obtained. The cyano group of 4-aryl-2-chloro- 3-cyano-1,4-dihydroquinolines was found to participate in the Grignard reaction to yield 1,2- addition products. 2-Chloro-3-cyano-6-m ethoxyquinoline with alkyl and phenyl magnesium halides yielded exclusively 1,4-addition products. Similarly with p-m ethoxyphenyl magnesium bromide, 1,4-addition products were isolated which participated in the Grignard reaction to yield the expected adducts. Unlike the other chloroquinoline derivatives, 2-chloro-3-cyano-7-methylquinoline with alkyl magnesium halide formed 1 ,2-addition products but with aryl magnesium halides, 1,4-addition products were isolated. The 4-alkyl-2-chloro-3-cyano-l,4-dihydroquinolines were unstable as compared to their 4-aryl analogs. A couple of the Grignard reaction products were found to be unstable on activated surface.

Hydrothermal Synthesis of Walnut-Like α-Ni(OH)2 Architectures and their In Situ Thermal Convention to NiO

2011 ◽  
Vol 412 ◽  
pp. 44-48
Author(s):  
Zhi Rong Suo ◽  
Hui Liu ◽  
Na Wei
Keyword(s):  
Thermal Decomposition ◽  
Polyethylene Glycol ◽  
Hydrothermal Synthesis ◽  
Formation Process ◽  
Hydrothermal Reaction ◽  
Reaction Times ◽  
Thermal Decomposition Process ◽  
Similar Morphology ◽  
Microwave Assisted

The walnut-like α-Ni (OH)2 architectures have been successfully synthesized through a microwave-assisted hydrothermal method using urea as a hydrolysis-controlling agent and polyethylene glycol (PEG) as a surfactant. The NiO architectures with similar morphology were obtained by a simple thermal decomposition process of the precursor α-Ni (OH)2. The as-obtained products were well characterized by XRD, SEM, TEM, and FTIR. The experimental results shown that walnut-like α-Ni (OH)2 architectures with a diameter of 2-6 μm. The formation process of Ni (OH)2 architectures was observed by SEM via different hydrothermal reaction times.

scholarly journals Green Chemistry Approach for Efficient Synthesis of Schiff Bases of Isatin Derivatives and Evaluation of Their Antibacterial Activities

2013 ◽  
Vol 2013 ◽  
pp. 1-5 ◽  
Author(s):  
Jnyanaranjan Panda ◽  
V. Jagannath Patro ◽  
Biswa Mohan Sahoo ◽  
Jitendriya Mishra
Keyword(s):  
Green Chemistry ◽  
Schiff Bases ◽  
Reaction Times ◽  
Antibacterial Activities ◽  
Primary Amines ◽  
Microwave Assisted Synthesis ◽  
Azomethine Group ◽  
Microwave Assisted ◽  
Isatin Derivatives

Microwave-assisted organic synthesis, a green chemistry approach, is nowadays widely used in the drug synthesis. Microwave-assisted synthesis improves both throughput and turnaround time for medicinal chemists by offering the benefits of drastically reduced reaction times, increased yields, and pure products. Schiff bases are the important class of organic compounds due to their flexibility, and structural diversities due to the presence of azomethine group which is helpful for elucidating the mechanism of transformation and rasemination reaction in biological system. This novel compound could also act as valuable ligands for the development of new chemical entities. In the present work, some Schiff bases of Isatin derivatives was synthesized using microwave heating method. Schiff base of Isatin were synthesized by condensation of the keto group of Isatin with different aromatic primary amines. They were characterized by means of spectral data and subsequently subjected to the in vitro antibacterial activities against gram positive and gram negative strains of microbes. It was observed that the compound with electron withdrawing substituents exhibited good antibacterial activities against almost all the micro organisms.

scholarly journals Microwave-assisted cyclizations promoted by polyphosphoric acid esters: a general method for 1-aryl-2-iminoazacycloalkanes

2016 ◽  
Vol 12 ◽  
pp. 2026-2031 ◽  
Author(s):  
Jimena E Díaz ◽  
María C Mollo ◽  
Liliana R Orelli
Keyword(s):  
Polyphosphoric Acid ◽  
General Procedure ◽  
Reaction Times ◽  
Ring Closure ◽  
Heterocyclic Synthesis ◽  
Microwave Assisted ◽  
Solvent Free Conditions ◽  
High Yields ◽  
Acid Esters ◽  
General Method

The first general procedure for the synthesis of 5 to 7-membered 1-aryl-2-iminoazacycloalkanes is presented, by microwave-assisted ring closure of ω-arylaminonitriles promoted by polyphosphoric acid (PPA) esters. 1-Aryl-2-iminopyrrolidines were easily prepared from the acyclic precursors employing a chloroformic solution of ethyl polyphosphate (PPE). The use of trimethylsilyl polyphosphate (PPSE) in solvent-free conditions allowed for the synthesis of 1-aryl-2-iminopiperidines and hitherto unreported 1-aryl-2-iminoazepanes. The cyclization reaction involves good to high yields and short reaction times, and represents a novel application of PPA esters in heterocyclic synthesis.

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