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PYRAZOLE, ISOTHIAZOLE AND ISOXAZOLE DERIVATIVES USEFUL AS AGRICULTURAL FUNGICIDES

The present invention relates to substituted pyrazole, isoxazole andisothiazole compounds which are of use in the field of agriculture as fungicides.

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Reference:
Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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Highly Regioselective Carbamoylation of Electron-Deficient Nitrogen Heteroarenes with Hydrazinecarboxamides

The use of hydrazinecarboxamides as a new class of carbamoylating agents has been established through the dehydrazinative Minisci reaction of electron-deficient nitrogen heteroarenes. A wide range of electron-deficient nitrogen heteroarenes, including isoquinoline, quinoline, pyridine, phenanthridine, quinoxaline, and phthalazine, underwent copper/acid-catalyzed oxidative carbamoylation with hydrazinecarboxamide hydrochlorides to afford structurally diverse nitrogen-heteroaryl carboxamides as single regioisomers in moderate to excellent yields. The functional group tolerance was substantially demonstrated in the direct carbamoylation of quinine obviating multistep sequences involving protecting groups and prefunctionalization of the heterocycle.

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Reference:
Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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Reaction of Allylic Tin Reagents with Nitrogen Heteroaromatics Activated by Alkyl Chloroformates: Regioselective Synthesis of alpha-Allylated 1,2-Dihydropyridines and Change of the Regioselectivity Depending on Methyl Substituents at the Allylic Moiety

Allyltin reagents readily react with pyridine and some substituted pyridines activated by alkyl chloroformates to give alpha-allylated 1,2-dihydropyridines regioselectively.Functional substituents such as halogeno, acetoxy, and formyl groups can be tolerated, demonstrating high chemoselectivity of the reactions.The regiochemistry of the attack on pyridine nuclei changes from alpha-addition to alpha- and gamma-addition (nonregioselective) to gamma-addition, depending on methyl substituents at the allylic moiety (from allyl to methallyl and crotyl to prenyl groups).It is also found that the reactions occur at the gamma-position of allylic tin reagents, indicating SN2′ character of the reactions.The present effective allylation method can be extended to isoquinoline and quinoline systems.

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Reference:
Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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Bulky alpha-diimine palladium complexes: Highly efficient for direct C-H bond arylation of heteroarenes under aerobic conditions

Through the strategy to enhance the bulkiness on both the backbone and the N-aryl moieties, we designed and synthesized a type of bulky alpha-diimine palladium complex (i.e., {[Ar-NC(R)-C(R)N-Ar]PdCl2, (Ar = 2-benzhydryl-4,6-dimethylphenyl)}, C1, R = H; C2, R = An; C3, R = Ph). The structures of these palladium complexes were well characterized, while C1 and C3 were further characterized by X-ray diffraction. The catalytic performances of the precatalysts were screened for direct C-H bond arylation of heteroarenes. The bidentate N,N-palladium complex C3 with both a backbone and N-aryl bulkiness was found to be a highly efficient precatalyst under aerobic conditions. With a low palladium loading of 0.5-0.1 mol%, a variety of heteroarenes with challenging bulky steric aryl bromides as well as heteroaryl bromides are all applicable for this cross-coupling reaction.

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Isoquinoline – Wikipedia,
Isoquinoline | C9H7N – PubChem

 

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Copper-Catalyzed Hydroxylation of (Hetero)aryl Halides under Mild Conditions

The combination of Cu(acac)2 and N,N?-bis(4-hydroxyl-2,6-dimethylphenyl)oxalamide (BHMPO) provides a powerful catalytic system for hydroxylation of (hetero)aryl halides. A wide range of (hetero)aryl chlorides bearing either electron-donating or -withdrawing groups proceeded well at 130 C, delivering the corresponding phenols and hydroxylated heteroarenes in good to excellent yields. When more reactive (hetero)aryl bromides and iodides were employed, the hydroxylation reactions completed at relatively low temperatures (80 and 60 C, respectively) at low catalytic loadings (0.5 mol % Cu).

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Reference£º
Isoquinoline – Wikipedia,
Isoquinoline | C9H3418N – PubChem

 

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Palladium-catalyzed coupling of ammonia and lithium amide with aryl halides

A mild, palladium-catalyzed coupling of aryl halides with ammonia or lithium amide to form primary arylamines as the major product is described. These reactions occurred with excellent selectivity for formation of the primary arylamine over formation of the diarylamine (9.5:1 to over 50:1 ratios of arylamine to diarylamine). In addition, the first organopalladium complex with a terminal -NH2 ligand has been isolated. This complex reductively eliminates to form arylamines. Copyright

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Isoquinoline – Wikipedia,
Isoquinoline | C9H3353N – PubChem

 

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C2-Alkenylation of N-heteroaromatic compounds: Via Br¡ãnsted acid catalysis

Substituted heteroaromatic compounds, especially those based on pyridine, hold a privileged position within drug discovery and medicinal chemistry. However, functionalisation of the C2 position of 6-membered heteroarenes is challenging because of (a) the difficulties of installing a halogen at this site and (b) the instability of C2 heteroaryl-metal reagents. Here we show that C2-alkenylated heteroaromatics can be accessed by simple Br¡ãnsted acid catalysed union of diverse heteroarene N-oxides with alkenes. The approach is notable because (a) it is operationally simple, (b) the Br¡ãnsted acid catalyst is cheap, non-toxic and sustainable, (c) the N-oxide activator disappears during the reaction, and (d) water is the sole stoichiometric byproduct of the process. The new protocol offers orthogonal functional group tolerance to metal-catalysed methods and can be integrated easily into synthetic sequences to provide polyfunctionalised targets. In broader terms, this study demonstrates how classical organic reactivity can still be used to provide solutions to contemporary synthetic challenges that might otherwise be approached using transition metal catalysis.

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Isoquinoline – Wikipedia,
Isoquinoline | C9H3077N – PubChem

 

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Novel betaines/mesoionic compounds via a simple and convenient MCR in aqueous micellar system: Synthesis of thiazolo[2,3-a]isoquinolin-4-ium derivatives

An inexpensive one-pot green methodology has been developed for the synthesis of thiazolo[2,3-a]isoquinolin-4-ium derivatives by the reaction of different derivatives of isoquinoline and 2-bromoacetophenone/bromoacetonitrile with benzoyl isothiocyanate in aqueous micellar medium.

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Isoquinoline – Wikipedia,
Isoquinoline | C9H3263N – PubChem

 

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Photo-induced Metal-Catalyst-Free Aromatic Finkelstein Reaction

The facile iodination of aromatic compounds under mild conditions is a great challenge for both organic and medicinal chemistry. Particularly, the synthesis of functionalized aryl iodides by light has long been considered impossible due to their photo-lability, which actually makes aryl iodides popular starting materials in many photo-substitution reactions. Herein, a photo-induced halogen exchange in aryl or vinyl halides has been discovered for the first time. A broad scope of aryl iodides can be prepared in high yields at room temperature under exceptionally mild conditions without any metal or photo-redox catalysts. The presence of a catalytic amount of elemental iodine could promote the reaction significantly.

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Isoquinoline – Wikipedia,
Isoquinoline | C9H3223N – PubChem

 

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Visible-light mediated carbamoyl radical addition to heteroarenes

The generation of carbamoyl radicals, followed by their addition to heteroarenes, was performed under mild conditions through a metal-free photocatalyzed decarboxylation of oxamic acids. The process has been applied to the carbamoylation of heteroaromatic bases using alpha-aminoacid-derived oxamic acids, leading to the corresponding amides without racemization.

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Reference£º
Isoquinoline – Wikipedia,
Isoquinoline | C9H3175N – PubChem