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Oxidation of aromatic N-heterocyclic compounds to N-oxides by Verticillium sp. GF39 cells

Verticillium sp. GF39, catalyzing the oxidation of 1-methylisoquinoline to 1-methylisoquinoline N-oxide, was found to be the highest N-oxide producer. Under the optimized reaction conditions, the whole cells of Verticillium sp. GF39 formed 5 mM 1-methylisoquinoline N-oxide from 1-methylisoquinoline with a molar conversion yield of 100% after a 10-h incubation at 20C. The whole cells also acted on pyridine, 2-methylpyridine, quinoline and isoquinoline and formed the corresponding N-oxides.

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A FORMATION OF PYRROLO<2,1-a>ISOQUINOLINE DERIVATIVES BY THE REACTION OF ISOQUINOLINE N-OXIDES WITH ETHYL PROPIOLATE

Diethyl pyrrolo<2,1-a>isoquinoline-1,3-dicarboxylates were obtained by the reaction of the corresponding isoquinoline N-oxides with ethyl propiolate

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Identification of aliphatic and aromatic tertiary N-oxide functionalities in protonated analytes via ion/molecule and dissociation reactions in an FT-ICR mass spectrometer

A mass spectrometric method is presented for the identification of compounds that contain the aliphatic or aromatic N-oxide functional group. This method utilizes gas-phase ion/molecule reactions of tri(dimethylamino)borane (TDMAB), which rapidly derivatizes protonated aliphatic and aromatic tertiary N-oxides, amides, and some amines via loss of dimethylamine in a Fourier transform ion cyclotron resonance mass spectrometer. The mechanism involves proton transfer from the protonated analyte to the borane, followed by addition of the analyte to the boron center and elimination of dimethylamine. The derivatized analytes are readily identified on the basis of their m/z value which is 98 Th (thomson) greater than that of the protonated analyte, and the characteristic boron isotope patterns. SORI-CAD of the product ions (adduct-(CH3)2NH) yields different fragment ions for aliphatic tertiary N-oxides, aromatic tertiary N-oxides, amides, and pyridines. Therefore, these analytes can be identified based on their characteristic fragment ions. This method was tested by examining two drug samples, Olanzapine and Olanzapine-4? N-oxide.

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Reactions of isoquinolinium salts with hydroxylamine derivatives, 3rd communication. Mechanism of amine oxide generation

2-Methylpapaverinium iodide (1) reacted with hydroxylamine to papaverine-N-oxide (2), but without a detectable intermediate and only in moderate yield, caused by the steric hindrance of the 1-substituent. The ring opened product of 2-dinitrophenylisoquinolinium salt with hydroxylamine, the enamine-oxime 3b gave rise to a 3-substituted cyclic nitrone (6), when heated with triethylamine. This alkali-stable compound was transformed with acid quantitatively to isoquinoline-N-oxide (4). The enaminonitrile 9c, treated with triethylamine showed cyclization to the iminoisoquinoline 10, which by loss of nitrous acid produced the tetracyclic azaindole 11. The 2-methoxyisoquinolinium salt 16 was cleaved with O-methylhydroxylamine to the resistant di(O-methyloximes) (20a/b), unable to form the amine oxide 4. From these and former results, a mechanism for the ring opening of cycliminium salts and the recyclization to amine oxides was proposed.

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Regioselective deoxygenative C[sbnd]H trifluoromethylthiolation of heteroaryl N-oxides with AgSCF3

A mild and efficient method for the regioselective deoxygenative C[sbnd]H trifluoromethylthiolation of heteroaryl N-oxides with AgSCF3 is presented, employing p-toluenesulfonic anhydride and tetra-n-butylammonium iodide as the activators. This reaction delivers a series of C2-trifluoromethylthiolated heteroaromatic compounds in moderate to excellent yields. It provides a complementary method for C[sbnd]H trifluoromethylthiolation reactions.

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A direct metal-free C2-H functionalization of quinoline N-oxides: A highly selective amination and alkylation strategy towards 2-substituted quinolines

An efficient one-pot methodology for C2-selective amination and alkylation of quinoline N-oxides towards 2-substituted quinolines was developed, via the reaction of various quinoline N-oxides with ammonia, a large variety of primary and secondary amines, as well as active methylene compounds in the presence of diethyl H-phosphonate and K2CO3 under metal free conditions at room temperature.

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Visible-Light-Induced Pyridylation of Remote C(sp3)?H Bonds by Radical Translocation of N-Alkoxypyridinium Salts

Metal-free, visible-light-induced site-selective heteroarylation of remote C(sp3)?H bonds has been accomplished through the design of N-alkoxyheteroarenium salts serving as both alkoxy radical precursors and heteroaryl sources. The transient alkoxy radical can be generated by the single-electron reduction of an N-alkoxypyridinium substrate by a photoexcited quinolinone catalyst. Subsequent radical translocation of the alkoxy radical forms a nucleophilic alkyl radical intermediate, which undergoes addition to the substrate to achieve remote C(sp3)?H heteroarylation. This cascade strategy provides a powerful platform for remote C(sp3)?H heteroarylation in a controllable and selective manner and is well suited for late-stage functionalization of complex bioactive molecules.

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Elimination of Carbon Monoxide by Electron Impact on Quinoline N-oxide, Carbostyril and 8-Hydroxyquinoline

Under electron impact, the molecular ions of quinoline N-oxide, carbostyril and 8-hydroxyquinoline lose carbon monoxide giving a fragment ion C8H7N (m/z 117), which was shown by collision-activated dissociation in each case to have the structure of the molecular ion of indole.Its formation from 8-hydroxyquinoline requires an unusual rearrangement.Isoquinoline N-oxide loses HCN rather than CO and gives a fragment which has the structure of the molecular ion of benzofuran.When the first three compounds were subjected to flash vacuum pyrolysis, quinoline N-oxide at 500-700 deg C gave carbostyril and indole was detected by gas chromatography/mass spectrometry.At 900 deg C carbostyril and 8-hydroxyquinoline both gave indole in small amounts, detected by gas chromatography/mass spectrometry.

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Sels de N-Alcoxyquinoleinium et de N-Alcoxyisoquinoleinium Porteurs d’une Fonction Ester dans leur Chaine Alcoxyle: Synthese et Reactivite vis-a-vis des Ions Cyanure

Reaction of ethyl alpha-bromoisobutyrate on quinoline 1 oxide and isoquinoline 2-oxide in the presence of silver perchlorate leads to the corresponding N-alkoxyl salts 1 and 2.On treatment with potassium cyanide, these salts are converted into 2-cyanoquinoline and 1-cyanoisoquinoline according to mode B of the Katritzky’s classification concerning the reaction of nucleophiles on N-alkoxypyridinium salts.When the reaction of canide ions were performed on salt 1 at 0 deg C in aqueous solution the dihydro aromatic adduct 4 was isolated.This result confirms the addition-elimination mechanism of the reaction studied.

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Molecular Complexes of Quinoline and Isoquinoline N-Oxides with Bromine

1:1 and 2:1 Complexes of quinoline and isoquinoline N-oxides with bromine have been synthesized for the first time. According to the data of electron and infrared spectroscopy, the bromine atoms in these complexes are coordinated at the oxygen atoms of the N-oxide group. In the complex with 4-nitroquinoline N-oxide, the bromine atom is coordinated at the nitro group.

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