Oxidation Of Tertiary Amines Research Articles

Study of the Asymmetric Induction of the 1,3-Dipolar Cycloaddition of Chiral Azomethine Ylides with Unactivated Double Bonds

The asymmetric induction of the 1,3-dipolar cycloaddition reaction between nonstabilized azomethine ylides generated by deprotonation of the corresponding tertiary amine N-oxides (1a-f) with a base and various unactivated olefins (2a-c) or dienes (2d-e) has been studied. The results show that an important induction can be reached with valinol derived N-oxide (1f). The elimination of the chiral substituent in 3-phenyl-N-(1-hydroxymethyl-propyl)-pyrrolidine (8b) allowed to determine the absolute configuration of the major enantiomer (12b) in accordance with the proposed transition state

First Example of Intramolecular 1,3-Dipolar Cycloaddition of Non-stabilized Azomethine Ylide Generated from Tertiary Amine N-Oxide

The reaction of two optically active 1-alkyl-3,4-diallyloxypyrrolidine 1 oxides, (9) and (15), under basic conditions has been examined. The 1-benzyl derivative (9), on reaction with lithium diisopropylamide, furnished a single pyrrolidine derivative (11) by intramolecular 1,3-dipolar cycloaddition of an N-benzylidene azomethine ylide (10), while the 1 -methyl derivative (15) reacted with tert-butyllithium in the presence of trimethylaluminum to afford only a single 7-azabicyclo[2.2.1]heptane derivative (19) by spontaneous intramolecular 1,3-dipolar cycloaddition of the endocyclic azomethine ylide (17)

Regioselective generation of iminium cation by PET processes: Its in situ trapping by intramolecular nucleophiles and synthesis of some biologically active heterocycles.

Efficient, mild and direct route for regiospecific iminium cation is developed by sequential two electron oxidation of several N-alkylated tertiary amines by photoinduced electron transfer processes. The regiospecificity of iminium cation arises from the deprotonation step of amine radical cation to generate α-amino radical which depends on the stereoelectronic factor subject to kinetic acidity of amine radical cation. Iminium cation is efficiently trapped insitu by internal nuleophiles to give cyclic compounds 14–18 and 22a–c. Stereoselective synthesis of cis α,α′-dialkylated piperidines and pyrrolidines 30a–c is achieved by nucleophilic opening of tetrahydro-1,3-oxazines 22a–c.

A facile and selective oxidation of sulfides to sulfones

Sulfides undergo a facile and selective oxidation to sulfones under mild conditions using a catalytic amount of osmium tetroxide and tertiary amine N-oxides ( N-methylmorpholine N-oxide or trimethylamine N-oxide). Both N-oxides are equally effective. The observed yields ranged between 60%–95%.

A new alkylation method of the carbon α to the nitrogen of secondary amines

A route to the alkylation of the carbon α to the nitrogen of secondary amines 1a,c–g is proposed which is based upon a new and efficient synthesis of oxazolidines 3 from β- hydroxy tertiary amine N-oxides 2.

ChemInform Abstract: Studies on Tertiary Amine Oxides. Part 84. Deoxygenative 2‐ Alkoxylation of Quinoline 1‐Oxide.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Theoretical study of the oxidation mechanism of aromatic amines

The overall mechanism of the chemical step involved in the electrochemical oxidation of tertiary aromatic amines has been investigated by means of the quantum-chemical AM1 method. By using the parent compound aniline as a model it is found that, in good accord with previous electrochemical data, dimerization of two radical cations takes place before deprotonation, the dimerization step involving a higher energy barrier.

Light-induced, iodine-catalyzed aerobic oxidation of unsaturated tertiary amines

Light-induced, iodine-catalyzed aerobic oxidation of unsaturated tertiary amines

ChemInform Abstract: Tertiary Amine Oxides. Part 14. Protic Solvent Effects on the Rate of Thermal Rearrangement of N‐(2,4‐Dinitrophenyl)piperidine N‐Oxide (I).

ChemInformVolume 21, Issue 9 Preparative Organic Chemistry ChemInform Abstract: Tertiary Amine Oxides. Part 14. Protic Solvent Effects on the Rate of Thermal Rearrangement of N-(2,4-Dinitrophenyl)piperidine N-Oxide (I). A.-K. S. AL-KAZZAZ, A.-K. S. AL-KAZZAZ Dep. Chem., Coll. Sci., Univ. Mosul, Mosul, IraqSearch for more papers by this authorS. Y. HANNA, S. Y. HANNA Dep. Chem., Coll. Sci., Univ. Mosul, Mosul, IraqSearch for more papers by this authorA.-H. KHUTHIER, A.-H. KHUTHIER Dep. Chem., Coll. Sci., Univ. Mosul, Mosul, IraqSearch for more papers by this author A.-K. S. AL-KAZZAZ, A.-K. S. AL-KAZZAZ Dep. Chem., Coll. Sci., Univ. Mosul, Mosul, IraqSearch for more papers by this authorS. Y. HANNA, S. Y. HANNA Dep. Chem., Coll. Sci., Univ. Mosul, Mosul, IraqSearch for more papers by this authorA.-H. KHUTHIER, A.-H. KHUTHIER Dep. Chem., Coll. Sci., Univ. Mosul, Mosul, IraqSearch for more papers by this author First published: February 27, 1990 https://doi.org/10.1002/chin.199009059AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume21, Issue9February 27, 1990 RelatedInformation

The [3+2] Intramolecular Cycloaddition Reaction of Azomethine Ylides Generated from Benzylic N-Oxides

Benzylic azomethine ylides (y) generated by deprotonation of the corresponding tertiary amine N-oxides (1a, 1b, 4) react intramolecularly with the suitably positioned unactivated double bond to yield ther corresponding fused membered pyrrolidines (2a, 2b, 5). A competitive evolution of the ylide is obseerved at low temperature leading to the corresponding head to head piperazines (3, 6, 8)

N-oxide promoted pauson-khand cyclizations at room temperature

Tertiary amine oxides have been utilized to effect cobalt-mediated intramolecular cyclizations of enynes (Pauson-Khand reactions) at room temperature. The stereoselectivity, range and limitations of this method are examined.

II - Oxydation catalytique d'aminomethyl-2 phenols par un systeme FeCl 2/Fe 0/O 2

2-aminomethyl phenols 1 ( a : R = CH 3 ; b : R = H) oxidized by molecular oxygen in presence of iron and iron(II) chloride in catalytic amount chiefly afford aldehyde 2, formamide 4 and oxazine 5. The mechanisms of these oxidations and the nature of the reactive species are discussed; in particular the possible intermediate role of tertiary amine oxide 1c in the oxidative dealkylation of tertiary amine 1a.

ChemInform Abstract: Oxidation of Tertiary Amines by Chromium(VI) Oxide Diperoxide.

AbstractAccording to a 2:1 stoichiometry Et3N and (I) are oxidized by CrOPA and its Mo‐analogue to give the amine oxides such as (II).

Oxidation of tertiary amines by monoamine oxidases

Oxidation of tertiary amines by monoamine oxidases

ChemInform Abstract: Preparation of Thieno(3,2‐e)(1,2)oxazepine, Thieno‐ and (1)Benzothieno‐(3,2‐g)(1,4)oxazonine, and 5H‐Thieno‐ and 1H‐(1)Benzothieno(3,2‐h)(1,5)oxazecine Derivatives by Ring Expansion Methods. X‐Ray Crystal Structure of 1‐Phenyl‐1,3,4,5,6,7‐hexahydro(1)benzothieno(3,2‐g)(1,4)oxazonine‐5‐carbonitrile.

10-Phenyl-4,5,6,7,8,10-hexahydrothieno[3,2-g][1,4]oxazonine-6-carbonitrile (6a) and 11-phenyl-4,6,7,8,9,11-hexahydro-5H-thieno[3,2-h][1,5]oxazecine-6-carbonitrile (7a) were prepared in moderate yields by cyanogen bromide-induced ring expansion of tetrahydrothieno [2,3- c] pyridinylalkanol precursors (4a) and (5a), respectively. 1-Phenyl-1,3,4,5,6,7-hexahydro[1]- benzothieno [3,2-g][1,4]oxazonine-5-carbonitrile (6b) and 1-phenyl-3,4,5,6,7,8-hexahydro-1H- [1] benzothieno [3,2-h][1,5]oxazecine-6-carbonitrie (7b) were similarly prepared from the [1] benzothieno [2,3-c] pyridinylalkanol precursors (4b) and (5b). The medium-ring cyanamides (6b) and (7b) were converted by standard methods into their N-methyl analogues (8b) and (9b). 6-Methyl-8-phenyl-4,5,6,8-tetrahydrothieno[3,2-e][1,2] oxazepine (13) was prepared by thermal Meisenheimer rearrangement of the corresponding tertiary amine N-oxide (12). The compounds (6a, b), (7a, b) and (13) are each the first reported examples of new heterocyclic systems. The crystal and molecular structure of (6b) has been determined by X-ray crystallographic methods.

Studies of Tertiary Amine Oxides. Part115. Carbon - 13 nuclear magnetic resonance spectra of some N-(4-substituted phenyl) piperidine, the corresponding N-oxides, and their thermal-rearrangement product

Abstract The carbon-13 chemical shifts of seven N-(4-substituted phenyl) piperidine; the corresponding N-oxides, and their thermal rearrangement products were analyzed and assigned. The N-oxidation effect on the carbon-13 chemical shift is discussed, a correlation of N-oxidation effect with substituent constant (σp, σm, σI and σR) has been studied; dual substituent-parameter equation produce better correlation.

ChemInform Abstract: Palladium Complex‐Catalyzed Oxidation of Unsaturated Tertiary Amines, Amides, and Imides (I), (III) with Molecular Oxygen.

ChemInformVolume 20, Issue 17 Preparative Organic Chemistry ChemInform Abstract: Palladium Complex-Catalyzed Oxidation of Unsaturated Tertiary Amines, Amides, and Imides (I), (III) with Molecular Oxygen. G. A. DZHEMILEVA, G. A. DZHEMILEVA Inst. khim. Bashkirsk. nauchn. tsentra Uralsk. otd. AN SSSR, UfaSearch for more papers by this authorV. N. ODINOKOV, V. N. ODINOKOV Inst. khim. Bashkirsk. nauchn. tsentra Uralsk. otd. AN SSSR, UfaSearch for more papers by this authorU. M. DZEHMILEV, U. M. DZEHMILEV Inst. khim. Bashkirsk. nauchn. tsentra Uralsk. otd. AN SSSR, UfaSearch for more papers by this author G. A. DZHEMILEVA, G. A. DZHEMILEVA Inst. khim. Bashkirsk. nauchn. tsentra Uralsk. otd. AN SSSR, UfaSearch for more papers by this authorV. N. ODINOKOV, V. N. ODINOKOV Inst. khim. Bashkirsk. nauchn. tsentra Uralsk. otd. AN SSSR, UfaSearch for more papers by this authorU. M. DZEHMILEV, U. M. DZEHMILEV Inst. khim. Bashkirsk. nauchn. tsentra Uralsk. otd. AN SSSR, UfaSearch for more papers by this author First published: April 25, 1989 https://doi.org/10.1002/chin.198917123AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume20, Issue17April 25, 1989 RelatedInformation

ChemInform Abstract: Preparation of Lactams via Oxidation of Cyclic, Tertiary, and Secondary Amines with Hg(II)‐EDTA Complex in Alkaline Medium.

AbstractThe oxidation method mentioned in the title is employed to various pyrrolidine, piperidine, and morpholine derivatives as shown in the reaction scheme, yielding the corresponding lactams.

ChemInform Abstract: Ruthenium‐Catalyzed Cytochrome P‐450 Type Oxidation of Tertiary Amines with Alkyl Hydroperoxides.

Le ruthenium catalyse la reaction d'amines tertiaires methylee avec l'hydroperoxyde de t-butyle pour donner les t-butylperoxymethylamines correspondantes hydrolysees en amines secondaires

Peroxidase as a model for reduction of tertiary amine oxides catalyzed by rat hepatic supernatant and microsomal fractions

Rat hepatic microsomal and 100,000 g supernatant fractions catalyzed an NADH- and FMN-dependent reduction of amine oxides. Horseradish peroxidase (HRP) served as a model for the amine oxide reductase located in rat hepatic 100,000 g supernatant fraction. The HRP-catalyzed reaction displayed saturation kinetics with respect to NADH and the amine oxide substrate; however, there was an optimum concentration for FMN after which inhibition was observed at increased concentrations of FMN. The reductase in the 100,000 g hepatic supernatant fraction closely paralleled HRP-catalyzed amine oxide reduction in coenzyme requirements, sensitivity to inhibitors, and substrate specificity. Moreover, the peroxidase activity of HRP and microsomal and 100,000 g supernatant fractions correlated with the NADH- and FMN-dependent amine oxide reductase activities of these enzyme preparations. The NADH- and FMN-dependent amine oxide reductase activity in 100,000 g supernatant fractions, however, did not parallel the aldehyde oxidase activity. Thus, the results indicate that there is an amine oxide reductase in rat hepatic 100,000 g supernatant fraction with catalytic properties that are modeled well by horseradish peroxidase.