Amine oxides amines, tert

N- Sulfonyloxaziridines Amine oxides from tert. amines R3N - R3N-.0... 

The oxidation of primary and secondary alcohols in the presence of 1-naphthylamine, 2-naphthylamine, or phenyl-1-naphthylamine is characterized by the high values of the inhibition coefficient / > 10 [1-7], Alkylperoxyl, a-ketoperoxyl radicals, and (3-hydroxyperoxyl radicals, like the peroxyl radicals derived from tertiary alcohols, appeared to be incapable of reducing the aminyl radicals formed from aromatic amines. For example, when the oxidation of tert-butanol is inhibited by 1-naphthylamine, the coefficient /is equal to 2, which coincides with the value found in the inhibited oxidation of alkanes [3], However, the addition of hydrogen peroxide to the tert-butanol getting oxidized helps to perform the cyclic chain termination mechanism (1-naphthylamine as the inhibitor, T = 393 K, cumyl peroxide as initiator, p02 = 98 kPa [8]). This is due to the participation of the formed hydroperoxyl radical in the chain termination ... 

Secondary amines (dialkylamines, benzyl tert-butyl amines and cyclic amines) can be oxidized to the nitrones using hydrogen peroxide in the presence of catalysts like Na2W04... 

In addition to the procedure given here for the oxidation of tert-octylamine to nitroso-tert-octane,2 the oxidation may be carried out with m-chloroperoxybenzoic acid or with a solution of peroxyacetic acid in ethyl acetate.4 The lead dioxide oxidation of alkyl hydrazines to alkyl radicals appears to have general application. In addition to tert-butylhydrazine, various secondary alkylhydrazines (e.g., bornylhydrazine and menthylhydrazine) have been used to good effect. The reduction of tri-tert-alkylhydroxyl amine to the di-tert-alkylamine has also been achieved with sodium in ammonia but the insolubility of the hydrophobic substrate makes this procedure difficult. The use of sodium naphthalenide gives higher yields and is more reproducible. 

Oxidative dealkylation of tert-amines.1 Oxidation of tert-N-methylamines with f-BuOOH (2 equiv.) catalyzed by this ruthenium complex results in a-(t-butyl-dioxy)alkylamines. N-Methyl groups are oxidized selectively in the presence of... 

Thio analogs of these compounds, for example, PhP(S)(NHR)2 can also be prepared similarly, from the corresponding thiophosphonic halides and amines or by oxidative addition of sulfur to diaminophosphines, RP(NR92 Phenylphosphonic acid diamides, PhP(Q)(NHBu )2 (Q = S, Se) were prepared from PhP(NHBfr)2 by oxidative addition of sulfur or selenium and the 0x0 derivative PhP(0)(NHBu )2 by oxidation with tert-butyl peroxide. Their lithiation produces unusual cyclic or polycyclic dUithium salts of the phosphonate dianions [PhP(Q)(NBfr)2] (Q = O, S, Se). The dimethylaluminum derivatives PhP(Q)(NBu )2AlMe2 (Q = S, Se) obtained from PhP(Q)(NHBu )2 with AlMes are fom-membered chelate rings. ... 

The bulk of oxidations with tert-butyl hydroperoxide consists of epoxidations of alkenes in the presence of transition metals [147, 215, 216, 217, 218]. In this way, a,p-unsaturated aldehydes [219] and ketones [220] are selectively oxidized to epoxides without the involvement of the carbonyl function. Other applications of tert-butyl hydroperoxide such as the oxidation of lactams to imides [225], of tertiary amines to amine oxides [226, 227], of phosphites to phosphates [228], and of sulfides to sulfoxides [224] are rare. In the presence of a chiral compound, enantioselective epoxidations of alcohols are successfully accomplished with moderate to high enantiomeric excesses [221, 222, 223]. 

Oae, S., Ogino, K. Rearrangements of tert-amine oxides. Heterocycles 1977, 6, 583-675. 

Tert-Amines - sec-amines.1 When a tertiary amine in pyridine is shaken with 2-nitropropane and CuCl under oxygen, it is converted into a nitrosamine (5), which can be isolated in yields of 15-65% and then reduced to a secondary amine. The reaction proceeds through oxidation to an amine oxide (2) with conversion of (1) into 2-nitro-2-propanol (3). This decomposes into acetone and nitrous acid. The nitrous acid traps the secondary amine formed from the amine oxide (2) after rearrangement to the carbinolamine (4). It is noteworthy that even... 

In one of the earliest examples of selective C-H bond functionalization of tertiary amines, Murahashi and co-workers established that the C-H bond adjacent to the nitrogen atom can be selectively oxidized with tert-butyl hydroperoxide (TBHP) using catalytic amounts of RuCl2(PPh3)3 (Scheme 2) [15]. 

CARBON OXYCHLORIDE (75-44-5) COCI2 Highly toxic and corrosive gas. Deconqioses slowly with water, producing hydrochloric acid and carbon oxides. Deconqjoses above 572°F/300°C, forming toxic and corrosive gases of hydrogen chloride and carbon monoxide chlorine. Reacts violently with strong oxidizers, amines, alkalis, anhydrous ammonia, isopropanol, chemically active metals aluminum, silicon tetrahydride, sodium. Forms shock-sensitive material with potassium. Incompatible with tert-alcohols. 

ETHYL CARBINOL (71-23-8) Forms explosive mixture with air (flash point 59°F/15°C). Violent reaction with strong oxidizers, potassium-tert-butoxide, triethylaluminum. Reacts, possibly violently, with acetaldehyde, alkalineearth and alkali metals, strong acids, strong caustics, aliphatic amines, benzoyl peroxide, chromic acid, chromium trioxide, dialkylzincs, dichlorine oxide, ethylene oxide, hypochlorous acid, isocyanates, isopropyl chlorocarbonate, lithium tetrahydroaluminate, nitric acid, nitrogen dioxide, nitronium tetrafluoroborate(l-), penta-fluoroguanidine, phosphorus pentasulfide, tangerine oil, triisobutylaluminum. Attacks some plastics, rubber, and coatings. 

Classification Tert. amine oxide Formula R-NO(CH3)2, R represents the coconut radical... 

Witcamide 6570 t[Witco http //www.witco.com] Undecylenamidopropylamine oxide Synonyms Amides, undecenic, N-[3-(dimethylamino) propyl], N-oxide N-[3-(Dimethylamino) propyl] undedenamide, N-oxide 10-Undecenamide, N-[3-(dimethylamino) propyl]-, N-oxide Undecenamide, N-[3-(dimethylamino) propyl]-, N-oxide Classification Tert. amine oxide Empirical CieH 2N202... 

Hydroperoxides in the presence of vanadium molybdenum, or titanium compounds give high yields of aliphatic tert. amine oxides from the corresponding amines and sulfones from thio-ethers or sulfoxides. 

Oxidation of tert. amines under mildly basic conditions Cyclic 1,1-aminoethers from aminoalcohols... 

Previous reviews have dealt with metal-catalyzed [93] and stoichiometric [94] oxidation of amines in a broad sense. This section will be limited to the selective oxidation of tertiary amines to N-oxides. Amine N-oxides are synthetically useful compounds [95, 96] and are frequently used as stoichiometric oxidants in osmium-[97-99] manganese- [100] and ruthenium-catalyzed [101,102] oxidations, as well as in other organic transformations [103-105]. Aliphatic tert-amine N-oxides are usefid surfactants [96] and are essential components in hair conditioners, shampoos, toothpaste, cosmetics, and so on [106]. Chiral N-oxides have been used in asymmetric catalysis involving metal-free catalytic transformations [107] as well as metal-catalyzed reactions where the N-oxide serves as a ligand [107, 108]. Chiral tertiary amine N-oxides were recently used as reagents in asymmetric epoxidation of a,(3-unsaturated ketones [109]. 

---