Butylamines, oxidation

Bromophenylazo)-2/-toluene, 309 (2-BromophenyI)-iVM7-azoxy (2-hydroxy-5-methylbenzene), 358 p-Bromophenylurea, 138-139 Bromopropadiene, 17 2,3-Butadienoic add, 16 iV-l-Butenylpiperazine, 92 Butter yellow, hazard of, 291 f-Butylamine, oxidation of, 323 -Butyl azide, 269 f-Butyl-OlW-azoxymethane, 349 t-Butyl p-Bromophenylazoformate, 328 t-Butyl 2-(p-bromophenyl)carbazate, 328 H-Butyl carbamate, 238-239 t-Butyl carbamate, 241-243... 

Note Although such a procedure was successful in related series, 4-methyl-1-piperazinamine (27) failed to give l-methyl-4-nitrosopiperazine (28) on treatment with tri-tert-butylamine oxide in tetranitromethane.1082... 

The first three tertiary amines in the aliphatic series were studied by Strecker and Baltes. The authors studied tri-n-butylamine, tri-n-hexylamine, and tri-n-heptyl-amine. Each amine was ozonated at dry ice temperature and treated with picric acid. The tri-n-butylamine oxide picrate readily deposited as crystals on standing. Although the latter two amine oxides formed oily products at first, on long standing in the refrigerator they gave crystals of the amine oxide picrates. The purified amine oxide picrates were analyzed by direct titration with perchloric acid. 

In the ozonation of tri-n-butylamine at —40°C. with an ozone-nitrogen stream, 1.2 to 1.6 mole equivalents of ozone were absorbed, and the yields of tri-n-butylamine oxide were 53% from chloroform and 6% from pentane solvents. The other products were the side chain oxidation products described by Henbest and Stratford (II). These results eliminate the possibility that the side chain oxidation is an ozone-initiated autoxidation. The mechanism outlined by Reaction 3 explains nicely both the requirement of ozone itself as the oxidizing agent and the solvent effect observed. Solvents such as chloroform would be expected to solvate the ozone-amine adduct (lb) and make the abstraction of the proton in Reaction 3 difficult. Thus, loss of molecular oxygen to give the amine oxide becomes the major reaction (Reaction 2). In pentane solu-... 

Two pieces of chemical evidence support the three-membered ring formulation. The bifunctional oxazirane prepared from glyoxal, tert-butylamine, and peracetic acid (6) can be obtained in two crystalline isomeric forms. According to the three-membered ring formula there should be two asymmetric carbon atoms which should allow the existence of meso and racemic forms. A partial optical resolution was carried out with 2-7i-propyl-3-methyl-3-isobutyloxazirane. Brucine was oxidized to the N-oxide with excess of the oxazirane. It was found that the unused oxazirane was optically active. 

Hydrogenation, of gallic add with rhodium-alumina catalyst, 43, 62 of resorcinol to dihydroresorcinol, 41,56 Hydrogen peroxide, and formic acid, with indene, 41, 53 in oxidation of benzoic add to peroxy-benzoic add, 43, 93 in oxidation of ieri-butyl alcohol to a,a/r, a -tetramcthyltetra-methylene glycol, 40, 90 in oxidation of teri-butylamine to a,<, a, a -tetramethyltetra-methylenediamine, 40, 92 in oxidation of Crystal Violet, 41, 2, 3—4... 

Dirheniumheptoxide 2154 is converted by TCS 14, in the presence of 2,2 -dipyri-dine, into the dipyridine complex 2160 [77]. Free ReCls, NbCls, and WCI5 react with HMDSO 7 and 2,2 -bipyridine to form bipyridine oxochloride complexes 2161 and TCS 14, with reversal of the hitherto described reactions of metal oxides with TCS 14. The analogous Mo complex 2162 undergoes silylahon-amination by N-trimethylsilyl-tert-butylamine 2163 to give the bis-imine complex 2164 and HMDSO 7 [77] (Scheme 13.22). 

Oxidative carbonylation generates a number of important compounds and materials such as ureas, carbamates, 2-oxazolidinones, and aromatic polycarbonates. The [CuX(IPr)] complexes 38-X (X = Cl, Br, I) were tested as catalysts for the oxidative carbonylation of amino alcohols by Xia and co-workers [43]. Complex 38-1 is the first catalyst to selectively prepare ureas, carbamates, and 2-oxazolidinones without any additives. The important findings were the identity of the counterion and that the presence of the NHC ligand influenced the conversions. 2-Oxazohdinones were formed from primary amino alcohols in 86-96% yield. Complex 38-1 also catalysed the oxidative carbonylation of primary amines to ureas and carbamates. n-Propylamine, n-butylamine, and t-butylamine were transformed into the... 

Electrophilic catalysis may play an important role in the case of the similar benzylic carbon, too. For an O-benzyl system, it was found in a 1997 experiment that palladium oxide is a much more effective catalyst than palladium metal when the catalyst has been prereduced with chemical reducing agents. This finding shows very clearly that the electrophilic character of the unreduced metal ions plays an important role in the hydrogenolysis of the benzyl C—O bonds. Additional support for this mechanism is the fact that a small amount of butylamine can inhibit the hydrogenolysis of the benzyl C—O bond. 

In a typical reaction, w-butylamine (0.052 g, 0.7 mmol) in 5 ml of acetone is treated with 95 ml of dimethyldioxirane in acetone solution (0.05 M). The solution is kept at room temperature for 30 min with the exclusion of light (Eq. 2.53). Aromatic amines are converted into nitro compounds by oxidation using OXONE itself.113... 

Tertiary amines have been oxidized to the corresponding nitro compounds with KMn04. For example, 2-methyl-2-nitropropane is prepared in 84% yield from t-butylamine with KMn04 (Eq. 2.55).117 In a similar fashion, 1-aminoadamantane has been oxidized to 1-nitroadamantane in 85% yield with KMn04 (see Eq. 2.63).118... 

Substitution of the 4-nitro group in 3,4-dinitrofuroxan 1176 by ammonia occurs readily, even at low temperature. Subsequent treatment of the obtained amine, product 1177, with r-butylamine results in formation of 4-amino-2-(/-butyl)-5-nitro-l,2,3-triazole 1-oxide 1178. However, there must be some additional side products in the reaction mixture, as the isolated yield of compound 1178 is only 17%. Upon treatment with trifluoroperacetic acid, the r-butyl group is removed. The obtained triazole system can exist in two tautomeric forms, 1179 and 1180 however, the 1-oxide form 1179 is strongly favored (Scheme 195) <2003CHE608>. 

The last few years have seen numerous applications of spin trapping to biological systems, and in these the trapping of hydroxyl radicals has assumed some importance. This work has been confined almost exclusively to nitrone scavengers 4 the fact that the hydroxyl adduct [6] of DMPO is much more persistent than that [7] of the commonly used nitrone, benzylidene-t-butylamine-N-oxide ( phenyl t-butyl nitrone ,3 or PBN) [3], may be due to a fragmentation reaction, with subsequent oxidation of the cr-hydroxybenzyl radical, as shown. 

The anion of di-isopropyl phosphorothiolothionic acid (26) reduces hydroxyl radicals, and the radical (27) so produced is detectable by e.s.r.33 Attempts to observe these radicals by photolysis of the free acid were unsuccessful. However, the use of a spin trap (e.g. TV-methylene-t-butylamine iV-oxide) enabled radicals in this system and other closely related systems [e.g. with (28)] to be observed by e.s.r. spectroscopy. 

According to Marshall [23] and Beech [26], the oxidation of the thiophenol linker would increase the reaction rate. To study this effect, the linker in resin (35) was oxidized to sulfone/sulfoxide using mCPBA. Cleavage reaction of resin (35) -OX with n-butylamine went to completion in less than 4 min (Fig. 12.20), compared with 24 h needed for this resin under the same conditions without oxidation. The rate constant was determined to be 0.0179, which was a 580-fold increase compared with the unoxidized form. This result indicated that a linker oxidation was preferred for high yield when the products will not be affected by oxidation conditions. 

Mole-nots, see Strychnine Mollan 0, see Bis(2-ethylhexyl) phthalate Mondur TD, see 2,4-Toluene diisocyanate Mondur TD-80, see 2,4-Toluene diisocyanate Mondur TDS, see 2,4-Toluene diisocyanate Monobromobenzene, see Bromobenzene Monobromobenzol, see Bromobenzene Monobromoethane, see Ethyl bromide Monobromomethane, see Methyl bromide Monobromotrifluoromethane, see Bromotrifluoromethane Monobutylamine, see Butylamine Mono-n-butylamine, see Butylamine Monobutyl ethylene glycol ether, see 2-Butoxyethanol Monochlorbenzene, see Chlorobenzene Monochlorethane, see Chloroethane Monochloroacetaldehyde, see Chloroacetaldehyde Monochlorobenzene, see Chlorobenzene Monochlorodibromomethane, see Dibromochloromethane Monochlorodiphenyl oxide, see 4-Chlorophenyl phenyl ether... 

The nitrolysis of tertiary amines in the form of fert-butylamines and methylenediamines has been used to synthesize numerous polynitramine-based energetic materials. In these reactions one of the N-C bonds is cleaved to generate a secondary nitramine and an alcohol the latter is usually 0-nitrated or oxidized under the reaction conditions (Equation 5.15). The ease in which nitrolysis occurs is related to the stability of the expelled alkyl cation. Consequently, the fert-butyl group and the iminium cation from methylenediamines are excellent leaving groups. 

For amines having an a-hydrogen atom, electrochemical oxidation leads to the imine as the first detectable intemrediate. In the absence of another nucleophile, this is not usually a useful reaction since the imine is hydrolysed by water present in the solvent leading to a mixture of products [80, 81], Oxidation of ten-butylamine, which has no a-hydrogen atom, leads to loss of a proton flrom the nitrogen atom and the dimerization of nitrogen centred radicals. The product isolated in moderate yields is azo-teri-butane 17 [82], The reaction can be carried out in an... 

Conversion of ketone 437 to hippocasine (105) was accomplished by Bom-ford-Stevens reaction via the following reaction sequence. Successive treatments of 437 with hydrazine, p-toluenesulfonyl chloride, and then lithium tert-butylamine gave hippocasine (105). The reaction occurred exclusively in the desired direction. Treatment of hippocasine (105) with methanolic hydrogen peroxide gave hippocasine oxide (106) (Scheme 54). 

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