Hydroxyl amine ethers

Hydroxyl amine ethers (> NO-R) react with peroxy radicals and generate nitroxy radicals, resulting in an slowdovm of chain oxidation degradation as shown in Formula 4.26. 

Styrene C6H5CH=CH2. Alkali Peroxy compds Vap in Air 1.1 to 6.1% > Ambient > Ambient Inhibitor—Methyl Ether of Hydroquinone—10-15 ppm, Phenol Subst-Hydroxyl Amine, etc. Store below 70°F. Avoid sparks in. vap/air mixt 17.4-17.8 490 Soln polymerization catalyzed with w or Ti tetrachloride. Also self polymerization... 

Mix 25 g 2,4,5-trimethoxyphenylacetone, 9.3 g hydroxyl-amine-HCI, 15.6 g K acetate and 400 ml 70% ethanol and reflux 3Vz hours. Evaporate in vacuum and extract the residue with 4X150 ml benzene. Wash combined extracts with 2X75 ml water dry and evaporate in vacuum the benzene (can purify the oil by dissolving in benzene and precipitate by adding petroleum ether) to get aout 20 g precipitate (test for activity). Dissolve 18.1 g precipitate in 200 ml methanol and hydrogenate. Acidify to get about 15 g (I). 

An imine moiety can, interestingly, be interposed in the ether linkage used to connect the two halogenated aromatic rings. The requisite oxime (55-1) is obtained in a straightforward fashion by reaction of imidazo acetophenone (54-2) with hydroxyl-amine alkylation with a,2,3-trichlorotoluene leads to oxiconazole (55-2) [60]. 

Bis (Hydroxylamino) Azide (called Dihydroxyl-Ammonium Trinitride by Dennis Isham), (NHaOH)a-HNs, mw 109.10, N64.20% col, trans, leaf-like crysts, nip 66° v sol in w, sol in ale and insol in eth. This compd was prepd in 1906 by Dennis Isham (Ref 1) upon evapg a mixt of hydroxyl amine and hydra-zoic acid, both in methyl ale solns. The recovered crysts were purified by dissolving in a mixt of 1 g methyl ale and 20 p ether, filtering and rapidly evapg the solvent in a vacuum desiccator (See also Ref 2). No expl props were determined (Also see Hydrazoic Acid)... 

When nitro benzene is reduced in neutral solutions by means of zinc in hot water or hot alcohol or when an ether solution of it is reduced by means of aluminium amalgam and water or when it is reduced electro-lytically, the product is phenyl hydroxyl amine. 

Zinc isopropyl iodide, (CHg)2CH.ZnI.—Zinc and isopropyl iodide are heated together and the product extracted with ether. With isoamyi nitrite it yields N.N-di-isopropyl hydroxylamine, and with nitroelhane, N-is opropy 1-N-(a./3-dimetli3dpropyl)-hydroxyl amine is... 

N-Phenylhydroxylamine, mp 83.5-85°C, can be isolated at this stage in 75-85% yields if desired, but it should be borne in mind that N-phenyl hydroxyl amine is not very stable. The isolation can be carried out by adding an equal volume of methylene chloride to the tetrahydrofuran solution which is then dried over magnesium sulfate and concentrated to low volume under reduced pressure. Addition of a little petroleum ether precipitates N-phenylhydroxyl amine which is then filtered and washed with petroleum ether. 

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