1-Hydroxy Hydroxylamin

The intramolecular nitrone-alkene cycloaddition reaction of monocyclic 2-azetidinone-tethered alkenyl(alkynyl) aldehydes 211, 214, and 216 with Ar-aIkylhydroxylamincs has been developed as an efficient route to prepare carbacepham derivatives 212, 215, and 217, respectively (Scheme 40). Bridged cycloadducts 212 were further transformed into l-amino-3-hydroxy carbacephams 213 by treatment with Zn in aqueous acetic acid at 75 °C. The aziridine carbaldehyde 217 may arise from thermal sigmatropic rearrangement. However, formation of compound 215 should be explained as the result of a formal reverse-Cope elimination reaction of the intermediate ct-hydroxy-hydroxylamine C1999TL5391, 2000TL1647, 2005EJ01680>. 

Investigation of the reaction of 3,3-disubstituted 1,2-dioxetanes with various heteroatom nucleophiles establishes the SN2 reactivity of these strained peroxides [134]. As reported in Sch. 80 for dioxetane 141, the sterically exposed oxygen of the peroxide bond becomes the site of nucleophilic attack to produce an anionic or zwitterionic adduct 142. Different reaction channels become available for the intermediate which depend on the chemical nature of the nucleophile. So epoxy alcohol 143, p-hydroxy hydroxylamine 144, diol 145, cyclic carbonate 146, and cyclic sulfite 147 can be obtained (Sch. 80) [134],... 

Beilstein Handbrjok Reference) AI3-28026 BRN 1731349 CCRIS 964 Diethylhydroxyl-amine N,N-Diethylhydroxyamine EINECS 223-055-4 Ethanamine, N-ethyl-N-hydroxy- Hydroxylamine, N,N-diethyl- N-Hydroxydiethylamine Pennstop 1866. Free radical scavenger used by the rubber industry as an emulsion polymerization inhibitor vapor phase inhibitor for olefin or styrene monomer recovery systems in-process inhibitor for production of styrene, divinyl benzene, butadiene and isoprene. Liquid mp = 10° bp = 133° d = 0.8669. ElfAtochem N. Am. 

Supplement 1942 195-449 Hydroxy-amines Aminoethyl alcohol, 274. Carbonyl-amines Aminoacetaldehyde, 307. Aminoacetone, 314. Hydroxy-carbonyl amines Glucosamine, 328. Aminocarboxylic acids Glycine, 333. Hydroxylamines, 534. Hydrazines, 546. Azo Compounds. 562. Oryano-metallic Compounds, 580. 

In 1888 Claisen (1888CB1149) first recognized a general synthesis of isoxazoles (283) by the condensation-cyclization of 1,3-diketones (280) with hydroxylamine. It is now generally accepted that the monoxime (281) of the 1,3-diketone and the subsequent 5-hydroxy-isoxazoline (282) are the intermediate products of the reaction. The isolation of the monoxime (281) and 5-hydroxyisoxazoline (282), which were both readily converted into the isoxazole (283) by treatment with acid or base, has been reported (62HC(17)l). 

Diethyl 4-hydroxyisoxazole-3,5-dicarboxylate (334) was prepared by the reaction of acetonedicarboxylic acid ester with nitrosyl chloride (78JHC1519). Other 4-hydroxyisoxazoles have been prepared by the reaction of 2-hydroxy (or acetoxy)-1,3-diketones with hydroxylamine (34JA2190, 62HC(i7)i, p. 149), and by hydrolysis of 4-isoxazolediazonium salts (62HC(17)1, p. 149). The parent 4-hydroxyisoxazole has not yet been reported. 

The first in this series to be reported was 4-oxoisoxazoline-3,5-dicarboxylic acid diethyl ester, which was formed by the reaction of nitrous acid on diethyl acetonedicarboxylate in 1891. Quilico described a number of syntheses in his 1962 review and the most general include the reaction of hydroxylamine and a-hydroxy-(or acetoxy)- 3-diketones and the conversion of 4-isoxazolediazonium salts to the hydroxy moiety (62HC(17)1, p. 3). Additional syntheses reported were the oxygenation of a 4-boric acid derivative (67JOM(9)l9) and peroxide oxidation of a 4-nitro-2-isoxazoline (Scheme 151) (79ZOR2436). 

Hydroxypregna-5,16-dien-20-one Acetate Oxime 3j5-Hydroxy-pregna-5,16-dien-20-one acetate (30 g) is dissolved in 300 ml of anhydrous pyridine and 6.75 g of hydroxylamine hydrochloride is added. The mixture is stirred until solution is achieved, left in a tightly closed container at room temperature for 4 days and then poured into 1.5 liters of water. The flask is rinsed with water and the combined separated crystals are collected on a Buchner funnel, washed with water and dried to constant weight in an oven at 100°. Yield 30 g (96.5% of theory) mp 220-223°. 

The name hydroxamic acid was first used by Losseii in 1869, in the case of oxalohj droxamic acid, obtained from diethyl oxalate and hydroxylamine. Where this grouping forms part of the main cyclic system, however, the compound is named as a derivative of this system. In this review, 2 and 3 would be named as 1-hydroxy-2-pyrrolidone and l-hydroxy-2-pyridone, respectively. 

The overall conversion of a 2-furyl ketal to a 6-substitutod l-hydroxy-2-pyridone (79) can be effected by electrolysis in methanol followed by reaction with hydroxylamine. A Grignard reagent can... 

A mixture of 3-hydroxy-4-phenylfurazan and 1,2,4-oxadiazole 243 was prepared from a-phenyl-a-hydroximino hydroxamic acid by acylation and subsequent treatment with 15% aqueous NaOH (Scheme 164) (25G201). The reaction of tetraacetate 244 with sodium acetate hydrate in glacial acetic acid at 70°C gives 3,4-dihydroxyfurazan (9%) (92URP1752734). a-Hydroximino ester 245 reacts with hydroxylamine to form furazan 246 in 25% yield (Scheme 164) (79JHC689). 

The hydroxy group of furazan 263 reacted with cyanogen bromide in glyme in the presence of Li2C03 to give cyanate 264 in 70-85% yield (97MI8). Upon treatment with Mc4NN3 and subsequently with a basic solution of hydroxylamine-0-sulfonic acid, /V-aminotetrazole 265 was obtained in 35% yield (Scheme 171). 

Several reactions giving rise to hydroxy- and amino-isoxazoles have also been investigated. Thus the reaction of alkoxymethylene-cyanoacetates and hydroxylamine leading to 5-amino- or 5-hydroxy-isoxazoles proved to be rather useful.It is of particular interest that, by changing the reaction conditions, Bauer and Nambury succeeded in obtaining isomeric aminoisoxazolones (24 25 26). It is also possible to prepare isoxazol-3-ones from some /S-ketoesters. ... 

Oxy-aldehyd, n, hydroxy aldehyde, -ammo-niak, n, oxyammonia (hydroxylamine), -azoverbindung, /. hydroxyazo compound, -benzol, n, hydroxybenzene (phenol), -bem-steinsaure. /, hydroxysuccinic acid (malic acid). -biazol, n. oxadiazole, oxdiazole. -bitumen, n, oxidized bitumen, -carbon-s ure, /, hydroxycarboxylic acid, -chlnoltn, n. hydroxyquinoline, -clunon, n. hydroxy-quinone. -chlorid, n. oxychloride, -chlor-kupfer, n. copper oxychloride, -cyan, n. oxycyanogen. 

N sodium hydroxide solution (5 ml) is added to a stirred suspension of S-methyllsothiosemi-carbazide hydroiodide (2.33 g) and hydroxylamine hydrochloride (0.70 g) In water (6 ml) and stirred for 48 hours. The solution is evaporated In vacuo to provide 1 -amino-3-hydroxy-guanidine. One-third of the residue is dissolved in 16 ml of ethanol and 2,6-dichlorobenzalde-hyde (0.6 g) Is added to this solution. The reaction mixture is then stirred for 48 hours. The solution is then evaporated in vacuo and the residue dissolved in ether (30 ml) and in hydrochloric acid (30 ml). The aqueous phase is rendered alkaline with 2 N sodium carbonate solution and extracted with ether. The ether layer is dried with sodium sulfate and evaporated. 

In recent years, possible alternatives to hydrazine have been suggested, and some have been used on plant. These include carbohydrazide (NH2NHCONHNH2), derivatives of hydroxylamine, e.g. diethyl hydroxy-lamine (HONfCiHjIi), ketoximes, and erythrobic acid (iso corbic acid). These are usually faster scavengers than hydrazine or activated hydrazine . 

Hydroxylamine sulfate, 5, 73 -Hydroxyphenylarsonic acid, 7, 4, 5 0-Hydroxy Propionic Acid, 7, 54, 55 Hypochlorous acid, 5, 31... 

Hydroxylamine-O-sulfonic acid for N-amination of pyridine, 43, 1 Hydroxylation of indene, 41, 53 2-Hydroxy-3-methylbenzoic add, oxidation to 2-hydroxyisophthalic acid by lead dioxide, 40, 48 Rydroxymethyleerrocene. 40, 52... 

Die Reduktion von N-Hydroxy-piperidin zu Piperidin (82% d. Th.) in 0,2 m waBr. Oxalsaure ist als indi-rekte elektrolytischc Reduktion anzusehen, weil das gleichzeitig anwesendc Titan(IV)-chlorid bei -0,5 V zu Titan(III) reduziert wird, das dann scinerseits das Hydroxylamin reduziert. ... 

N-Diphenylmethylen- 374 N-Diphenylmethylen-O-aminocarbonyl- 612 N-[l,3-Diphenyl-propyl-(2) - 374 N-[l,3-Diphenyl-propyliden-(2)]- 374, 377, 380 N-(4-Halogen-phenyI)- 683 N-Heptyl- 375 N-Heptyl-N-acetyl- 376 N-Heptyliden- 375 N-Hcptyliden-O-acetyl- 376 0-(2-Hydroxy-athyl)-N-athoxycarbonyl- 133 N-(4-Hydroxy-phenyl)- 683 0-(2-Hydroxy-l-phenyl-athyI)-N-athoxycarbonyI-aus 0-(ci-AthoxycarbonyI-benzyl)-N-athoxycar-bonyl-hydroxylamin und Lithiumalanat 133 N-Isopropyl- 682 N-Isopropylidcn- 613 N-Methyl- 133, 682 O-Methyl-N-bcnzyliden- 377 O-Methyl-N-benzyliden- 375 0-Methyl-N-(4-chlor-benzyl)- 375 0-Methyl-N-(4-chlor-benzyliden)- 375 N-Methy -N,0-diacetyI- 682 N-(4-Methyl-phenyl)- 683 0-McthyI-N-( 1 -phenyl-athyliden)- 375 N-(4-Methylthio-phenyl)- 684 N-(4-Nitro-benzyl)- 374 N-[4-Nitro-benzyliden - 374, 377 N-(2-Nitro-phenyl)- 562 N-(4-Nitro-phenyl)- 682 N-Nitroso-N-cyclohexyl- 697 N-Octyl- 374 N-Octyl-(2)-N-acetyl- 376 N-Octyliden- 374 N-0ctyliden-(2)-0-acctyl- 376 N-(Pentafluor-phenyl)-0,N-diacetyl- 697 N-Phenyl- 474, 481, 682, 783 N-Phenylacetyl-O-benzoyl- 265 N-(l-Phenyl-athyl)- 374 N-(l-Phenyl-athyl)-N-acetyl- 376 N-(l-Phenyl-athyliden)-374, 613 N-( l-Phenyl-athyliden)-0-acetyl- 376 N-[ 1 -Phenyl-buten-( 1 )-yl-(3)-iden]- 582 N-f4-Phenyl-butyl-(2)-iden]- 581 N-Phcnyl-N,0-diacetyl- 682 N-(4-Phenylthio-phenyl)- 684 N-Propyl-N-cyclohexyl- 376 N-Propyl-N-isopropyl- 376 O-Sulfonyl- 481 N-(4-Sulfonyl-phenyI)- 683 N-(2-Vinyl-phenyl)- 698... 

The pathway used by a strain of Mycobacterium sp. for the degradation of 4-nitrotoluene is initiated by reduction to the hydroxylamine and rearrangement to 3-hydroxy-4-aminotoluene before further degradation (Spiess et al. 1998). 

A somewhat related sequence leads to trilostane (111), a compound that inhibits the adrenal gland more specifically the agent blocks some of the metabolic responses elicited by the adrenal hormone ACTH in experimental animals. Reaction of the hydroxy-methylene derivative 108, obtained from testosterone, with hydroxylamine gives the corresponding isoxazole (109). Oxidation of the C-4,5 double bond by means... 

The five-coordinate complexes Ir(CO)(PPh3)2L, where HL = /3-diketone, A-benzoyl-A-phenyl-hydroxylamine, salicylaldehyde, 8-hydroxyquinoline, 2-hydroxybenzophenone, 2-hydroxy-8-methoxybenzophenone, were prepared from [Ir(CO)(PPh3)2Cl].632 The resulting compounds all underwent oxidative addition reactions with Br2. Reaction of [(cod)2IrCl]2 with N-substituted 3-hydroxy-2-methyl-4-pyridine gives the bichelated complex (389). 33... 

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