Hydroxamate method

A sensitive and reproducible colorimetric determination of the tropane alkaloids by the ferric hydroxamate method has been described,18 and so has the nitration and dehydration of tropane alkaloids on the microgram scale on tie. plates.19... 

Miller s hydroxamate method [41], widely used for the preparation of mono-bactams, surprisingly scores a single application useful for penem synthesis [42]. Chiral 0-butyl hydroxamate 91 was prepared by aldol reaction of crotonalde-hyde with synthon 90a (Sn(OTf )2/iV-ethylmorpholine), followed by temporary 0-TBDMS protection of obtained 90b and displacement with butoxyamine. Lactamization of 91 under Mitsunobu conditions (PPh3/DEAD) afforded 92, an equivalent (by alkene oxidative cleavage and deprotection) of enantiomerically pure 4-acetoxyazetidinone. 

In vitro release tests were carried out on 200 mg samples of polymer films, by determining pilocarpine release to a stirred aqueous medium (pH 6.98 phosphate buffer, 10.0 ml) at 30 °C. Solution samples (2.0 ml) were withdrawn at appropriate intervals, and were replaced with an equal amount of fresh buffer. Pilocarpine was analyzed spectrophotometrically by the ferric hydroxamate method described by Gibbs and Tuckerman... 

I. S. Gibbs and M. M. Tuckerman, Optimal Ferric Hydroxamate Method for Determination of Intact Pilocarpine, J. Pharm. Sci. 59 395 (1970). 

Preparation of broken chloroplasts from spinach, the reaction conditions, ATP determination by the luciferase assay, and acetyl phosphate determination by the hydroxamate method, were as in Shinohara and Sakurai (1982) unless otherr wise stated. Adenine nucleotides were analyzed by HPLC (Waters model QA-1) column, IEX-5 0 (Toyo Soda Chemical Co., Tokyo) elution medium UOO mM K-phosphate buffer (pH U.6)-20 (v/v) acetonitrile flow rate, 0.5 ml/min. Preparation of thylakoids from A. nidulans and of chromatophores from R. rubrum will be described elsewhere (Shinohara et al., in preparation). 

The hydrogenolysis of hydroxamic acids (22) and hydra2ides (23) has also been used to synthesi2e amides. One of the earliest methods for the preparation of amides consists of treating acid chlorides with dry ammonia or an amine (24). 

Succinyl coenzyme A trisodium salt [108347-97-3] M 933.5. If it should be purified further then it should be dissolved in H2O (0.05g/mL) adjusted to pH 1 with 2M H2SO4 and extracted several times with Et20. Excess Et20 is removed from the aqueous layer by bubbling N2 through it and stored frozen at pH 1. When required the pH should be adjusted to 7 with dilute NaOH and used within 2 weeks (samples should be frozen). Succinyl coenzyme A is estimated by the hydroxamic acid method [J Biol Chem 242 3468 1967]. It is more stable in acidic than in neutral aqueous solutions. [Methods Enzymol 128 435 7956.]... 

In 2000, an efficient three-step procedure for the synthesis of 5-substituted 3-isoxazolols (without formation of undesired 5-isoxazolone byproduct) was published. The method uses an activated carboxylic acid derivative to acylate Meldrum s acid, which is treated with A,0-bis(ten-butoxycarbonyl)hydroxylamine to provide the N,0-di-Boc-protected P-keto hydroxamic acids 14. Cyclization to the corresponding 5-substituted 3-isoxazolols 15 occurs upon treatment with hydrochloric acid in 76-99% yield. 

The cyclic hydroxamic acid (104) obtained by this route had previously been prepared by the two methods illustrated. These exemplify well the variants possible within route (ii). 

The following discussion of hydroxamic acids includes saturated systems, e.g., 2, compounds such as 3, derived from aromatic systems, 7V-hydroxyimides such as 7V-hydroxyglutarimide (78), and certain of their derivatives including thiohydroxamic acids. Naturally occurring cyclic hydroxamic acids are discussed to show the range of structural types that has been found, hut macrocyclic polyhydroxamic acids are mentioned very briefly, because several comprehensive reviews of these compounds are already available. The main purpose of this review is to summarize the methods available for the synthesis of cyclic hydroxamic acids, to outline their characteristic reactions, and to present some useful physical data. Their synthesis and some biological properties have previously been reviewed by Coutts. ... 

Because of the great range of structures containing cyclic hydroxamic acid functions it is difficult to give a concise summary of the available synthetic methods. Nevertheless, the vast majority of published syntheses depend on condensation reactions involving only familiar processes of acylation or alkylation of hydroxylamine derivatives. The principles of such syntheses are outlined in a number of typical examples in Section III, A but no attempt has been made to cover all reported cases. 

By this method, Chauveau and Mathis have prepared cyclic hydroxamic acids (41) containing a sulfur atom in the ring. The acyclic precursors (40) were formed by alkylation of a thiol anion. 

Perhaps the most reliable method for the reductive cyclization of a nitro ester to a hydroxamic acid is that which involves treatment with sodium horohydride in the presence of palladium on charcoal. Although under these conditions aromatic nitro compounds are reduced to amines, o-nitro esters such as 53, in which the ester group is suitably oriented with respect to the nitro group, give good yields of cyclic hydroxamic acids (54). Coutts and his co-... 

During a study of azonitrones (70), Forrester and Thomson showed that reaction with toluene-p-sulfinic acid resulted in nitrogen evolution and formation of the hydroxamic acid (66) together with the pyrrolidone (71) and the amidine (72). These workers suggested the following reaction course. Although the yield of hydroxamic acid was high, the method is not likely to be of preparative value. 

The method which has been of most preparative value is that established by Panizzi el and Di Maio and Tardella. Benzene-sulfonhydroxamic acid (74), known as Piloty s acid, reacts with a cyclic ketone (73) in alkaline media at 0 , to produce the ring-expanded hydroxamic acids (75 and 76) in approximately equal yield. 

Reduction of cyclic hydroxamic acids generally leads to lactams or the corresponding amines. Chemical methods have frequently been preferred to catalytic hydrogenation, probably because the choice of... 

When primary nitro compounds are treated with sulfuric acid without previous conversion to the conjugate bases, they give carboxylic acids. Hydroxamic acids are intermediates and can be isolated, so that this is also a method for preparing them. Both the Nef reaction and the hydroxamic acid process involve the aci form the difference in products arises from higher acidity, for example, a difference in sulfuric acid concentration from 2 to 15.5 M changes the product from the aldehyde to the hydroxamic acid. The mechanism of the hydroxamic acid reaction is not known with certainty, but if higher acidity is required, it may be that the protonated aci form of the nitro compound is further protonated. 

Polymer-bound 1-hydroxybenzotriazole 1008 reacts with carboxylic acids in the presence of 1,3-diisopropylcarbo-diimide (1,3-DIC) and DMAP to produce esters 1009. Treated with hydroxylamine, esters 1009 are converted to hydroxamic acids 1010 (Scheme 167) <20030BC850>. Starting 1-hydroxybenzotriazole 1008 is recycled in the process and can be used for other syntheses. This method is well suited for automated synthesis of a library of hydroxamic acids. In similar applications of polymer-supported 1-hydroxybenzotriazole 1008, a wide variety of amides is synthesized <1997JOC2594, 2002JC0576>. 

If a measurement of total fatty acid concentration is desired, short of attempting to sum the amounts of each compound found by gas chromatography, some indirect method must be employed. Harwood and Huyser [94] made iron (III) hydroxamates of the fatty acids and measured these colorimetrically. 

Dehydration of O-silylated hydroxamic acids is used as a general method in the synthesis of nitrile oxides (95) in the presence of trilluoromethanesulfonic anhydride and triethylamine. 

A general synthetic method for acyclic a-alkoxynitrones (196) involves the alkylation with triflates of hydroxamic acids (195) in neutral conditions (Scheme 2.69) (352). Similarly, the synthesis of cyclic methoxynitrone of pyrrolines (197) has been carried out (353). 

The presence in the heterocycle of additional basic centers or those open to alkylation can lead to a change in reaction directions. It essentially limits the application of this method in the formation of a-methoxy nitrones. In such cases, it is reasonable to use diazomethane and, depending on the structure of hydroxamic acid (198-201) the yields of a-methoxy nitrones (197), (202-204) can rise from 17% up to 62% (Scheme 2.70) (353). 

Acyl nitroso compounds (3, Scheme 7.2) contain a nitroso group (-N=0) directly attached to a carbonyl carbon. Oxidation of an N-acyl hydroxylamine derivative provides the most direct method for the preparation of acyl C-nitroso compounds [10]. Treatment of hydroxamic acids, N-hydroxy carbamates or N-hydroxyureas with sodium periodate or tetra-alkyl ammonium periodate salts results in the formation of the corresponding acyl nitroso species (Scheme 7.2) [11-14]. Other oxidants including the Dess-Martin periodinane and both ruthenium (II) and iridium (I) based species efficiently convert N-acyl hydroxylamines to the corresponding acyl nitroso compounds [15-18]. The Swern oxidation also provides a useful alternative procedure for the oxidative preparation of acyl nitroso species [19]. Horseradish peroxidase (HRP) catalyzed oxidation of N-hydroxyurea with hydrogen peroxide forms an acyl nitroso species, which can be trapped with 1, 3-cyclohexanone, giving evidence of the formation of these species with enzymatic oxidants [20]. 

Chrysocolla (CuOxSi02 Cu= 10-36%, SG — 2-2.4) is the most studied mineral of all the oxide minerals. Extensive laboratory studies have been conducted by numerous researchers [9-11]. The laboratory research work indicates that chrysocolla can be floated using the sulphidization method, as shown in Figure 19.4, or by hydroxamate collectors. However, none of these processes have been applied at an industrial scale. 

In 1983, Prasad et al.12 first reported the condensation of chloromethyl polystyrene with /V-hydroxyphthalimide to give the ester, hydrazinolysis of which yielded the desired resin-bound hydroxylamine. However, the sole purpose of this reagent was to react with, and hence extract ketones from, a complex steroidal mixture, and its use for the solid-phase synthesis of hydroxamic acids was not explored. Recently, the exploitation of the above solid-phase approach for the synthesis of hydroxamic acids was independently reported by three groups,7-9 all of which differ only in the method for the initial anchoring of TV-hydroxyphtha-limide to an 4-alkoxybenzyl alcohol functionalized polystyrene or trityl chloride polystyrene. Subsequent /V-deprotection was... 

An official gas chromatographic method [29] is available from the determination of volatile fatty acids in sewage sludge. This method is based on gas liquid chromatographic estimation with a flame ionization detector, and is applicable up to 2000mg total volatile fatty acids per litre, while the concentrations of individual fatty acids can also be determined. Where this method is not practicable an empirical method based on the spectrophotometric determination of ferric hydroxamates can be used, giving a value for total fatty acids expressed as acetic acid. For control purposes a rapid test is described in which the volatile fatty acids are determined by electrometric titrimetry on the neutralized sludge obtained from the determination of alkalinity. 

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