Reaction kinetics of several alkyl arsenite hydrolyses

Baer, Carl D.; Edwards, John O.; Rieger, Philip H.; Silva, C. M.

doi:10.1021/ic00151a031

Cited by 12 publications

(5 citation statements)

References 9 publications

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“…As expected, rates of hydrolysis of arsenite esters are faster than arsenate esters, e.g. k(triisopropyl arsenate) 2.8s -1 [116] and k(triisopropyl arsenite) 0.123s -1 [110] under similar conditions. The ease of hydrolysis of arsenate esters relative to phosphate esters has important consequences for their biological activity [8].…”

Section: R2aso(oh) + H + ~[R2as(oh)2 ] +supporting

confidence: 75%

“…From this there are two longer P-O bonds (P-O 1.54/~) corresponding to P-OH and one shorter P-O bond (P-O 1.47/~) corresponding to P=O, although the H atoms were not located. The kinetics of hydrolysis of a number of alkyl arsenites have been studied [110] in order to understand better the fate of arsenites in biological systems. It has been found that hydrolysis occurs with exclusive As-O bond fission [110]: H20 + As(OR)3 ~ HOAs(OR)2 + ROH --* --.…”

Section: R2aso(oh) + H + ~[R2as(oh)2 ] +mentioning

confidence: 99%

“…The kinetics of hydrolysis of a number of alkyl arsenites have been studied [110] in order to understand better the fate of arsenites in biological systems. It has been found that hydrolysis occurs with exclusive As-O bond fission [110]: H20 + As(OR)3 ~ HOAs(OR)2 + ROH --* --. H3AsO 3 + ROH…”

Section: R2aso(oh) + H + ~[R2as(oh)2 ] +mentioning

confidence: 99%

“…k for MeOH/OAs(OMe)3 is 194 s-1 [115]) while probable reaction times of phosphate esters are hours in neutral solution at 100 °C. Like arsenite ester hydrolysis [110], trialkyl arsenate hydrolysis involves As-O bond cleavage [116]: HEO + OAs(OR)3 ~ OAs(OH)(OR)2 + ~ ~ OAs(OH)3 + ROH Neutral hydrolysis of phosphate triesters in some cases involves C-O bond fission and is slow at 100 °C so direct rate comparison is not possible, however it is clearly much slower than for arsenate hydrolysis [116]. As expected, rates of hydrolysis of arsenite esters are faster than arsenate esters, e.g.…”

Section: R2aso(oh) + H + ~[R2as(oh)2 ] +mentioning

confidence: 99%

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The structure and reactivity of arsenic compounds: Biological activity and drug design

Dhubhghaill

Sadler

1991

Structure and Bonding

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Section: R2aso(oh) + H + ~[R2as(oh)2 ] +supporting

confidence: 75%

Section: R2aso(oh) + H + ~[R2as(oh)2 ] +mentioning

confidence: 99%

Section: R2aso(oh) + H + ~[R2as(oh)2 ] +mentioning

confidence: 99%

Section: R2aso(oh) + H + ~[R2as(oh)2 ] +mentioning

confidence: 99%

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The structure and reactivity of arsenic compounds: Biological activity and drug design

Dhubhghaill

Sadler

1991

Structure and Bonding

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“…For the other oxoanions it is likely that O-alkylation takes place in many cases but the alkylated derivatives are unstable in aqueous solution and they hydrolyze to give the original substrates or they decompose during GC separation. For example, the alkyl esters of sulfuric and sulfurous acids, arsenic and arsenious acids are reported to hydrolyze quite fast in aqueous solutions. Sulfur containing substrates give S-alkylation.…”

Section: Resultsmentioning

confidence: 99%

Vapor Generation of Inorganic Anionic Species After Aqueous phase Alkylation with Trialkyloxonium Tetrafluoroborates

D’Ulivo

Pagliano²,

Onor³

et al. 2009

Anal. Chem.

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Aqueous phase reaction of trialkyloxonium tetrafluoroborates, R 3 O + BF 4 -(RdMe, Et) has been tested in the alkylation of simple inorganic anionic substrates such as halogen ions, cyanide, thiocyanate, sulphide and several oxoanions or their corresponding oxoacids. Gaseous products were separated and identified by gas chromatography mass spectrometry (GC-MS). Alkylated derivatives RI, RBr, RCl were obtained for iodide, bromide, and chloride, respectively, while for fluoride its conversion efficiency to RF is very poor. RCN and R 2 S were obtained for cyanide and sulphide, while thiocyanate gives RSCN as a main reaction product with a minor amount of alkylisothiocyanate, RNCS (<7%). Among tested oxoanions only nitrites and nitrates give volatile derivatives under the form of RsOsNO and RsOsNO 2 , respectively. Reaction performed by adding Et 3 O + BF 4 -in CH 2 Cl 2 to aqueous sample with extraction in the organic phase of reaction products, failed to identify other less volatile reaction products. Using 2 mL sample in 4 mL reaction vial (T ) 25°C), 100 µL of 2 M Et 3 O + BF 4 -and injecting 250 µL of headspace into GC-MS, detection limits (3 s) are in the range of 1-280 ng mL -1 . Application to determination of bromide in groundwater certified reference material (BCR-612, 252 ( 10 µg kg -1 of bromide) gave results in excellent agreement with certified values. The method, being not responsive to iodate, allows the selective determination of iodide in the presence of iodate. Total iodine can be determined after reduction of iodate to iodide by NaBH 4 . Application of the method to iodide-iodate speciation in table salt gave results in excellent agreement with parallel analysis performed by ion chromatography as a reference method.

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