Unexpected stoichiometry in the cleavage of bis(4-nitrophenyl) phosphate and 4-nitrophenyl phosphorochloridate by alkaline hydrogen peroxide

Meja-Radillo, Yamilet; Yatsimirsky, Anatoly K.; Foroudian, Houshang J.; Gillitt, Nicholas D.; Bunton, Clifford A.

doi:10.1002/1099-1395(200009)13:9<505::aid-poc277>3.0.co;2-n

Cited by 11 publications

(25 citation statements)

References 20 publications

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“…The second‐order rate constant for the hydroperoxide ion system was calculated from the slope of the straight line of k obs versus [Nu] and is reported in Table . It agrees with literature data for the hydrolysis of phosphodiesters …”

Section: Resultssupporting

confidence: 92%

“…of 4‐nitrophenolate ion (NP) and mono(4‐nitrophenyl)peroxyphenolate ( 1 ), which could readily form peroxyphosphate ( 2 ), which then gives inorganic products ( 3 ) under reaction conditions . This could be supported by the literature reporting fast intramolecular substitution by a peroxide ion that was postulated in the peroxydolysis of bisaryl oxalates, e.g., bis(2,4‐dinitrophenyl)oxalate, leading to formation of a cyclic peroxyoxalate …”

Section: Resultsmentioning

confidence: 76%

“…Takasaki, Bunton, Nome, and their research group have reported detailed mechanism for the cleavage of BNPP and BDNPP with hydroperoxide, benzohydroxamate, and laurylhydroxamate ions. The reaction of BDNPP with hydroperoxide ion forms peroxy intermediate that gives organic products identified by electrospray ionization–mass spectrometry (ESI‐MS) and nuclear magnetic resonance (NMR) spectra data.…”

Section: Resultsmentioning

confidence: 99%

“…They observed that the polymer accelerates the dephosphorylation reaction in micellar media. Bunton and his coworkers have investigated that cleavage of BNPP and 4‐nitrophenyl phosphorochloridate by alkaline hydrogen peroxide. They observed very high liability of the peroxo intermediate in terms of an intramolecular nucleophilic substitution by the peroxo group at phosphorus.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic hydrolysis of phosphodiesters by nucleophilic ions in gemini micellar media

Kumar¹,

Satnami

Barbero

et al. 2014

J. Phys. Org. Chem.

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The catalytic hydrolysis of bis(4‐nitrophenyl)phosphate (BNPP) and bis(2,4‐dinitrophenyl)phosphate (BDNPP) catalyzed by α‐nucleophiles in gemini micellar media was investigated at 27 °C. The cationic gemini surfactants, i.e., alkanediyl‐α‐ω‐bis(hydroxyethylmethylhexadecylammonium bromide) (16‐s‐16 MEA 2Br−, where s = 4 and 6) were used. Nucleophilic reactivity of α‐nucleophiles such as hydroperoxide (HOO−), acetohydroxamate (AHA−), and butane 2,3‐dione monoximate ions (BDMO−) were compared. The kinetic rate data were treated by applying the pseudophase model. The cationic gemini surfactants show unusual rate acceleration toward the cleavage of phosphodiesters with nucleophiles. These studies reveal that the hydroperoxide ion shows the highest catalytic activity reported so far with an unprecedented acceleration rate, 107 times faster than that of the uncatalyzed reaction. The possible mechanism for the BNPP and BDNPP cleavage promoted by α‐nucleophiles is proposed on the basis of kinetic analysis. Copyright © 2014 John Wiley & Sons, Ltd.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 76%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Catalytic hydrolysis of phosphodiesters by nucleophilic ions in gemini micellar media

Kumar¹,

Satnami

Barbero

et al. 2014

J. Phys. Org. Chem.

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“…), gives a rate constant in the plateau region of 0.40 × 10 −5 s −1 , 1.95 × 10 −5 s −1 , 1.75 × 10 −5 s −1 , 2.00 × 10 −5 s −1 , and 1.10 × 10 −5 s −1 . The first‐order rate constant for the hydrolysis of BNPP by hydroxide ion at pH 11.0 is about 3.28 × 10 −9 s −1 . Table indicates the kinetic rate data for the reaction of BNPP with different concentrations of BDMO, α‐benzoin oxime, AHA, BHA, and SHA at pH 11.0.…”

Section: Resultsmentioning

confidence: 99%

Comparative studies on reaction of bis(p‐nitrophenyl) phosphate and α‐nucleophiles in cationic micellar media

Kumar

Satnami

Ghosh

et al. 2012

J of Physical Organic Chem

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We studied the cleave of bis(p‐nitrophenyl) phosphate (BNPP) over a pH range of 7.0–12.0 in the presence of cationic micelles of cetyldiethylethanolammonium bromide, cetyldimethylethanolammonium bromide, cetylpyridinium bromide, cetyltrimethylammonium bromide, and cetylpyridinium chloride by using different α‐nucleophiles, viz acetohydroxamate, benzohydroxamate, salicylhydroxamate, butane‐2,3‐dione monooximate, and α‐benzoin oximate ions. With the use of α‐nucleophiles in cationic micellar media, the hydrolytic cleavage of BNPP was found to be approximately 105‐fold faster than its spontaneous hydrolysis. All reactions followed pseudo‐first‐order kinetics. The effect of various concentrations of cationic micelles for the reaction of BNPP and α‐nucleophiles has been studied. The variation of kobs values of the reactions depends on the micellar structure, that is, head groups, hydrophobic tail length, and counter ion. Copyright © 2012 John Wiley & Sons, Ltd.

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Role of peroxophosphate intermediates in reactions of tris(4‐nitrophenyl) phosphate and phenyl phosphoro‐chloridate with alkaline hydrogen peroxide

Foroudian

Gillitt

Bunton

et al. 2001

J of Physical Organic Chem

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Reaction of alkaline hydrogen peroxide with tris(4-nitrophenyl) phosphate generates ca 1.5 equiv. of 4nitrophenol per mole of substrate with no evidence of build-up of an intermediate, and reaction of bis(4-nitrophenyl) phosphate anion is too slow to give a product. The initially formed bis(4-nitrophenyl) peroxophosphate is assumed to decompose to the phosphate ester by reaction with H 2 O 2 or to eliminate 4-nitrophenoxide ion with the formation of a transient cyclic peroxophosphate. Reaction of phenyl phosphorochloridate anion with HO 2 À does not give phenoxide ion by this intramolecular reaction. Semi-empirical and ab initio simulations indicate that elimination of aryloxide ion from an aryl peroxophosphate should generate a cyclic rather than an open-chain peroxophosphate.

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Unexpected stoichiometry in the cleavage of bis(4-nitrophenyl) phosphate and 4-nitrophenyl phosphorochloridate by alkaline hydrogen peroxide

Cited by 11 publications

References 20 publications

Catalytic hydrolysis of phosphodiesters by nucleophilic ions in gemini micellar media

Catalytic hydrolysis of phosphodiesters by nucleophilic ions in gemini micellar media

Comparative studies on reaction of bis(p‐nitrophenyl) phosphate and α‐nucleophiles in cationic micellar media

Role of peroxophosphate intermediates in reactions of tris(4‐nitrophenyl) phosphate and phenyl phosphoro‐chloridate with alkaline hydrogen peroxide

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