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

Foroudian, Houshang J.; Gillitt, Nicholas D.; Bunton, Clifford A.; Yatsimirsky, Anatoly K.

doi:10.1002/poc.367

Cited by 4 publications

(6 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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%

“…On the basis of the aforementioned studies, nucleophilic catalyzed mechanism is proposed for the catalytic cleavage of BNPP and BDNPP by hydroperoxide and butane 2,3‐dione monoximate ions, which is similar to other reported data . As shown in Scheme , the hydroperoxide (HOO − ) is proposed to be the active ion in the hydrolysis of BNPP under the reaction conditions employed in these kinetics studies.…”

Section: Resultssupporting

confidence: 84%

“…We believe that the reaction of HOO − with BNPP − simultaneously releases almost 1 equiv. 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%

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.

View full text Add to dashboard Cite

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.

show abstract

Section: Resultssupporting

confidence: 92%

Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 76%

See 1 more Smart Citation

Catalytic hydrolysis of phosphodiesters by nucleophilic ions in gemini micellar media

Kumar¹,

Satnami

Barbero

et al. 2014

J. Phys. Org. Chem.

View full text Add to dashboard Cite

show abstract

“…), 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%

“…The first-order rate constant for the hydrolysis of BNPP by hydroxide ion at pH 11.0 is about 3.28 Â 10 À9 s À1 . [33][34][35][36][37] Table 2 indicates the kinetic rate data for the reaction of BNPP with different concentrations of BDMO, a-benzoin oxime, AHA, BHA, and SHA at pH 11.0. It is found that a-nucleophiles in cationic micellar media display significant catalytic activity for the cleavage of BNPP ( Table 2).…”

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

View full text Add to dashboard Cite

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.

show abstract

Reaction of Bis(2,4-dinitrophenyl) Phosphate with Hydrazine and Hydrogen Peroxide. Comparison of O- and N- Phosphorylation

et al. 2004

Self Cite

View full text Add to dashboard Cite

Nonionic hydrazine reacts with anionic bis(2,4-dinitrophenyl) phosphate (BDNPP), giving 2,4-dinitrophenyl hydrazine and dianionic 2,4-dinitrophenyl phosphate by an S(N)2(Ar) reaction, and at the phosphoryl center, giving 2,4-dinitrophenoxide ion and a transient phosphorylated hydrazine that rearranges intramolecularly to N-(2,4-dinitrophenyl)-N-phosphonohydrazine. Approximately 58% of the reaction at pD = 10 occurs by N-phosphorylation, as shown by (31)P NMR spectroscopy. Reaction of HO(2)(-) is wholly at phosphorus, and the intermediate peroxophosphate reacts intramolecularly, displacing a second 2,4-dinitrophenoxide ion, or with H(2)O(2), giving 2,4-dinitrophenyl phosphate and O(2). Rate constants of O- and N-phosphorylation in reactions at phosphorus of NH(2)NH(2), HO(2)(-), and NH(2)OH and its methyl derivatives follow Bronsted relationships with similar slopes, but plots differ for oxygen and nitrogen nucleophiles. The reaction with NH(2)NH(2) has been probed by using both NMR spectroscopy and electrospray ionization mass and tandem mass spectrometry, with the novel interception of key reaction intermediates in the course of reaction.

show abstract

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

Cited by 4 publications

References 16 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

Reaction of Bis(2,4-dinitrophenyl) Phosphate with Hydrazine and Hydrogen Peroxide. Comparison of O- and N- Phosphorylation

Contact Info

Product

Resources

About