3774-76-3

Upstream product

• 77-98-5 tetraethylammonium hydroxide 
• 4264-83-9 disodium (4-nitrophenyl)phosphate 
• 100-02-7 4-nitro-phenol 
• 68-05-3 tetraethylammonium iodide 
• 56-34-8 tetraethylammonium chloride 
• 71-91-0 tetraethylammonium bromide 
• 546-71-4 paraoxon 
• 1153-45-3 4-nitrophenyl 4-methylbenzenesulfonate 
• 311-45-5 paraoxon 

Downstream Products

• 62774-76-9 (1α,2α,6α)-2-(4-Nitrophenoxy)-7-oxabicyclo<4.1.0>hept-3-en 
• 62774-76-9 (1α,2β,6α)-2-(4-Nitrophenoxy)-7-oxabicyclo<4.1.0>hept-3-en 
• 62774-77-0 (1α,2α,3β,5β,7α)-2-(4-Nitrophenoxy)-4,8-dioxatricyclo<5.1.0.0^3,5>octan 
• 62774-77-0 (1α,2α,3α,5α,7α)-2-(4-Nitrophenoxy)-4,8-dioxatricyclo<5.1.0.0^3,5>octan 

Relevant academic research and scientific papers

ETUDE CINETIQUE DE L'HYDROLYSE DU PARANITROPHENYLPHOSPHATE DANS L'ACETONITRILE FAIBLEMENT AQUEUX. PROCESSUS DISSOCIATIF.

Basic hydrolysis of paranitrophenylphosphate in acetonitrile of low water content (0.02 to 0.5 M) is an unimolecular process, with likely a phosphenium cation as intermediate.Comparison with reaction in water - also occuring through an unimolecular process - indicates that the large rate enhancement in CH3CN (3E6 for =0.02 M) is entropy controlled.

Reactivity of methoxide ion in concentrated methanolic solutions of Et4NOCH3 and Et4NCl

Bimolecular rate constants k were determined for reactions of 4-nitrophenyl 4-toluenesulfonate, diethyl 4-nitrophenyl phosphate, and ethyl 4-nitrophenyl ethylphosphonate with tetraethylammonium methoxide Et4NOCH3 in methanol at 25°C over a wide range of Et4NOCH3 concentrations, where the reagent acts simultaneously as electrolyte, and at [Et4NOCH3] ≤ 0.1 M (reagent) with variation of Et4NCl (electrolyte) concentration. The relation logk = logk0 + b[Et4NX] is fulfilled up to [Et4NX] = 3.5 M, indicating that the electrolyte affects the reaction rate through restructurization of methanol as reaction medium.

Salt Effects on Proton Transfer from Nitrophenols to Amine or Pyridine Bases in Acetonitrile

The addition of MClO4 (M+ = Li+ and Na+) to 1.0 x 10-1 mol dm-3 2,4-dinitrophenol and the equivalent concentration of γ-picoline (4-methylpyridine) in acetonitrile caused a promoted proton transfer from the phenol to the base to the extent of 62 and 23 percent for 0.1 mol dm-3 Li+ and Na+, respectively.Alkaline-earth metal perchclorates (M(ClO4)2) had larger effects even at low concentrations of M2+, e. g., the proton-transfer ratio was 90 percent for 1.0 x 10-2 mol dm-3 Mg(ClO4)2.The effects of M2+ decreased with increasing size of the cation: Mg2+ > Ca2+ > Sr2+ > Ba2+.With the addition of MClO4 or M(ClO4)2, a higher proton transfer ratio was observed for 2,5-dinitrophenol + γ-collidine than for 2,4-dinitrophenol + γ-picoline.The salt effects of MClO4 or M(ClO4)2 on the acid-base reactions were accounted for by the formation of triple cations or complex species of M+ or M2+ with the phenolate ions (B represents base): (NO2)2 PhOH-B + 2M+ ->/-(M+)2 + BH+; (NO2)2PhOH-B + M2+ ->/-M2+ + BH+.The stronger the base, the greater the proton transfer (based on the addition of salts) from the phenols.The effects of LiClO4 on 2,4,6-trinitrophenol (picric acid) + 2-chloropyridine were very small; however, the effects on the proton transfer from 2- and 4-nitrophenol to triethylamine were very large.The extent of the proton transfer (based on the addition of LiClO4) from nitrophenols in the presence of appropriate bases was coincident with the order of the formation constants of ion aggregates (ion pairs and triple ions) for lithium nitrophenolates in acetonitrile: 2- >> 4-, 2,5- > 2,4- >> 2,4,6-.The "free" phenolate ions were produced by the addition of tetraalkylammonium halides (R4N+X-: R = Et, n-Bu; X- = Cl-, Br-, I-) to the nitrophenols in the presence of bases inacetonitrile: (NO2)nPhOH-B + 2X- ->?- + BH+(X-)2.The presence of a base was not essential for the deprotonation of picric acid with R4NX.