48168-03-2

Upstream product

• 115-86-6 phosphoric acid triphenyl ester 
• 91-20-3 naphthalene anion radical 
• 85-01-8 phenanthrene radical anion 
• 100-47-0 cyanobenzene 
• 90-12-0 1-methylnaphthalene radical anion 
• 791-28-6 C₁₈H₁₅OP^(1-) 
• 10359-36-1 4-nitro-phenyl diphenyl phosphate 
• 110-86-1 pyridine 
• 2524-64-3 chlorophosphoric acid diphenyl ester 
• 70677-19-9 diphenyl phosphorobromidate 
• 62-53-3 aniline 
• 64-17-5 ethanol 
• 14057-64-8 phenyl phosphate^(2-) 
• 88284-48-4 2-(trimethylsilyl)phenyl trifluoromethanesulfonate 

Downstream Products

• 1421362-56-2 [Co₂(4-bromo-2,6-bis(((2-hydroxyethyl)(pyridin-2-ylmethyl)amino)methyl)phenolate^(1-))(diphenylphosphate)₂]⁽¹⁺⁾ 
• 1421362-54-0 [Co₂(ethyl 4-hydroxy-3,5-bis(((2-hydroxyethyl)(pyridin-2-ylmethyl)amino)methyl)benzoate^(1-))(diphenylphosphate)₂]⁽¹⁺⁾ 
• 357979-11-4 2-deoxy-2-fluoro-3,4,6-tri-O-acetyl-α-D-glucopyranosyl 1-diphenylphosphate 

Relevant academic research and scientific papers

Micellar Effects upon Substitutions by Nucleophilic Anions

Micellar effects upon of OH- with p-nitrophenyl diphenyl phosphate or 2,4-dinitro-1-chloronaphthalene have been examined with cetyltrimethylammonium surfactants, (CTAX, X=Cl, Br, (SO4)1/2).Demethylations of methyl benzene- or naphthalene-2-sulfonate by halide ion have been examined. in micelles of CTACl, CTABr, CTA(SO4)1/2, or cetyltrimethylammonium mesylate (CTAOMs) and for demethylation by OH- or SO32- in CTA(SO4)1/2 or CTAOMs.The rate enhancements have been treated in terms of concentrations of the substrates and the nucleophilic anion at the micellar surface.The anion concentrations depended upon nonspecific Coulombic and specific interactions that were calculated by solving the Poisson-Boltzmann equation.The same structural parameters were used in fitting data for reactions with Cl- or Br- as nucleophiles and for systems with Cl- or Br- as inert anions that were competing with OH- or SO32-.The treatment is applicable to mixtures of database to mixtures of dilute mono- and dianions.

The Aryne Phosphate Reaction**

Condensed phosphates are a critically important class of molecules in biochemistry. Non-natural analogues are important for various applications, such as single-molecule real-time DNA sequencing. Often, such analogues contain more than three phosphate units in their oligophosphate chain. Consequently, investigations into phosphate reactivity enabling new ways of phosphate functionalization and oligophosphorylation are essential. Here, we scrutinize the potential of phosphates to act as arynophiles, paving the way for follow-up oligophosphorylation reactions. The aryne phosphate reaction is a powerful tool to—depending on the perspective—(oligo)phosphorylate arenes or arylate (oligo-cyclo)phosphates. Based on Kobayashi-type o-silylaryltriflates, the aryne phosphate reaction enables rapid entry into a broad spectrum of arylated products, like monophosphates, diphosphates, phosphodiesters and polyphosphates. The synthetic potential of these new transformations is demonstrated by efficient syntheses of nucleotide analogues and an unprecedented one-flask octaphosphorylation.

Effect of heteroatom insertion at the side chain of 5-alkyl-1H-tetrazoles on their properties as catalysts for ester hydrolysis at neutral pH

Herein we introduce tetrazole and its suitably designed derivatives as powerful ester-cleaving reagents. By first performing a detailed ab initio computational study, we found that, in the side chain of 5-alkyl-1H-tetrazoles, introduction of a heteroatom (e.g., N, O, or S at the α-position of the tetrazole ring) raises the charge on the tetrazole nucleus significantly. All calculations have been performed using restricted Hartree-Fock (RHF) and hybrid ab initio/DFT (B3LYP) methods employing 6-31G* and 6-31+G* basis sets. To estimate the nucleophilicity of these reagents, the charges on conjugate bases of various tetrazole derivatives have been calculated using natural population (NBO) analysis in gas phase and in water. Free energy of protonation (fep) of the 1H-tetrazole derivatives (1-7), free energy of solvation, ΔGaq, and the corresponding pKa values have been calculated by self-consistent reaction field (SCRF) methods applying the polarized continuum model (PCM). Since the calculation indicates that incorporation of heteroatom leads to enhanced nucleophilicity in their deprotonated anionic tetrazole forms, a series of 5-substituted 1H-tetrazole derivatives have been synthesized. These compounds indeed catalyze the hydrolysis of p-nitrophenyl diphenyl phosphate (PNPDPP) and p-nitrophenyl hexanoate (PNPH) efficiently in cationic cetyl trimethylammonium bromide (CTABr) micelles at pH 7.0 and 25 °C. The pseudo-first-order rate constants (k obs) were determined for each catalyst against both substrates. The experimental and theoretical results show that, to achieve better k obs values for the cleavage of PNPDPP and PNPH under micellar conditions, charge on the N- atom (nucleophile) of conjugate base is important. Replacing the α-CH2 in alkyl substituent with S (3), NH (4), or O (5) enhances the accumulation of charge on N- in conjugate bases of tetrazoles and subsequently increases their intrinsic nucleophilic reactivity toward hydrolytic reactions. Significantly large rate enhancements were observed for the cleavage of PNPDPP and PNPH at pH 7.0 in the presence of catalytic system 5/CTABr over background (only CTABr). Tetrazole 4 (α-isomer) showed 4-5-fold superior reactivity over 6 (β-isomer) under identical conditions. Natural charges obtained from NBO analysis (B3LYP/ 6-31+G*) are -0.94 and -0.852 on N- in the conjugate bases of 4 and 6, respectively. This also predicts that 4 is a better nucleophile than 6. All the newly synthesized tetrazole derivatives in micellar media display true catalytic properties by cleaving several fold excess of substrates.

Kinetics of radical heterolysis reactions forming alkene radical cations

Rate constants for heterolytic fragmentation of β-(ester)alkyl radicals were determined by a combination of direct laser flash photolysis studies and indirect kinetic studies. The 1,1-dimethyl-2-mesyloxyhexyl radical (4a) fragments in acetonitrile at ambient temperature with a rate constant of khet > 5 × 109 s-1 to give the radical cation from 2-methyl-2-heptene (6), which reacts with acetonitrile with a pseudo-first-order rate constant of k = 1 × 106 s-1 and is trapped by methanol in acetonitrile in a reversible reaction. The 1,1-dimethyl-2-(diphenylphosphatoxy)hexyl radical (4b) heterolyzes in acetonitrile to give radical cation 6 in an ion pair with a rate constant of khet = 4 × 106 s-1, and the ion pair collapses with a rate constant of k ≤ 1 ± 109 s -1. Rate constants for heterolysis of the 1,1-dimethyl-2-(2,2- diphenylcyclopropyl)-2-(diphenylphosphatoxy)ethyl radical (5a) and the 1,1-dimethyl-2-(2,2-diphenylcyclopropyl)-2-(trifluoroacetoxy)ethyl radical (5b) were measured in various solvents, and an Arrhenius function for reaction of 5a in THF was determined (log k = 11.16-5.39/2.3RT in kcal/mol). The cyclopropyl reporter group imparts a 35-fold acceleration in the rate of heterolysis of 5a in comparison to 4b. The combined results were used to generate a predictive scale for heterolysis reactions of alkyl radicals containing β-mesyloxy, β-diphenylphosphatoxy, and β-trifluoroacetoxy groups as a function of solvent polarity as determined on the ET(30) solvent polarity scale.

Laser flash photolysis kinetic studies of enol ether radical cations. Rate constants for heterolysis of α-methoxy-β-phosphatoxyalkyl radicals and for cyclizations of enol ether radical cations

Two series of enol ether radical cations were studied by laser flash photolysis methods. The radical cations were produced by heterolyses of the phosphate groups from the corresponding α-methoxy-β-diethylphosphatoxy or β-diphenylphosphatoxy radicals that

Reinvestigation of the 31P NMR evidence for the formation of diorganyl phosphoropyridinium intermediates

The 31P nuclear magnetic resonance (NMR) evidence for the formation of diorganyl phosphoropyridinium intermediates was reinvestigated. It was found that equilibria of these reactions were heavily shifted to the left. The concentrations of the putative diorganyl phosphoropyridinium chlorides/bromides were usually below the detection level of this spectroscopic method. The results showed that when diphenyl iodophosphate was subjected to reaction with pyridine, the formation of a diorganyl phosphoropyridinium intermediate was observed.

Phosphomonoesters and phosphodiesters derived from the photohydrolysis of 2-methoxy-5-nitrophenyl substituted phosphotriesters

Phosphotriesters composed of one or two 2-methoxy-5-nitrophenyl group(s) can be quantatively photohydrolyzed in aqueous acetonitrile to yield the desired phosphodiester or phosphomonoester, respectively. Photohydrolysis occurs by attack of hydroxide at both the phosphoryl phosphorus and at the ipso-carbon in the triplet exited state of the 2-methoxy-5-nitrophenyl substituted phosphoesters. The photophysical studies described within imply that this type of reaction may be synthetically useful.

ELECTROCHEMICAL REACTIONS OF PHOSPHORIC ACID DERIVATIVES. I. HOMOGENEOUS REDUCTION OF TRIARYL PHOSPHATES BY MEANS OF ORGANIC ELECTRON CARRIERS

The mechanism of the reduction of triaryl phosphates at homogeneous conditions by means of electrochemically generated radical anions of organic molecules, acting as electron carriers, has been studied, as well as at heterogeneous conditions.In both cases the reduction process is controlled by a retarded electron transfer to the substrate, followed by rapid bond rupture in the radical anion formed.

Hydrolysis of toxic organophosphorus compounds by o-iodosobenzoic acid and its derivatives

The 1,2,2-trimethylpropyl and the 1-methylethyl esters of methylphosphonofluoridic acid (soman and sarin, respectively), ethyl N,N-dimethylphosphoramidocyanidate (tabun), and the diethyl 4-nitrophenyl ester of phosphoric acid (paraoxon) are hydrolyzed eff

Modelling of Micellar Effects upon Substitution Reactions with Moderately Concentrated Hydroxide Ion

Cationic micelles of cetyltrimethylammonium chloride and bromide (CTACl and CTABr) speed reactions of 2,4-dinitro-1-naphthyl chloride (DNNC) and p-nitrophenyl diphenyl phosphate (pNPDPP) with OH-.The pseudophase ion-exchange model fits the data