640-60-8

Usage

Uses

Used in Pharmaceutical Industry:
P-Toluenesulfonic Acid Phenyl Ester is used as an intermediate in the synthesis of Diclofenac-13C6 Sodium Salt (D436453), which is a labeled analogue of Diclofenac Sodium Salt (D436450). This application is crucial for the development of pharmaceuticals that can be used in research and therapeutic applications, particularly in the area of drug metabolism and pharmacokinetic studies. The use of Phenyl Tosylate in this context aids in the production of compounds that can provide valuable insights into the behavior of drugs within the body, ultimately contributing to the advancement of medical treatments.

Purification Methods

Crystallise the ester from MeOH or glacial acetic acid. [Beilstein 11 H 99, 11 II 47, 11 III 200, 6 IV 271.]

Upstream product

• 110-86-1 pyridine 
• 98-59-9 p-toluenesulfonyl chloride 
• 108-95-2 phenol 
• 78497-67-3 2,4-dinitro-6-methylphenyl p-toluenesulfonate 
• 139-02-6 sodium phenoxide 
• 71-43-2 benzene 
• 4973-66-4 methyl thiotosylate 
• 102-09-0 bis(phenyl) carbonate 
• 6192-52-5 p-toluenesulfonic acid monohydrate 
• 108-86-1 bromobenzene 
• 108-88-3 toluene 
• 104-15-4 toluene-4-sulfonic acid 
• 164594-13-2 Phenyl[2-(trimethylsilyl)phenyl]iodonium trifluoromethanesulfonate 
• 91228-44-3 2-thienylphenyliodonium tosylate 

Downstream Products

• 21784-96-3 n-butyl 4-methylphenyl sulfide 
• 91638-69-6 3-methylbutyl p-tolyl sulfide 
• 91485-21-1 1-<(p-methylphenyl)sulfonyl>-3-methylbutane 
• 7402-77-9 4-tosylphenol 
• 32569-84-9 ethoxyethynylbenzene 
• 640-57-3 phenyltolylsulfone 
• 1153-45-3 4-nitrophenyl 4-methylbenzenesulfonate 
• 16634-83-6 2-nitro-toluene-4-sulfonic acid-(4-nitro-phenyl ester) 
• 100-29-8 1-ethoxy-4-nitrobenzene 
• 1216-95-1 p-tolyl p-methoxyphenyl sulfone 
• 108-95-2 phenol 
• 1072-16-8 2,7-dimethyloctane 
• 599-66-6 bis(4-methylphenyl) sulfone 
• 13249-99-5 α-naphthyl p-methylphenyl sulphone 

Relevant academic research and scientific papers

Unprecedented regioselective tosylation studies of 2-ene 4,5,6,7-polyol derived from d-ribose

[DMAPTs]+Cl- was employed as a new facile unprecedented regioselective tosylation procedure for 2-ene 4,5,6,7-polyol derived from d-ribose involving chemoselective ditosylation and regioselective allylic tosyl hydrolysis upon work up with sat. NaCl (brine) solution in a single operation by minimizing the side products obtained under classical regioselective tosylation. The same reagent was also employed for rapid quantitative base free tosylation of aniline, phenol, and 2-naphthol. A tentative mechanism for the afore said regioselective tosylation was also proposed.

Nickel-Catalyzed Photodehalogenation of Aryl Bromides

Herein, we describe a Ni-catalyzed photodehalogenation of aryl bromides under visible-light irradiation that utilizes tetrahydrofuran as hydrogen source. The protocol obviates the need for exogeneous amine reductants or photocatalysts and is characterized by its simplicity and broad scope, including challenging substrate combinations.

Identification of organophosphorus simulants for the development of next-generation detection technologies

Organophosphorus (OP) chemical warfare agents (CWAs) represent an ongoing threat but the understandable widespread prohibition of their use places limitations on the development of technologies to counter the effects of any OP CWA release. Herein, we describe new, accessible methods for the identification of appropriate molecular simulants to mimic the hydrogen bond accepting capacity of the PO moiety, common to every member of this class of CWAs. Using the predictive methodologies developed herein, we have identified OP CWA hydrogen bond acceptor simulants for soman and sarin. It is hoped that the effective use of these physical property specific simulants will aid future countermeasure developments.

Facile synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazides

A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.

Practical Electro-Oxidative Sulfonylation of Phenols with Sodium Arenesulfinates Generating Arylsulfonate Esters

A practical and sustainable synthesis of arylsulfonate esters has been developed through electro-oxidation. This reaction employed the stable and readily available phenols and sodium arenesulfinates as the starting materials and took place under mild reaction conditions without additional oxidants. A wide range of arylsulfonate esters including those bearing functional groups were produced in good to excellent yields. This reaction could also be conducted at a gram scale without a decrease of reaction efficiency. Those results well demonstrated the potential synthetic value of this reaction in organic synthesis.

The Synthesis and Catalytic Activity of New Mixed NHC-Phosphite Nickel(0) Complexes

Herein we describe the synthesis and isolation of the first low-valent NHC-phosphite nickel complexes of general formula Ni(NHC)[P(OAr)3]2. These three-coordinate Ni(0) compounds were fully characterized, including by X-ray crystallography that highlighted their trigonal planar geometry. The representative complex Ni(IMes)[P(OPh)3]2 was used to show that a phosphite ligand is readily substituted in the presence of an aldehyde or nitrile. These stoichiometric studies then led to an investigation of their catalytic properties in the Suzuki-Miyaura cross-coupling reactions between aryl tosylates and aryl boronic acids, a first for such a NHC-Ni catalyst. Finally, mechanistic investigations led to the isolation of a well-defined oxidative addition product.

Quantum Dot-Catalyzed Photoreductive Removal of Sulfonyl-Based Protecting Groups

This Communication describes the use of CuInS2/ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl-protected phenols. For a series of aryl sulfonates with electron-withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD-binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor–acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions.

Palladium-Catalyzed Cyclobutanation of Aryl Sulfonates through both C-O and C-H Cleavage

A palladium-catalyzed cyclobutanation of aryl sulfonates with strained alkenes has been developed. The methodology is featured to achieve the cleavage of both C-O and C-H bonds of phenol derivatives in one pot. Under the reaction conditions, in addition t

Highly-chemoselective step-down reduction of carboxylic acids to aromatic hydrocarbons: Via palladium catalysis

Aryl carboxylic acids are among the most abundant substrates in chemical synthesis and represent a perfect example of a traceless directing group that is central to many processes in the preparation of pharmaceuticals, natural products and polymers. Herein, we describe a highly selective method for the direct step-down reduction of carboxylic acids to arenes, proceeding via well-defined Pd(0)/(ii) catalytic cycle. The method shows a remarkably broad substrate scope, enabling to direct the classical acyl reduction towards selective decarbonylation by a redox-neutral mechanism. The utility of this reaction is highlighted in the direct defunctionalization of pharmaceuticals and natural products, and further emphasized in a range of traceless processes using removable carboxylic acids under mild, redox-neutral conditions orthogonal to protodecarboxylation. Extensive DFT computations were conducted to demonstrate preferred selectivity for the reversible oxidative addition and indicated that a versatile hydrogen atom transfer (HAT) pathway is operable.

Electron Donor-Acceptor Complex Enabled Decarboxylative Sulfonylation of Cinnamic Acids under Visible-Light Irradiation

Visible-light-induced decarboxylative sulfonylation of cinnamic acids with aryl sulfonate phenol esters enabled by the electron donor-acceptor complex is developed. The method offers a mild and green approach for the synthesis of vinyl sulfones with excellent functional group compatibility under photocatalyst and oxidant-free conditions.