363-30-4

Upstream product

• 393-52-2 2-Fluorobenzoyl chloride 
• 108-95-2 phenol 
• 445-29-4 o-fluoro-benzoic acid 
• 98-80-6 phenylboronic acid 
• 100-66-3 methoxybenzene 

Downstream Products

• 3892-68-0 (2-fluoro-benzoyl)-sulfanilyl-amine 
• 108-95-2 phenol 
• 445-29-4 o-fluoro-benzoic acid 
• 1677-27-6 3H-1,2-benzodithiol-3-one 

Relevant academic research and scientific papers

Conversion of esters to thioesters under mild conditions

We report conversion of esters to thioestersviaselective C-O bond cleavage/weak C-S bond formation under transition-metal-free conditions. The method is notable for a general and practical transition-metal-free system, broad substrate scope and excellent functional group tolerance. The strategy was successfully deployed in late-stage thioesterification, site-selective cross-coupling/thioesterification/decarbonylation and easy-to-handle gram scale thioesterification. Selectivity and computational studies were performed to gain insight into the formation of weak C-S bonds by C-O bond cleavage, which contrasts with the traditional trend of nucleophilic additions to carboxylic acid derivatives.

Enol Ester Intermediate Induced Metal-Free Oxidative Coupling of Carboxylic Acids and Arylboronic Acids

A facile, efficient and environmentally friendly methodology for the preparation of phenolic esters is realized via metal-free coupling of carboxylic acids and arylboronic acids. This sequential one pot reaction, employing methyl propiolate as an activating reagent, proceeds through the formation of enol ester intermediate, followed by a nucleophilic attack on the C-O bond under the oxidation of hydrogen peroxide. These studies display that enol esters, despite previously being overlooked as synthetic intermediates, would be the valuable building blocks for developing carbon–carbon and carbon–heteroatom bond-forming reactions.

Evaluation of the role of isostructurality in fluorinated phenyl benzoates

In this report, the occurrence of three-, two-, and one-dimensional (3D, 2D, and 1D) isostructurality in phenyl benzoate (D00) and their fluorinated analogues was investigated in terms of their molecular assembly in solid state structures. A onedimensional C-H?O=C chain is observed as a robust motif (～ -21 kJ/mol) in the formation of the supramolecular architectures in these isostructural compounds. The isomorphous crystal structures exhibit 3D isostructurality or vice versa. The crystal packing shows that weak intermolecular C-H ? F, C-H ? O, C- H ? π interactions, and π ? π stacking are the main contributors providing stability toward the crystal lattice. The nature and energetics of all the geometrically or energetically equivalent building blocks associated with similar or different intermolecular interactions delineate the role of different molecular pairs in the crystal structures. The fingerprint plots of the isostructural set of crystal structures help to understand the similarities and the differences in the various interatomic contacts. A comparison of these crystal structures with fluorinated N-phenyl benzamides shows the change in supramolecular assembly in terms of intermolecular interactions as well as the lattice energy due to the participation of a strong donor (N-H).

Erbium trifluoromethanesulfonate catalyzed Friedel-Crafts acylation using aromatic carboxylic acids as acylating agents under monomode-microwave irradiation

Erbium trifluoromethanesulfonate is found to be a good catalyst for the Friedel-Crafts acylation of arenes containing electron-donating substituents using aromatic carboxylic acids as the acylating agents under microwave irradiation. An effective, rapid and waste-free method allows the preparation of a wide range of aryl ketones in good yields and in short reaction times with minimum amounts of waste.

Rational design and bioimaging applications of highly selective fluorescence probes for hydrogen polysulfides

Reactive sulfur species have received considerable attention due to their various biological functions. Among these molecules, hydrogen polysulfides (H2Sn, n > 1) are recently suggested to be the actual signaling molecules derived from hydrogen sulfide (H2S). Hydrogen polysulfides may also have their own biosynthetic pathways. The research on H2Sn is rapidly growing. However, the detection of H 2Sn is still challenging. In this work we report a H 2Sn-mediated benzodithiolone formation under mild conditions. Based on this reaction, specific fluorescent probes for H 2Sn are prepared and evaluated. The probe DSP-3 shows good selectivity and sensitivity for H2Sn.

Palladium-catalyzed aerobic oxidative coupling of acyl chlorides with arylboronic acids

The first example of a palladium-catalyzed aerobic oxidative coupling of acyl chlorides with arylboronic acids has been developed, leading to a wide range of aryl benzoates in good to excellent yields. This catalytic system shows broad functional group tolerance. Preliminary mechanistic experiments using deuterium labeling showed that the oxygen atom was derived from dioxygen. Copyright

Kinetic study of hydrolysis of benzoates. Part XXV. Ortho substituent effect in alkaline hydrolysis of phenyl esters of substituted benzoic acids in water

The second-order rate constants k2 for alkaline hydrolysis of phenyl esters of meta-, para-and ortho-substituted benzoic acids, X-C 6H4CO2C6H5 (X = H, 3-Cl, 3-NO2, 3-CH3, 4-NO2, 4-Cl, 4-F, 4-CH 3, 4-OCH3, 4-NH2, 2-NO2, 2-CN, 2-F, 2-Cl, 2-Br, 2-I, 2-CH3, 2-OCH3, 2-CF3, 2-NH2), and of substituted phenyl esters of benzoic acid, C 6H5CO2C6H4-X (X = 2-I, 2-CF3, 2-C(CH3)3, 4-Cl, 4-CH3, 4-OCH3, 4-NH2), have been measured spectrophotometrically in water at 25 °C. The substituent effect in alkaline hydrolysis of phenyl esters of para-substituted benzoic acids, similar to that for ethyl esters of para-substituted benzoic acids, was found to be precisely described by the Hammett relationship (p = 1.7 in water). The log k value for alkaline hydrolysis of phenyl and ethyl esters of meta-, para- and ortho-substituted benzoic acids, X-C6H4CO2R, was nicely correlated with log km,p,ortho = log ko + (ρ)m,pσ + (ρI)orthoσI + (ρ° R)orthoσ°R + δ orthoΕsB where σ, σI, σ°R are the Hammett polar, Taft inductive and Taft resonance (σ°R = σ° - σI) substituent constants, respectively. Ε SB is the steric scale for ortho substituents calculated on the basis of the log k values for the acid hydrolysis of ortho-substituted phenyl benzoates in water owing to the ortho substituent in the phenyl of phenyl benzoates. In water, the main factors responsible for changes in the ortho substituent effect in alkaline hydrolysis of phenyl and ethyl esters of ortho-substituted benzoic acids, X-C6H4CO2R, were found to be the inductive and steric factors while the role of the resonance term was negligible ((ρ°R)ortho ca. 0.3). In alkaline hydrolysis of substituted benzoates in neat water, the ortho inductive effect appeared to be 1.5 times and steric influence 2.7 times higher than the corresponding influences from the ortho position in the phenyl of phenyl benzoates. The contributions of the steric effects in alkaline hydrolysis of esters of ortho-substituted benzoic acids was found to be approximately the same as in acid hydrolysis of esters of ortho-substituted benzoic and acid esterification of ortho-substituted benzoic acids.