57606-64-1Relevant articles and documents
Effect of charged and ortho substituents on 17O NMR chemical shifts of substituted phenyl tosylates in DMSO
Nummert, Vilve,Piirsalu, Mare,Toom, Lauri,Kesvatera, T?nu,Leito, Ivo,Koppel, Ilmar A.
, (2018/07/31)
The 17O nuclear magnetic resonance chemical shifts for 31 ortho-substituted, para-substituted, and meta-substituted phenyl esters of 4-methylbenzenesulfonic acid (phenyl tosylates, 4-CH3-C6H4SO2OC6H4-X) with the neutral and charged substituents in phenoxy part were measured in DMSO-d6 at 50°C. The chemical shifts, δ(17O), of the sulfonyl (SO2) and single-bonded phenoxy (O─Ph) oxygens for para and meta derivatives in the case of neutral substituents showed a good correlation with the Taft σI and σ°R substituent constants. The influence of the ortho substituents on the δ(17O) chemical shifts of the sulfonyl oxygens and single-bonded phenoxy oxygens was found to be described well with the Charton equation: δ(17O)ortho?=?δ(17O)H?+?ρI σI?+?ρRσ°R?+?δEBs when the data treatment was performed separately for electron-donating +R substituents and electron-withdrawing ?R substituents. The substituent constants, σ°X±, for the charged substituents (4-N+(CH3)3I?, 3-N+(CH3)3I?, 2-N+(CH3)3I?, 4-COO?N+Bu4, 3-COO?N+Bu4, 2-COO?N+Bu4) calculated from the δ(17O) chemical shifts for phenyl tosylates in DMSO prove that in DMSO, the compounds involving charged substituents are predominantly in ion pair form and not dissociated into free ions. The same conclusion was drawn recently from the carbonyl IR stretching frequencies, νCO, and the carbonyl carbon 13C chemical shifts for substituted phenyl benzoates, C6H5CO2C6H4-X, in DMSO. It was shown that for ion pairs of the charged substituents in DMSO and concentrated aqueous salt solution, the same substituent constant, σ°X±, could be used.
Direct Carboxylation of Aryl Tosylates by CO2 Catalyzed by in situ-Generated Ni0
Rebih, Fatima,Andreini, Manuel,Moncomble, Aurlien,Harrison-Marchand, Anne,Maddaluno, Jacques,Durandetti, Muriel
supporting information, p. 3758 - 3763 (2016/03/08)
A novel Ni0-catalyzed carboxylation of aryl tosylates with carbon dioxide has been achieved under moderate temperatures and atmospheric pressure. In this procedure, the active Ni0 species is generated in situ by simply mixing the Ni0 precatalyst [NiBr2(bipy)] with an excess of manganese metal. This approach requires neither a glove-box nor the tedious preparation of sophisticated intermediate organometallic derivatives. This mild, convenient, and user-friendly process is successfully applied to the valorization of carbon dioxide and the synthesis of versatile reactants with broad tolerance of substituents.
Dimerization of Aryl Sulfonates by in situ Generated Nickel(0)
Maddaluno, Jacques,Durandetti, Muriel
supporting information, p. 2385 - 2388 (2015/10/19)
A mild and user-friendly nickel-catalyzed method for the reductive homocoupling of aromatic tosylates is presented. The reaction proceeds between room temperature and 60 °C, with stable substrates (ArOTs) easily prepared from inexpensive and commercially available phenols or naphthols. It relies on a catalytic amount (10 mol%) of a robust catalyst (NiBr2bipy) that does not require the preparation of sensitive organometallic intermediates. Yields are good to excellent.
New preparative method of aryl tosylates by using organobismuth reagents
Sakurai, Naoto,Mukaiyama, Teruaki
, p. 928 - 929 (2008/02/12)
A new method for the preparation of aryl tosylates by using pentavalent bismuth is described. Treatment of 10-arylphenothiabismine 5,5-dioxides, m-chloroperoxybenzoic acid (MCPBA) and p-toluenesulfonic acid monohydrate in dichloromethane affords aryl tosy
A new preparative method of aryl sulfonate esters by using cyclic organobismuth reagents
Sakurai, Naoto,Mukaiyama, Teruaki
, p. 771 - 790 (2008/09/18)
A new method for the preparation of aryl sulfonate esters by using a cyclic pentavalent bismuth is described. Aryl sulfonate esters are formed in good to high yields by treating 10-arylphenothiabismine 5,5-dioxides, m-chloroperoxybenzoicacid (m-CPBA)and various sulfonic acids in dichloromethane.
Graphite/methanesulfonic acid (GMA) as a new reagent for sulfonylation of phenols and thia-Fries rearrangement of aryl sulfonates to sulfonylphenols
Sharghi, Hashem,Shahsavari-Fard, Zahra
, p. 42 - 52 (2007/10/03)
A new facile method for direct sulfonylation of phenols was developed. Graphite in methanesulfonic acid (GMA) was used to prepare sulfonylphenols by sulfonylation of phenol and naphthalene derivatives with p-toluenesulfonic acid (=4-methylbenzenesulfonic acid) (Table 1) and the thia-Fries rearrangement of aryl sulfonates (Table 4). Mechanistic studies showed that the sulfonylation reaction of phenols in GMA occurred through an initial sulfonate formation followed by a thia-Fries rearrangement of the aryl sulfonate by an intermolecular mechanism (Scheme 3).
