Benzoic acid, 4-chloro-, 1,1′-anhydride

General procedure: To a solution of iodine (0.1573 g, 0.62 mmol) in CH2Cl2 (2 mL) was added with triphenylphosphine (0.1626 g, 0.62 mmol) in one portion at 0 oC. Carboxylic acid (0.41 mmol)was subsequently added into the mixture, followed by addition of triethylamine (0.17 mL, 1.23mmol) at 0 oC. The reaction mixture was allowed to warm up to room temperature and stirred until completion of the reaction (typically within 10 min). The crude mixture was concentrated under reduced pressure and then purified by column chromatography (CC) using 5-10percent ethylacetate in hexane to give the desired anhydride product.General procedure: TsCl (0.5 mmol, 0.10 g) was added to the mixture of carboxylic acid (1 mmol) and KGeneral procedure: General procedure: The oxidative self-coupling reaction was carried out in atwo-necked round bottomed ask tted with a condenser under an airatmosphere. In a typical experiment, a mixture of aromatic aldehyde (1 mmol)and CuCl2 (13 mg, 10 mol percent) in MeCN (2 mL) was placed in the ask at roomtemperature. Then, TBHP (in decane (5-6 M), 1.5 equiv) was added to thereaction mixture slowly over a 5 min period, and the mixture was placed in anoil bath with magnetic stirring at 80 °C. After completion (TLC), the reactionmixture was cooled to room temperature and ethyl acetate (10 mL) andaqueous saturated NaHCO3 (10 mL) were added. The organic layer wascollected and dried with Na2SO4. The solvent was removed under reducedpressure. The residue was puried by column chromatography on silica gel(petroleum ether/ethyl acetate, 9:1) to afford the pure product.General procedure: A reaction vessel was charged with a mixture of phenylboronic acid (0.5 mmol), K2CO3 (1.0 mmol), catalyst 2 (0.5 mol %) in toluene (2.0 mL), and stirred for about 20 min under nitrogen atmosphere. Then benzoic anhydride or benzoyl chloride was then added. The mixture was heated to 60 C and incubated in an oil bath at 60 C for 12 h under nitrogen atmosphere. After the completion of the reaction, the mixture was quenched by 5 mL water and then extracted with ethyl acetate (3×10 mL). The combined organic layer was dried over MgSO4. After removal of the solvent in vacuo, the product was obtained by purifying on preparative TLC, eluting with ethyl acetate/petroleum ether and the yield was calculated based on the phenylboronic acid (the purified products were identified by NMR spectra and comparison of the melting points with the literature data). In the recycle experiment, the residue was subjected to a second run of the acylation reaction by charging with the same substrates (benzoic anhydride or benzoyl chloride, phenylboronic acid, dioxane, and K2CO3) without further addition of cyclopalladated catalyst 2.General procedure: Step 1 In a three-necked 100 mL flask under N2-atmosphere, the corresponding benzoic acid (32 mmol) was suspended in anhydrous toluene (21 mL, 1.5 M). A few drops of anhydrous DMF (126 muL, 1.6 mmol, 0.05 equiv) and SOCl2 (3.0 mL, 41.5 mmol, 1.3 equiv) were added atr.t. sequentially. The mixture was heated to 70 C and stirred at this temperature for 1 hour, then cooled to r.t. and the excess SOCl2 was purged from the system by flushing with N2 for 15 min. The solution of the benzoyl chloride was used without purification in the next step. Step 2 In a three-necked flask under N2-atmosphere, the corresponding benzoic acid (32 mmol, 1.0 equiv) was suspended in anhydrous toluene (21 mL, 1.5 M). Anhydrous pyridine (3.1 mL, 38.3 mmol, 1.2 equiv) was added to the mixture and the resulting solution was cooled to0 C. A solution of the corresponding benzoyl chloride from Step 1 was added at such rate that the temperature was kept under 20 C, while a white precipitate formed. The resulting suspension was heated at reflux for 2 h then cooled to r.t. The precipitate (Pyr·HCl) was filtered, washed with toluene, and the filtrate was evaporated. The residue was dissolved in CH2Cl2 (100 mL), washed with 10% HCl (10 mL) then washed with cc. NaHCO3 (3 × 10 mL) and brine (10 mL). The organic layer was dried over Na2SO4, filtered and evaporated to dryness. Pure anhydrides were obtained in 91-98% yield; NMR data were consistent with the reported values.

Molecular Weight:295.1
XLogP3:4.5
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:4
Exact Mass:293.9850495
Monoisotopic Mass:293.9850495
Topological Polar Surface Area:43.4
Heavy Atom Count:19
Complexity:298
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes