II Toluenesulfonate

Related Reagents. Chi Diphenylphosphinate (CuDDP) Cu 3-methylsalicylate (CuMeSal). 

Eduardo Pena-Cabrera Universidad de Guanajuato, Guanajuato, Mexico 

Rodriguez-Cendejas, C. G. Liebeskind, L. S. Pena-Cabrera, E., ARKIVOCimS, (vl), 250. 

Solubility soluble in acetonitrile and many polar solvents. Analysis of Reagent Purity metal content determined by EDTA complexometry using a murexide indicator anion determination using acid cation exchange resin followed by titration of eluted acid with NaOH.  

Preparative Methods readily isolated as a pale-blue hexahydrate complex from aqueous reaction of either / -toluenesulfonic acid and copper(II) carbonate or stoichiometric amounts of silver(I) p-toluenesulfonate and copper(II) chloride dihydrate. The reagent is prepared in situ via reaction of copper oxide and p-toluenesulfonic acid in refluxing CHsCN.  

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The reaction is reversible and reaches equilibrium slowly. Generally, acidic catalysts ate used, such as strong stilfiiric acid, hydrochloric acid, boron trifluotide, and ii-toluenesulfonic acid (27). Batchwise and continuous processes ate used for the esterification reaction. 

Anion Source for Palladium Catalysis. The reagent serves as a source of weakly coordinating anions in the palladium-catalyzed formation of mixed phenyl ureas, a known class of commercially available herbicides, using palladium(II) acetate, copper(II) toluenesulfonate, and 2,2 -dipyridyl as the catalyst system. Other studies have suggested that use of this reagent to form palladium salts may have useful applications in the reductive carbonylation of nitroaromatic compounds to give isocyanates via initial carbamate formation (eq 2). ... 

Similar positive effects could also be achieved by reducing the acid content of iron(III)-toluenesulfonate by ion exchanging. Layers of PEDOT toluene-sulfonate are formed in the course of alcohol evaporation even at room temperature. These layers are practically insoluble and can be rinsed with water to remove iron(II)-toluenesulfonate and excess iron(III) salt. After rinsing and drying, they exhibit an electrical conductivity of up to 1000 S/cm. 

The reaction of 20 g (0.177 mole) of 1,3-cyclohexanedione (Chapter 5, Section II) with 21.8 g (0.22 mole) of maleic anhydride and 0.1 g of/j-toluenesulfonic acid in 150 ml of isopropenyl acetate is conducted as described above to give about 70% of the recrystallized product, mp 156-159°. 

To a solution of 1 g of the mixture of 3-ketal-isomers of compound (II) in 10 cc of acetic anhydride is added a solution of 700 mg of p-toluenesulfonic acid in 7 cc of ecetic anhydride. The reaction mixture is kept at room temperature and under stirring for 5 hours. After some time e crystalline product begins to precipitate and the precipitation is complete by diluting with water. The precipitate is filtered and crystallized from methanol to give 17a-ethynvl-19-nor-testosterone 3,17-diecetate (III), melting point 175°C to 17B°C. 

The exocyclic C — C double bond in the chlorin can be reduced by catalytic hydrogenation in tetrahydrofuran/water in the presence of palladium(II) acetate with triethoxysilane as hydrogen source to yield under kinetic control cw-stereoisomers, which can be transformed by treatment with /)-toluenesulfonic acid in methanol to the thermodynamically favored trans-isomers.27d... 

Polycondensation At room temperature, 0.4% mass of Sn(II) chloride dihydrate (SnCl2-2H20) and 0.4% mass of p-toluenesulfonic acid monohydrate (p-TSA) are introduced into the mixture. The mixture is heated to 180°C under mechanical stirring. The pressure is reduced stepwise to reach 13 mbar, and file reaction is continued for 20 h. The reaction system becomes gradually viscous, and a small amount of L-lactide is formed and refluxed through the reflux condenser. At file end of the reaction, the flask is cooled down, file product is dissolved in chloroform and subsequently precipitated into diethyl ether. The resulting white fibrous solids are filtered and dried under vacuum (average yield 67%). 

Oxazoles have attracted considerable interest due their presence as subunits of several biologically active compoimds or as rigid mimetics of a peptidic ring. A first synthesis of 2-phenyl-4,5-substituted oxazoles 54 [47] was described by microwave-assisted reaction of enolizable ketones with benzoni-trile in the presence of mercury(II) p-toluenesulfonate (Scheme 17). 

Recently, Grubbs138 demonstrated that olefin isomerization of allyl-lic ethers and alcohols is catalyzed by Ru(II)(H20)6(tos)2 (tos = p-toluenesulfonate) in aqueous medium. The olefin migration products, enols, and enol ethers thus generated are unstable and are hydrolyzed instantly to yield the corresponding carbonyl compounds (Eq. 3.34). 

Raghavan and coworkers have reported on the preparation of 4-hydroxybenzoic add esters (parabans) possessing antimicrobial activity by esterification of 4-hydroxybenzoic acid (Scheme 6.153) [299]. Optimum results were obtained using the alcohol (1-butanol) as solvent in the presence of catalytic amounts of zinc(II) chloride or p-toluenesulfonic acid (pTsOH) under atmospheric conditions. After 5 min of microwave irradiation at 120 °C, ca. 40% conversion to the ester was observed. Related studies on the synthesis of long-chain aliphatic esters have been described by Mariani and coworkers [300]. 

Prepare 6-methoxy-l-indanone (I) (JCS 1986(1962)) using polyphosphoric acid made by diluting 500 g of the commercial acid with 120 g 85% phosphoric acid. 2.5 g (I) in 176 ml ether and reflux one hour with 0.27 g lithium aluminum hydride. Cool and carefully add water and filter when bubbling stops (can use Celite filter aid). Dry and evaporate in vacuum and store twelve hours at -15° (under N2 if possible) to precipitate the white 6-methoxy-l-indanol (II) (recrystallize-n-hexane). 2.5 g (II) in 73 ml benzene and reflux one-half hour with 0.2 g p-toluenesulfonic acid. Cool, add water and separate the phases. Extract the aqueous phase with ether and combine with benzene phase and dry, evaporate in vacuum to get 5-methoxy-indene (III) (can distill 110-45/10). 1.53 g (III) and 1.39 g N.N-diethyl-aminoethyl-Cl.HCI in benzene (prepare the free base in benzene as described previously). Reflux four hours with 0.42 g sodamide, cool, wash with water and dry, evaporate in vacuum to get the indene analog of 6-methoxy DET as a dark liquid (can crystallize as oxalate). Alternatively, dissolve 2.51 g (III) in ether and treat (under N if possible) with 12 ml 1.6M buty-Li in hexane at 0-10°. After two hours cool to -30° and add 12 ml more of butyl-Li. Add ether suspension of 2.5 g N,N-diethylaminoethyl-CI. HCI over one-half hour and warm to room temperature. Filter, evaporate in vacuum to get the 6-methoxy-DET analog. 

Under the catalysis of mercury(II) oxide and p-toluenesulfonic acid, allenic /8-keto esters 43 and 45 afforded the furan derivatives 44 and 46 [27]. 

Carbonylation of IBPE and other 2-arylethanols with various organosoluble Pd-catalysts was studied in detail with special emphasis on the role of the promoters p-toluenesulfonic acid and LiCl [55], Some of the catalytic species, such as [PdCl(PPh3)2] formed from [Pd(PPh3)4] or from Pd(II) precursors in aqueous methylethylketone (MEK) under reaction conditions (54 bar CO, 105 °C) were identified by P NMR spectroscopy. Ibuprofen was obtained in a fast reaction (TOP = 850 h" ) with 96% yield (3-IPPA 3.9 %), while the carbonylation of l-(6-methoxynaphtyl)ethanol gave 2-(6-methoxynaphtyl)propionic acid (Naproxen) with high selectivity (97.2 %) but with moderate reaction rates (TOP = 215 h" ). 

II, 20-dione, which is reacted with methylmagnesium bromide in the presence of lithium bromide to give 3a-hydroxy-16a-methylpregnan-ll,20-dione (27.1.39), after which a Ha-hydroxyl group is added. This is done by a reaction with acetic anhydride in the presence of p-toluenesulfonic acid, forming the 3-acetoxy-17-enolacetate 27.1.40, which is epoxidized by perbenzoic acid 27.1.41, and the product is hydrolyzed by an alkali to give an oxyketone... 

Scheme 19. Synthesis of the poly[2]catenand 51b via demetalation of the poly[2]catenate 51a (i) 4-(dimethylamino)pyridine-p-toluenesulfonic acid 1 1 complex plus AT V -diisopro-pylcarbodiimide (ii) KCN, THF.

II, isoidide IM, isomannide IS, isosorbide. p-Toluenesulfonic acid. The exact amount was not determined. 

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