Phenyl tosylate

Sulfur compounds have also been widely studied as activating agents for polyesterification reactions. p-Toluenesulfonyl chloride (tosyl chloride) reacts with DMF in pyridine to form a Vilsmeir adduct which easily reacts with carboxylic acids at 100-120° C, giving highly reactive mixed carboxylic-sulfonic anhydrides.312 The reaction is efficient both for aromatic dicarboxylic acid-bisphenol312 and hydroxybenzoic acid314 polyesterifications (Scheme 2.31). The formation of phenyl tosylates as significant side products of this reaction has been reported.315... 

A great variety of benzo[b]fiirans of type 60 were synthesized by conversion of the corresponding o-(3-hydroxy-3-methylbutynyl)phenyl tosylates in the presence of base (KOH, K2CO,)<96H(43)101>. 

Similarly phenyl tosylates are changed to corresponding hydrocarbons at room temperature and pressure. 

Rates of the alkaline hydrolysis of 12 ortho-, meta- and ) ara-X-substituted phenyl tosylates, 4-MeC6H4S02C6H4X, in aqueous 0.5 m Bu4NBr over a wide temperature range have been analysed using the modified Fujita-Nishioka multi-parameter equation. It was concluded from both these and previously reported data by the same group that solvent electrophilicity was the main factor responsible for changes in the ortho, meta and para polar substituent effects with medium.60... 

Kenner and Murray found that Raney nickel hydrogenation reduces phenyl tosylates to the corresponding hydrocarbons, at room temperature and pressure." Other examples. On the other hand, tosylates of aliphatic alcohols are merely hydrolyzed to the corresponding alcohols. "... 

The reactions discussed so far involved either reaction with nucleophiles or cycload ditions whose mechanisms are reasonably well understood. However, reactions at the I or the ipso-carbon of the phenyl as well as perhaps the a-carbon of the alkyne are possible, as are other reactions whose mechanisms are not yet known. For example, either thermal or photochemical decomposition of 93 results in iodoalkyne (94) and phenyl tosylate (95) (equation 44). Reaction of 96 with 2-lithiofuran (97) resulted in an exchange of carbon ligands and formation of 98 the analogous 2-lithiothiophene (99) gave 100 (equation 45). 

Sttlfone sjmthesh. The reaction of phenyl tosylate with n-butyllithium gives n-butyl p-tolyl sulfone in 85% yield. This synthesis is general for sulfonate esters, and any oiganolithium compound can be used. ... 

The analysis of reaction rate and thermodynamic parameters in the reaction of phenylmagnesium bromide with phenyl tosylate in THF/toluene binary solvents provides support for the asynchronous S a mechanism comprising a four-centre transition state for the sulfonate addition of Grignard reagents. The relative changes in the rate constants are strictly bound to changes in the equilibrium constant for complex... 

Unfortunately, no oxidative addition was found to occur with phenyl tosylate even at refluxing temperatures (Table 8.12, entry 9). The formation of organomanganese tosylates was also confirmed by the subsequent cross-coupling reaction with different electrophiles. The tosylates listed in Table 8.12 reacted with benzoyl chloride to afford the corresponding ketones in moderate to excellent yields (44-86%). Once again, the coupling reaction vras carried out at... 

Although diaryliodonium salts are generally synthesized under transition metal-free conditions, an interesting rhodium- and copper-catalyzed synthesis was recently published. Arenes with N-containing directing groups were reacted with DIB/TsOH to provide aryl(phenyl) tosylates (Scheme 4b) which were chemoselectively applied in various metal-catalyzed transformations [86]. Salts with an oxime ether substituent could be obtained under rhodium- and silver-catalyzed conditions (see Sect. 3.1.2) [86]. 

In the nucleophilic substitution reactions of isopropyl />-substituted benzenesul-fonates with amines in acetonitrile an SNl-type mechanism was favoured. The alkaline hydrolyses of a range of ortho- and para- substituted phenyl tosylates in various solvents from pure water to 80% DMSO have been studied at different temperatures. The results showed that altering the concentration of hydroxide ion affected the activation entropy, especially for the or//jo-isomers. 

Treatment of the Pd(PPF-f-Bu)[P(o-tol)3] 30 with phenyl tosylate in benzene at room temperature formed the resulting phenylpalladium(II) tosylate complex 32 in good yields via an initial dissociation of the P(o-tol)3 ligand creating the more reactive bisphoshine palladium(O) species. The palladium(II) complex, holding the phenyl group cis to the less sterical hindered phosphino group, was produced as the... 

H-Azepine, 2-methyl-1-methoxycarbonyl-rearrangement, 7, 504 1 //-Azepine, 3-methyl-1 -methoxycarbonyl-cycloaddition reactions, 7, 520 IH-Azepine, 1-phenyl-synthesis, 7, 542 1 H-Azepine, N-phthalimido-formation, 7, 508 IH-Azepine, N-sulfonyl-UV spectra, 7, 501 1 H-Azepine, tetrahydromethylene-synthesis, 7, 540 IH-Azepine, N-p-tosyl-protonation, 7, 509 synthesis, 7, 537 3H-Azepine, 3-acyl-2-alkoxy-synthesis, 7, 542-543 3H-Azepine, 3-acyl-2-methoxy-rearrangements, 7, 505 3H-Azepine, 2-alkoxy-hydrolysis, 7, 510... 

Although there is usually a preference for anti elimination in acyclic systems, syn elimination is competitive in some cases. In acyclic systems, the extent of anti versus syn elimination can be determined by use of stereospecifically deuterated substrates or by use of diastereomeric reactants which will give different products by syn and anti elimination. The latter approach showed that elimination from 3-phenyl-2-butyl tosylate is a stereospecific anti process. ... 

On the contrary, tnfluoromethyl groups severely impede Sj l or reactions when located a to the reaction site. However, aminolysis of l-phenyl-2,2,2,-tri-fluoroethyl tosylate [Sd] and tnfluoroethyl chloride [ST] and its corresponding nonaflate [SS] can be performed under severe conditions (equation 76). 

Abbreviations aapy, 2-acetamidopyridine Aik, alkyl AN, acetoniuile Ar, aryl Bu, butyl cod, 1,5-cyclooctadiene COE, cyclooctene COT, cyclooctatetraene Cp, cyclopentadienyl Cp , penta-methylcyclopentadienyl Cy, cyclohexyl DME, 1,2-dimethoxyethane DME, dimethylformamide DMSO, dimethyl sulfoxide dmpe, dimethylphosphinoethane dppe, diphenylphosphinoethane dppm, diphenylphosphinomethane dppp, diphenylphosphinopropane Et, ethyl Ec, feirocenyl ind, inda-zolyl Me, methyl Mes, mesitylene nb, norbomene orbicyclo[2.2.1]heptene nbd, 2,5-norbomadiene OTf, uiflate Ph, phenyl PPN, bis(triphenylphosphoranylidene)ammonium Pi , propyl py, pyridine pz, pyrazolate pz, substituted pyi azolate pz , 3,5-dimethylpyrazolate quin, quinolin-8-olate solv, solvent tfb, teti afluorobenzobaiTelene THE, tetrahydrofuran THT, tetrahydrothiophene tmeda, teti amethylethylenediamine Tol, tolyl Tp, HB(C3H3N2)3 Tp , HB(3,5-Me2C3HN2)3 Tp, substituted hydrotiis(pyrazol-l-yl)borate Ts, tosyl tz, 1,2,4-triazolate Vin, vinyl. 

Two closely related indoles fused to an additional saturated ring have been described as CNS agents. The first of these is obtained in straightforward manner by Fischer indole condensation of functionalized cyclohexanone 0 with phenyl hydrazine (19). The product, cyclindole (21) shows antidepressant activity. The fluorinated analogue flucindole (26) can be prepared by the same scheme. An alternate route starting from a somewhat more readily available intermediate involves as the first step Fischer condensation of substituted phenyl hydrazine with 4-hydroxycyclohexanone (23). The resulting alcohol (24) is then converted to its tosylate (25). Displacement by means of dimethyl amine leads to the antipsychotic agent flucindole (26). ... 

It was of interest to determine whether glycosides of 6-deoxy-D-xylo-hex-5-enopyranose were susceptible to enzyme hydrolysis by / -glucosi-dase. Since aromatic glucosides are hydrolyzed by this enzyme at a much faster rate than aliphatic glycosides, phenyl 6-deoxy-/ -D-rt/Zo-hex-5-enopyranoside (18) was prepared (20). Phenyl / -D-glucopyranoside was converted to the 6-tosylate by selective esterification and then, by conventional procedures, transformed to phenyl 2,3,4-tri-0-acetyl-6-deoxy-... 

The tosylate of (2>RP35)-3-phenyl-2-butanol undergoes E2 elimination on treatment with sodium ethoxide to yield (Z)-2-pheny)-2-butene. Explain, using Newman projections. 

In light of your answer to Problem 11.49, which alkene, E or Z, would you expect from an E2 reaction on the tosylate of (2/ ,3R)-3-phenyl-2-butanol Which alkene would result from E2 reaction on the (25,3 P) and (25,35) tosy-lates Explain. 

Alkalimetallhydride reduzieren nicht. Man isoliert ausschlieBlich Olefine22. Bei der Umsetzung von Cyclo-hexanon-N-phenyl-N-tosyl-hydrazon mit Lithiumhydrid erhalt man die Azo-Stufe der Bamford-Stevens-Reaktion unter Bildung von Phenylazo-cyclohexen1. ... 

Methoxymcthoxy-l-tosyl-3- phenyl-azetidin > 3-Melhoxymethoxy-3-phenyl-azetidin 69% d.Th. 

Pyrrolidino-1 -(2-cyan-athyl)- 560 2-Pyrrolidino-l-methyl- 560 Tosylhydrazono- 371 4 -T osylhydrazono -1 - tert. -b u tyl - 36 9 (Tosyl-phenyl-hydrazono)- 368... 

The following abbreviations are commonly used for substituent groups in structural formulae Ac (acetyl), Bn or PhCH2 (benzyl), Bz or PhCO (benzoyl), Et (ethyl), Me (methyl), Me3Si (not TMS) (trimethylsilyl), Bu Me2Si (not TBDMS) (rerf-butyldimethylsilyl), Ph (phenyl), Tf (triflyl = trifluoromethanesulfonyl), Ts (tosyl = toluene-p-sulfonyl), Tr (trityl). 

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