Thiophenoxides arylation

EtSNa, DMF, reflux, 3 h, 94-98% yield.Potassium thiophenoxide has been used to cleave an aryl methyl ether without causing migration of a double bond. odium benzylselenide (PhCH2SeNa) and sodium thiocre-solate (p-CH3C6H4SNa) cleave a dimethoxyaryl compound regioselec-tively, reportedly as a result of steric factors in the former case and electronic factors in the latter case. ... 

CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Chrysene, 58,15, 16 fzans-Cinnamaldehyde, 57, 85 Cinnamaldehyde dimethylacetal, 57, 84 Cinnamyl alcohol, 56,105 58, 9 2-Cinnamylthio-2-thiazoline, 56, 82 Citric acid, 58,43 Citronellal, 58, 107, 112 Cleavage of methyl ethers with iodotri-methylsilane, 59, 35 Cobalt(II) acetylacetonate, 57, 13 Conjugate addition of aryl aldehydes, 59, 53 Copper (I) bromide, 58, 52, 54, 56 59,123 COPPER CATALYZED ARYLATION OF /3-DlCARBONYL COMPOUNDS, 58, 52 Copper (I) chloride, 57, 34 Copper (II) chloride, 56, 10 Copper(I) iodide, 55, 105, 123, 124 Copper(I) oxide, 59, 206 Copper(ll) oxide, 56, 10 Copper salts of carboxylic acids, 59, 127 Copper(l) thiophenoxide, 55, 123 59, 210 Copper(l) trifluoromethanesulfonate, 59, 202... 

See also ALKANETHIOLS, ALKENEBIS(SULFONIUM PERCHLORATES) allyl trifluo-ROMETHANESULFONATES, ARENEDIAZO ARYL SULFIDES BIS(ARENEDIAZO) sulfides, BIS(SULFURDIIMIDES DIAZONIUM SULFATES, DIAZONIUM SULFIDES AND DERIVATIVES METAL AMIDOSULFATES, METAL PHOSPHORUS TRISULFIDES METAL SULFATES, METAL SULFIDES, NON-METAL SULFIDES SULFONIC ACID ESTERS, SULFUR BLACK, SULFUR ESTERS THIOPHENOXIDES, XANTHATES ... 

Of particular interest was the reaction of two equivalents of potassium phthalimide with PFB using 18-crown-6 in refluxing acetonitrile. This reaction with either small molecules or the polymeric analogs represents a novel approach to arylimide synthesis via PTC. After 4 hr. under nonoptimized PTC reaction conditions, disubstitution afforded the bisimide 6 in ca. 50% yield. This shows that phthalimide anion, a considerably poorer nucleophile than either the phenoxide or thiophenoxide, is a strong enough nucleophile in the presence of 18-crown-6 to displace aryl fluoride with facility, and demonstrates that the synthesis of polyimides, an important class of thermally stable polymers, is feasible by this PTC polycondensation route. 

In the reaction of activated aryl halides with phenoxide and thiophenoxide in chloro- or o-dichloro-benzene at reflux, pyridinium salts (48 R, R = —-CH2CH2CHMeCH2CH2— R = Me, Bu", n-C6Hi3 R = CH2CHEtBu, CH2BU1) proved to be superior catalysts to simpler onium salts, like TBAB, due mainly to their greater thermal stability.162... 

Interaction of 2-, 3- or 4-chlorobenzenediazonium salts with (9-alkyldithiocarbon-ate ( xanthate ) solutions [8] or thiophenoxide solutions [9] produces explosive products, possibly arenediazo aryl sulfides. The intermediate diazonium xanthate produced during the preparation of m-thiocresol can be dangerously explosive under the wrong conditions [8], while the reaction of 3-nitrobenzenediazonium chloride with xanthate solution at 70—75°C proceeds with near-explosive evolution of nitrogen [4]. The product of interaction of 2-chlorobenzenediazonium chloride and sodium 2-chlorothiophenoxide exploded violently on heating to 100°C, and the oil... 

Sodium thiophenoxide and bis phenyliodonium acetylene triflate afforded cleanly l,2-bis(phenylthio)acetylene [6]. Alkynyl iodonium salts have alkynylated several arene sulphonates which were converted into alkynyl aryl sulphones. The process is probably the best among other methods, as far as yield, availability of starting materials, non-toxicity and ease of handling are concerned. 

Unconjugated thioethers are not reducible in aqueous solution in aprotic solvents alkyl aryl sulfides, ArSR, are reducible at relatively negative potentials ( —2.5 V (SCE)) [118] with C-S cleavage to ArS and R- the latter may be reduced further. Reduction of diphenylsulfide gives equal amounts of benzene and thiophenoxide ion ... 

Aryl triflates have been used to generate arynes via other routes than metal-halogen exchange. For example, fluoride ion displacement of the trimethylsilyl group in 26 provides a convenient route to benzyne under mild conditions. The required benzyne precursor 26 was prepared from o-trimethylsilylphenoxytrimethylsilane by sequential treatment with BuLi and (Tf)20. Analogous aryne precursors have also been prepared less directly, as in the case of amide benzyne 31. Examples of 32 include various methylfurans, diphenylsobenzofuran and tetraphenylcyclopentadienone. Examples of nucleophiles include methanol, phenol, lithium thiophenoxide and others. 

Cleavage of esters, ethers, and lactones. The reagent resembles CsHaSLi (3, 188 5, 415) and CaHsSNa (4, 465) in reactivity for cleavage of hindered esters and methyl aryl ethers. In addition it cleaves lactones to methylthio carboxylic acids an example is the conversion of butyrolactone to CHGSCH2CH2CH2COOH in 69% yield. A direct comparison indicates that this reagent is superior to lithium thiophenoxide for cleavage of the lactone 1 to 2. 

Selective N-dealkylation in the presence of N-aryl linkages may be induced by pyridine hydrochloride, and selective N-debenzylation by thiophenoxide anion. ... 

Early work performed by Lenz et al. in the 1960s demonstrated this approach by using electrophilic aromatic substitution to produce poly(phenylene sulfide) [91] (Scheme 1.10). In this case, an aryl halide is the electrophile, which is substituted by the metal thiophenoxide nucleophile. In the monomer, the metal sulfide is a strong electron-donating group, which deactivates the para position where electrophilic substitution must take place. Conversely, the polymer chain end is only weakly deactivated by the sulfide bond, rendering the polymeric aryl halide more reactive than the monomeric aryl halide. Unfortunately, Lenz was unable to characterize molecular weight distribution due to the insolubility of the resultant polymers. 

Nitrophenyl l-thio-P-o-mannopyranoside has been synthesized by reaction of acetochloromannose [207] or the mannosyl bromide 2 [202] with the sodium salt of 4-nitrothiophenol. A similar reaction between sodium thiophenoxide and aceto-bromomannose in HMPT gives phenyl 1-thio-P-D-mannopyranoside quantitatively [208]. In a related reaction the sodium salt of 1-thio-P-D-mannopyranose has been alkylated with benzyl bromide as in Schmidt s approach (Section 13.2.4) to give benzyl P-thiomannoside in 86% yield [209]. P-Linked 1-thiomannopyranosides can also be prepared by BFs-catalyzed anomerization of the readily available a-anomers [46]. The Lindberg protocol has also been used for the synthesis 1-thio-P-D-mannopyranosides [146, 149]. Aryl 1-thio-p-mannofuranosides have been syn-... 

In 2010, Ueda and Hartwig reported on an iridium-catalyzed asymmetric allylation of sodium sulfinates 345 to branched allylic sulfones 348 with high regioselectivities and enantioselectivities (Scheme 46.40). Notably, the reaction proceeded with a broad range of acyclic allylic carbonates 346 and aryl and alkyl sodium sulfinates 345. Most recently, Zhao et al. developed the catalytic asymmetric allylic alkylations of acyclic allylic carbonates 346 using sodium thiophenoxide and alkyl thiolates 348 to give good-to-excellent selectivities for branched products 350 with excellent enantioselectivities. 

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