2-thiophenoxides

The process implications of equation 3 go beyond the weU-known properties (27—29) of NMP to faciUtate S Ar processes. The function of the aminocarboxylate is also to help solubilize the sulfur source anhydrous sodium sulfide and anhydrous sodium hydrogen sulfide are virtually insoluble in NMP (26). It also provides a necessary proton acceptor to convert thiophenol intermediates into more nucleophilic thiophenoxides. A block diagram for the Phillips low molecular weight linear PPS process is shown in Eigure 1. 

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. ... 

Fluoro- or 2,2-difluoro-l-bromoalkanes readily undergo nucleophilic substitution in the presence of sodium thiophenoxide [45] (equation 41)... 

Condensation of thiophenoxide anions with various fluonnated polychloro- or polybromoethanes gives fluoroalkyl phenyl sulfides [57, 52, 55], These formal substitutions involve fluonnated olefins as intermediates [52, 55], In the case of perhalogenated ethanes, the mechanism shows a similarity with that of dihalo-genodifluoroinethane [52] (equations 46 and 47)... 

Thiophenol, TEA, DMF or dioxane." In the case of dimethyl phosphonates, this method can be used to remove selectively only one methyl group. Lithium thiophenoxide is also effective. ... 

The trichloro derivative reacts rapidly at room temperature with sulfide, hydrosulfide, alkylmercaptide, or thiophenoxide ions in the solid phase, in water, or in organic solvents. 

The above product was dissolved in dimethylformamide (65 ml), sodium thiophenoxide (0.89 g) was added thereto, and the resultant mixture was stirred at room temperature for 1 hour. To the resultant mixture, acetone (650 ml) was added, and the separated crystals were collected by filtration and washed with acetone and ether in order to give the objective compound in the form of the sodium salt (1.3 g). 

I n the above procedure, the use of 4-hydroxy-1,5-naphthyridine-3-carbonyl chloride in place of 4-hydroxy-1,5-naphthyridine-3-carboxyllc acid N-succinimide ester can also afford the same objective compound as above. The use of sodium thio-n-propoxide in place of sodium thiophenoxide can also give the objective compound in the form of the sodium salt. 

Interests in the phase transfer catalysis (PTC) have grown steadily for the past several years [68-70]. The use of PTC has recently received industrial importance in cases where the alternative use of polar aprotic solvents would be prohibitively expensive [71-74]. Thus, the potential application of the phase transfer catalyzed aromatic nucleophilic displacement reactions between phenoxide or thiophenoxide and activated systems has... 

As expected, the addition of arenediazonium ions to thiophenols does not involve the thiophenol molecule, but rather the thiophenoxide ion (Price and Tsunawaki, 1963). Dediazoniation with the formation of a diarylsulfide (6.16) is competitive with the formation of the diazo thioether 6.15 (Scheme 6-9 van Zwet et al., 1970). Whereas the early investigators detected only one isomer, (Z)- and (ii)-forms were... 

Since both reactions form phenol, Bunnett coined the phrase ad eundem competition, from the Latin, meaning (leading) to the same (product, singular). As such, a product ratio cannot allow the determination of h2oAoh However, if one adds thiophenoxide ion, PhS-, as a third competing reagent for benzyne, then diphenyl sulfide is formed,... 

The softer, less basic potassium bromide and iodide did not react with the thiirene dioxide 19b. The latter was also inert towards potassium thiocyanate, selenocyanate or nitrile. It did react, however, with potassium thiophenoxide in DMF at room temperature to yield, most probably, the vinyl sulfmate 138 isolated as the corresponding sulfone39 (equation 56). 

Owing to the reversible nature of the allylic sulfenate/allylic sulfoxide interconversion, the stereochemical outcome of both processes is treated below in an integrated manner. However, before beginning the discussion of this subject it is important to point out that although the allylic sulfoxide-sulfenate rearrangement is reversible, and although the sulfenate ester is usually in low equilibrium concentration with the isomeric sulfoxide, desulfurization of the sulfenate by thiophilic interception using various nucleophiles, such as thiophenoxide or secondary amines, removes it from equilibrium, and provides a useful route to allylic alcohols (equation 11). 

Carboxylic acids, a-bromination of 55, 31 CARBOXYLIC ACID CHLORIDES, ketones from, 55, 122 CARBYLAMINE REACTION, 55, 96 Ceric ammonium nitrate [Ammonium hexa mtrocerate(IV)[, 55, 43 Chlorine, 55, 33, 35, 63 CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Cinnamomtnle, a-phenyl- [2-Propeneni-tnle 2,3-diphenyl-], 55, 92 Copper(l) iodide, 55, 105, 123, 124 Copper thiophenoxide [Benzenethiol, copper(I) salt], 55, 123 CYCLIZATION, free radical, 55, 57 CYCLOBUTADIENE, 55, 43 Cyclobutadieneiron tricarbonyl [Iron, tn-carbonyl(r)4-l,3-cyclo-butadiene)-], 55,43... 

Lithium, methyl, 55,7, 10 Lithium, phenyl-, 55,11 Lithium phenylthio(alkyl)cuprates, 55,122 LITHIUM, phenyltluo(fe/f-butyl)cuprate [Lithium, phenylthio( 1,1 -dimethyl-ethyl)cupiate, 55,122 Lithium, 1-propenyl-, 55, 111 LITHIUM, ( >l-propenyl-, 55, 103 Lithium thiophenoxide [Ben7enethiol, lithium salt], 55, 122... 

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... 

N-benzyl-N-phenethyl-N,N-dimethylammonium chloride loses predominantly benzyl when heated with thiophenoxide, giving stable N,N-dimethylphenethylamine (47) ... 

A more elaborate spiroquinolizidine unit 463 was obtained by simply heating a basic thiophenoxide solution of thioether 461, presumably by addition-elimination of thiophenoxide to give 462, which then cyclized by a second addition-elimination sequence involving the piperidine nitrogen atom, giving 463, an advanced intermediate, in a total synthesis of ( )-halichlorine (Scheme 110) <2004PNAS12079>. 

Nucleophilic substitution reactions in the selenophene series have attracted some interest. Debromination of bromonitro compounds [(50, X = S, Se) and (53, X = S, Se)] with sodium thiophenoxide and sodium selenophen-oxide72 was studied. Selenophene compounds were four times more reactive than the thiophene derivatives. The position of attack, a or /), had very little influence on the rate ratio. The kinetics of the side-chain nucleophilic reactions of selenophene derivatives, shown in Scheme 4, has been reported.7 3... 

Oximes 509 can be converted to their tosylates 510, but use of a large excess of KOH converts them directly into 27/-azirincs 511 (Scheme 82) <2003JOC9105>. The benzotriazolyl moiety in azirines 511 can be substituted by nucleophiles (organomagnesium reagents, potassium phthalimides, and sodium thiophenoxide) to give disubstituted azirines 512. 

In the presence of sodium thiophenoxide, elemental sulfur reacts with 4 or 1 to afford 1,2,4,5-tetrathianes. Huisgen116 suggested a mechanism where the oligothiolate species PhSx attacks the thione carbon as an initial step. 

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