Methyl p-toluenesulfinate

C=0 group, or sp3 carbon. This last point can perhaps be best appreciated by comparing the rate of-alkaline hydrolysis of methyl p-toluenesulfinate (140) (Bunton and Hendy, 1962) with the rate of alkaline hydrolysis of methyl p-toluate (141) (Jafife, 1953) under the same conditions. One sees that the... 

All of the reactions so far mentioned involved as nucleophiles either organometallic reagents or one, PhNH-, that is much more basic than any of those in Table 6. That complete inversion is also the stereochemical course of a substitution involving a rather weak nucleophile has also been neatly demonstrated by Mikolajczyk et al. (1979). In the presence of a small amount of an acid catalyst optically active,, 4C-labeled methyl p-toluenesulfinate undergoes exchange with methanol as shown in (151), a process that also... 

The checkers find that this wash eliminates methyl p-toluenesulfinate as a contaminant in the crude product. 

Methyl sesamol, 353, 354 3-Methylsulfonyl-2,5-dihydrofurane, 270 Methylthiotrimethylsilane, 113 Methyltitanium trichloride, 270-271 (S)-(—)-Methyl p-toluenesulfinate, 405 l-Methyl-2-trimethylsiloxy-l, 3-butadiene, 271-272... 

Methyl p-toluenesulfinate, ( )-CH3Ce,HiSOCH3. Mol. wt. 170.23, b.p. 129-130°/ 14 mm. Caution The reagent can cause a persistent skin rash. 

THIOLS Sodium borohydride, sulfurated. a,p-TOLUENESULFINYL KETONES Methyl p-toluenesulfinate. 

A. Ethyl N- p-tolylsulfonylmethyl)carhamate,[Carbamic acid, (4 -methyl-phenylsulfonylmethyl)-, ethyl ester]. A solution of 178 g. (1.0 mole) of sodium p-toluenesulfinate (Note 1) in 1 1. of water is placed in a 3-1., three-necked daak, equipped with a condenser, an efficient mechanical stirrer, and a thermometer. After addition of 100 ml. (108 g.) of a 34—37% solution of formaldehyde ca. 1.2-1.4 moles) (Note 2), 107 g. (1.2 moles) of ethyl carbamate (Note 3), and 250 ml. of formic acid (Note 4), the stirred solution is heated to 70°. Soon after this temperature is reached, the reaction mixture becomes turbid by separation of the... 

Esterification of p-toluenesulfinic acid with (- )-menthol gives a mixture of two diastereomers, which equilibrate to the pure (-)-menthyl (S)-p-toluenesulfinate diastereomer in the presence of hydrochloric acid (80% yield). The report includes an improved procedure for reaction of 1 with CH,MgI to give (R)-( + )-methyl p-tolyl sulfoxide.1... 

Neopentyl tosylate p-Toluenesulfinic acid, neopentyl ester (8) Benzenesulfinic acid, 4-methyl-2,2-dimethylpropyl ester (9) (13146-08-2)... 

The method was used in studies of a fungal heterogalactan.150 The polysaccharide was subjected to successive tritylation, methylation, detritylation, p-toluenesulfonylation, reaction with sodium iodide, and, finally, reaction with sodium p-toluenesulfinate. The product was then treated with sodium methylsulfinyl carbanion in dimethyl sulfoxide, the product remethylated, and the polysaccharide material recovered by gel chromatography. The polymer was hydrolyzed, and the sugars in the hydrolyzate were analyzed, as the alditol acetates, by g.l.c.-m.s.1 The analysis revealed that —60% of the hexose residues that were unsubstituted at C-6 had been eliminated. As the product was still polymeric, it was concluded that these residues had constituted a part of side chains linked to a main chain of (1 — 6)-linked D-galactose residues. 

SULFINIMINES (THIOOXIMINE S-OXIDES) ASYMMETRIC SYNTHESIS OF METHYL (R)-(+)- 3-PHENYLALANATE FROM (S)-(+)-N-(BENZYLIDENE)-p-TOLUENESULFIN AMIDE (Benzenepropanoic acid, p-amino-, (R)-, methyl ester from Benzenesulfinamide, 4-methyl-N-(phenylmethylene)- [S-(E)]-)... 

SULFINIMINES (THIOOXIMINE S-OXIDES) ASYMMETRIC SYNTHESIS OF METHYL (R)-(+)-p-PHENYLALANATE FROM (S)-(+)-N-(BENZYLIDENE)-p-TOLUENESULFIN AMIDE. 

A quite general method of access to optically pure sulfoxides is due to Andersen [96-98] a menthyl sulfinate ester is reacted with a Grignard reagent. Both enantiomers of menthyl p-toluenesulfinate are commercially available. A large-scale preparation of (-)-menthyl (S)-p-toluenesulfinate as well as that of (7 )-(+)-methyl p-tolyl sulfoxide is described [99] by Solladi et al. Other related approaches are presented and discussed in [86]. 

Chiral bis-sulfoxides with a C2 symmetry axis can be readily prepared from the known (W)-methyl p-tolyl sulfoxide and commercially available methyl (S)-p-toluenesulfinate. Such chiral ligands are very attractive because of their easy synthesis and their ready availability in both enantiomers from inexpensive starting materials. Their complexes with Fel3 are shown to be good chiral catalysts for asymmetric Diels-Alder reactions [48] (Eq. 8A.26). 

The reaction of 60 with an excess of alkane- or arenesulfinyl chloride affords sulfinate esters 61-(R) and 61-fSj in good yields and moderate selectivity [(4-10) 1]. The diastereomeric sulfinates were separated either by crystallization or by column chromatography. Two arene- and two alkanesulfinates were prepared optically pure by the reported method (Scheme 18). The major isomer of the methanesulfinate was used in the synthesis of o.p. (R) methyl p-tolyl sulfoxide 62 in 76% yield, while the p-toluenesulfinate was used to obtain the (S)-p-phenoxyphenyl p-tolyl sulfoxide 63 in 70% yield. 

The four-coordinate iridium(I) complex [Ir(02S-p-tolyl)(CO)(PPh3)2] (70) (02S-p-tolyl = p-toluenesulfinate) has been prepared from [Ir(CO)(PPh3)2(MeCN)]+ and sodium p-toluenesul-finate.163 This complex contains an O-bonded sulfinate ligand, as indicated by IR spectral evidence.98 On addition of methyl iodide to (70), an iridium(III) complex with O-bonded sulfinate is formed. 

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