Methyl P-tolyl Sulfoxide Research Articles

Substituent Effect on the Enantioface-Differentiating Reaction of (R)-[Lithiomethyl p-Tolyl Sulfoxide] with m- or p-Substituted Acetophenones

Abstract When lithiomethyl p-tolyl sulfoxide derived from (R)-(+)-[methyl p-tolyl sulfoxide] was allowed to react with acetophenones which have a variety of m- or p-substituents, the corresponding diastereometic mixture of β-hydroxy sulfoxides (RsSc and RsRc) was produced. The degree of enantioselectivity was affected by the nature of the substituent on benzene ring. The logarithms of the RsSc/RsRc values thus obtained gave a good correlation with Hammett’s σ values, affording a negative straight line. The results have been discussed in view of the stereochemical cource of the reaction.

A new entry to homochiral difluorinated compounds

Some homochiral compounds containing a difluoromethylene unit along with oxygen and nitrogen functionalities have been obtained starting from α,α-difluorocarboxylic esters and (+)-(R)-methyl p-tolyl sulfoxide.

ChemInform Abstract: Chiral Sulfur Compounds. Part 11. Diastereoselective Additions of (R)-(+)-Methyl p-Tolyl Sulfoxide Anion to Imines. Asymmetric Synthesis of (R)-(+)-Tetrahydropalmatine.

The sulfoxides (II) are deprotonated and subsequently coupled with imines such as (I) to produce predominantly the adducts (III).

Synthesis of (S)-.beta.,.beta.,.beta.-trifluorolactic acid and (S)-.alpha.-methoxy-.alpha.-(trifluoromethyl)phenylacetic acid from (R)-methyl p-tolyl sulfoxide

Synthese asymetrique. Obtention du 1er produit du titre par acylation d'un derive lithie du (R)-methyl-phenylsulfoxyde, puis reduction selective de la trifluorosulfinylpropanone obtenue et O-benzylation. Traitement par l'acide trifluoroacetique et la 2,4,6-trimethylpyridine, hydrolyse en presence de chlorure mercurique, oxydation et obtention de l'ester par action du diazomethane. Obtention du deuxieme par hydroxyalkylation du derive lithie du (R)-methyl p-tolylsulfoxyde, methylation, hydrolyses successives en presence de chlorure cuivrique et oxydation de l'aldehyde obtenue

Chiral sulfur compounds. II. Diastereoselective additions of (R)-(+)-methyl p-tolyl sulfoxide anion to imines. Asymmetric synthesis of (R)-(+)-tetrahydropalmatine

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTChiral sulfur compounds. II. Diastereoselective additions of (R)-(+)-methyl p-tolyl sulfoxide anion to imines. Asymmetric synthesis of (R)-(+)-tetrahydropalmatineStephen G. Pyne and Branko DikicCite this: J. Org. Chem. 1990, 55, 6, 1932–1936Publication Date (Print):March 1, 1990Publication History Published online1 May 2002Published inissue 1 March 1990https://doi.org/10.1021/jo00293a045RIGHTS & PERMISSIONSArticle Views467Altmetric-Citations62LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (646 KB) Get e-Alerts Get e-Alerts

X-ray structural studies of?-cyclodextrin inclusion complexes with racemic andS(?) methyl-p-tolylsulfoxides

In order to clarify the reason why the stereospecific sulfoxides undergo racemization in solution but not in the complex crystal with β-cyclodextrin (β-CD) in the solid state, a crystal structure analysis of two β-CD inclusion complexes with methyl-p-tolylsulfoxide (MTSO) having a chiral sulfur atom was carried out.

α-PHOSPHORYL SULFOXIDES 7.1CHIROPTICAL PROPERTIES OF α-PHOSPHORYL SULFOXIDES

Abstract The paper describes the synthesis and chiroptical properties of (+)-α-phosphoryl sulfoxides of general formulae, R1 2P(X)CHR2S(O)Tol-p (where R1=MeO, EtO. Ph, Me2N, X=O,S, R2=H,Me, Cl) obtained from (-)-(S)-menthyl p-toluenesulfinate and the corresponding α-phosphonate, α-thiophosphonate and α-phosphinoxide anions. The CD curves of (+)-α-phosphoryl sulfoxides are of the same shape with two Cotton effects of opposite sign. At 240–245 nm one observes the positive Cotton effect while that at 220 nm is negative. The CD spectra of all (+)-α-phosphoryl sulfoxides measured are almost identical with that of (+)-(R)-methyl p-tolyl sulfoxide indicating that they have the S-chirality at sulfur. The change of ethanol for isooctane as a solvent does not influence the UV and CD spectra.

X-Ray Structural Studies of Some β-Cyclodextrin Inclusion Complexes with Stereoisomeric Methyl-P-Tolylsulfoxides. Protective Effect During Irradiation in the Solid State.

Abstract In order to clarify the reason why the stereospecific sulfoxides undergo racemization in solution but not in the complex crystal with β-cyclodextrin(β-CD) in the solid state, we carried out the crystal structure analysis of two β-CD inclusion complexes with methyl-p-tolylsulfoxide (MTSO) having a chiral sulfur atom.

Synthesis of optically active α-sulfinylacetaldehyde

Optically active α-sulfinylacetaldehyde is prepared by formylation of the (R)-methyl p-tolylsulfoxide anion with N-formylpiperidine.

Improved Preparation of Optically Active Methylp-Tolyl Sulfoxide

An improved large scale procedure for the preparation of optically pure methyl p-tolyl sulfoxide is described as well as a large scale preparation of optically pure (-) menthyl (S)-p-tolylsulfinate.

Circularly polarized luminescence studies of the adduct complexes formed by (R)-methyl p-tolyl sulfoxide with various europium(III) .beta.-diketonate complexes

Circularly polarized luminescence spectroscopy has been used to study the ternary complexes formed by europium(III) ..beta..-diketonate complexes and methyl p-tolyl sulfoxide. Adduct complexes having 1:1 and 1:2 chelate/substrate stoichiometries were formed, depending on the degree of fluorination in the ..beta..-diketone chelate rings. Enhancements in the Eu(III) luminescence intensities and lifetimes were used to evaluate the formation constants of the adduct complexes. In the 1:1 adduct complexes, the Eu(III) chirally was determined primarily by vicinal effects. In the 1:2 adduct complexes, evidence was obtained that indicated that presence of weak configurational effects due to geometrical isomerism. 21 references, 6 figures, 4 tables.

Catalytic Activity of PdCl2 Complexes Having Sulfur Compounds as Ligands

Abstract The PdCl2 complexes coordinated with methyl p-tolyl sulfoxide (1:2), methylthiomethyl p-tolyl sulfoxide (1:2), and 1,3-bis[(p-tolylsulfinyl)methylthio]propane (1:1) as ligands were prepared. Among these complexes, bis(methyl p-toly sulfoxide)palladium dichloride catalyzed effectively cyclotrimerization of diphenylethyne and rearrangement of 3-acetoxy-1-tridecene to 1-acetoxy-2-tridecene.

THE PREPARATION OF OPTICALLY ACTIVE β-KETO SULFOXIDES BY THE REACTION OF α-LITHIOMETHYL p-TOLYL SULFOXIDE WITH ETHYL CARBOXYLATES IN THE PRESENCE OF (—)-SPARTEINE

Abstract Treatment of 2 equivalents of racemic α-lithiomethyl p-tolyl sulfoxide (1) with ethyl carboxylates (2, C2H5O—CO—R) possessing a variety of groups R in the presence of (−)-sparteine afforded the corresponding optically active β-keto sulfoxides (3, p-CH3C6H4—SO—CH2—CO—R) together with optically active methyl p-tolyl sulfoxide which has the opposite configuration to 3.

ChemInform Abstract: AN ENANTIOMER DIFFERENTIATING REACTION OF P‐TOLYLSULFINYLCARBANION WITH (‐)‐MENTHYL CARBOXYLATES

AbstractBei der Umsetzung der optisch aktiven Menthylester (I) mit dem inaktiven p‐Tolylsulfinylcarbanion (II) erhält man neben Menthol (V) die optisch aktiven β‐Ketosulfide (III) und das optisch aktive p‐Tolylsulfoxid (IV) in sehr guten Ausbeuten.

AN ENANTIOMER DIFFERENTIATING REACTION OF p-TOLYLSULFINYLCARBANION WITH (−)-MENTHYL CARBOXYLATES

Abstract Treatment of (−)-menthyl carboxylates(2) with 2 equiv of p-tolylsulfinylcarbanion(1) afforded the corresponding optically active β-keto sulfoxides(3) together with optically active methyl p-tolyl sulfoxide. The enantiomeric purity and the predominant configuration of the products were discussed.

ChemInform Abstract: MOLECULAR STRUCTURE AND ABSOLUTE CONFIGURATION OF CIS‐DICHLORO((S)‐METHYL P‐TOLYL SULFOXIDE)(3‐METHYL‐1‐BUTENE)PLATINUM(II)

Chemischer InformationsdienstVolume 8, Issue 45 Physical Organic Chemistry ChemInform Abstract: MOLECULAR STRUCTURE AND ABSOLUTE CONFIGURATION OF CIS-DICHLORO((S)-METHYL P-TOLYL SULFOXIDE)(3-METHYL-1-BUTENE)PLATINUM(II) R. G. BALL, R. G. BALLSearch for more papers by this authorN. C. PAYNE, N. C. PAYNESearch for more papers by this author R. G. BALL, R. G. BALLSearch for more papers by this authorN. C. PAYNE, N. C. PAYNESearch for more papers by this author First published: November 8, 1977 https://doi.org/10.1002/chin.197745100AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume8, Issue45November 8, 1977 RelatedInformation

Cationic rhodium(I) sulfoxide complexes. Synthesis and spectroscopic properties

Displacement of the labile acetone ligand from [Rh(diene)(PPh3)(acetone)]A (diene = 1,5-cyclooctadiene (COD), norbornadiene (NBD); A = PF6−, SbF6−) allows facile coordination of dialkyl or alkyl aryl sulfoxides, and [Rh(diene)(PPh3)(sulfoxide)]+ complexes have been synthesized using dimethyl sulfoxide (DMSO), tetramethylene sulfoxide (TMSO), di-n-propyl sulfoxide (NPSO), (S,S;S,R)-(+)-2-methylbutyl methyl sulfoxide (MBMSO), methyl phenyl sulfoxide (MPSO), (R)-(+)-methyl-p-tolyl sulfoxide (MPTSO), and (R)-t-butyl p-tolyl sulfoxide (TBPTSO).Diaryl sulfoxides appear to coordinate in solution but no solid compounds could be isolated. The upfield shifts of the sulfoxide resonances (1H nmr), reflecting shielding by the adjacent phenyl groups of PPh3, and the decrease in ν(SO) on coordination, are indicative of O-bonding in all cases. Infrared data indicate that the frequency shift of ν(SO) upon O-coordination is roughly proportional to the strength of the metal–oxygen bond for a range of transition metal DMSO and TMSO complexes.

ENANTIOFACE DIFFERENTIATING ASYMMETRIC REACTION BY p-TOLYLSULFINYLCARBANION

Abstract The enantioface differentiating reaction by p-tolylsulfinylcarbanion(2), derived from (+)-(R)-methyl p-tolyl sulfoxide (1), toward unsymmetrical ketones (3) is described. The carbanion(2) readily reacts with 3 to produce a mixture of (RSRC)- and (RSSC)-β-hydroxy sulfoxides (4). The ratio of the diastereoisomers in 4 and the absolute configuration of the predominant diastereoisomer were determined with the aid of NMR and the specific rotation of alcohol(6) which was prepared by desulfurization of 4.

ChemInform Abstract: THE MOLECULAR STRUCTURE AND ABSOLUTE CONFIGURATION OF CIS‐DICHLORO((S)‐METHYL P‐TOLYL SULFOXIDE)((R)‐STYRENE)PLATINUM(II)

Chemischer InformationsdienstVolume 7, Issue 52 Physical Organic Chemistry ChemInform Abstract: THE MOLECULAR STRUCTURE AND ABSOLUTE CONFIGURATION OF CIS-DICHLORO((S)-METHYL P-TOLYL SULFOXIDE)((R)-STYRENE)PLATINUM(II) R. G. BALL, R. G. BALLSearch for more papers by this authorN. C. PAYNE, N. C. PAYNESearch for more papers by this author R. G. BALL, R. G. BALLSearch for more papers by this authorN. C. PAYNE, N. C. PAYNESearch for more papers by this author First published: December 28, 1976 https://doi.org/10.1002/chin.197652079AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume7, Issue52December 28, 1976 RelatedInformation

β-Disulfoxides. II. The Preparation of Some Optically Active β-Disulfoxides

Abstract α-Sulfinylcarbanions (1) derived from methyl-substituted sulfoxides readily react with arenesulfinic esters (2) to give the corresponding β-disulfoxides (3) in good yields. The reaction was conducted using (−)-menthyl (−)-(S)-benzenesulfinate ((−)-(S)-2b), (−)-menthyl (−)-(S)-p-toluenesulfinate ((−)-(S)-2c), and α-p-tolylsulfinylcarbanion derived from (+)-(R)- or (−)-(S)-methyl p-tolyl sulfoxide to produce (R,S)- and/or (S,S)-diastereoisomers of five β-disulfoxides (3a–e). The configurational assignment for the diastereoisomers obtained was accomplished by a combination of NMR and polarimetric analyses.