Facile Method for the Preparation of Triarylsulfonium Bromides Using Grignard Reagents and Chlorotrimethylsilane as an Activator

Imazeki, Shigeaki; Sumino, Motoshige; Fukasawa, Kazuhito; Ishihara, Mariko; Akiyama, Toru

doi:10.1055/s-2004-829113

Cited by 20 publications

(9 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A precipitate formed (≤3 % of the initial weight) and was filtered and washed with methanol. This material contained sulfur and gave signals compatible with a sulfonium salt in accordance with a polymer from 1 9. IR: $\tilde {\nu}$ = 1630, 1500, 1235, 765 cm –1 .…”

Section: Methodsmentioning

confidence: 87%

Photochemical Arylation Reactions by 4‐Chlorothioanisole

Lazzaroni¹,

Dondi²,

Fagnoni³

et al. 2007

Eur J Org Chem

View full text Add to dashboard Cite

The photochemistry of 4‐chlorothioanisole (1) was investigated in various solvents, and it was found to involve the reduction to thioanisole as the main process. This occurs by heterolytic fragmentation of the triplet state of 1 and formation of the triplet 4‐thiomethoxyphenylium ion, as supported by DFT calculations. The cation is trapped by alkenes and, less efficiently, by benzene, resulting in new examples of the recently emerging arylation reactions by SN1 substitution of phenyl halides. The products from alkenes involve the phenonium ion as a further intermediate. The product distribution differs from the analogous reactions via 4‐methoxyphenylium for including a larger proportion of 4‐(β‐substituted alkyl)‐ rather than 4‐allylthioanisoles derivatives in alcohols, for the lower fraction of rearranged α‐substituted 4‐alkylthioanisoles and for the formation of some 4‐cyclopropylthioanisole with allyltrimethylsilane. The difference is accounted for by the more developed dipolar character of the C–C cyclopropane bonds in the intermediate phenonium, as indicated by DFT calculations.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

show abstract

Section: Methodsmentioning

confidence: 87%

Photochemical Arylation Reactions by 4‐Chlorothioanisole

Lazzaroni¹,

Dondi²,

Fagnoni³

et al. 2007

Eur J Org Chem

View full text Add to dashboard Cite

show abstract

“…The NB anion was prepared by addition of a perfluoroalkyl iodide to norbornene by electron transfer . The GB anion was prepared by sulfinatodehalogenation induced in situ intramolecular ring formation. , The PAG cation, triphenylsulfonium (TPS), was synthesized in the form of TPSBr by using a Grignard reagent and chlorotrimethylsilane as an activator . After room temperature metathesis reactions between the sodium sulfonates and TPSBr, the TPS salts were obtained in high yield and high purity.…”

Section: Resultsmentioning

confidence: 99%

“…Unless stated, all the other chemicals and solvents were received from Sigma-Aldrich and used directly. Triphenylsulfonium bromide (TPSBr) was prepared according to the literature . PFOS-containing PAG (TPS PFOS) was prepared by metathesis reaction of potassium perfluorooctyl sulfonate (Synquest Laboratories, Inc.) and TPSBr.…”

Section: Methodsmentioning

confidence: 99%

Sulfonium Salts of Alicyclic Group Functionalized Semifluorinated Alkyl Ether Sulfonates As Photoacid Generators

Ayothi

Yueh

et al. 2009

Chem. Mater.

View full text Add to dashboard Cite

We describe new sulfonium salts incorporating semifluorinated sulfonate anions and their successful application as photoacid generators (PAGs) intended to solve the environmental problems caused by perfluorooctyl sulfonate (PFOS). By utilizing simple and unique chemistries based on 5-iodooctafluoro-3-oxapentanesulfonyl fluoride, a series of alicyclic-group functionalized octafluoro-3-oxapentanesulfonate anions were prepared in high purity and high yield. Triphenylsulfonium (TPS) salts of norbornyl and γ-butyrolactone groups functionalized octafluoro-3-oxapentanesulfonates were extensively studied. They have excellent thermal stability and good solubility in various polar solvents. Their optical and thermal properties were thoroughly investigated. Angle resolved X-ray photoelectron spectroscopy (XPS) analysis confirmed that the new TPS salts are uniformly distributed in polymer films, whereas TPS PFOS is heavily segregated to a polymer film surface. Lithographic performance of the new salts together with TPS PFOS and triphenylsulfonium perfluorobutyl sulfonate (TPS PFBS) in model positive tone resists was evaluated and compared at 193 nm (both dry and immersion) and extreme ultraviolet (EUV) wavelengths. Resist compositions containing the new salts are capable of resolving sub-100 nm dense lines and spaces at both tested wavelengths. Especially, a pattern of 42 nm dense lines was successfully demonstrated in 193 nm immersion exposures. A specific TPS salt of monosaccharide-functionalized octafluoro-3-oxapentanesulfonate, a "sweet" PAG, was also synthesized and studied. This PAG is capable of resolving 90 nm lines in 193 nm lithography. These new PAGs show comparable performance with TPS PFBS and better performance than TPS PFOS, which makes them very promising environmentally friendly candidates for high resolution lithography applications.

show abstract

“…All used reagents 1 , 2 , 3 , 4 , and 6 are literature known compounds and were prepared according to the known literature; the spectral data is identical with the corresponding literature sources. Namely, ortho -hydroxyarylenaminones 1 , which we used several times in our previous research, corresponding O-substituted derivatives 6 , and sulfonium salts 2 and 3 are literature described substances. All arenesulfonyl chlorides 4 used here are commercially available and were purchased from appropriate vendors.…”

Section: Methodsmentioning

confidence: 99%

Arylation of ortho-Hydroxyarylenaminones by Sulfonium Salts and Arenesulfonyl Chlorides: An Access to Isoflavones

Mkrtchyan

Iaroshenko

2021

J. Org. Chem.

View full text Add to dashboard Cite

Herein we disclose three new methods for the straightforward and efficient synthesis of 3-arylchromones following the arylation of ortho-hydroxyarylenaminones by vast diversities of bench-stable and easy-to-use sulfonium salts and arenesulfonyl chlorides. Both developed methods, namely the light-mediated photoredox and electrophilic arylation, showed good efficiency, and are feasible for the preparation of 3-arylchromones in good-to-excellent yields. This work showcases the first described attempt where the sulfonium salts and arenesulfonyl chlorides were successfully utilized for the construction of the chromone heterocycle system.

show abstract

Facile Method for the Preparation of Triarylsulfonium Bromides Using Grignard Reagents and Chlorotrimethylsilane as an Activator

Cited by 20 publications

References 2 publications

Photochemical Arylation Reactions by 4‐Chlorothioanisole

Photochemical Arylation Reactions by 4‐Chlorothioanisole

Sulfonium Salts of Alicyclic Group Functionalized Semifluorinated Alkyl Ether Sulfonates As Photoacid Generators

Arylation of ortho-Hydroxyarylenaminones by Sulfonium Salts and Arenesulfonyl Chlorides: An Access to Isoflavones

Contact Info

Product

Resources

About