3353-89-7

Basic information

• Product Name: TRIPHENYLSULFONIUM BROMIDE
• Synonyms: TRIPHENYLSULFONIUM BROMIDE;Triphenyl sulphonium bromide;Triphenylsulfonium Bromid
• CAS NO: 3353-89-7
• Molecular Formula: Br*C₁₈H₁₅S
• Molecular Weight: 343.28
• Product Categories: Iodonium Sulfonium & Oxonium Compounds;Sulfonium Compounds
• Mol File: 3353-89-7.mol

Chemical Properties

• Melting Point: 293 °C
• Appearance: /
• CAS DataBase Reference: TRIPHENYLSULFONIUM BROMIDE(CAS DataBase Reference)
• NIST Chemistry Reference: TRIPHENYLSULFONIUM BROMIDE(3353-89-7)
• EPA Substance Registry System: TRIPHENYLSULFONIUM BROMIDE(3353-89-7)

Safety Data

• Hazardous Substances Data: 3353-89-7(Hazardous Substances Data)

Usage

Uses

Triphenylsulfonium Bromide is used in the preparation of sulfonium salt photoacid generator for deep-UV microlithography.

Preparation

Triphenylsulfonium bromide synthesis: A 3.0 M solution of phenylmagnesium bromide in diethyl ether (50 ml, 0.15 mole) was distilled under vacuum with slow heating from 20° to 80°C. Benzene (40 ml) was added, followed by n-heptane (300 ml). The resulting mixture was stirred and a solution of diphenylsulfoxide 10.1 g, (0.050 mol), in benzene (60 ml) was added during 1 hour at 80°C. The mixture was stirred for 3 hours and cooled to room temperature. An 25% aqueous hydrobromic acid solution (180 ml) was slowly added to the reaction mixture (exotherm-). The layers were separated and the organic layer was extracted twice with 5% aqueous hydrobromic acid (2 x 30 ml). The combined aqueous extracts were extracted three times with dichloromethane (3×250 ml). The dichloromethane extracts were dried over magnesium sulfate, filtered and the organic solvent evaporated to leave triphenylsulfonium bromide (10.2 g, 60%), which was crystallized from dichloromethane/diethyl ether. M.p. 285-7°C.

Upstream product

• 945-51-7 1,1'-sulfinylbisbenzene 
• 71-43-2 benzene 
• 108-86-1 bromobenzene 
• 106-38-7 para-bromotoluene 
• 100-58-3 phenylmagnesium bromide 

Downstream Products

• 3138-53-2 triphenyl sulfonium ; dichloro bromide 
• 62787-21-7 3,5-di-tert-butylphenyl phenyl ether 
• 139-66-2 diphenyl sulfide 
• 39950-36-2 [1,1'-biphenyl]-2-yl(phenyl)sulfane 
• 59090-57-2 [1,1'-biphenyl]-4-yl(phenyl)sulfane 
• 113792-74-8 3-phenyldiphenyl sulfide 
• 2741-16-4 isopropoxybenzene 
• 71-43-2 benzene 
• 1030379-05-5 triphenylsulfonium 5-iodooctafluoro-3-oxa-pentanesulfonate 
• 902096-36-0 C₇H₈F₆NO₆S₂^(1-)*C₁₈H₁₅S⁽¹⁺⁾ 
• 902096-34-8 C₁₅H₁₅F₆O₆S₂^(1-)*C₁₈H₁₅S⁽¹⁺⁾ 
• 926925-07-7 C₁₈H₁₅S⁽¹⁺⁾*C₂₄H₃₅F₆O₆S₂^(1-) 
• 913976-47-3 C₁₀H₁₄F₆NO₅S₂^(1-)*C₁₈H₁₅S⁽¹⁺⁾ 

Relevant articles and documents

Facile method for the preparation of triarylsulfonium bromides using Grignard reagents and chlorotrimethylsilane as an activator

Triarylsulfonium bromides were synthesized by the reaction of diaryl sulfoxides with aryl Grignard reagents in the presence of TMSC1 followed by treatment with HBr aqueous solution. Triarylsulfonium bromides bearing three identical substituents on sulfur atom were synthesized by the treatment of dimethyl sulfite or thionyl chloride with 5 equivalents of Grignard reagent in the presence of TMSC1.

Preparation and characterization of the first organosulfonium azides

The first triorganosulfonium azides [Me3S]N3 and Ph3S]N3 were prepared by reaction of the corresponding sulfonium bromides/iodides with silver azide and characterized by spectroscopic methods. The molecular stru

PROCESS FOR PRODUCING TRIARYLSULFONIUM SALT

An object of the present invention is to provide a method for effectively producing a triarylsulfonium salt having a structure that only one aromatic ring of three aromatic rings on the cation portion thereof is different from the other two aromatic rings (hereinafter, abbreviated as a triarylsulfonium salt relating to the present invention) in a high yield without forming any byproduct. The present invention relates to a method for producing a triarylsulfonium salt represented by the general formula [4]: wherein, two R1's represent each hydrogen atom, halogen atom, alkyl group, haloalkyl group having 1 to 4 carbon atoms, alkoxy group, acyl group, hydroxyl group, amino group, nitro group or cyano group; R represents an aryl group which may have a substituent selected from a halogen atom, an alkyl group, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group, an alkylthio group, a N-alkylcarbamoyl group and a carbamoyl group, and the above substituent is different from one represented by the above R1; and A1 represents a strong acid residue, comprising reacting a diaryl sulfoxide represented by the general formula [1]: wherein, R1 represents the same as above, and an aryl Grignard reagent represented by the general formula [2]: ????????RMgX?????[2] wherein, X represents a halogen atom; R represents the same as above, in the presence of an activator with high affinity for oxygen of 3 to 7.5 equivalents relative to the above diaryl sulfoxide, and then reacting the resultant reaction mixture with a strong acid represented by the general formula [3]: ????????HA1?????[3] wherein, A1 represents the same as above, or a salt thereof.

Photochemistry of triarylsulfonium salts

The photolysis of triphenylsulfonium, tris(4-methylphenyl)sulfonium, tris(4-chlorophenyl)sulfonium, several monosubstituted (4-F, 4-Cl, 4-Me, 4-MeO, 4-PhS, and 4-PhCO), and disubstituted (4,4′-Me2 and 4,4′-(MeO)2) triphenylsulfonium salts was examined in solution. It was found that direct irradiation of triphenylsulfonium salts produced new rearrangement products, phenylthiobiphenyls, along with diphenyl sulfide, which had been previously reported. Similarly, the triarylsulfonium salts, with the exception of the [4-(phenylthio)phenyl]diphenylsulfonium salts, gave the new rearrangement products. The mechanism for direct photolysis is proposed to occur from the singlet excited state to give a predominant heterolytic cleavage along with some homolytic cleavage. The heterolytic cleavage gives phenyl cation and diphenyl sulfide, whereas homolytic cleavage gives the singlet phenyl radical and diphenylsulfinyl radical cation pair. These pairs of intermediates then produce the observed photoproducts by an in-cage recombination mechanism and also by reactions with the solvent. The effect of solvent viscosity, solvent polarity, anion, and aryl substituent was examined. The triplet sensitization of the sulfonium salts was also investigated. In contrast to previous reports, the triplet state of the sulfonium salt is labile, leading to a triplet geminate radical pair of phenyl radical and diphenylsulfinyl radical cation. These species ultimately form benzene and diphenyl sulfide as products. Direct photolysis of the [4-(phenylthio)phenyl]diphenylsulfonium salt, gave exclusively diphenyl sulfide, benzene, and acid and decomposes via the triplet excited state.

Synthesis of triarylsulfonium salts

A triarylsulfonium salt is prepared in high yield and high purity by a two-step process involving a aryl Grignard reagent reacted with a diarylsulfoxide in a solvent which is a mixture of aliphatic and aromatic hydrocarbons, followed by a second step which is metathesis with ZMF6, where Z is a metal or metal-like anion, and M is antimony, arsenic or phosphorus, preferably employing an ammonium salt and carried out in a non-aqueous solvent.