13921-09-0

Basic information

• Product Name: Benzene, [(1-ethylpropyl)thio]-
• CAS NO: 13921-09-0
• Molecular Formula: C11H16S
• Molecular Weight: 180.314
• Mol File: 13921-09-0.mol

Chemical Properties

• CAS DataBase Reference: Benzene, [(1-ethylpropyl)thio]-(CAS DataBase Reference)
• NIST Chemistry Reference: Benzene, [(1-ethylpropyl)thio]-(13921-09-0)
• EPA Substance Registry System: Benzene, [(1-ethylpropyl)thio]-(13921-09-0)

Safety Data

• Hazardous Substances Data: 13921-09-0(Hazardous Substances Data)

Upstream product

• 1809-10-5 3-bromopentane 
• 3111-52-2 potassium thiophenolate 
• 917-54-4 methyllithium 
• 75-03-6 ethyl iodide 
• 1822-73-7 phenylthioethylene 
• 584-02-1 2-pentanol 
• 882-33-7 diphenyldisulfane 
• 108-98-5 thiophenol 
• 930-69-8 sodium thiophenolate 
• 2386-64-3 ethylmagnesium chloride 
• 78031-08-0 [(bromodifluoromethyl)sulfanyl]benzene 
• 113410-20-1 (1-Methyl-2-nitro-butylsulfanyl)-benzene 

Downstream Products

• 100-68-5 methyl-phenyl-thioether 
• 813436-63-4 (pentan-3-ylsulfonyl)benzene 

Relevant articles and documents

Base-Mediated Radical Borylation of Alkyl Sulfones

A practical and direct method was developed for the production of versatile alkyl boronate esters via transition metal-free borylation of primary and secondary alkyl sulfones. The key to the success of the strategy is the use of bis(neopentyl glycolato) diboron (B2neop2), with a stoichiometric amount of base as a promoter. The practicality and industrial potential of this protocol are highlighted by its wide functional group tolerance, the late-stage modification of complex compounds, no need for further transesterification, and operational simplicity. Radical clock, radical trap experiments, and EPR studies were conducted which show that the borylation process involves radical intermediates.

Sulfonium ylide formation and subsequent C[sbnd]S bond cleavage of aromatic isopropyl sulfide catalyzed by hemin in aqueous solvent

Heme is an abundant and widely existed cofactor for a variety of metalloenzymes, whose broader use is generally impeded by its high instability and poor solubility. Here we report an environment-benign and efficient strategy for the sulfonium ylide formation and subsequent C[sbnd]S bond cleavage of aromatic isopropyl sulfides, which was catalyzed by hemin in assistance of Triton X-100. This aqueous catalytic system exhibited good functional group tolerance to a variety of sulfides and diazo esters. And the reaction mechanism was preliminarily proposed on the basis of designed reactions. Furthermore, the cleavage of C[sbnd]S bond followed by introducing a functional ester group to aromatic sulfides, may potentially be employed for the late stage functionalization (LSF) of organosulfur drug in the future.

Transalkylation of alkyl aryl sulfides with alkylating agents

The reaction of methyl iodide with tert-butylphenylsulfide in DMF leads to a transalkylation that produces methylphenylsulfide. This transalkylation reaction was further studied by 1H NMR spectroscopy. The polarity of the solvent, the electron density on the sulfur atom, and the strength of the alkylating agent (MeI, EtI, BuI, dimethyl sulfate, or dimethyl carbonate) played important roles in the reaction. The suggested mechanism of the reaction involves the formation of a dialkyl aryl sulfonium salt that subsequently eliminates the radical. This mechanism was supported by the observation of higher conversion rates for compounds with more branched alkyl groups on the sulfur atom, which may lead to the formation of more stable radicals.

Lithium-titanium exchange of tertiary α-sulfonyl carbanions: Synthesis, structure, dynamics and reactivity of bis(1-sulfonylalkyl) titaniums

Lithium-titanium exchange of tertiary α-sulfonyl carbanions with ClTi(OiPr)3 and Cl2Ti(OiPr)2 in diethyl ether gave bis(1-sulfonylalkyl) titaniums and not the corresponding (1-sulfon-ylalkyl) titaniums. X-ray crystal structure analysis of di(iso-propoxy) bis[1-(phenylsulfonyl) cyclobutyl]titanium and di-(isopropoxy) bis[1-(phenylsulfonyl) isopropyl]titanium showed asymmetric distorted octahedral complexes, having hexaco-ordinate Ti atoms, two C-Ti bonds, four Ti-O bonds, and two four-membered Ti-O-S-Cα rings. According to 1H NMR spectroscopy bis(1-sulfonylcycloalkyl) titaniums are non-flux-ional at room temperature. This suggests that chiral bis(1-sulfonylalkyl) titaniums should be configurationally stable. The bis(1-sulfonylalkyl) titaniums are stable at room temperature towards β-H elimination. They selectively add to benzaldehyde in the presence of acetophenone but do not react with methyl iodide. The reaction of tertiary acyclic α-sulfonyl carbanions with ClTi(OiPr)3 in tetrahydrofuran (THF) gives different titanium derivatives with unspecified structures, which not only selectively react with benzaldehyde in the presence of acetophenone but are also alkylated by methyl iodide.

Experimental and theoretical investigation of the enantiomerization of Lithium α-tert-butylsulfonyl carbanion salts and the determination of their structures in solution and in the crystal

Dynamic NMR (DNMR) spectroscopy of [R1C(R2)SO 2R3]Li (R1, R2 = alkyl, phenyl; R3 = Ph, tBu, adamantyl, CEt3) in [D8]THF has shown that the S-tBu, S-adamantyl, and S-CEt3 derivatives have a significantly higher enantiomerization barrier than their S-Ph analogues. C α-S bond rotation is most likely the rate-determining step of the enantiomerization of the salts bearing a bulky group at the S atom and two substituents at the Cα atom. Ab initio calculations on [Me(Ph)- SO 2tBu]- gave information about the two Cα-S rotational barriers, which are dominated by steric effects. Cryoscopy of [R1C(R 2)SO2tBu]Li in THF at -108°C revealed the existence of monomers and dimers. X-ray crystal structure analysis of the monomers and dimers of [R1C(R2)SO2tBu]Li·L n (R1 = Me, Et, tBuCH2, PhCH2, tBu; R2 = Ph, L = THF, 12-crown-4, PMDTA) and [R1C(R 2)SO2Ph]Li·2diglyme [R1 = R2 = Me, Et; R1-R2 = (CH2)5] showed them to be O-Li contact ion pairs (CIPs). The monomers and dimers have a Cα-S conformation in which the lone-pair orbital at the Cα atom bisects the O-S-O angle and a significantly shortened Cα-S bond. The Cα atom of [R1C(R2)SO2R 3]Li·Ln (R1 = Ph; R3 = Ph, tBu) is planar, whereas the Cα atom of [R1C(R 2)SO2R3]Li·Ln (R1 = R2 = alkyl) is strongly pyramidalized in the case of R3 = Ph and most likely planar for R3 = tBu. Ab initio calculations on [MeC- (Me)SO2R]- gave a pyramidalized Cα atom for R = Me and a nearly planar one for R = CF3 and tBu. The [R1C(R 2)SO2-tBu]Li salts were characterized by 1H, 13C, and 6Li NMR spectroscopy. 1H{ 1H} and 6Li{1H} NOE experiments are in accordance with the existence of O-Li CIPs. 1H and 13C NMR spectroscopy of [R1C(R2)SO2tBu]Li in [D 8]THF at low temperatures showed equilibrium mixtures of up to five different species being most likely monomeric and dimeric O-Li CIPs with different configurations. According to 7Li NMR spectroscopy, the addition of HMPA to [MeC(Ph)SO2tBu]Li in [D8]THF at low temperatures causes the formation of the separated ion pair [MeC(Ph)SO 2tBu]Li(HMPA)4.

The effect of ring size on reactivity: The diagnostic value of 'rate profiles'

The rates of cycloalkyl phenyl sulfide formation of a series of homologous bromocycloalkanes upon treatment with sodium benzenethiolate have been determined to ascertain the effect of ring size on reactivity. The 'rate profile', i.e., reaction rate vs. ring size, for these nucleophilic substitutions (SN2) was determined. A linear free-energy relationship could be derived from computed hydride affinities of cycloalkanes and rates of typical SN1 reactions, whereas rates of SN2 reactions exhibited a strong discrepancy from the seven- up to the twelve-membered rings. This discrepancy was rationalized by a careful examination of the geometry of the intermediates and transition states involved in these reactions.

α-arylsulfanyl-α-fluoro carbenoids: Their novel chemistry and synthetic applications

(Chemical equation presented) The bromine-magnesium exchange reactions of arylthiobromodifluoromethanes with Grignard reagents have been studied. Upon trapping with electrophiles, alkyl aryl sulfides and ketenedithioacetals are obtained. The reaction is p

Metalation reactions. XXIV. Metalation of (vinylthio)benzene

The addition of organolithium compounds to (vinylthio)benzene (1) and then an electrophilic quenching followed by a further metalation/electrophilic quenching is a general method to prepare in one pot (alkylthio)benzenes ortho, alpha-substituted with equal or different groups. The direct dimetalation of 1 affords the ortho, alpha-dilithiated species 15 besides other by-products. Starting from 15 it is possible to obtain in one step ortho, alpha-substituted (vinylthio)benzenes and heterocyclic compounds.

A simple and efficient method for preparation of unsymmetrical sulfides

A simple and high efficient method for preparation of unsymmetrical sulfides is described.

IONIC DENITROHYDROGENATION OF α-NITRO OR β-NITRO SULFIDES WITH TRIETHYLSILANE

The nitro groups of α-nitro or β-nitro sulfides are replaced by hydrogen on treatment with triethylsilane in the presence of Lewis acid.