13894-21-8

Basic information

• Product Name: ETHYNYL P-TOLYL SULFONE
• Synonyms: 1-(ethynylsulfonyl)-4-Methylbenzene;Ethynyl p-Tolyl Sulfone;ETHYNYL P-TOLYL SULFONE;P-TOLUENESULFONYLACETYLENE;TOSYLACETYLENE;p-Toluenesulfonylacetylene, Tosylacetylene
• CAS NO: 13894-21-8
• Molecular Formula: C₉H₈O₂S
• Molecular Weight: 180.22
• Product Categories: Acetylenes;Functionalized Acetylenes;Sulfur Compounds (for Synthesis);Synthetic Organic Chemistry
• Mol File: 13894-21-8.mol

Chemical Properties

• Melting Point: 73-74 °C(lit.)
• Boiling Point: 297.9°C at 760 mmHg
• Flash Point: 155.6°C
• Appearance: /
• Density: 1.219g/cm³
• Vapor Pressure: 0.00233mmHg at 25°C
• Refractive Index: 1.552
• Storage Temp.: Inert atmosphere,Room Temperature
• Solubility: organic solvents: soluble(lit.)
• BRN: 2556169
• CAS DataBase Reference: ETHYNYL P-TOLYL SULFONE(CAS DataBase Reference)
• NIST Chemistry Reference: ETHYNYL P-TOLYL SULFONE(13894-21-8)
• EPA Substance Registry System: ETHYNYL P-TOLYL SULFONE(13894-21-8)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• Hazardous Substances Data: 13894-21-8(Hazardous Substances Data)

Usage

Uses

Used in Chemical Synthesis:
ETHYNYL P-TOLYL SULFONE is used as a synthetic intermediate for the preparation of various organic compounds. Its unique structure allows for a range of reactions, making it a valuable building block in the synthesis of complex molecules.
Used in Pharmaceutical Industry:
ETHYNYL P-TOLYL SULFONE is used as a starting reagent for the synthesis of optically active indan-2-ols. These indan-2-ols are important in the development of pharmaceutical compounds, as they can exhibit biological activities and serve as key components in the design of new drugs.
Used in Organic Chemistry Research:
In the field of organic chemistry, ETHYNYL P-TOLYL SULFONE is used as a starting reagent for the synthesis of 2-(4-methylphenylsulfonyl)ethenyl (tosvinyl, Tsv) protected derivatives. These derivatives are essential for the development of new synthetic routes and the exploration of novel chemical reactions.
Overall, ETHYNYL P-TOLYL SULFONE is a versatile and valuable compound in the fields of chemical synthesis, pharmaceutical research, and organic chemistry, with applications ranging from the development of new drugs to the exploration of novel synthetic pathways.

Synthesis Reference(s)

The Journal of Organic Chemistry, 57, p. 697, 1992 DOI: 10.1021/jo00028a053

Purification Methods

Recrystallise the sulfone from pet ether, *C6H6 or EtOH (m 66o), and dry it in a vacuum. [Beilstein 6 III 1397, 6 IV 2160.]

InChI:InChI=1/C9H8O2S/c1-3-12(10,11)9-6-4-8(2)5-7-9/h1,4-7H,2H3

Upstream product

• 66823-38-9 1-ethynylsulfanyl-4-methyl-benzene 
• 67960-27-4 4-(toluene-4-sulfonyl)-isoxazol-5-ylamine 
• 34452-56-7 trimethylsilyl p-tolylsulfonylacetylene 
• 125803-61-4 ethynylphenyl-iodonium-1,1,1-trifluoromethanesulfonate 
• 824-79-3 sodium 4-methylbenzenesulfinate 
• 4526-53-8 cis-1,2-bis-(p-tolylthio)ethylene 
• 1576-35-8 toluene-4-sulfonic acid hydrazide 
• 98-59-9 p-toluenesulfonyl chloride 
• 14630-40-1 Bis(trimethylsilyl)ethyne 
• 106-45-6 para-thiocresol 
• 86409-89-4 (E)-1-(phenylseleno)-2-(p-tolylsulfonyl)ethene 
• 68819-94-3 p-tolyl benzeneselenosulfonate 
• 455-16-3 p-toluenesulfonyl fluoride 
• 4301-14-8 acetylenemagnesium bromide 

Downstream Products

• 13894-23-0 trans-1-Dimethylamino-2-p-tolylsulfonyl-aethylen 
• 13894-24-1 (E)-N,N-diethyl-2-((4-methylphenyl)sulfonyl)ethene-1-amine 
• 13894-26-3 (E)-1--2-tosylethylene 
• 75233-20-4 1-Methyl-4-[((1E,4E)-octa-1,4-diene)-1-sulfonyl]-benzene 
• 83060-74-6 7-methoxycarbonyl-2-p-toluenesulfonyl-7-azanorbornadiene 
• 83060-74-6 (1S,4R)-2-(Toluene-4-sulfonyl)-7-aza-bicyclo[2.2.1]hepta-2,5-diene-7-carboxylic acid methyl ester 
• 75233-11-3 1-((E)-3,4-Dimethyl-penta-1,4-diene-1-sulfonyl)-4-methyl-benzene 
• 75233-10-2 1-Methyl-4-((E)-3,3,4-trimethyl-penta-1,4-diene-1-sulfonyl)-benzene 
• 75233-12-4 1-((E)-3-Cyclopent-1-enyl-but-1-ene-1-sulfonyl)-4-methyl-benzene 
• 114250-62-3 3-(p-toluenesulfonyl)propiolic acid 
• 769-26-6 2-ethynyl-1,3,5-trimethylbenzene 
• 74331-74-1 2,6-dimethylphenylacetylene 
• 85850-65-3 C₁₉H₁₈O₃S 
• 89438-33-5 2-(Methylphenylamino)-3-phenyl-5-(p-tolylsulfinyl)furan 

Relevant articles and documents

A New Synthesis of Alkynyl Sulfones and Single Crystal X-ray Structure of p-(Tolylsulfonyl)ethyne

The reaction of mono- or bis(alkynyliodonium) triflate salts with sodium p-toluenesulfinate under mild conditions affords alkynyl sulfones in 60-95percent yields.

A simplified method for the preparation of ethynyl P-tolyl sulfone and ethynyl phenyl sulfone

Silica gel mediated desilylation of aryl 2-(trimethylsilyl)ethynyl sulfones was found to greatly simplify the synthesis of the acetylenic sulfones, ethynyl p-tolyl sulfone 1 and ethynyl phenyl sulfone 2. Each were easily prepared in good yield and high purity on a multigram scale from bis(trimethylsilyl)acetylene 3.

Large π-Conjugated Metal-Organic Frameworks for Infrared-Light-Driven CO2Reduction

It remains challenging to excite traditional photocatalysts through near-infrared (NIR) light. Attempts to use NIR-light-response materials for photochemical reduction usually suffer from inapposite band position due to extremely narrow band gaps. Here, w

Covalent Adaptable Networks with Tunable Exchange Rates Based on Reversible Thiol–yne Cross-Linking

The design of covalent adaptable networks (CANs) relies on the ability to trigger the rearrangement of bonds within a polymer network. Simple activated alkynes are now used as versatile reversible cross-linkers for thiols. The click-like thiol–yne cross-linking reaction readily enables network synthesis from polythiols through a double Michael addition with a reversible and tunable second addition step. The resulting thioacetal cross-linking moieties are robust but dynamic linkages. A series of different activated alkynes have been synthesized and systematically probed for their ability to produce dynamic thioacetal linkages, both in kinetic studies of small molecule models, as well as in stress relaxation and creep measurements on thiol–yne-based CANs. The results are further rationalized by DFT calculations, showing that the bond exchange rates can be significantly influenced by the choice of the activated alkyne cross-linker.

Metal-free synthesis of activated ynesulfonamides and tertiary enesulfonamides

An operationally simple synthesis of activated ynesulfonamides and enesulfonamides is described. Ynesulfonamides can be obtained through reaction of sulfonylamides with activated bromoalkynes and Triton B in a short time at room temperature. Likewise, terminal alkynes react with sulfonylamides to provide enesulfonamides. Z/E enesulfonamides can be transformed exclusively into E enesulfonamides.

Synthesis, Structural and Optical Properties of Tetrabenzoporphyrin Complexes Bearing Four or Eight Peripheral Phenyl Groups

A series of free-base and phosphorus(V) complexes of tetrabenzoporphyrin (TBP) and some phosphorus(V) porphyrins containing four or eight phenyl groups on the periphery have been synthesized and characterized by X-ray crystallography, electronic absorption, and magnetic circular dichroism (MCD) spectroscopy, together with quantum chemical calculations. All phosphorus TBP and meso-tetraphenyl porphyrin complexes adapted ruffled conformations due to the small P(V) ion, although the Zn(II)TBPs containing eight phenyl (Φ) groups at the so-called β and α positions showed planar and saddled structures in the solid state, due to, respectively, marginal or severe steric hindrance between the neighboring Φ groups. All P(V)TBPs showed the Soret and Q bands beyond 450 and 700 nm, respectively, which are some of the longest wavelengths exhibited by metallated TBPs reported to date. Of the eight Φ group-substituted P(V)TBPs, those substituted at α positions always showed absorption bands at longer wavelengths than those at β positions, which was reproduced by calculated absorption spectra. The Soret band positions of meso-tetraphenylated P(V) species without fused benzo-groups (ca. 430–440 nm) were also some of the longest among metalloporphyrins of this type.

Gold-Catalyzed Dehydrazinative C(sp)–S Coupling Reactions of Arylsulfonyl Hydrazides with Ethynylbenziodoxolones for Accessing Alkynyl Sulfones

A gold(III)-catalyzed dehydrazinative coupling reaction between arylsulfonyl hydrazides and ethynylbenziodoxolone reagents was realized for the synthesis of alkynyl sulfones. The scope and versatility of the reaction were demonstrated by the efficient synthesis of 23 derivatives with diverse structural features.

Synthesis of Azacyclic Nucleoside Analogues via Asymmetric [3 + 2] Cycloaddition of 9-(2-Tosylvinyl)-9H -purines

With 9-(2-tosylvinyl)-9H-purines as the dipolarophiles, a series of chiral azacyclic nucleosides with four continuous stereocenters were obtained in 86-99% yields, >20:1 dr, and 94 → 99% ee via the Cu(I)-catalyzed asymmetric [3 + 2] cycloaddition. Both (E)- and (Z)-9-(2-tosylvinyl)-9H-purines were suitable dipolarophiles, enriching the structure diversity of azacyclic nucleosides. Furthermore, when α-methyl imino ester was explored, the corresponding azacyclic nucleoside with a chiral quaternary stereocenter could also be afforded with excellent results. (Chemical Equation Presented).

A facile and reliable method for the synthesis of tetrabenzoporphyrin from 4,7-dihydroisoindole

A new route to tetrabenzoporphyrins from the closest possible precursor of the unstable isoindole was developed. A key feature of this route is a dramatic facilitation of the aromatization of annelated rings, which is the most serious bottleneck in previo

Synthesis of a fluorine-18 labeled derivative of epibatidine for in vivo nicotinic acetylcholine receptor PET imaging

Epibatidine (exo-2-(2'-chloro-5'-pyridyl)-7-azabicyclo[2.2.1]heptane), a natural compound isolated from the skin of the Ecuadorian poison frog Epipedobates tricolor, is the most potent nicotinic acetylcholine receptor (nAChR) agonist reported to date. In order to visualize and quantify in vivo these receptors in human brain using Positron Emission Tomography (PET), [18F]norchlorofluoroepibatidine (exo-2-(2'-[18F]fluoro-5'-pyridyl)-7-azabicyclo[2.2.1]heptane), a fluorine-18 (t(1/2): 110min) radiolabeled derivative of epibatidine has been designed. The corresponding 2'-bromo-, 2'-iodo- and 2'-nitro exo-2-(5'-pyridyl)-7-azabicyclo[2.2.1]heptane analogues as labeling precursors, as well as norchlorofluoroepibatidine as a reference compound have been synthesized by reductive, stereoselective, palladium-catalyzed Heck-type coupling between an N-Boc protected azanorbornene and the corresponding halopyridine. [18F]Norchlorofluoroepibatidine has been radiolabeled with fluorine-18 by nucleophilic aromatic substitution from the corresponding Boc-protected halo- and nitro precursors using [18F]FK-K222 complex in DMSO by conventional heating (at 150-180°C for 10min) or microwave activations (at 100 Watt, for 1 to 2.5min), followed by TFA-removal of the protective group. Typically, using the microwave activation procedure, 60-80mCi (2.22-2.96 GBq) of pure [18F]norchlorofluoroepibatidine could be obtained in less than 2h (110-115min) from the bromo labeling precursor, with specific radioactivities of 1.5-2.5Ci/μmol (55.5-92.5GBq/μmol) calculated for End of Bombardment. The preliminary PET experiments in baboon (Papio papio) with [18F]norchlorofluoroepibatidine show a high uptake and a rapid accumulation of the radiotracer into the brain within 30min. In the thalamus, a nAChR rich area, uptake of radioactivity reached a maximum at 40min (10% I.D./100mL tissue). The ratio of radioactivity thalamus/cerebellum (the latter being a nAChR poor area) was 2 at 40min and increased with time, up to 4.3 at 160min. Its specific regiodistribution and its high ratio of specific-to-nonspecific binding confirm the ideal profile of [18F]norchlorofluoroepibatidine as a suitable radioligand for PET imaging of nAChRs in the brain. Copyright (C) 1999 Elsevier Science Ltd.