The flash thermolysis of γ-sultines

Durst, Tony; Finlay, John D.; Smith, David J.

doi:10.1039/p19790000950

Cited by 14 publications

(8 citation statements)

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“…The equilibrium is similar to the thermal decomposition of β‐lactones to produce CO 2 and an olefin through a carbene . β‐Sultines have only a limited thermal stability and they readily lose SO 2 producing olefins, while thermolysis of γ‐sultines occurs at much higher temperatures …”

Section: Mechanismmentioning

confidence: 87%

“…[64,65] b-Sultines have only a limited thermal stability and they readily lose SO 2 producing olefins, while thermolysis of g-sultines occurs at much higher temperatures. [66][67][68][69][70] The reaction of SO 2 with the diradical zigzag edge to form 1 and/or 2 is similar to the reverse reaction of the thermal extrusion of SO 2 to form a double bond. [71,72] These results [52] .…”

Section: Thermally Stable Reactive Intermediatesmentioning

confidence: 99%

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Kinetics and mechanisms in flow systems: reduction of SO₂ on carbons

Humeres

Moreira

2012

J of Physical Organic Chem

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Surface‐science studies of some reactions have allowed postulating the mechanisms using a variety of techniques. The surface chemistry of Group IV elements has been particularly studied recently because Si, Ge, and C are semiconductors, and the surface organic chemistry to functionalize these elements has seen immense progress in recent years. In this review article we describe the methodology used to study the mechanism of a solid–gas reaction, the reduction of SO2 on carbons, and the necessary conditions that allowed the measurement of the solid conversion and product distribution when the kinetics was chemically controlled and the reaction had reached the steady state. The reaction was first‐order with respect to SO2 and with respect to carbon and the stoichiometry was determined from the product distribution. The reaction proceeds through two thermally stable reaction intermediates bound to the surface, a six‐membered ring 1,3,2‐dioxathiolane and a five‐membered ring 1,2‐oxathietene 2‐oxide or γ‐sultine, both species being in equilibrium. The reaction was shown to be reversible. The primary product is an episulfide that, after a series of consecutive reactions of atomic sulfur, is able to free sulfur. The reactivity of the intermediates and the episulfide was studied for several reactions and consistent mechanisms were postulated from the X‐ray photoelectron spectroscopy and solid state nuclear magnetic resonance spectra. Aminolysis and the reaction with alkyl halides resulted on the insertion of the alkyl moiety in the episulfide primary product, while the thiolysis and photolytic alcoholysis resulted in the insertion of the alkyl moiety in the oxidized intermediates. Copyright © 2012 John Wiley & Sons, Ltd.

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Section: Mechanismmentioning

confidence: 87%

Section: Thermally Stable Reactive Intermediatesmentioning

confidence: 99%

Kinetics and mechanisms in flow systems: reduction of SO₂ on carbons

Humeres

Moreira

2012

J of Physical Organic Chem

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“…1,3‐Dihydrobenzothiophene ( 2 ) was prepared according to a literature method:9c,d A mixture of α,α′‐dibromo‐ o ‐xylene ( 1 ; 3.0 g, 11.4 mmol), sodium sulfide (7.5 g, 31.2 mmol), and benzyltriethylammonium chloride (36 mg, 0.158 mmol) in CH 2 Cl 2 /H 2 O (1:1, 10 mL) was stirred in the dark at room temperature for 15 h. The organic layer was separated, washed several times with water, dried with sodium sulfate, concentrated, and distilled at 80 °C under 0.8 torr pressure to give 2 as a colorless oil (960 mg, 62 %). 1 H NMR (500 MHz, CDCl 3 ): δ =4.27 (s, 4 H; CH 2 S), 7.20–7.24 ppm (m, 4 H; ArH).…”

Section: Methodsmentioning

confidence: 99%

Benzo[c]thiophene–C₆₀ Diadduct: An Electron Acceptor for p–n Junction Organic Solar Cells Harvesting Visible to Near‐IR Light

Zhen

Obata

Nakamura

2012

Chemistry An Asian Journal

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We synthesized a new 56-π-electron fullerene derivative through a Diels-Alder cycloaddition of benzo[c]thiophene that featured a relatively low temperature, closer to stoichiometric use of the diene, and easy product purification. The 56-π-electron benzo[c]thiophene diadduct (BTCDA) has a LUMO energy level of 0.09 to 0.18 eV higher than that of 58-π-electron fullerenes, and therefore, the BTCDA-based organic photovoltaic device exhibited a higher open-circuit voltage and power-conversion efficiency (PCE). When used with a binary-donor system, including visible-light-harvesting tetrabenzoporphyrin (BP) and near-IR-harvesting titanyl phthalocyanine (TiOPc), the device had a PCE that was 1.5-3 times higher (2.8%) than that for devices with BP or TiOPc alone because the binary-donor device can utilize light between λ=350 and 950 nm.

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“…Cage Oxetanes 1 (5,7,11,7.05'9]dodec-ll-ene-6,10diones). Cage oxetanes lak-cl were prepared by the general method of ref 1 and 2.…”

Section: Methodsmentioning

confidence: 99%

“…Thermal Rearrangement of Cage Oxetanes lab and lbl. Compound lal (150 mg, 0.38 mmol) was dissolved in 50 mL of xylene that had been allowed to stand over anhydrous K2C03, and the solution was refluxed for 5 h. After evaporation of the solvent, the resulting yellow solid was chromatographed on silica gel by elution with chloroform to give 7al (7-hydroxy-2,6,7,8btetramethyl-3,3a-diphenyl-l-oxacyclopenta-3a,8b-dihydrobenzo- [5] fur an) as yellow crystals. A similar workup gave 7bl from lbl.…”

Section: Methodsmentioning

confidence: 99%