Mechanism of sulphur monoxide extrusion

Chow, Yuan L.; Tam, J. N. S.; Blier, J. E.; Szmant, H. Harry

doi:10.1039/c29700001604

“…The first fraction can be isolated in near quantitative yield by the same eluent and was identified (98%) as the corresponding olefin ( 15 from 8 ; 16 from 9 ). By eluting with methanol, the second fraction was identified as the corresponding 2,5-dihydrothiophene 1-oxides as oily, pure product in the case of dienes 5 , 17 , 22 , and a solid product in the case of diene 20 ; the yields are generally high (70−80% yield) compared to other SO sources. − The identity of sulfoxides 6 , 19 , 21 , and 23 was confirmed by 1 H and 13 C NMR as well as by mass spectrometry.…”

Section: Trapping Of Sulfur Monoxide (So)mentioning

confidence: 91%

“…Up to now, the main method to generate SO has been by the pyrolysis of ethylene episulfoxide ( 1 ) at ca . 100 °C. , Other less-used methods of SO production have involved the thermal decomposition of sulfoxide 2 and heterocycle 3 …”

Section: Introductionmentioning

confidence: 99%

Effective Precursors for Sulfur Monoxide Formation

Abu‐Yousef

¹

,

Harpp

²

1997

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When triphenylmethanesulfenyl chloride (12) (or its thio 13 or dithio homolog 14) are treated with hindered olefins 15 and 16, thiiranes 10 and 11 are produced in high isolated yields (ca. 94%). Treatment of 10 and 11 with m-chloroperoxybenzoic acid (m-CPBA) leads to the formation of thiirane 1-oxides 8 and 9 (99% isolated yields). The structures of 8-11 were established by (1)H and (13)C NMR, mass spectrometry as well as by X-ray. Thermal decomposition of either 8 or 9 smoothly delivers sulfur monoxide to various 1,3-dienes giving cyclic sulfoxides in good yield. A variety of conditions were employed to optimize the yield of the trapped adducts.

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“…1,2 Until now, the main method for generating SO has been the pyrolysis of episulfoxides 1,[3][4][5] and other sulfoxides of varying structures. 6,7 The reactive SO molecule has been trapped as a thiophene-1-oxide with dienes and trienes. 8,9 Certain transition metal complexes have also been used to trap SO.…”

mentioning

confidence: 99%

“…The Pt-S distances, 226.2 pm, are equal. Structures of these binuclear A-frame bis(diphenylphosphino)methane (dppm) complexes have been reported: Pd 2 Cl 2 (µ-SO)-(µ-dppm) 2 (5), 17,18 Pd 2 Cl 2 (µ-SO 2 )(µ-dppm) 2 (6), 27 Pd 2 Cl 2 -(µ-S)(µ-dppm) 2 (7), 27 Ni 2 Cl 2 (µ-SO)(µ-dppm) 2 (8), 19 Ir 2 -(CO) 2 (µ-N-tol)(µ-dppm) 2 , 26 and Rh 2 (CO) 2 (µ-S)(µ-dppm) 2 . 28 Their Pt analogues, however, have not been structurally characterized.…”

mentioning

confidence: 99%

“…Two Pt and four P atoms are planar within 9 pm. The coordination environment about Pt(1) and Pt( 2) is that of a slightly distorted square plane with the coordination angles in the range 87.81(8)-92.99 (7)°and 87.60(8)-92.84(7)°, respectively. The ligating atoms lie alternatively 9 pm around Pt(1) and 14 pm around Pt(2) above and below the least-squares planes of PtP 2 SCl.…”

mentioning

confidence: 99%

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Two Routes to Bis(μ-diphenylphosphino)methane Diplatinum Halides Bridged by Sulfur Monoxide

Huang

¹

,

Guzei

²

,

Espenson

³

1999

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The use of simple chemical methods to generate and study reactive molecules has attracted some attention, but relatively little attention has been paid to sulfur monoxide. 1,2 Until now, the main method for generating SO has been the pyrolysis of episulfoxides 1,3-5 and other sulfoxides of varying structures. 6,7 The reactive SO molecule has been trapped as a thiophene-1-oxide with dienes and trienes. 8,9 Certain transition metal complexes have also been used to trap SO. 10 Atoms and small molecules are known to insert into the Pt-Pt bond of the platinum(I) complex Pt 2 (µ-dppm) 2 X 2 , 1 (X ) Cl, Br, I), to produce so-called A-frame molecules Pt 2 (µ-dppm) 2 X 2 (µ-Y), 2, Y ) S, SO 2 , CH 2 (from CH 2 N 2 ), CO, We recently uncovered a reaction (eq 1) that gradually generates SO in solution. 16 Sulfur monoxide was then either oxidized or, in separate experiments, trapped with a diene. We reasoned that SO logically could also be trapped by the Pt(I) complex 1, eq 2, to form Pt 2 (µ-dppm) 2 (µ-SO), 3.This reaction was successful, providing what we believe is the first µ-SO complex of platinum. Related complexes have been made with Pd 17,18 and Ni, 19 not through direct SO insertion but by oxidation of a µ-S complex. With that in mind, we carried out a parallel (and superior) synthesis of 3 based on an oxidation reaction, eq 3.The lemon-yellow compounds 1 and the yellow 2 (µ-S) were prepared by established procedures. 20,21 From reaction 3 22 a pure yellow product, 3a, was isolated in 92% yield. Recrystallization from chloroform-hexane afforded yellow crystals. The product was identified and characterized by elemental analysis, NMR, 23 and singlecrystal X-ray diffraction. 24 The iodide derivative 3b was similarly obtained in 86% yield as a yellow solid and (1) Abu-Yousef, I. A.; Harpp, D. N. Brown, M. P.; Puddephatt, R. J.; Rashidi, M.; Seddon, K. R. J. Chem. Soc., Dalton Trans. 1977, 951. (21) Brown, M. P.; Fisher, J. R.; Franklin, S. J.; Puddephatt, R. J. J. Chem. Soc., Chem. Commun. 1978, 749. (22) Compound 2a (250 mg, 0.20 mmol) and MTO (2.5 mg, 10 µmol) in 15 mL of chloroform were treated with 1 equiv of hydrogen peroxide.

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(((2S,3R)‐2,3‐Diphenylaziridin‐1‐yl)imino)‐ λ 4‐sulfanone

Saito

2024

Encyclopedia of Reagents for Organic Synthesis

0

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image [3003056‐18‐3] C 14 H 12 N 2 OS (MW 256.32) InChI = 1S/C14H12N2OS/c17‐18‐15‐16‐13(11‐7‐3‐1‐4‐8‐11)14(16)12‐9‐5‐2‐6‐10‐12/h1‐10,13‐14H/t13‐,14+,16? InChIKey = NPPOMHKZTUKVAS‐MZBDJJRSSA‐N (reagent used as an –S(O)– building block donor for the synthesis of sulfoxides and sulfinamides 1 ) Physical Data: mp 74–75 °C (decomposed). Solubility: soluble in benzene, chloroform, DMSO, ether, THF, and toluene. Form Supplied in: white to pale yellow solid, not commercially available. cis ‐Stilbene is a typical impurity. Analysis of Reagent Purity: reagent purity determined by 1 H NMR spectroscopy. Preparative Methods: prepared in three steps from commercially available cis ‐stilbene and N ‐aminophthalimide. The preparation of cis ‐2,3‐diphenyl‐1‐aziridinamine 2 is carried out by oxidative cyclization 3 and hydrazinolysis. The free hydrazine is treated with thionyl chloride in the presence of triethylamine to yield the sulfinylhydrazine ( 1 ). After workup, ( 1 ) is in high purity and used without further purification. Impure samples cannot typically be upgraded by any traditional methods. image Handling, Storage, and Precautions: store neat, refrigerate, inert atmosphere. Can be stored for at least one month at −20 °C. At room temperature, a sample gradually changes into a sticky solid over a week, likely because of the formation of cis ‐stilbene.

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Mechanism of sulphur monoxide extrusion

Cited by 15 publications

References 0 publications

Effective Precursors for Sulfur Monoxide Formation

Effective Precursors for Sulfur Monoxide Formation

Two Routes to Bis(μ-diphenylphosphino)methane Diplatinum Halides Bridged by Sulfur Monoxide

(((2S,3R)‐2,3‐Diphenylaziridin‐1‐yl)imino)‐ λ 4‐sulfanone

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