<sup>13</sup>C NMR and <sup>1</sup>H NMR chemical shifts of bis(1,1‐dimethylethyl) disulfide and bis(1,1‐dimethylethyl) trisulfide and their oxide derivatives

Freeman, Fillmore; Lee, Choonsun

doi:10.1002/mrc.1260260913

Cited by 7 publications

(4 citation statements)

References 47 publications

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“…Finally, the chemical shifts observed for the tert -butyl group bonded to the sulfenyl sulfur of 9 are slightly lower field than the ones of the corresponding monoxide 8 . These results are consistent with other NMR studies. , The 1 H NMR were very difficult to interpret owing to problems with overlapping signals.…”

Section: Tert-butylsulfenyl Tert-butyl Vic-disulfoxide (9)supporting

confidence: 92%

“…Oxidized Derivatives of Disulfides. The preparation and characterization of the oxidized derivatives of disulfides mentioned here were previously reported. ,, …”

Section: Methodsmentioning

confidence: 99%

“…The preparation, characterization, and applications of thiosulfonates and vic- disulfoxides (α - disulfoxides) has been extensively reviewed . In contrast, only a few dioxide derivatives of alkyl trisulfides (RS 3 O 2 R‘) have been isolated and characterized. − A variety of sulfenic sulfonic thioanhydrides 1 have been reported and were prepared by nonoxidative, synthetic procedures , …”

mentioning

confidence: 99%

“…Although various dioxides 1 have been reported, − ,, little is known about their chemical properties or their preparation by direct oxidation. In addition, little has been reported on the trisulfide dioxide derivatives 4 and 5 . 4a,c, Therefore, it was decided to further investigate this class of compounds, focusing on the di -tert -butyl derivatives.…”

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confidence: 99%

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Synthesis and Decomposition of Some Dialkyl Oxide Derivatives of Organotrisulfides

Derbesy

Harpp

1996

J. Org. Chem.

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Section: Tert-butylsulfenyl Tert-butyl Vic-disulfoxide (9)supporting

confidence: 92%

“…Oxidized Derivatives of Disulfides. The preparation and characterization of the oxidized derivatives of disulfides mentioned here were previously reported. ,, …”

Section: Methodsmentioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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Synthesis and Decomposition of Some Dialkyl Oxide Derivatives of Organotrisulfides

Derbesy

Harpp

1996

J. Org. Chem.

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Die Organoschwefelchemie der Gattung Allium und ihre Bedeutung für die organische Chemie des Schwefels

Block

1992

Angewandte Chemie

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Dieser Aufsatz ist ein Streifzug durch die Organoschwefelchemie der Gattung Allium, zu der unter anderem Knoblauch und Zwiebel gehören. Wir berichten über die Biosynthese der S‐Alk(en)yl‐L‐cystein‐S‐oxide (Aroma‐ und Geruchsvorstufen) in den intakten Pflanzen und darüber, wie diese Vorstufen beim Zerschneiden oder Zerdrücken der Pflanzen durch Allinase‐Enzyme zu Sulfensäuren — hochreaktiven Organoschwefel‐Zwischenprodukten — gespalten werden. Während im Knoblauch aus 2‐Propensulfensäure Allicin, ein Thiosulfinat mit antibiotischen Eigenschaften, entsteht, wird in Zwiebelgewächsen 1‐Propensulfensäure zum Sulfin (Z)‐Propanthial‐S‐oxid, dem tränenreizenden Faktor (LF), umgelagert. Zu den Highlights aus der Chemie der Zwiebel zählen die Zuordnung der Stereochemie des tränenreizenden Faktors und der Mechanismus seiner Dimerisierung; die Isolierung, Charakterisierung und Synthese von Thiosulfinaten, die möglichst genau Geschmack und Aroma einer gerade zerschnittenen Zwiebel nachahmen, sowie von anderen ungewöhnlichen Verbindungen wie den Zwiebelanen (Dithiabicyclo[2.1.1]hexanen), einem Bissulfin (Butandithial‐S,S′‐dioxid), anti‐thrombotischen und antiasthmatischen Cepaenen (α‐Sulfinyldisulfiden) und vic‐Disulfoxiden. Besonders bemerkenswert in der Chemie des Knoblauchs sind die Entdeckung des Ajoens, eines wirksamen Antithrombosemittels aus Knoblauch, und die Aufklärung der ungewöhnlichen Reaktionssequenz, die beim Erhitzen von Diallyldisulfid abläuft, das in Wasserdampf‐destilliertem Knoblauchöl vorkommt. Diskutiert werden [3,3]‐ und [2,3]‐sigmatrope Umlagerungen unter Beteiligung von Schwefel (z.B. Sulfoxid‐beschleunigte Thio‐ und Dithio‐Claisen‐Umlagerungen) und Cycloadditionen mit Thiocarbonylsystemen. Angesichts der kulinarischen Bedeutung der Allium‐Gewächse sowie deren Anwendung in der Volksmedizin wird schließlich noch die physiologische Wirksamkeit der Inhaltsstoffe dieser Pflanzen erörtert: Krebsvorbeugung, antimikrobielle Aktivität, Wirksamkeit als Lock‐ oder Abwehrstoffe bei Tieren oder Insekten, Geruchs‐, Geschmacks‐ und tränenreizende Eigenschaften, Wirkung auf den Fett‐Metabolismus, Hemmung der Plättchenaggregation im Fall von Ajoen. Anmerkungen über Mundgeruch und Sodbrennen durch Zwiebeln oder Knoblauch dürfen natürlich nicht fehlen.

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The Organosulfur Chemistry of the Genus Allium – Implications for the Organic Chemistry of Sulfur

Block

1992

Angew. Chem. Int. Ed. Engl.

982

701

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A Cook's tour is presented of the organosulfur chemistry of the genus Allium, as represented, inter alia, by garlic (Allium sativum L.) and onion (Allium cepa L.). We report on the biosynthesis of the S-alk(en)yl-L-cysteine S-oxides (aroma and flavor precursors) in intact plants and on how upon cutting or crushing the plants these precursors are cleaved by allinase enzymes, giving sulfenic acids-highly reactive organosulfur intermediates. In garlic, 2-propenesulfenic acid gives allicin, a thiosulfinate with antibiotic properties, while in onion I-propenesulfenic acid rearranges to the sulfine (2)-propanethial S-oxide, the lachrymatory factor (LF) of onion. Highlights of onion chemistry include the assignment of stereochemistry to the LF and determination of the mechanism of its dimerization; the isolation, characterization, and synthesis of thiosulfinates which most closely duplicate the taste and aroma of the freshly cut bulb, and additional unusual compounds such as zwiebelanes (dithiabicyclo(2.1. llhexanes), a bissulfine (a 1,4-butanedithial S,Y-dioxide), antithrombotic and antiasthmatic cepaenes (asulfinyl disulfides), and vic-disulfoxides. Especially noteworthy in the chemistry of garlic are the discovery of ajoene, a potent antithrombotic agent from garlic, and the elucidation of the unique sequence of reactions that occur when diallyl disulfide, which is present in steam-distilled garlic oil, is heated. Reaction mechanisms under discussion include [3,3]-and [2,3]-sigmatropic rearrangements involving sulfur (e.g. sulfoxide-accelerated thio-and dithio-Claisen rearrangements) and cycloadditions involving thiocarbonyl systems. In view of the culinary importance of alliaceous plants as well as the unique history of their use in folk medicine, this survey concludes with a discussion of the physiological activity of the components of these plants: cancer prevention, antimicrobial activity, insect and animal attractive/repulsive activity, olfactory-gustatory-lachrymatory properties, effect on lipid metabolism, platelet aggregation inhibitory activity and properties associated with ajoene. And naturally, comments about onion and garlic induced bad breath and heartburn may not be overlooked.

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¹³C NMR and ¹H NMR chemical shifts of bis(1,1‐dimethylethyl) disulfide and bis(1,1‐dimethylethyl) trisulfide and their oxide derivatives

Cited by 7 publications

References 47 publications

Synthesis and Decomposition of Some Dialkyl Oxide Derivatives of Organotrisulfides

Synthesis and Decomposition of Some Dialkyl Oxide Derivatives of Organotrisulfides

Die Organoschwefelchemie der Gattung Allium und ihre Bedeutung für die organische Chemie des Schwefels

The Organosulfur Chemistry of the Genus Allium – Implications for the Organic Chemistry of Sulfur

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13C NMR and 1H NMR chemical shifts of bis(1,1‐dimethylethyl) disulfide and bis(1,1‐dimethylethyl) trisulfide and their oxide derivatives

Cited by 7 publications

References 47 publications

Synthesis and Decomposition of Some Dialkyl Oxide Derivatives of Organotrisulfides

Synthesis and Decomposition of Some Dialkyl Oxide Derivatives of Organotrisulfides

Die Organoschwefelchemie der Gattung Allium und ihre Bedeutung für die organische Chemie des Schwefels

The Organosulfur Chemistry of the Genus Allium – Implications for the Organic Chemistry of Sulfur

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Product

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¹³C NMR and ¹H NMR chemical shifts of bis(1,1‐dimethylethyl) disulfide and bis(1,1‐dimethylethyl) trisulfide and their oxide derivatives