Rearrangement of Benzyl Sulfides to Mercaptans and of Sulfonium Ions to Sulfides Involving the Aromatic Ring by Alkali Amides<sup>1,2</sup>

Hauser, Charles R.; Kantor, Simon W.; Brasen, Wallace R.

doi:10.1021/ja01107a032

Cited by 59 publications

(15 citation statements)

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“…Both benzyl methyl sulphide and dibenzyl sulphide underweilt the Stevens rearrangement, more typical of the reactions of quaternary a~ninoniun~ compounds. Similar rearrangeinents have been reported for some sulphonium co~npounds (4,9). Although allylamine-Noxides show allylic rearrangement: from nitrogen to oxygen (10, l l ) , related allyl (12) and benzyl (4) sulphoxides and sulphones do not rearrange.…”

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confidence: 54%

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Aliphatic Chemistry of Fluorene: Part Viii. Benzyl 9-Fluorenyl Sulphoxide and Some 9-Fluorenyl Sulphides

Bavin¹

1962

Can. J. Chem.

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Allyl 9-fluorenyl sulphide, benzyl 0-fluorenyl sulphide, and di-0-fluorenyl s~~l p h i d e are stable to boiling ethereal phenyl lithiun~, in marlied contrast to the corresponding ethers. Benzyl 9-fluorenyl sulphoside has been prepared and shown to be more weakly acidic than 9-fluorenyl sulphones.Wittig and co-worlcers have reported ( I ) that the anions (I) derived from certain 9-fluorenyl ethers rearrange to the corresponding 9-substituted-9-fluorenyl allioxides (11). Of particular interest to the present study were the ailions of the allyl and benzyl ethers (I, R = CHZCH=CH2 and CGHbCH?, respectively) which rearranged very rapidly a t -10". The anion of di-9-fluorenyl ether rearranged a t room temperature but those of other allryl and aryl ethers required elevated temperatures and longer reactioil times.These reactions belong to a wider group lcnown as the Stevens rearrangement (2, pp. 527-528; 3, pp. 282-283; 4). Most of the published work has been concerned with ethers (1,5, 6,7,8) but Hauser and co-worlcers have examined some sulphides (4). Both benzyl methyl sulphide and dibenzyl sulphide underweilt the Stevens rearrangement, more typical of the reactions of quaternary a~ninoniun~ compounds. Similar rearrangeinents have been reported for some sulphonium co~npounds (4,9). Although allylamine-Noxides show allylic rearrangement: from nitrogen to oxygen (10, l l ) , related allyl (12) and benzyl (4) sulphoxides and sulphones do not rearrange. Allyl phenyl sulphide and allyl p-tolyl sulphide possibly undergo the ortho Claiseil rearrangement (13; cf. ref. 14) b u t more slowly than the correspo~lding ethers. Ulllilie the ether, t-butyl phenyl sulpllide does not rearrange when distilled (15, IG).We have now prepared by a general method (17) allyl 9-fluorenyl sulphide, beilzyl 9-fluorenyl sulphide, and di-9-fluorenyl sulpl~ide. All three sulphides dissolved in ethereal solutioils of phenyl lithiuin with formation of the deep red color associated with fluorene anions of this type (1, 18) but the color was apparently unchanged after boiling under reflux for up t o 24 hours. Hydrolysis with water regenerated the original sulphides. Thus the anions of the sulphides are more stable than those of the ethers, resembling the 9-fluorenyl-triallrylai~linoi~ium compounds in not undergoiilg the ortho rearrangement (19).

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“…282-283; 4). Most of the published work has been concerned with ethers (1,5,6,7,8) but Hauser and co-worlcers have examined some sulphides (4). Both benzyl methyl sulphide and dibenzyl sulphide underweilt the Stevens rearrangement, more typical of the reactions of quaternary a~ninoniun~ compounds.…”

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confidence: 99%

Aliphatic Chemistry of Fluorene: Part Viii. Benzyl 9-Fluorenyl Sulphoxide and Some 9-Fluorenyl Sulphides

Bavin¹

1962

Can. J. Chem.

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“…This can be understood by considering that the irradiation of a sulfonium chloride group may generate sulfonium ylides: [21,22,23]. X-ray exposure may also induce the nucleophilic attack of the sulfonium groups by water and Bottom scan shows the precursor sulfonium polymer.…”

Section: Surface Species Of Ppvmentioning

confidence: 99%

Interface formation of metals and poly(p-phenylene vinylene): surface species and band bending

Ettedgui

Hsieh

Gao

1997

Polym. Adv. Technol.

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We used X‐ray photoemission spectroscopy (XPS) to investigate the surface species of poly(p‐phenylene vinylene) (PPV) and its interface formation with Ca and Al. PPV surfaces compositions varied with sample preparation. For relatively ""clean'' surfaces with 4–5% O, analysis of the O 1s peak revealed four types of oxygen species, namely carbonyl (C=O), hydroxyl (C–OH), ether (C–O–C) and the carboxylic groups (HO–C=O). The oxygen groups, excluding ether, reacted with Al or Ca to form the corresponding metal oxides. Chemical interactions between the metals and the phenylene and vinylene units to yield new species were not detected. For sulfur‐free surfaces, a C 1s peak shift of +0.5 eV followed the deposition of 15–30 Å of Ca on PPV. For sulfur‐containing surfaces, the C 1s peak shift was −0.5 eV. We attribute this difference to the interaction of metal atoms with the sulfur impurities. For Al/PPV, a C 1s peak shift occurred at <2 Å of Al deposition and reached a constant value of about +0.4 eV after ⪅8 Å of Al. Again, the direction of the peak shift depended on the presence of sulfur impurities. We attribute the C 1s peak shifts to surface band bending and to Schottky barrier formation. Since surface oxidation of PPV can inhibit band‐bending, our overall results suggest that the barrier height at the metal/PPV interface is highly sensitive to the surface preparation and relatively insensitive to the work function of the metals. The shift seen by XPS in the C 1s core level spectra of PPV points clearly to charge transfer and Schottky barrier formation at the interface as a result of metal deposition. These results imply that the metal/polymer interface is not rigid and that triangular barrier tunneling fails to take into account the effect of barrier formation. We propose a band‐bending modified tunneling (BBMT) model to explain charge transfer at the Ca/polymer interface. © 1997 John Wiley & Sons, Ltd.

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“…For example, dibenzyl sulfide has been shown to undergo Sommelet rearrangement (Eq. 2-68; Hauser et al, 1953). In addition to this [2,3] sigmatropic rearrangement (which will be discussed in greater detail in Chapter 7), dibenzyl sulfide also undergoes Wittig rearrangement, a [1,2] sigmatropic process (Eq.…”

Section: Rearrangementmentioning

confidence: 99%

“…2-72 ;Hayashi and Baba, 1975) may actually occur by an intramolecular addition-elimination route as depicted. In an important study of solvation…”

mentioning

confidence: 99%

Sulfur-Containing Carbanions

1978

Organic Chemistry: A Series of Monographs

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Rearrangement of Benzyl Sulfides to Mercaptans and of Sulfonium Ions to Sulfides Involving the Aromatic Ring by Alkali Amides^1,2

Cited by 59 publications

References 5 publications

Aliphatic Chemistry of Fluorene: Part Viii. Benzyl 9-Fluorenyl Sulphoxide and Some 9-Fluorenyl Sulphides

Aliphatic Chemistry of Fluorene: Part Viii. Benzyl 9-Fluorenyl Sulphoxide and Some 9-Fluorenyl Sulphides

Interface formation of metals and poly(p-phenylene vinylene): surface species and band bending

Sulfur-Containing Carbanions

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Rearrangement of Benzyl Sulfides to Mercaptans and of Sulfonium Ions to Sulfides Involving the Aromatic Ring by Alkali Amides1,2

Cited by 59 publications

References 5 publications

Aliphatic Chemistry of Fluorene: Part Viii. Benzyl 9-Fluorenyl Sulphoxide and Some 9-Fluorenyl Sulphides

Aliphatic Chemistry of Fluorene: Part Viii. Benzyl 9-Fluorenyl Sulphoxide and Some 9-Fluorenyl Sulphides

Interface formation of metals and poly(p-phenylene vinylene): surface species and band bending

Sulfur-Containing Carbanions

Contact Info

Product

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About

Rearrangement of Benzyl Sulfides to Mercaptans and of Sulfonium Ions to Sulfides Involving the Aromatic Ring by Alkali Amides^1,2