The Isomerization by Base of Alkyl Allyl Sulfides to Alkyl Propenyl Sulfides. The Mechanism of the Reaction<sup>1</sup>

Tarbell, D. S.; Lovett, William E.

doi:10.1021/ja01591a063

Cited by 52 publications

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“…Mixed divinyl nitroalkyl orthoacetates, prepared by the acid-catalyzed reaction of ketene divinyl acetal with nitroalkanols, are converted to nitro alkyl acetates by hydrolysis (105,236,278).…”

Section: A Synthetic and Other Applications Of Ortho Ester Hydrolysesmentioning

confidence: 99%

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Reactions of Ortho Esters Which Result in Carbon-Oxygen and Carbon-Halogen Bond Formation

1970

Carboxylic Ortho Acid Derivatives - Preparation and Synthetic Applications

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In this chapter are considered reactions of trialkyl orthocarboxylates and tetraalkyl orthocarbonates which result in the formation of new carbonoxygen or carbon-halogen bonds. In most of these reactions the ortho ester (or an alkoxycarbonium ion derived from it) functions as an alkylating agent.Many of these reactions are useful synthetic tools. These include formation and hydrolysis of cyclic ortho ester derivatives of diols and triols (which serve to protect the hydroxyl groups of the polyols, and provide means for their mild monoacylation), alkylation of phenols, enols and acids (to form ethers and esters), and conversion of carbonyl compounds to acetals and ketals. Other reactions, such as the alkylation of halogens by ortho esters, are of only limited synthetic utility, while still others, such as the acidcatalyzed hydrolyses of ortho esters, are of interest primarily because of the light they shed on the mechanisms of reactions of ortho esters with nucleophilic reagents.

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Section: A Synthetic and Other Applications Of Ortho Ester Hydrolysesmentioning

confidence: 99%

“…Hydrolysis of tetraethyl orthocarbonate in heavy water has been used as a convenient synthesis of C 2 H 5 OD (236,278).…”

Section: A Synthetic and Other Applications Of Ortho Ester Hydrolysesmentioning

confidence: 99%

Reactions of Ortho Esters Which Result in Carbon-Oxygen and Carbon-Halogen Bond Formation

1970

Carboxylic Ortho Acid Derivatives - Preparation and Synthetic Applications

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“…Durch Umsetzung von Allylbromid (XXI) mit 8-Mercapto-acrylester-Na-Salz wurde die Verbindung XXII erhalten, welche im 1R.-Spektrurn die fur endstandige Vinylgruppen charakteristischen Banden bei 990 und 930 cm-1 aufweist. Die durch Verseifung der Estergruppe erhaltenc Saure liess sich durch Behandlung mit Kalium-t-butylat in Dimethylsulfoxid zu XXIII isomerisieren [7], das im 1R.-Spektrum die fur trans-Athylenverbindungen typische Bande bei 950 cm-1 besitzt. Auch die NMR.-Spektren der Verbindungen XXIII und XXIV sind rnit den angenommenen Strukturen in Ubereinstimmung.…”

Section: XVIunclassified

Synthesen substituierter Butenolide

Haefliger¹,

Petrzilka²

1966

Helvetica Chimica Acta

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“…The infrequency with which allyl and benzyl groups inigrate from sulphur to carboil 111,~y be due t o d-orbital resonance diininishillg the charge on the potential inigration terillinus (cf. the effect of sulphur on the stability of anions (20,21,24)). Siinilar reasoils have been put forward t o account for the failure of thiophcnol acetate t o undergo the Fries rearrangement (26).…”

Section: B4vin: Aliphatic Chemistry Of Fluorenementioning

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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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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The Isomerization by Base of Alkyl Allyl Sulfides to Alkyl Propenyl Sulfides. The Mechanism of the Reaction¹

Cited by 52 publications

References 0 publications

Reactions of Ortho Esters Which Result in Carbon-Oxygen and Carbon-Halogen Bond Formation

Reactions of Ortho Esters Which Result in Carbon-Oxygen and Carbon-Halogen Bond Formation

Synthesen substituierter Butenolide

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

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The Isomerization by Base of Alkyl Allyl Sulfides to Alkyl Propenyl Sulfides. The Mechanism of the Reaction1

Cited by 52 publications

References 0 publications

Reactions of Ortho Esters Which Result in Carbon-Oxygen and Carbon-Halogen Bond Formation

Reactions of Ortho Esters Which Result in Carbon-Oxygen and Carbon-Halogen Bond Formation

Synthesen substituierter Butenolide

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

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The Isomerization by Base of Alkyl Allyl Sulfides to Alkyl Propenyl Sulfides. The Mechanism of the Reaction¹