91763-46-1Relevant articles and documents
Sulfated tungstate as hydroxyl group activator for preparation of benzyl, including p-methoxybenzyl ethers of alcohols and phenols
Katkar, Kamlesh V.,Veer, Sachin D.,Akamanchi, Krishnacharya G.
supporting information, p. 1893 - 1901 (2016/11/25)
Sulfated tungstate was found to be an effective heterogeneous and reusable catalyst for hydroxy group activation–mediated preparation of benzylic ethers including p-methoxybenzylic ethers of a wide range of alcohols and phenols under mild reaction conditions.
The synthetic potential of graphite-catalyzed alkylation
Sereda, Grigoriy A.,Rajpara, Vikul B.,Slaba, Ryan L.
, p. 8351 - 8357 (2008/02/07)
Unmodified graphite is introduced as a mild catalyst for alkylation of aromatic compounds and primary alcohols, applicable when utilization of strong Lewis acids is not feasible. The electrophilic intermediate has a significant carbocationic character and can be formed on a partially rate-limiting step.
Lewis acid-catalyzed reductive etherification of carbonyl compounds with alkoxyhydrosilanes
Miura, Katsukiyo,Ootsuka, Kazunori,Suda, Shuntaro,Nishikori, Hisashi,Hosomi, Akira
, p. 313 - 315 (2007/10/03)
The TMSI-catalyzed reaction of aldehydes and ketones with alkoxydimethylsilanes gave unsymmetrical ethers in good to high yields. This reductive etherification is superior to the conventional method using two kinds of silicon reagents in terms of atom eff
Hypervalent (tert-butylperoxy)iodanes generate iodine-centered radicals at room temperature in solution: Oxidation and deprotection of benzyl and allyl ethers, and evidence for generation of α-oxy carbon radicals
Ochiai, Masahito,Ito, Takao,Takahashi, Hideo,Nakanishi, Akinobu,Toyonari, Mika,Sueda, Takuya,Goto, Satoru,Shiro, Motoo
, p. 7716 - 7730 (2007/10/03)
1-(tert-Butylperoxy)-1,2-benziodoxol-3(1H)-one (1a) oxidizes benzyl and allyl ethers to the esters at room temperature in benzene or cyclohexane in the presence of alkali metal carbonates. Since this reaction is compatible with other protecting groups such as MOM, THP, and TBDMS ethers, and acetoxy groups, and because esters are readily hydrolyzed under basic conditions, this new method provides a convenient and effective alternative to the usual reductive deprotection. Oxidation with 1a occurs readily with C-H bonds activated by both enthalpic effects (benzylic, allylic, and propargylic C-H bonds) and/or polar effects (α-oxy C-H bonds), generating α-oxy carbon-centered radicals, which can be detected by nitroxyl radical trapping. Measurement of the relative rates of oxidation for a series of ring-substituted benzyl n-butyl ethers 2d and 2p-s indicated that electron-releasing groups such as p-MeO and p-Me groups increase the rate of oxidation, and Hammett correlation of the relative rate factors with the σ+ constants of substituents afforded the reaction constant ρ+ = -0.30. The large value of the isotope effect obtained for the oxidation of benzyl n-butyl ether 2d (k(H)/k(D) = 12-14) indicates that the rate-determining step of the reactions probably involves a high degree of benzylic C-H bond breaking. The effects of molecular dioxygen were examined, and the mechanism involving the intermediacy of the tert-butylperoxy acetal 5 and/or the hydroperoxy acetal 32 is proposed. Particularly noteworthy is the finding that (tert-butylperoxy)iodane 1a can generate the tert-butylperoxy radical and the iodine-centered radical 33a, even at room temperature in solution, via homolytic bond cleavage of the hypervalent iodine(III)-peroxy bond.
Action of Lewis Acids on Aromatic Acetals
Alphonse, I.,Arulraj, S. J.
, p. 820 - 822 (2007/10/02)
Acetals of the type X.C6H4CH(OR)2, where R = Et, n-Bu and isoamyl, and X = H and CH3, react with antimony perchloride and ferric chloride in anhydrous 1,2-dichloroethane to give benzyl alkyl ether, alkyl benzoate, benzyl ester, α,β-unsaturated aldehyde, benzaldehyde and a small quantity of benzyl alcohol. p-Nitrobenzaldehyde di-n-butyl acetal gave only p-nitrobenzaldehyde and a trace of p-nitrobenzyl alcohol.The mechanism of the formation of benzyl alkyl ether is explained by a hydride ion transfer and that of α,β-unsaturated aldehyde by an aldol type of condensation.The aliphatic and aromatic aldehydes produced in the reaction could undergo Tischenko reaction in the presence of antimony or iron alkoxides to give the esters.
Action of Boron Trifluoride on Aromatic Acetals
Alphonse, I.,Arulraj, S. J.
, p. 199 - 200 (2007/10/02)
Acetals of the type X-C6H4CH(OR)2 (where R = Et, n-Bu and isoamyl and X = H, CH3) react with boron trifluoride in anhyd. 1,2-dichloroethane to give benzyl alkyl ethers, α,β-unsaturated aldehydes and benzaldehyde.However, p-nitrobenzaldehyde di-n-butyl acetal gives only p-nitrobenzaldehyde.The formation of benzyl alkyl ethers is explained by a hydride ion transfer mechanism and that of α,β-unsaturated aldehyde by an aldol-type of condensation.
