122210-83-7

Upstream product

• 1445-91-6 (S)-1-phenylethanol 
• 75-05-8 acetonitrile 
• 103-50-4 dibenzyl ether 
• 74-88-4 methyl iodide 
• 98-85-1 1-Phenylethanol 
• 75-36-5 acetyl chloride 

Relevant academic research and scientific papers

An Iron-Based Dehydration Catalyst for Selective Formation of Styrene

We report the synthesis and crystal structure of [Fe(OTf)2(FOX)] (A). This robust iron(II) complex was successfully applied as a homogeneous catalyst for the dehydration of 1-phenylethanol to styrene. Even at low catalyst loadings and moderate reaction temperatures,A showed a high catalytic efficiency. It was found to selectively activate the benzylic alcohol group of 1-phenylethanol. This is challenging since the vinyl system of styrene is highly reactive. In contrast to most of the other dehydration processes, the use of a Br?nsted acid was not necessary. Furthermore, mechanistic insights into this E1-type transformation and its competing SN1-type side reactions are reported. [Fe(cHexOH)(OTf)(FOX)][OTf] (B), an alcohol adduct ofA, [Fe(H2O)2(FOX)][OTf]2(C), the completely hydrated derivative ofA, and [μ-O{Fe(OTf)(FOX)}2][OTf]2(D), a dinuclear oxidation product ofA, were also characterized and are discussed.

Boyer's Reaction and Transetherification: Mechanism and New Perspectives

The progress and stereochemistry of Boyer's reaction were analyzed using several simple, chiral, alcoholic substrates, a variable amount of BiBr3 and different solvents. Basic solvents inhibit the reaction, while cyclohexane works very well; thus, it was our choice for the present study. In contrast to previous works, BiBr3 behaves as a true catalyst, being not consumed during the reaction. Although poisoning of the catalyst occurs to some extent, it does not prejudice the reaction yields (>90%). Gas chromatography/mass spectrometry (GC-MS) monitoring of the reaction revealed that, for example, in the presence of alcohol rac-1, isomeric ethers 4 transetherificate to 3. We propose a unifying mechanistic model for both Boyer's and transetherification reactions, in which the electronic properties of n-adducts intermediates, formed by combination of bismuth(III) of BiBr3 and oxygen atoms of alcohols and ethers, play the key role for both the reactivity and the stereochemical outcome of the reaction.

Organohalide-catalyzed dehydrative O-alkylation between alcohols: A facile etherification method for aliphatic ether synthesis

Organohalides are found to be effective catalysts for dehydrative O-alkylation reactions between alcohols, providing selective, practical, green, and easily scalable homo- and cross-etherification methods for the preparation of useful symmetrical and unsymmetrical aliphatic ethers from the readily available alcohols. Mechanistic studies revealed that organohalides are regenerated as reactive intermediates and recycled to catalyze the reactions.

Thiazolium-based catalysts for the etherification of benzylic alcohols under solvent-free conditions

Thiazolium and imidazolium hybrid materials were prepared by radical reactions between a mercaptopropyl-modified SBA-15 mesoporous silica and bis-vinylthiazolium or bis-vinylimidazolium dibromide salts. These hybrid materials were characterized by several techniques and were employed in the etherification reaction of 1-phenylethanol. Solvent-free conditions at 160C under different gas phases (oxygen, air, nitrogen and argon) were used. The thiazolium-based material displayed excellent performances. Further studies were carried out using unsupported thiazolium salts, with or without a methyl group at the C-2 position of the thiazolium moiety. These studies allowed us to propose a reaction mechanism. The supported thiazolium-based material was successfully used in the etherification reaction of two other benzylic alcohols and also in seven consecutive cycles. This work represents the first use of thiazolium-based compounds as catalysts for the etherification reaction of alcohols.

Gold catalysis: Alkyl migration in the addition of alcohols to nitriles

Benzhydroles and nitriles upon gold-catalysed conversion deliver symmetrical ethers and/or N-substituted carboxylic amides. While with most phosphane ligands tested, the dominating product is always the ether, with the trimesitylene ligand the amides are the major products. The reaction conditions are much milder than those reported previously. Mechanistic control experiments with a chiral alcohol prove the intermediacy of carbenium ions, further studies with not readily ionisable alcohols indicate that for the benzhydroles the carbenium ions and gold(I)-hydroxy complexes are intermediates.

A stereocontrolled approach to ethers with two α stereocentres

The stereocontrolled synthesis of enantiomeric pairs of four ethers, in which the oxygen atom is flanked by two α stereocentres, has been achieved using a chiral base/arene chromium tricarbonyl activation approach. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Reactions of Thianthrene Cation Radical with Acyclic and Cyclic Alcohols

Thianthrene cation radical perchlorate (Th(.+)*ClO4(-)) reacted readily with cycloalkanols (C5, C7, C8, and C12), alkan-2-ols (C3, C5, C6, and C8), 3-hexanol, neopentyl alcohol, a number of benzyl alcohols, dl- and (S)-1-phenylethanol, cyclopentyl- and cyclohexylmethanols, the exo- and endo-borneols, and norborneols.Reactions were carried out with an excess of the alcohol in acetonitrile solution containing 2,6-di-tert-butyl-4-methylpyridine.Products were alkenes, ethers, and N-substituted acetamides, depending on the structure of the alcohol.Thianthrene (Th) and its 5-oxide (ThO) were formed in equal amounts.The sum of amounts of products from the alcohol was equal to the amount of ThO.All reactions are interpretable on the basis of the ultimate formation and further reactions of a 5-alkoxythianthreniumyl ion (ROTh(+)).The predominant formation of nortricyclene from the norborneols is striking and is discussed.Swern-Moffatt-type oxidations of the alcohols were not observed.

EFFECT OF THE NATURE OF THE ACYLATING AGENT ON THE ASYMMETRIC ACYLATION OF ALCOHOLS

During the acylation of racemic 1-phenylethanol by the action of carboxylic acid anhydrides in the presence of S-(-)-N,N-dimethyl-α-phenylethylamine the unreacted alcohol is enriched in the S isomer.Its optical purity increases with increase in the steric demands of the anhydride from 2percent for acetic anhydride to 9percent for benzoic anhydride.When carboxylic acid chlorides are used, optically active 1-phenyl-1-chloroethane and bis-1-phenylethyl ether are isolated in addition to S-(-)-1-phenylethanol.