91967-68-9

Upstream product

• 104-85-8 para-methylbenzonitrile 
• 67-63-0 isopropyl alcohol 
• 23304-24-7 p-tolyldiazomethane 
• 109-92-2 ethyl vinyl ether 
• 132907-18-7 3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene 
• 3587-58-4 isopropoxymethyl chloride 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 589-18-4 4-Methylbenzyl alcohol 
• 104-82-5 4-Methylbenzyl chloride 
• 104-87-0 4-methyl-benzaldehyde 

Relevant academic research and scientific papers

Reductive Etherification via Anion-Binding Catalysis

Reductive condensations of alcohols with aldehydes/ketones to generate ethers are catalyzed by a readily accessible thiourea organocatalyst that operates in combination with HCl. 1,1,3,3-tetramethyldisiloxane serves as a convenient reducing reagent. This strategy is applicable to challenging substrate combinations and exhibits functional group tolerance. Competing reductive homocoupling of the carbonyl component is suppressed.

Comparative activity of aryl, alkyl, and cycloalkyl halides in the suzuki reaction catalyzed with acyclic diaminocarbene complex of palladium

Relative activity of halogenated arenes, alkanes, and alkanes in the Suzuki reaction catalyzed with acyclic diaminocarbene complex of palladium has been investigated. Under all the investigated conditions, 4-iodoanisole has been more active than the alkyl

Lanthanide(III) triflate-catalyzed thermal- and microwave-assisted synthesis of benzyl ethers from benzyl alcohols

The lanthanide(III) trifluoromethanesulfonate-catalyzed condensation of benzyl alcohols with primary and secondary alcohols is described. This reaction proceeds readily with benzyl alcohols that have an alkyl or aryl substituent at the α-, ortho-, or para-position using microwave radiation or heating. The intra-molecular variant of this reaction leads to cyclic benzofurans.

The Reduction of Nitrile with 2-Propanol over Hydrous Zirconium Oxide

The vapor-phase reduction of nitriles with 2-propanol proceeded efficiently over hydrous zirconium oxide to give the corresponding alcohols in high yields.

REACTIVITY OF 3,6-DIMETHOXY-3,6-DIMETHYLCYCLOHEXA-1,4-DIENE: NUCLEAR VERSUS BENZYLIC NUCLEOPHILIC SUBSTITUTION

The treatment of cis/trans-3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene (ca. 1/1 mixture; easily prepared electrochemically in multigram scale from p-xylene) under acidic conditions (acetic, trifluoroacetic, sulfuric, or a Lewis acid) yields almost exclusively 2-methoxy-1,4-dimethylbenzene 4, through a trasposition reaction.The use of aqueous hydrochloric or hydrofluoric acid gives 2,5-dimethylphenol 12, and with hydrogen chloride a mixture of 2- and α-chloro-p-xylene (13, 14) is isolated.Different oxygen-, nitrogen-, and sulfur-containing nucleophiles (alcohols,thiols, or hydrazoic acid) react with 3 under acid catalysis giving the corresponding products resulting from a nuclear or/ and benzylic substitution on p-xylene (15 - 20).The reaction of compound 3 with organolithium reagents affords exclusively benzylic products 21 in a regiospecific manner.In all cases the mixtures of isomers are separated by column chromatography.The lithiation of compound 3 with lithium powder or lithium naphthalenide fails, giving p-xylene.A probable mechanism is proposed for the studied reactions.

THE EFFECT OF ARYL SUBSTITUENTS ON ARYLCARBENE REACTIVITY

Substituted (p-MeO, p-Me, H, p-Cl, p-Br, m-Br, m-MeO, 3,4-Cl2, p-CO2Me, m-CN and p-CN) monophenylcarbenes are generated in a binary mixture of substrates (methanol, cis-4-methyl-2-pentene and cyclohexane) and the relative rate of O - H insertion into methanol to stereospecific cyclopropanation of the olefin to C - H insertion into cyclohexane are calculated from the ratios of products and substrates.It is found (i) that the reactivities of the substrates decrease in the order of methanol, olefin and cyclohexane and (ii) that electron-donating substituents generally lead to reaction with the more reactive substrates while the reaction with the less reactive substrates is favoured in the case of electron-withdrawing substituents.These results are interpreted in terms of the change in the electrophilicity of the singlet arylcarbene by the substituents rather than the change in the singlet-triplet equilibrium.

Effects of Substituents and Generation Methods on Insertion-Addition Selectivities of ''Arylcarbene'' in Alcohol-Olefin Binary Mixtures. Intervention of Reaction of Diazo Compounds Masquerading as Carbenes

A Hammett study of the insertion-addition selectivity (Ki/ka) and cyclopropanation stereoselectivity (kc/kt) of "arylcarbene" generated either photolytically or thermally in 2-propanol-ethyl vinyl ether binary mixtures showed that ρ values are highly sensitive to the generation method.Thus, plots of ki/ka and kc/kt vs. ? (?+) in the photolytic run gave ρ values of -0.96 (r = -0.96) and -0.15 (r = -0.95), respectively, whereas similar values are +1.4 (r = 0.93) and -1.1 (r = -0.96) in the thermal run.The results along with the effects of precursor, temperature, and sensitizer on the product distributions are interpreted as indicating that, while free carbene is involved in the photolytic run, the ground-state diazo compound is masquerading as carbene in its thermal reaction with the olefin.

Temperature and Substituent Effects on Regioselectivity in the Insertion of Arylcarbene into Alcohols

Photolysis of aryldiazomethanes in methanol, ethanol, and 2-propanol gave OH insertion products along with small amounts of CH insertion products at ambient temperature.However, the CH insertion products increased significantly at the expense of the ether as the temperature was lowered.The attempted sensitized decomposition of the diazomethane did not lead to an increase in the CH insertion products presumably because of a rapid singlet-triplet equilibrium.The key intermediate leading to the CH insertion is suggested to be ground-state triplet arylcarbene, based on the accumulated spectroscopic as well as chemical evidence for the intervention of the triplet arylcarbene in the low-temperature photolysis of aryldiazomethanes.Substituents on the phenyl ring also have an appreciable effect on the insertion selectivity.At room temperature, the OH/CH insertion selectivity increased with the electron-donating ability of the substituents.This is interpreted in terms of the substituent effect on the transition state of OH insertion, where there is a deficiency of electrons at the benzylic carbon atom, rather than on the stability of singlet carbene.At low temperature, both electron-donating and -withdrawing substituents facilitate OH insertion, indicating the change in substituents induces a concomitant change in the insertion mechanism, presumably due to decreasing nucleophilicity of carbene with increasing electron-withdrawing ability as well as decreasing proton-donor activity of alcohol with decreasing temperature.This may also reflect the effect of the substituent on the singlet-triplet energy gap.