34284-44-1

Upstream product

• 67-56-1 methanol 
• 591-49-1 1-methylcyclohex-1-ene 
• 186581-53-3 diazomethane 
• 590-67-0 1-Methylcyclohexanol 
• 38772-60-0 2-Bromo-1-methoxy-1-methyl-cyclohexane 
• 1192-37-6 methylenecyclohexane 
• 623-26-7 terephthalonitrile 
• 1129-35-7 4-cyanobenzoic acid methyl ester 
• 4313-57-9 2,5-dihydrotoluene 
• 74-88-4 methyl iodide 
• 1638-26-2 1,1-Dimethylcyclopentane 
• 108-94-1 cyclohexanone 
• 7664-93-9 sulfuric acid 

Downstream Products

• 931-77-1 1-bromo-1-methylcyclohexane 

Relevant academic research and scientific papers

Hydride-Transfer Reactions in the Gas Phase. 2. Anchimeric Assistance in the H(-) Transfer from 1,1-Dimethylcyclopentane to Alkyl Cations

The gas-phase hydride transfer from the title compound to several ionic acceptors GA(+) = CH5(+), C2H5(+), s-C3H7(+), and t-C4H9(+) was studied by mass spectrometric and radiolytic methods in the pressure range 1.1E-8 - 700 Torr.Analysis of the irradiated mixtures points to the exclusive formation of rearranged products, with those with methyl migration prevailing over those with ring expansion.Thermochemical considerations, isotope labeling experiments, and deuterium isotope effect measurements concur in defining the detailed mechanism of the gas-phase hydride transfer, which involves significant anchimeric assistance of the methyl and methylene groups adjacent to the reaction center.The primary and the secondary α-D kinetic isotope effects, measured in the hydride transfer from the methylene moieties adjacent to the quaternary carbon of tthe title compound to either s-C3H7(+) or t-C4H9(+), amount to 2.70 (s-C3H7(+)) and 1.89 (t-C4H9(+)) and to 1.77 (s-C3H7(+)) and 1.15 (t-C4H9(+)), respectively.These values are interpreted in terms of a transition state, which is placed rather late along the reaction coordinate, and wherein the assistance of the neighboring (methyl or methylene) group to the departing hydride increases by decreasing the strength of the GA(+) acceptor.The results obtained from the present gas-phase investigation are discussed and compared with those of related gas-phase and solution data.

Nucleophilic Alkoxylations of Unactivated Alkyl Olefins and α-Methyl Styrene by Photoredox Catalysis

N,N-diisobutylaminophenyl-phenothiazine is a strongly reducing catalyst that allows – for the first time – the photoredox catalytic addition of alcohols to alkyl olefins as non-activated substrates to products with Markovnikov orientation. The irradiation at 365 nm does not require any additional reagent. Using α-methyl styrene as activated substrate we additionally show that this photoredox catalytic method tolerates other functional groups, including allyl, alkynyl, cyanide, and even acid-labile Boc groups within the substrate scope.

Microwave mediated protection of hindered phenols and alcohols

Hindered phenols and alcohols were protected as their corresponding ethers using different alkylating agents in presence of KOH/DMSO under microwave irradiation.

Efficient addition of alcohols, amines and phenol to unactivated alkenes by AuIII or PdII stabilized by CuCl2

The nucleophilic addition of alcohols, amines and phenol to unactivated alkenes catalyzed by cationic gold and palladium becomes limited due to the fast reduction into metallic gold under reaction conditions. The presence of CuCl2 retards the reduction of AuIII and PdII, strongly increasing the turnover number of gold and palladium catalysts. It is shown that new AuIII-CuCl2 and PdII-CuCl 2 catalysts are active and selective for the nucleophilic addition of alcohols, amines and phenol to unactivated alkenes. This journal is The Royal Society of Chemistry.

Effective Au(III)-CuCl2-catalyzed addition of alcohols to alkenes

Alkenes can be activated by Au(III) catalysts, and the effective addition of alcohols to alkenes can be carried out under mild conditions with Au(III), provided that catalytic amounts of CuCl2 are added, which significantly stabilize the cationic Au(III). The Royal Society of Chemistry.

The photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction (Part 4): methanol-olefins, methyl 4-cyanobenzoate

Dicyanobenzene-1,4 (1) and -1,2 are known to undergo substitution upon irradiation, in the presence of an olefin, in acetonitrile-methanol (3:1) solution.The products are 1:1:1 (methanol:olefin:aromatic) adducts, substituted on the aromatic ring with loss of a cyano group.This reaction, referred to as the photo-NOCAS (nucleophile-olefin combination, aromatic substitution) reaction, has been shown to be fairly general with regard to the olefin and the nucleophile that can be incorporated.Less is known about the scope of the reaction incorporating other electron-withdrawing substituted aromatic molecules.The purpose of this study was to determine if methyl 4-cyanobenzoate (10) would also take part in this reaction, to form 4-substituted aromatic esters.Irradiation of acetonitrile-methanol solutions of 10 and olefins 2,3-dimethyl-2-butene (2) and 1-methylcyclohexene (5) gave cyclic imine esters, 11 and 13, respectively, instead of photo-NOCAS products.The photo-NOCAS products were obtained when the codonor biphenyl (4) was added to the irradiation mixture.Formation of the cyclic imine ester is attributed to excitation of the charge-transfer complex formed between 10 and the olefin.The addition of biphenyl (4) serves to generate the contact radical ion pair (CRIP) upon irradiation of the charge-transfer complex between 10 and 4.This CRIP can dissociate to the solvent-separated radical ions, the radical cation of 4 can accept an electron from the olefin, and the olefin radical cation can go on to give the photo-NOCAS products.Irradiation of a solution of 10 and 2 in nonpolar solvent (benzene) gave the oxetane, believed to arise from the exciplex.In addition to photo-NOCAS products from 10, 4-cyanophenylketones 17 and 23 are also formed by attack of the β-alkoxyalkyl radical at the carboxyl carbonyl.The differences in behaviour between 1,4-dicyanobenzene (1) and methyl 4-cyanobenzoate (10) under these reaction conditions are described and explained.

Composition of Mixtures of Hydrocarbons after BIRCH-Reduction of Substituted Benzenes and Acid Catalyzed Addition of Alcohols to Alkylsubstituted Cyclohexenes and Carbohexa-1,4-dienes

10 different benzene hydrocarbons 1, indane, tetraline, anisol and phenol are reduced by sodium in liquid ammonia in the presence of methanol to the BIRCH products 2.The product mixture compositions are determined through capillary GLC.On storage at +6 deg C some rearomatization of the 1,4-cyclohexadienes 2 occurs.Data of the 1H- and 13C-.n.m.r. spectra and also mass spectra of the BIRCH 1,4-dienes 2 are given.For comparison 4-alkoxycyclohexenes 4 and 1-alkoxy-1-methylcyclohexanes 8 are prepared and spectroscopically characterized.Acid-catalyzed addition of alcohols to the 1,4-cyclohexadienes systems is a slow process and gives the 4-alkoxy-4-alkylcyclohex-1-enes (4) only in moderate yields up to 30percent.Most of the products are dimers 5 and also oligomers 6 of the parent hydrocarbons 2.

Three Component Reactions. XX. Methoxymercuration of Cyclohexa-1,4-dienes

The methoxymercuration of several cyclohexa-1,4-dienes leads to insoluble mixtures of mono- and bismercuricompounds 2-4 and 5-7.After reduction with NaBH4/NaOH mixtures of methoxycyclohexenes and bismethoxycyclohexanes result.The result of capillary gaschromatographic analyses and n.m.r. spectra allows a semiquantitative evaluation of the reaction pathways.

IODINE MEDIATED SYNTHESIS OF ALKYL TERTIO-ALKYL ETHERS

Mixed alkyl t-alkyl ethers have been prepared by the selective coupling of the alcohol precursors.Dehydration was promoted by iodine under hydrogen pressure at 100 deg C.

THE PHOTOCHEMICAL NUCLEOPHILE-OLEFIN COMBINATION, AROMATIC SUBSTITUTION REACTION (PART 2): METHANOL-CYCLIC OLEFINS, 1,4-DICYANOBENZENE

Direct irradiation of acetonitrile-methanol (3:1) solutions of 1,4-dicyanobenzene and the cyclic olefins, cyclohexene, 1-methylcyclohexene, norbornene, and 2-methylnorbornene, leads to formation of regio- and stereoisomers of the 1:1:1 (alcohol : olefin : aromatic) adducts.This reaction can be photosensitized by electron transfer; addition of electron donors, biphenyl or phenanthrene, to the irradiation mixture generally increases the efficiency and yield of adduct formation.The efficiency of the reaction and the ratio of isomeric adducts are also affected by the addition of salts, particularly magnesium perchlorate.All of the possible regio- and stereoisomers from cyclohexene and 1-methylcyclohexene have been identified, two from cyclohexene and four from 1-methylcyclohexene.Three of the four possible isomers from norbornene were characterized; the endo, endo isomer was not detected.There are eight possible isomers from 2-methylnorbornene; six were detected and five have been isolated and identified.The two sterically hindered isomers, those having both the 4-cyanophenyl and the methoxy groups in the endo position, and exo-3-(4-cyanophenyl)-endo-2-methoxy-exo-2-methylnorbornane, were not characterized.The structures of the products were established largely on the basis of the 1H and 13C nuclear magnetic resonance spectra.The mechanism of the reaction is discussed, with emphasis on those factors that may affect the product ratio.The most striking observation is that the reaction is regioselective when magnesium perchlorate is added to the irradiation mixture.