Ar-Cyclohexylation

Ar-Cyclohexylation In the cyclohexylation DCC behaves as a typical alkylating agent. Promoters include H2SO4 and AlClj. 

Abbreviations Aik, alkyl AN, acetonitrile Ar, aryl Bu, butyl cod, 1,5-cyclooctadiene Cp, cy-clopentadienyl Cp , pentamethylcyclopentadienyl Cy, cyclohexyl dppm, diphenylphosphinome-thane dpme, Ph2PC2H4PMe2 Et, ethyl fod, 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octane-dionate HOMO, highest occupied molecular orbital LUMO, lowest unoccupied molecular orbital Me, methyl MO, molecular orbital nbd, norbornadiene Nuc, nucleophile OTf, triflate Ph, phenyl Pr, propyl py, pyridine THE, tetrahydrofuran TMEDA V,V,M,M-tetramethylethylenediamine. 

Abbreviations aapy, 2-acetamidopyridine Aik, alkyl AN, acetoniuile Ar, aryl Bu, butyl cod, 1,5-cyclooctadiene COE, cyclooctene COT, cyclooctatetraene Cp, cyclopentadienyl Cp , penta-methylcyclopentadienyl Cy, cyclohexyl DME, 1,2-dimethoxyethane DME, dimethylformamide DMSO, dimethyl sulfoxide dmpe, dimethylphosphinoethane dppe, diphenylphosphinoethane dppm, diphenylphosphinomethane dppp, diphenylphosphinopropane Et, ethyl Ec, feirocenyl ind, inda-zolyl Me, methyl Mes, mesitylene nb, norbomene orbicyclo[2.2.1]heptene nbd, 2,5-norbomadiene OTf, uiflate Ph, phenyl PPN, bis(triphenylphosphoranylidene)ammonium Pi , propyl py, pyridine pz, pyrazolate pz, substituted pyi azolate pz , 3,5-dimethylpyrazolate quin, quinolin-8-olate solv, solvent tfb, teti afluorobenzobaiTelene THE, tetrahydrofuran THT, tetrahydrothiophene tmeda, teti amethylethylenediamine Tol, tolyl Tp, HB(C3H3N2)3 Tp , HB(3,5-Me2C3HN2)3 Tp, substituted hydrotiis(pyrazol-l-yl)borate Ts, tosyl tz, 1,2,4-triazolate Vin, vinyl. 

Treatment of 2 -anilinofluorans with ketones such as acetone or 2-butanone in hydrochloric acid in the presence of iron(III) chloride gives 4,4 -alkylidenebis(A-fluoran-2-ylaniline)s. Thus, 2 -anilino-6 -(A-cyclohexyl-/V-methylainino)-3 -methylfluoran, (86) is treated with acetone in hydrochloric acid in the presence of iron(III) chloride to give 2,2-bis(4-[6 -(N-cy c 1 o hexyl-Ar-methy 1 amino)-3 -methylfluoran-2 -ylamino]phenyl (propane (87)60 (Eq. 9). 

Ar = Ph, 3-CF3Ph, 2-MeOPh, 4-MeOPh, 3-pyridyl, 1-cyclohexyl, 1-naphthyl... 

The direct high-pressure animation of ethylene with ammonia to give ethylamine occurs in the presence of acidic zeolite catalysts such as H-elinoptilolite, H-erionite or H-offretite38. Primary amines R1NH2(R1 = Bu, cyclohexyl, PhCH2, Ph or Ar) have been monoalkylated by reaction with di-t-butyl dicarbonate, followed by successive treatment of... 

Ar= Ph and (methyl, alkoxy, halo, nitro) derivatives, 3-pyridyl, 1-naphthyl, 4-cyclohexenyl, cyclohexyl (55-94 %)... 

Typical procedure for group-transfer radical cyclization preparation of compound 3bP (Ar = p-CF3CgH4) To a solution of 2-(allyloxy)cyclohexyl 4-(trifluoromethyl)phenyl... 

Conducted in toluene. BHA = 2,6-di-ter -butyl-4-methoxyphenyl Naph = naphthyl Cy = cyclohexyl Ar = 2,6-diisopropylphenyl ent = enantio. Molar equivalents to the amounts of organolithium. 

The reaction of Ph 3P=CH2 with benzoyl isocyanate takes place in a 1 2 ratio with loss of benzene to afford the ylide 173 <71JOC2029> and treatment of either Ph3P=CHC02Me or Ph3P=CHC02Et with aryl cyanates, Ar-O-CN, results in formation of the pyrimidine ylides 174 <67CB187>. An alternative means of access to 171 (R = cyclohexyl) is provided by... 

Ar, C6H3-Ph2-2,6 Ar", C6H3-Me2-2,6 TIPT, S-C6H2-i-Pr3-2,4,6 Np, CH2CMe3 Cy, cyclohexyl OTf, triflate. c Short-lived. 

To evaluate the influence of the organic R group of the RS-thioether function and to allow a comparison with ArS(CH2)4SAr (see above), Cul was reacted with 1,4 bis(cyclohexyl)butane CyS(CH2)4SCy. The colorless crystals obtained by reaction in a 1 1 metal to ligand ratio were found to be of composition... 

No cyclic tautomers of C-aryl- (83LA1937) and C-cyclohexyl-A-(3-hydroxypropyl)nitrone 39 (R = Ar, QHn) (84CZ283) were observed in solution on H-NMR spectroscopy. However, acylation of these nitrones gave 0-acyl derivatives with the cyclic structure. A mixture of two isomers ([B]/[A] = 0.43, H-NMR) was detected (84CZ283) in a CDC13 solution of the nitrone 39 (R = Me). 

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