6-Methyl-2-phenyl-6-heptene

Epoxidation of (Z)-2-methyl-2-hepten-l-ol gave epoxy alcohol 61 (80% yield, 89% ee) [2], of (Z)-2-methyl-4-phenyl-2-buten-l-ol gave 62 (90%, 91% ee) 177], and of (2T)-1 -hydroxy squalene gave 63 (93%, 78% ee) [85]. The epoxy alcohol 64 had >95% ee after recrystallization [91], In the epoxidation of (Z)-2-r-butyl-2-buten-l-ol, the allylic alcohol with a C-2 r-butyl group, the epoxy alcohol was obtained in 43% yield and with 60% ee [38], These results lead one to expect that other 2,3Z-disubstituted allylic alcohols will be epoxidized in good yield and with enantioselectivity similar to that observed for the 3Z-monosubstituted allylic alcohols (i.e., 80-95% ee). 

Male moths and butterflies have proven to be an especially rich source of interesting natural products. The sex pheromone produced in the wing glands of the lesser waxmoth, Achroia grisella, is composed of n-undecanal and (Zj-ll-octadecenal (98), whereas that of the greater waxmoth also contains n-undecanal (.99) but is dominated by n-nonanal (100). The scent brushes of male noctuid moths produce large amounts of aromatic compounds and terpenes which are believed to function as aphrodisiacs (101). Benzaldehyde, 2-phenyl ethanol, benzyl alcohol, 6-methyl-5-hepten-2-one, pinocarvone, and isobutyric acid have been identified in the secretions of different noctuid species (102), and it appears that these pheromones may possess some chemotaxonomic value. 

JV- Methyl-iV-(2 -methyl-phenyl)amino]-2-pentene (194) (Z)-3-[iV-Methyl-iV-(2 -methylphenyl)-amino]-2-pentene (195) ( )-4-(iV-Phenylamino)-3-heptene... 

Cyclisation of a stirred mixture of 3-methyi-6-(6-methyi-5-hepten-2-yi)-2,4-hexadienoic acid in refluxing acetic anhydride containing fused sodium acetate during 30 hours led to 5-methyl-2-(6-methyl-5-hepten-2-yl)phenyl acetate in 70% yield (ref.60). 

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. 

One mole of isoprene reacted with one mole of acetoacetate by using a bidentate phosphine as ligand (56). Reaction of 2,3-dimethylbutadiene with acetoacetate was carried out by using PdCl2 in the presence of sodium phenoxide. When PPh3 was used, a 1 2 adduct was obtained. On the other hand, use of P-phenyl-l-phospha-3-methyl-3-cyclopentene (105) at 100°C caused the 1 1 addition to give 3-carbomethoxy-5,6-dimethyl-5-hepten-2-one (106), from which 5,6-dimethyl-5-hepten-2-one (107) was formed. This compound is the useful intermediate for a-irone synthesis (96). 

The hydroformylation of several olefins in the presence of Co2(CO)8 under high carbon monoxide pressure is reported. (S)-5-Methylheptanal (75%) and (S)-3-ethylhexanal (4.8%) were products from (- -)(S)-4-methyl-2-hexene with optical yields of 94 and 72%, respectively. The main products from ( -)(8)-2,2,5-trimethyl-3-heptene were (S)-3-ethyl-6,6-di-methylheptanal (56.6%) and (R)-4,7,7-trimethyloctanal (41.2%) obtained with optical yields of 74 and 62%, respectively. (R)(S)-3-Ethyl-6,6-dimethylheptanal (3.5% ) and (R)(S)-4,7,7-trimethyloctanal (93.5%) were formed from (R)(S)-3,6,6-trimethyl-l-heptene. (+/S)-l-Phenyl-3-methyl-1-pentene, under oxo conditions, was almost completely hydrogenated to (- -)(S)-l-phenyl-3-methylpentane with 100% optical yield. 3-(Methyl-d3)-l-butene-4-d3 gave 4-(methyl-d3)pentarwl-5-d3 (92%), 2-methyl-3-(methyl-d3)-butanal-4-d3 (3.7%), 3-(methyl-d3)pentanal-2-d2,3-d1 (4.3%) with practically 100% retention of deuterium. The reaction mechanism is discussed on the basis of these results. 

S)-l-Phenyl-3-methyl-l-pentene, initially synthesized to extend the data obtained with (+)(S)-2,2,5-trimethyl-3-heptene, under usual oxo conditions is almost completely hydrogenated with an optical yield of practically 100% while the hydroformylation products are barely detectable. 

Methyl-5-oxo-4-phenyl-2,5-dihydro- VI/2, 614f. 5-Hepten-3-in l-(2-Furyl)-2-oxo-IV/lb, 845... 

Thus, total 1,3-asymmetric induction is observed and the tram configuration is determined on the basis of the H-NMR spectrum. On the other hand, when (E)-5-hepten-2-ol is cyclized under similar conditions, a tram Ids diastereomeric ratio of 75 25 is observed, probably due to the decreased steric hindrance of a methyl group compared to a phenyl group. Tertiary alcohols have also been cyclized and the low asymmetric induction observed is due to the difficulty of the substrate to discriminate between two similar substituents on the same carbon atom. In all cases diastereomeric ratios are determined by an analysis of H-NMR spectra40. 

Cerveny et al. (7J) report hydrogenation of nine olefinic substrates (1-hexene, ethyl acrylate, allyl phenyl ether, allylbenzene, 3-butene-l-ol, 2-butene-l-ol, 3-butene-2-ol, 2-methyl-2-propene-l-ol, l-heptene-4-ol) in seven solvents (cyclohexane, diethyl ether, toluene, methanol, benzene, ethyl acetate, and 1,4-dioxane) on 5% Pt on silica gel. No linear relation could be proved for any of the substrates when Eq. (21) was applied to the set of data obtained in the hydrogenations. In all cases correlation points for benzene and toluene did not fit. On omitting these points, experimental data satisfied Eq. (21), but linear regression gave a nonzero absolute term q on the righthand side of the equation ... 

The authors also investigated Diels-Alder reactions of 1050 (Scheme 1.280). For example, reaction of 1050 with methyl acrylate first afforded the bis-oxazabicy-clo[2.2.1]heptene 1053, which fragmented to the diketone 1054. Recyclization of 1054 gave the bis-pyrrole 1055, from which 5-phenyl-2-propanoyl-3-pyrrolecar-boxylic acid methyl ester 1056 was isolated after hydrolysis. Ethylene diamine... 

A soln. of 2-acetyl-5-methyl-6-phenyl-2,3-dihydro-4H-l,2-diazepin-4-one in methanol exposed 3 hrs. to sunlight in a Pyrex flask -> 2-acetyl-5-methyl-6-phenyl-l,2-diazabicyclo[3.2.0]-6-hepten-4-one. Y 88%. F. e. s. J.-L. Derocque,W. J. Theuer, and J. A. Moore, J. Org. Chem. 33, 4381 (1968). 

Polymerizations of many internal olefins, like 2-butene, 2-pentene, 3-heptene, 4-methyl-2-pen-tene, 4-phenyl-2-butene, and others, with Ziegler-Natta catalysts, are accompanied by monomer rearrangements. The isomerizations take place before insertions into the chains. The double bonds migrate from the internal to the a-positions ... 

Poly(4-(hexadecyloxy)-benzolc acld-4-[(2-methyl-1-oxo-2-propenyl) oxy] phenyl ester) - 4,200 Benzene/heptene, 52/48, 66/34 [67]... 

Solvolysis of bicyclo[3,l,l]hept-6-yl, bicyclo[3,2,0]hept-6-yl, and bicyclo[4,l,0]-hept-2-yl dinitrobenzoates with a-methyl substituents gave product mixtures containing 20-35 % of 3-methylcyclohept-3-en-ol with a-phenyl substituents, no cyclo-heptene product was obtained. 

Benzoyl-5-methyl-4-phenyl-l,2-diazabicyclo[3.2.0]-3-hepten-6-ol added to methylene chloride containing anhydrous pyridine hydrochloride, and allowed to stand 2 hrs. at 25° 2-benzoyl-6-methyl-7-phenyl-8-oxa-2,3-diazabicyclo[3.2.1]oct-6-ene. Y 70%. S.M. Rosen and J. A. Moore, J. Org. Chem. 37, 3770 (1972). 

---