Methyl phenyl, hydrate

H-Tellurin 2,6-Dimethyl-4-oxo-E12b, 802 (1,4-Diin + Li2Te) Telluroxid Methyl-phenyl- (Hydrate) E12b, 645 (RR TeCI2 + NH3/ H20)... 

Dimethyl-I,l -biphenyl has been prepared by a wide variety of procedures, but few of these are of any practical synthetic utility Classical radical biarjl syntheses such as the Gomberg reaction or the thermal decomposition of diaroyl peroxides give complex mixtures of products m which 4,4 dimethyl-l.l -biphenyl is a minor constituent A radical process maj also be involved in the formation of 4,4 dimethyl-1, l -biphenyl (13%) by treatment of 4-bromotoluene with hydrazine hydrate 5 4,4 -Dimethyl-l,l -biphenyl has been obtained in moderate to good yield (68-89%) by treatment of either dichlorobis(4-methyl phenyl)tellurium or l,l -tellurobis(4-methylbenzene) with degassed Raney nickel in 2 methoxyethyl ether 6... 

Phenyl hydrate, see Phenol Phenyl hydride, see Benzene Phenyl hydroxide, see Phenol Phenylic acid, see Phenol Phenylic alcohol, see Phenol Phenylmethane, see Toluene Phenyl methanol, see Benzyl alcohol Phenyl methyl alcohol, see Benzyl alcohol iV-Phenylmethylamine, see Methylaniline... 

Until quite recently the isolation of optically active seienoxides has been limited to those contained in steroids (isolated as diastereoisomeis). < The difficulty in obtaining these compounds was attributed to the racemization through the achiral hydrated intermediates. Simple optically active sel enoxides (S-11% ee) were first prepared by kinetic resolution. Direct oxidation of selenides to seienoxides was first reported using optically active oxaziridine derivatives under anhydrous conditions, but the extent of the asymmetric induction was somewhat unsatisfactory with methyl phenyl selenide as substrate (8-9% Recently much improved enantiomeric excesses (45-73%) were achieved with new oxaziridine reagents such as (70). An attempt at the asymmetric oxidation of more bulky selenides was independently carried out using Bu OCl in the presence of (-)-2-octanol (equation 55), but resulted in unsatisfactory enantioselectivities (ee 1%). Much better results were obtained by the oxidation of p-oxyalkyl aryl selenides (ee 18-40% equation 56) 27 gjyj selenides (ee 1-28%) using... 

Derivation Reaction of methyl phenyl ether and chloral hydrate. 

From 1960, Pracejus studied the base-catalyzed methanolysis of ketenes in depth [45]. Using 0-acetylquinine as a catalyst, he obtained (S)-methyl hydrat-ropate in 74% ee at -110 °C from methyl phenyl ketene. An inversion of absolute configuration occurred on raising of the temperature. 

Indazolo[2,3-c]chinazolin388 Ein Gemisch von 20,9 g (0,1 mol) 3-(2-Amino-phenyl)-indazol, 22 g (0,15 mol) Tricthoxy-mcthan und 2g 4-Methyl-benzolsulfonsaure-Hydrat in 500 m/ Ethanol wird unter Riihren 30 min zum RuckfluB erhitzt. Der ausgefallene Nicdcrschlag wird nach dem Abkiihlen abgesaugt und mit Ethanol und Diethylether gewaschen Ausbeute 16 g (73%) Schmp. 167-169° (gelbliche Nadeln). 

The salts of some enamines crystallize as hydrates. In such cases it is possible that they are derived from either the tautomeric carbinolamine or the amino ketone forms. Amino ketone salts (93) ( = 5, 11) can serve as examples. The proton resonance spectra of 93 show that these salts exist in the open-chain forms in trifluoroacetic acid solution, rather than in the ring-closed forms (94, n = 5, 11). The spectrum of the 6-methylamino-l-phenylhexanone cation shows a multiplet at about 2.15 ppm for phenyl, a triplet for the N-methyl centered at 7.0 ppm and overlapped by signals for the methylene protons at about 8.2 ppm. The spectrum of 93 ( = 11) was similar. These assignments were confirmed by determination of the spectrum in deuterium oxide. Here the N-methyl group of 93 showed a sharp singlet at about 7.4 ppm since the splitting in —NDjMe was much reduced from that of the undeuterated compound. 

Alkylquinazolines are catalytically reduced to the corresponding 3,4-dihydro derivatives/ The only example of a 4-substituted quin-azoline which was reduced to its 3,4-dihydro derivative is 2-chloro-4-phenylquinazoline which gave 4-phenyl-3,4-dihydroquinazoline/ 4-Methylquinazolines are susceptible to oxidation, as is shown by the attempted nitration of 2,4-diraethylquinazoline which causes the removal of the methyl group with formation of 4-hydroxy-2-methyl-6-nitroquinazoline/ When the 4-substituent is —C(Et) (C02Et)2 recrystallization of the picrate from ethanol is sufficient to convert it to 4-hydroxyquinazoline/ Similar hydrolyses occur in acid solution and the mechanism undoubtedly involves a hydrated intermediate/... 

Deactivation (weak) from the adjoining ring does not prevent facile disubstitution of 4-methyl- and 4-phenyl-2,7-dichloro-1,8-naphthyridines wdth alkoxides (65°, 30 min), p-phenetidine (ca. 200°, 2 hr), hydrazine hydrate (100°, 8 hr), or diethylaminoethylmer-captide (in xylene, 145°, 24 hr) mono-substitution has not been reported. Nor does stronger deactivation prevent easy 2-oxonation of 5,7-dimethoxy-l-methylnaphthyridinium iodide wdth alkaline ferricyanide via hydroxide ion attack adjacent to the positive charge and loss of hydride ion by oxidation. 

Benzopyran-3-one, l,4-dihydro-6,7-dimethoxy-], 55, 45 Isocyamde, benzyl-, 55, 98 Isocyanide, butyl-, 55, 98 ISOCYANIDE, tert-butyl- [Isocyamde, 1,1-dimethylethyl-], 55, 96 Isocyamde, cyclohexyl-, 55, 98 Isocyamde, dodecanyl-, 55, 98 Isocyamde, ethyl, 55,98 Isocyamde, methyl, 55, 98 Isocyamde, phenyl-, 55, 98 (-)-2,3 4,6-Di-0-isopropylidene-2-keto-L-gulomc acid, hydrate [L-jcy/o-2-Hex-ulosomc acid, bis-<9-( 1 -mcthylcthyl-ldene)-], 55,80, 81 ISOXAZOl F, 3-(4-chlorophenv1)-5-(4-methoxyphenyl)-, 55, 39 Isoxazole,5 -(4-chloropheny l)-3-(4-me th-oxyphenyl)-, 55,42... 

Stability of the compounds 86 varies dramatically with the nitrogen substituent. Methyl" and phenyl s derivatives (86 R = Me or Ph) are moderately stable crystalline solids—often hydrated (87 or 88 X = OH). The 2,4-dinitrophenyl derivative [86 R = C6H3(NO2)2, R = H] is less stable but can be isolated as orange prisms (mp 112°C)5° It readily rearranges to the diaryl ether 96 (mp 128°C) with which it was originally confused.5The monomeric 5-nitro-2-pyridyI derivative is similarly unstable and in solution dimerizes giving adduct 97a. 5 5 The 4,6-di-methylpyrimidin-2-yl derivative can only be isolated as the dimers 97b and... 

Pyrolysis of the ethylene acetal of bicyclo[4.2.0]octa-4,7-diene-2,3-dione yields a-(2-hydroxyphenyl)-y-butyrolactonc 11 a mechanism involving a phenyl ketene acetal is proposed. Tartrate reacts with methanediol (formaldehyde hydrate) in alkaline solution to give an acetal-type species (9) 12 the formation constant was measured as ca 0.15 by H-NMR. Hydroxyacetal (10a) exists mainly in a boat-chair conformation (boat cycloheptanol ling), whereas the methyl derivative (10b) is chair-boat,13 as shown by 1 H-NMR, supported by molecular mechanics calculations. 

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