Hydrazine 1-benzyl-1-phenyl

Phenyl isocyanate, with ethyl hydrazine-carboxylate to give 4-phenyl-l-car-bethoxysemicarbazide,51,122 Phenylmercuric acetate, with methallyl alcohol to yield 2-methyl-3-phenyl-propionaldehyde, 51, 17 1-PHENYL-1,3-PENTADIYNE, 50, 97 1-PHENYL-1,4-PENTADIYNE. 50, 97 a-Phenylpentanal, from 2-benzyl-4,4,6-trimethyl-5,6-dihydro-l,3(4H)-... 

Die Hydrolyse von 4(5)-Nitroso-5(4)-phenyl-imidazolen in Gegenwart von Phenyl-hydrazin fiihrt zu 3-(a-Phenylhydrazono-benzyl)-1,2,4-oxadiazolen1244 ... 

Hydrazine bisthiosemi, clethodim, clofentezine, diclomazine, difenzoquat, ferimzone, flupoxam, maleic hydrazide, metamitron, methidathion, metribuzin, pymetrozine, tebuthiuron, thiazafluron, triclopyr Hydrazine (acetyl) metamitron Hydrazine (tertiobutyl) tebufenozide Hydrazine (p.tertio butyl benzyl) pyridaben Hydrazine (2.4 dichloro phenyl) sulfentrazone Hydrazine (dimethyl) daminozide Hydrazine (2.6 dimethyl phenyl) oxadixyl... 

Phenylethylamine has been made by a number of reactions, many of which are unsuitable for preparative purposes. Only the most important methods, from a preparative point of view, are given here. The present method is adapted from that of Adkins,1 which in turn was based upon those of Mignonac,2 von Braun and coworkers,3 and Mailhe.4 Benzyl cyanide has been converted to the amine by catalytic reduction with palladium on charcoal,5 with palladium on barium sulfate,6 and with Adams catalyst 7 by chemical reduction with sodium and alcohol,8 and with zinc dust and mineral acids.9 Hydrocinnamic acid has been converted to the azide and thence by the Curtius rearrangement to /3-phenyl-ethylamine 10 also the Hofmann degradation of hydrocinnamide has been used successfully.11 /3-Nitrostyrene,12 phenylthioaceta-mide,13 and the benzoyl derivative of mandelonitrile 14 all yield /3-phenylethylamine upon reduction. The amine has also been prepared by cleavage of N- (/3-phenylethyl) -phthalimide 15 with hydrazine by the Delepine synthesis from /3-phenylethyl iodide and hexamethylenetetramine 16 by the hydrolysis of the corre-... 

The reactivity of the carbonyl group in a,/3-unsaturated dialdoses was studied in more detail. The interaction with phenylhydrazine and its derivatives led to different results. 3-0-Benzyl-l,2-0-cyclo-hexyl idene-5,6-dideoxy-a-D-xyZo-hept-5-e nodialdo-l,4-furanose (56) gave57 a (2,4-dinitrophenyl)hydrazone. Action of (2,4-dinitrophenyl)-hydrazine on derivatives 67 led18 to complex mixtures. In the case of the acetylated derivatives (66), as well as of branched-chain derivatives (69), the interaction with (2,4-dinitrophenyl)hydrazine resulted in the formation of the expected hydrazones (Refs. 24 and 51, respectively). The interaction with phenylhydrazine was, however, proved to proceed by two paths in this case. Only the nitro derivatives (66, R = p-nitrophenyl) and (69, R = p-nitrophenyl) were shown24,51 to form the expected hydrazones. The phenyl derivative 66 (D-galacto, R = Ph) and p-methoxyphenyl derivative 69 (R = p-MeOC8H4) afforded substituted pyrazolines (74) (Ref. 24) and (75) (Ref. 51), respectively, as a result of subsequent intramolecular addition of a... 

BNTI was prepared as outlined in Scheme 3.15. Condensation of Boc-phenylhydrazine (145) with benzyl bromide gave Boc-iV -benzyl-iVi-phenyl-hydrazine (146) which was treated with naltrexone to give BNTI [205]. 

Ethoxy-phenyl)- X/2, 215 (2-Methoxy-benzyl)- X/2, 47 (4-Methoxy-benzyl)- E16a, 432 (Hydrazin-Alkyl.) 2-(l-Methyl-2-oxo-propyliden)-l-(2-butenyliden)- El4b, 660 (Hydrazon + 2-En-al) (2-Phenoxy-ethyl)- E16a, 427 (N-Alkyl.)... 

Benzyl-1 -(3-hydroxy-propyl)- E16a, 487 (R2N —NO —Red.) 2-(2-Hydroxy-butyl)-l-phenyl- El6a, 601 (R-NH-NH2 + Oxiran) 2-(2-Hydroxy-2-methyl-propyl)- 3 -phenyl- E16a, 601 (R-NH-NH2 + Oxiran) (4-Isopropyloxy-benzyl)- E16a, 432 (Hydrazin-Alkyl.) (4-Propyloxy-benzyl)- E16a, 432 (Hydrazin-Alkyl.)... 

Butyloxy-benzyl)- E16a, 432 (Hydrazin-Alkyl.) [3-(4-Methoxy-phenyl)-l -methyl-propyl]- E16a, 446 (Hydrazon-Red.)... 

Ethanol 2-[2-(Dimethylamino-ethyl)-methyl-amino]-l-phenyl- E21f, 5795 (CO-NR2 -> CH2-NR2) Hydrazin l-(3-tert.-Butyl-4-hydroxy-5-methyl-benzyl)-l-methyl- E16a, 477 (N-Benzylier.)... 

Abbreviations Ac acetyl AIBN azobisisobutyronitrile All allyl Bn benzyl Bz benzoyl ClAc chloroacetyl DAST diethylaminosulfur trifluoride DBU l,8-diazabicyclo[5.4.0]-undec-7-ene DDQ 2,3-dichloro-5,6-dicyano-/)-benzoquinone DMDO dimethyldioxirane DMTST dimethyl(methylthio)sulfonium trifluoromethanesulfonate Fmoc 9-fluorenyl-methoxycarbonyl HDTC hydrazine dithiocarboxylate IDCP iodonium di-collidine perchlorate Lev levulinoyl MBz 4-methylbenzoyl Me methyl MEK methyl ethyl ketone MP 4-methoxyphenyl NBS iV-bromosuccinimide NIS A-iodosuccinimide Pent n-pentenyl Pfp pentafluorophenyl Ph phenyl Phth phthaloyl Piv pivaloyl PMB 4-methoxybenzyl TBAF tetrabutylammonium fluoride TBDMS tcrt-butyldimethylsilyl TBDPS tert-butyldiphenylsilyl TCA trichloroacetyl TES triethylsilyl Tf trifluoromethanesulfonyl TMS trimethylsilyl Tol 4-methylphenyl Tr trityl Troc 2,2,2-trichloroethoxycarbonyl Ts tosyl. 

Nonafluor-2-trifluormethyl-2-penten reagiert mit 1,1-Dimethyl-hydrazin2374,2375 oder Benzal-dehyd-hydrazon701 zu 5-Fluor-l-methyl-3-pentafluorethyl-4-trifluormethyl- bzw. 5-Fluor-l-(a-fluor-benzyl)-3-pentaftuorethyl-4-fluormethyl-1 H-pyrazol. In hoher Ausbeute werden mit Phe-nyl-hydrazin 5-Fluor-l-phenyl-lH-pyrazole erhalten2063 ... 

Mit Phenyl- und Benzyl-hydrazin kdnncn die Zwischenstufcn gefaBt werden, die dann bei Basen-Einwir-kung 1 H-Pyrazole bilden981-1445-1651. 

Zur Reaktion von 3-Carboxy-2-(a-phenylhydrazono-benzyl)-oxiran zu 1,3-Diphenyl-lH-pyr-azol s.Bd. VIll/2a, S. 1008 (1973). Mit Natriumacetat in Ethanol am RiickfluB erhitzt, geben 3-Aroyl-2-carboxy-oxiran und Hydrazin-Hydrat oder Phenyl-hydrazin die entsprechenden 3-Ar y 1-5-car boxy-lH-pyrazole1322. 

Setzt man 2-Acetyl-l-phenyl-hydrazin mit Phosgen um, so erhalt man 2-Acetyl-3-hydroxy-IH-indazol544. Die Reaktion von 1-Benzyl-l-phenyl-hydrazin mit Harnstolf in Diphenylethcr oder in der Schmelze liefert /-Renzyl-3-hydroxy-1 H-indazol538 hlK. 

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