Hydrazine phenyl-, acetate

It was observed in those cases in which the oxidation was arrested too soon that an appreciable amount of silver chloride was deposited when the solution was concentrated. Furthermore, the mother liquor, when treated with phenyl-hydrazine in acetic acid, deposited some yellow crystalline D,L-mannose phenylhydrazone, m. p. 195-200° (Maquenne block). It is apparent that too vigorous oxidation results in the formation of hexoses. 

However, in the reaction of cyclohexanone, benzylisonitrile, 4-methoxy-phenyl-hydrazine and acetic acid a dihydro-cinnoline was formed by a novel MCR (Scheme 10.4). 

A line of slope 0-94 has been drawn through the points for alkylamines. The deviation of hydroxylamine and hydrazine is 16,000 and 400-fold, respectively, which is somewhat greater than for the term. The alpha-effect is about 10 times greater in general base-catalyzed aminolysis of phenyl acetates than in uncatalyzed aminolysis (Bruice and Benkovic, 1964). In addition, a large alpha-effect is observed in the methoxyl-amine-catalyzed hydrolysis of ethyl trifluoroathiolacetate (Fedor and Bruice, 1965). Even in the general base-catalyzed dehydration of... 

Treatment of N-2,4-dinitrophenylpyridinium chloride (778) with phenyl-hydrazine in acetic acid causes reductive cyclization to yield the pyrido[l,2-ajimidazole (779). 3-Aminocrotononitrile, MeC(NH2)=CHCN, condenses with quinoline 1-oxide and isoquinoline 2-oxide to form the tricyclic compounds (780) and (781), respectively." The imidazo[5,l-a]isoquinoline derivative (783) is obtained by the action of phenyl isothiocyanate on the sodium salt of the Reissert compound (782)." ° Triethyl phosphite reduces the o-nitrophenyldipyr-rolylmethane (784 R=N02) to the nitrene (784 R = N), which forms the pyrrolo[3,2-6]quinoline derivative (785) by an intramolecular insertion reac-tion." 3-Amino-177-isoindole (786) reacts with acetylacetone in the presence of perchloric acid to yield the pyrimidoisoindolium salt (787). ... 

The rate of reaction of 2-(4-imidazolyl)phenyl acetate with hydrazine is enhanced by a factor of about 20 and mechanisms analogous to 37 and equation 10 are possible [55]. 

Prepare a solution of phenylhydrazine by dissolving 1 0 g. of phenyl-hydrazine hydrochloride and 1 5 g. of crystallised sodium acetate in 10 ml. of water if the resulting solution is turbid, filter. Add a solution of 0 5 ml. of cycZohexanone in 8 ml. of water to the reagent... 

Hippuric acid, cyclization to 2 phenyl-5 oxazolone with acetic anhydride, 47,101 Holarrhimine, 46, 61 Hydrazine, reaction with cinnamalde-hyde, 47, 99... 

Treatment of 5-(dichlorophenylmethyl)-3-phenyl[ 1,2,4]triazin-6( 1H)-one 357 or the respective ketone with hydrazine or phenylhydrazine gave 358, which were cyclized with acetic acid to pyrazolo[4,3-c][ 1,2,4]triazines 359 (84PHA504 85MI2) (Scheme 77). 

Refluxing of hydrazine 60 in acetic acid in the presence of sodium acetate resulted in the formation of 6-methyl-3-oxo-8-phenyl-3,4-dihydro-2/7-pyrimido[6,l-r-][l,2,4]triazine-9-carbonitrile 61 in good yield <1997IJB269> (Equation 2). 

The treatment of (2-benzoylamino-5-iodobenzoyl-amino)acetic acid ethyl ester 88 with hydrazine hydrate for 4h yielded hydrazine derivative 2-benzoylamino-iV-hydrazinocarbonylmethyl benzamide 89, which on refluxing with sodium acetate and acetic acid for 8 h resulted in the formation of 6-iodo-10-phenyl-3//-3,4,9,10a-tetra-azaphenanthren-2-one 90 <2000IJH59> (Scheme 5). 

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)-... 

B. 4-Phenyl-l-carbethoxysemicarbazide. In a 1-1. three-necked round-bottomed flask equipped with a liquid-sealed mechanical stirrer (Note 3), a constant-pressure dropping funnel, and a reflux condenser fitted with a drying tube containing silica gel is placed a solution of 52 g. (0.5 mole) of ethyl hydrazine-carboxylate in 550 ml. of dry benzene (Note 4). The solution is cooled in an ice bath, and the stirrer is started. To the solution is added 59.7 g. (55 ml., 0.5 mole) of phenyl isocyanate (Note 5) dropwise over a period of 45 minutes. After about one-half of the isocyanate has been added, a white precipitate of the product appears, and the reaction mixture becomes progressively thicker. After addition is complete the ice bath is removed, and the mixture is stirred at room temperature for 2 hours and then is heated under reflux for 2 hours. The suspension is allowed to cool to room temperature, and 4-phenyl-1-carbethoxysemi-carbazide is isolated by suction filtration, washed with 500 ml. of benzene, and dried in a vacuum desiccator. The yield is 108 g. (97%), m.p. 151-152°. The product is not further purified before being used in the next step. It may be recrystallized from ethyl acetate to yield white crystals, m.p. 154-155°, vmax 1645, 1687, 1797, and 3300 cm.-1 (Note 6). 

Nitro-2-hydrazinotoluene, It golden-yel or orn-yel ndls with a violet tinge (from ale), mp 179-80° diffc sol in hot ale xylene was prepd by heating the K salt of N-[4-Nitro-2-methyl-phenyl] -hydrazine-N,N -disul-fonic acid with coned HC1 (Refs 1 3) 3-Nitro-4-hydmzinotoluene, dk-red ndls (from eth), mp 110—11° v sol in acet sol in eth, chlf benz si sol in petr eth was prepd by diazotizing 2-nitro-4-methylaniline with Zn chloride HC1. Its Hydrochloride salt, C7H9N3O2+HCI, orn-red ndls or plates (from w) dec at 190-91° (Refs 2 4)... 

Treatment of 3-acetylpyridines (140, R = H, Et) with hydrazine in refluxing glacial acetic acid produced the N-unsubstituted bicycles.132 1-Phenyl derivatives 141 (R = H, Me, Ph), however, were provided from acid-catalyzed cyclization of the corresponding hydrazones.133,134... 

Mesoionic pyrido[2,l- >][1,3]oxazines (54) afforded 4-oxo-4//-pyrido[l,2-a]pyrimidin-l-iumolates (55) and 4//-quinolizin-4-one (56) with phenyl iso(thio)cyanates [78LA1655 79CB1585 82ZN(B)222] and dimethyl acetylenedicarboxylate (79CB1585), respectively. Reaction of 2-cyano-3-methyl-lH,6//-pyridol[l,2-a][3,l]benzoxazine-l,6-dione with ammonium acetate and hydroxylamine, hydrazines, primary aliphatic or aromatic amines, and (thio)ureas gave 5-unsubstituted and 5-substituted 2-cyano-3-methyl-l//,6H-pyrido[l,2-a]quinazoline-l,6-diones (93CCC1953). 

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