1, R = COCH3) reagiert mit aromatischen Aldehyden zu den 4-Cinnamoyl-Derivaten 2 (Tab. l), mit aromatischen Aminen und mit Hydrazin zu den Imino-Verbindungen 3 (Tab. 2) bzw. 4. Aus 3-Methyl-1-phenyl-pyrazolon (1, R = H) und Natrium-[tc-anilino-benzyll-sulfonat entsteht das 4-[a-Anilino-benzyl]-Derivat 8, das auch aus dem 4-Benzyliden-pyrazolon 7 erhalten werden kann. 7 und Derivate addieren Nitroalkane zu den Verbindungen 9 (Tab. 4). Die Pyrano-pyrazol-Derivate 10-12 werden aus Pyrazolonen und P-Ketosaureestern hergestellt. 1 (R = H) kondensiert mit Acetoacetaniliden, rnit p-Tolyl-thiocarbaniliden und mit Thioacetamid zu den 4-substituierten Pyrazolonen 13 und 14; es 1aBt sich auch rnit Aryliden(bzw. Cycloalky1iden)-acetophenonen zu den Derivaten 15 umsetzen. Condensation Reactions of 3-Methyl-I-phenyl-2-pyruzolin-5-one and its Derivatives 4-Acetyl-3-methyl-l-phenyl-2-pyrazolin-5-one(1, R = COCH3) reacts with aromatic aldehydes to give the 4-cinnamoyl derivatives 2 (table 1). Condensation with aromatic amines and hydrazine 1 (R = COCH3) gives the imino compound 3 (table 2) and 4, respectively. The reaction of 3-methyl-1-phenylpyrazolone (1, R = H) with sodium tc-anilinobenzylsulfonate leads to 4-[tc-anilinobenzyl] derivative 8; this is also obtained from the 4-arylidenepyrazolone 7. The compound 7 and its derivatives add nitro alkanes, giving 9ad (table 4). Pyranopyrazole derivatives 10 -12 have been synthesized from pyrazolones and (3-ketocarboxylic esters. 1 (R = H) condenses with acetoacetanilides, with p-tolyl thiocarbanilide, and with thioacetamide to produce the 4-substituted pyrazolones 13 and 14. It has also been converted to the derivatives 15 by reaction with arylideneacetophenones.

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Reduction of 1-bromo-l-nitrocyclohexane (I) was then studied using an excess of zinc and ammonium bromide. In this case the only product isolated was cyclohexylamine hydrobromide (IV).When nitrocyclohexane is reduced under the same conditions cyclohexylamine hydrobromide is also formed. When, however, the reaction is stopped after only one hour, N-cyclohexylhydroxylamine (V) is formed as is reported in the literature.2•3The structure of the hydrobromide was confirmed by treatment with aqueous alkali and preparation of W-cyclohexylbenzamide (VI) from the resulting free amine. EXPERIMENTAL 1-Bromo-1-nitrocyclohexane was prepared in 60% yield according to the procedure of Iffland and Criner.4 *Melting points and boiling points are uncorrected. Analyses by Mr. E. M. Hubbard and associates and by Galbraith Laboratories, Knoxville, Tenn.Zinc reduction of 1-bromo-l-nitrocyclohexane (I), (a) To nitrocyclohexane (II). 1-Bromo-l-nitrocyclohexane (20.8 g., 0.10 mole) was mixed with 250 ml. of methanol and 17.6 g. (0.18 mole) of ammonium bromide, 11.6 g. of 90% zinc dust (0.16 mole) added and heating of the mixture begun. As in Klager's experiment, a white precipitate formed almost immediately with concomitant disappearance of the zinc dust. However, the reaction was not stopped at this point but allowed to reflux for 12 hr. further. At the end of the reaction a white solid was still present. After cooling, this solid was removed by filtration, washed with methanol, dried (Abderhalden), and analyzed.

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4 : 4'-and 2 : d'-Dimethoxydiphenyl condense with succinic anhydride in presence of aluminium chloride to give f3-2-methoxy-!j+-methoxyphenyland b-Cmethoxy-3-o-methoxyphenyl-benzoylpropionic acid, respectively. Condensation of diphenyl and the a h v e derivatives with methylsuccinic anhydride gives two products in each case, Ar*COCH,*CHMe*CO&I and Ar.COCHMe*CH,*CO,H. Two acids of the former type are cyclised to naphthalene derivatives. 4Methoxydiphenyl gives four products, two of each type.Fluorene gives similarly a product of each type, and the a-methyl acid is converted into 3'-methyl-2 : 3-benzofluorene.SEVERAL investigators have reported that condensed plynuclear compounds such as naphthalene (Haworth, , respectively), and some phenolic ethers such as anisole and o-, m-, and P-tolyl methyl ether, condense with methylsuccinic anhydride in presence of aluminium chloride to give only the P-aroyl-a-methylpropionic acid. We have studied in this investigation whether this is true for diphenyl and some of its derivatives and fluorene. The products were always mixtures of the a-and the p-methyl acid, Ar*CO*CH,*CHMeCO,H and Ar-COCHMeCH2-C0,H, in which the former predominated. The structures of the a-methyl acids were deduced from the facts that they were the less soluble isomers (Org. Reactions, 1949, 5, 243) and with an alcoholic solution of salicylaldehyde and dry hydrogen chloride gave precipitates of the coloured py-ryium derivatives (cf. Mitter and De, J . Indian Ckm. Soc., 1939, 16, 199; Desai and Wali, PYOC. Indian A c d . Sci., 1937, 6, A , 135). The other isomers failed to give this reaction.Thus, diphenyl and methylsuccinic anhydride in nitrobenzene gave a mixture of the acids (Ia and b) in the ratio of 12 : 1. The yield of the latter acid increased when nitrobenzene was replaced by s-tetradoroethane. The position of attack on the diphenyl nucleus was elucidated by oxidising both acids to diphenyl4carboxylic acid. (Ib) R1 = H, R* = Me (11)The a-methyl-keto-acid (Ia) was reduced by Clemmensen's method to the butyric acid (11), which was cyclised with phosphoric oxide to the tetralone (111). This was reduced by lithium aluminium hydride to the tetralin (IV), which was dehydrogenated with selenium to 2-methyl-7-phenylnaphthalene (V). 4 : 4'-and 2 : 2'-Dimethoxydiphenyl condensed with succinic anhydride to give the acids (VIc; Ar = P-MeOC,H,, R3 = OMe, R4 = H) and (VIc; Ar = o-MeO*C,H,, R3 = H, Part IV, 4 : 4'-Dimethoxydiphenyl and Succinic Anhydride.-A stirred mixture of 4 : 4'-dimethoxydiphenyl (10 g.), aluminium chloride (13.4 g.), and nitrobenzene (50 ml.) was treated portionwise with a solution of succinic anhydride (5-2 g.) in nitrobenzene (200 ml.), then left overnight. The product was decomposed with ice and hydrochloric acid and treated with benzene, and the organic layer was extracted with sodium carbonate solution (charcoal), which was later acidiiied. The precipitated acid ( 14.6 g. ; m. p. 123-125") was ~-2-methoxy-S-p-mcthoxy~hcnyZbenz~Zpropionic acid (VIc; Ar = p-MeO*C,H,, Rs = OMe, R 4 = H), colo...