The conversion of isonicotinic acid and its derivatives to l-methylisonipecotic acid and its derivatives has been accomplished by several different series of reactions (1). In some instances incomplete reduction of the pyridine ring occurred giving dihydro-or tetrahydro-pyridines (la, b). Unfortunately, these partially reduced compounds were not completely characterized and the comparison of the various materials is difficult. We have had occasion to repeat certain of these procedures and as a result have found errors in the literature and are able to report additional derivatives of l-methylisonipecotic acid and 1-methyl-l,2,3,6-tetrahydroisonicotinie acid.Supniewski and Serafinowna (la) (referred to as SS in this paper) reported that the reduction of methyl isonicotinate methiodide (la) over Adams' catalyst gave either methyl 1-methylisonipecotate hydriodide (Ilia) or methyl 1-methyl-

When the carbons of carborane participate in exocyclic rings the thermal rearrangement of the ortho carborane nucleus to the meta configuration is opposed. These molecules as a whole therefore resist degradation at elevated temperature. Chemically these cyclics are stable under acid conditions but the silicon-carborane carbon bond is attacked by bases. Additional types of cyclic silazanes are reported and reactions of some functional groups at the silicon atoms are described. Results and DiscussionConsiderable evidence of both a chemical and a physical nature has been amassed to establish the skeletal structure of 1,2-dicarbaclovodod ecaborane (12) (carborane) as an icosahedron of ten boron atoms and two atoms in which the carbon atoms are in nearest proximity or ortho to each other,1-6 although other structures have been postulated.

Reductions with lithium aluminum hydride have been characterized by the high degree of predictability of the products (1). In a few instances groups were anomalously reduced due to the structure of the compound treated with this reagent (1). Recently, however, three interesting molecular rearrangements have been reported to occur with lithium aluminum hydride indicating a new type of reaction with this reagent. Cram (2) has shown that the phenyl groups of the ptoluenesulfonic acid esters of either 2-phenyl-3-pentanol or 3-phenyl-2-pentanol undergo rearrangement by a Wagner-Meerwein reaction to form a mixture of 2and 3-phenylpentane on treatment with lithium aluminum hydride. Cope (3) reported the formation of bicyclo[3.3.0]octane-l-methanol by a reductive rearrangement, resembling a Favorski rearrangement, of bicyclo[3.3.1]nonan-9one. N-Ethyl-and N-propyl-aniline have been isolated in addition to the ex-SUMMARY Acetophenone oxime and six para-substituted-acetophenone oximes were reduced with lithium aluminum hydride. The products from normal reduction, 1 -(p-substituted-phenyl) -1-ethylamine (I), and from reduction with rearrangement, p-substituted-N-ethylaniline (II), were isolated from every reaction. The yield of the product of reductive-rearrangement, II, was shown to increase with an increase in electron-releasing capacity of the para-substituent.

REACTIONS OF 1-METHYL-4-HALO-4-PIPER1DYL PHENYL KETONES 333 in methanol). The mixture was heated for 6 hr. and allowed to stand overnight. The solvent was removed by distillation under reduced pressure, and the residue was washed with 150 ml. of ether. The ether solution was distilled under reduced pressure to give 1.9 g. (83%) of 2-methoxv-6methyl-2-phenyl-l-ox-6-azaspiro [2.5 ¡octane

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