Vil’yams, V. V. published the artcileRing isomerization of nitrogen heterocycles. Reaction of N-methyl-3-aminomethylpiperidine with nitrous acid, Application In Synthesis of 14613-37-7, the publication is Doklady TSKhA (1965), No. 115(Pt. 1), 247-53, database is CAplus.
N-Methyl-3-aminomethylpiperidine (I) diazotized under the conditions of Demjanov rearrangement gave 39.8% N-methyl-3-hydroxymethylpiperidine (II), about 5% N-methyl-3-methyltetrahydropyridine (III), and 15% 1-methyl-1,5,5,6-tetrahydro-2H-azepine (IV). To the ice-cooled solution of 25.6 g. I and 28.8 g. 85% H3PO4 in 200 cc. H2O was added 14.5 g. NaNO2 in 50 cc. H2O, the mixture heated, saturated with Na2CO3, and extracted with dichloroethane to give 1.14 g. 1:4.4 mixture of III and IV (b55 84-90°, d20200 0.8514, n20D 1.4585, MRD 35.61), 10.27 g. of II, b1.5 63-4°, d2020 0.9745, n20D 1.4771, δ20 34.69 erg/cm.2, MRD 37.47; chloroplatinate m. 213° (decomposition) (EtOH-Et2O). II was also obtained in 74.9% yield by reduction of ethyl N-methyl nicotinate (V) with LiAlH4 in Et2O. V, b1 46-7°, d2020 0.9773, n20D 1.4545, MRD 47.175, was prepared in 89.3% yield as follows: 15.1 g. Et nicotinate was refluxed 6 hrs. with 21.3 g. MeI in 50 cc. MeOH, the solvent evaporated, the residue dissolved in 50 cc. H2O, and the solution treated with freshly prepared AgCl (from 25.5 g. AgNO3 and 9.36 g. NaCl) and after filtration hydrogenated over Pt at 3 atm. 23 references.
Doklady TSKhA published new progress about 14613-37-7. 14613-37-7 belongs to piperidines, auxiliary class Piperidine,Amine, name is (1-Methylpiperidin-3-yl)methanamine, and the molecular formula is C14H12O2, Application In Synthesis of 14613-37-7.
Referemce:
https://en.wikipedia.org/wiki/Piperidine,
Piperidine | C5H11N – PubChem