Taguchi, Tanezo published the artcileHeteroalicyclic aminoalkanols. II. Reactions of DL-2-piperidylmethanol involving the formation of DL-1-azabicyclo[4.1.0]heptane, Quality Control of 27483-92-7, the main research area is .
2-Piperidylmethanol (I) (5 g.) in 5 cc. Et2O treated simultaneously with stirring at 0° with 6 g. BzCl in 20 cc. Et2O and 20 cc. aqueous NaOH and stirred 1 h. at room temperature yielded 7.2 g. 1-Bz derivative (II) of I, granules, m. 94-5° (Et2O). II (0.5 g.) in 20 cc. 2% aqueous HCl gave 0.53 g. benzoate (III) of I.HCl, rods, m. 243-4° (MeOH-EtOH). II with 2% HBr gave similarly 91% I.HBr, needles, m. 233-4° (decomposition) (EtOH). III.HCl (0.2 g.) stirred 0.5 h. with 10 cc. 5% aqueous NaOH yielded 0.15 g. II, granules, m. 74° (Et2O). I (1.15 g.) in 10 cc. Et2O treated dropwise with 9 cc. aqueous NaOH and then with 3 g. BzCl and stirred 3 h. yielded 2.8 g. 1-benzoyl-2-piperidylmethanol benzoate (IV), granules, m. 65-7° (Et2O-ligroine). II (0.5 g.) in 5 cc. C6H6 and 5 cc. 10% aqueous NaOH treated dropwise with stirring with 0.4 g. BzCl gave 0.66 g. IV, m. 65°. I ( 1 g.), 0.88 cc. BzH, and 10 cc. C6H6 refluxed 1 h. with 1 cc. AcOH with the azeotropic removal of H2O gave 1.3 g. V, b8 134-6°. V (0.5 g.) in 2 cc. CHCl3 treated dropwise with cooling and stirring with 0.4 g. Br in 2 cc. CHCl3 and then stirred with 2 cc. 10% aqueous NaOH gave 0.67 g. III.HBr, needles, m. 233° (EtOH). 2-ClCH2 analog (VI) (4 g.) of I.HCl and 2 g. CS(NH2)2 in 12 cc. EtOH refluxed 10 h. gave 2.5 g. 2-(2-pyridylmethyl)-2-thiopseudourea-2HCl (VIa.2HCl), needles, m. 182-4° (EtOH), and 0.8 g. VII.HCl, rods, m. 186-8° (BuOH). VIa.2HCl (0.2 g.) in 2 cc. BuOH refluxed 1 h. yielded 0.18 g. VII.HCl, needles, m. 186-8° (BuOH). VIa.2HCl (50 mg.) in 2 cc. EtOH treated successively with 0.57 cc. 2% alc. KOH, 41 mg. 2,4-(O2N)2C6H3Cl in 2 cc. EtOH, and 1.14 cc. 2% alc. KOH yielded 25 mg. 1-(2,4-dinitrophenylamidino)-2-(2,4-dinitrophenylthiomethyl)piper-idine, brownish yellow granules, m. 185-7° (decomposition). 1-Methyl-2-piperidylmethanol (VIII) (3 g.) in 30 cc. dry Et2O and then 1.8 cc. CS2 added dropwise with cooling and stirring to 0.46 g. powd. Na in 25 cc. dry Et2O, treated with 1.24 cc. MeI in 5 cc. dry Et2O, and worked up gave 3.1 g. Me 1-methyl-2-piperidylmethyl xanthate (IX), yellow oil; picrate, yellow needles, m. 124-6° (EtOH); IX.HCl m. 134-5° (EtOH-Et2O). The alk. hydrolysis of IX yielded VIII. VIII (4 g.) heated 0.5 h. at 130° yielded 3.5 g. S-(1-methyl-2-piperidylmethyl) S’-Me dithiolcarbonate (X), light yellow oil, b1 119-20°; picrate m. 164-5° (EtOH). VIII (7 g.) in 20 cc. dry CHCl3 refluxed 3 h. with 6 cc. SOCl2 gave 7.1 g. 2-ClCH2 analog (XI) of VIII.HCl, needles, m. 159-61° (Me2CO). XI.HCl (3 g.) and 1.23 g. CS(NH2)2 in 10 cc. EtOH refluxed 4 h. yielded 2.8 g. 2-(1-methyl-2-piperidylmethyl)-2-thiopseudourea-2HCl (XII.2HCl), needles, m. 192-3° (BuOH). XII.2HCl (0.7 g.) heated 1 h. on the water bath with 5 cc. 2N NaOH and treated with a stream of air gave 0.68 g. bis(1-methyl-2-piperidylmethyl) disulfide (XIII); dipicrate m. 153-5° (MeOH). X (1 g.) and 40 cc. 5% alc. NaOH heated I hr. on the water bath, treated dropwise with 10% alc. HCl (EtSH evolved), and the crude product treated in aqueous K2CO3 with air overnight yielded 0.8 g. XIII picrate, m. 151-4° (MeOH). VIII.MeI (8 g.) and Ag2O from 12 g. AgNO3 and 20 cc. 10N NaOH stirred 5 h., filtered, and evaporated, and the residue heated 3 h. at 100° in vacuo under N gave 1 g. VIII and 1.1 g. Me2N(CH2)5CHO, b3 168-70°; picrate m. 146-8° (H2O). I (6 g.) added with cooling to 5 cc. concentrated H2SO4 and heated gradually to 240° yielded 7.4 g. 2-HO3SOCH2 analog (XIV) of I, rods, m. 262-3° (decomposition) (MeOH). XIV (6 g.) in 40 cc. H2O and 100 cc. 10% aqueous NaOH distilled and the distillate treated with solid KOH gave 0.2 g. XV, b80 65°, which polymerized completely within several hrs., even under N; XV picrate m. 151-2° (Et2O-AcOEt). XV (0.1 g.) in Et2O stirred 1 h. and treated with K2CO3, and the basic product treated with picric acid gave the picrate of I, m. 115° (EtOH-Et2O). XV (0.1 g.) in Et2O treated with dry HCl and kept overnight gave VI.HCl, m. 187-8°. XV (0.1 g.) in Et2O treated overnight with 0.1 g. MeBr in Et2O gave 0.16 g. 2-bromomethyl-1,1-dimethylpiperidinium bromide (XVI), granules, m. 230° (EtOH). XV (0.14 g.), 0.1 g. CS(NH2)2, 1.32 cc. N HCl, and 2 cc. H2O stirred a few min., treated with an addnl. 1.32 cc. N HCl, and stirred 1 h., and the crude product refluxed 1 h. in BuOH gave VII isolated as the picrate, m. 1523° (H2O). I (3 g.) in 30 cc. 48% aqueous HBr refluxed 10 h. yielded 4.1 g. 2-bromomethylpiperidine-HBr (XVII.HBr), needles, m. 188-90° (EtOH). XVII.HBr (0.5 g.) in 10 cc. Et2O treated overnight with 20 cc. 10% MeBr-Et2O gave 0.57 g. XVI, granules, m. 233-4° (decomposition) (EtOH).
Chem. Pharm. Bull. (Tokyo) published new progress about Alcohols. 27483-92-7 belongs to class piperidines, name is 2-(Chloromethyl)-1-methylpiperidine hydrochloride, and the molecular formula is C7H15Cl2N, Quality Control of 27483-92-7.
Referemce:
Piperidine – Wikipedia,
Piperidine | C5H11N – PubChem