NOV. 5, 1939
L I E R C U R I C A C E T A T E OXIDATION O F L I E D I U M
Using the general method of introducing an aldehyde function on pyrrole,46compound (b) was converted to 1,3,4-trimethyl-2-( 1',3',4'- trimethyl-2'-pyrrolidyl) -5-pyrrolecarboxaldehyde, b.p. 90' (1.9 mm.), n% 1.5438, ~ 2 : : 4 1650 cm." 272 ( e 9000), 304 mp ( E 6830).46 2,i,5-Trimethylpyrrolidine,47b.p. 113-114", n 2 4 J 1.4212, ~ was converted to the hydrochloride, m.p. 185-187.5', colorless prisms from ether-ethanol. Anal. Calcd. for C7H&lN: C, 56.17; H , 10.78; hT, 9.36. Found: C, 56.28; H , 10.56; N, 9.57. 1,2,2,5-Tetramethylpyrrolidine.-Methylation of 2,2,5trimethylpyrrolidine in the usual manner with formic acid and formalin produced 1,2,2,5-tetramethylpyrrolidine,b.p. 128-130", tZ27,5D 1.4273. Anal. Calcd. for CsH17N: C, 75.52; H , 13.47; h ' , 11.01. Found: C, 75.65; H , 13.61; N, 11.22. The picrate crystallized from ethanol in the form of yellow needles, m.p. 241-241.5' dec. (reported48 224-226'). Anal. Calcd. for C1aHnor';aO.i: C, 47.19; H , 5.66; N, 15.72. Found: C, 47.22; H , 5.55; K, 15.78. The perchlorate crystallized from isopropyl alcohol as colorless needles, m.p. 223.5225'. Anal. Calcd. for C8H&1N04: C, 42.20; H, 7.97; S , 6.15. Found: C, 42.22; H , 7.70; N, 6.00. The hydrochloride separated from ethanol-ether as colorless prisms, m.p. 212-213'. (45) R. M. Silverstein, E. E. Ryskiewicz a n d C . Willard, O Y ~ . Syntheses, 36, 74 (1966). (46) See W. Herz a n d J. Brasch. J . Org, Chem., 23, 1513 (1958). (47) R. B. h l o 5 e t t and J. L. White, i b i d . , 17. 407 (1962). (48) R . Luke3 a n d M . VePerH, Coil. Czech. C h e m C o m m u n s . , 19, 263 (19.54).
[CONTRIBUTION FROM
Unsaturated Amines. XV.
THE
RINGSC O N T A I N I N G teYt-NITROGEN
5631
Anal. Calcd. for CsH&lN: C, 58.70; H , 11.08; N, 8.56. Found: C, 58.64; H, 10.89; N, 8.50. Mercuric Acetate Oxidation of 1,Z,Z,S-Tetramethylpyrro1idine.-Oxidation of 9.0 g. (0.071 mole) of 1,2,2,5-tetramethylpyrrolidine was carried out in the usual manner except that the final ethereal solution was treated dropwise with a solution of 1: 1 70% perchloric acid:ethanol until the mixture was acid to congo red. Recrystallization of the precipitated salt from isopropyl alcohol yielded 12.45 g. (78y0) of 1,2,5,5-tetramethyl-A1-pyrroliniumperchlorate, colorless needles, m.p. 189-191', vN,::"' 1677 cm.-l. Anal. Calcd. for CsH&1N04: C, 42.57; H , 7.15; N, 6.21; 0, 28.23. Found: C, 42.53; H , 7.06; N, 6.15; 0, 28.15. The corresponding base, 1,2,5,5-tetramethyl-Az-pyrroline, was distilled under nitrogen, b.p. 89" (120 mm.), n Z 4 ~ 1635(s) (C=C) and 1.4639, but decomposed rapidly, 1695(vw)cm. (possible hydrolysis of some of the enamine by water vapor to the aminoketone).36 The picrate crystallized from ethanol as yellow-orange needles, m.p. 223-224' dec., v:::"' 1677 cm.-l(> C=N+NH*Cl-). The same product was obtained when the oxidation conditions were 3 hours a t steam-bath temperature and the same isolation procedure was employed. Anal. Calcd. for C Z ~ H M C ~ ~C, N 49.10; ~ S ~ : H, 9.27; C1, 18.11; h7,7.15; S, 16.36; mol. wt., 587.4 (undissociated). Found: C, 48.99; H, 9.22; C1, 18.20; N, 6.98; S, 16.96; mol. wt., 214 (ebullioscopic in ethanol). Raney Nickel Desulfurization-Alkylation of 2,4,6-Tris(6'-methylaminohexyl)-trithiane Tribydrochloride. General Procedure for Desulfurization-Alkylation Reactions .Pyrophoric nickel was prepared from commercial Raney nickel by washing several times with absolute ethanol, centrifuging and then refluxing 3 hours in absolute ethanol. A mixture of 19 g. of nickel and 0.6 g. (1.1 mmoles) of 2,4,6tris-(6'-methylaminohexyl)-trithiane trihydrochloride in 50 ml. of 7070 ethanol was heated a t reflux for 2 days. The mixture was centrifuged, and the liquid was decanted from the nickel, which was washed twice with hot ethanol and once with water. The washings were combined and acidified with 12 N hydrochloric acid. Most of the ethanol was removed under reduced pressure, and the acidic solution was extracted with ether to remove non-basic materials. The solution was basified with potassium hydroxide and extracted three times with ether. The dried ethereal solution was treated with picric acid in ethanol. Partial evaporation and then the dropwise addition of water yielded crystalline material, and recrystallization from aqueous ethanol furnished ethylmethylheptylamine picrate, yellow needles, m.p. 60-62.5' (after solidification and remelting, a t 57.558.5'), yield 0.6 g. (4970). A-0 depression in melting point was observed on admixture rvith an authentic sample (see below).
ht-NITROGEN
5633
Anal. Calcd. for C1eHzsN40,: C, 49.73; H, 6.78; N , 14.50. Found: C,49.65; H,6.66; N, 14.67. When methylheptylaminel' in aqueous ethanol was treated with Raney nickel as described above, ethylmethylheptylamine picrate was isolated, m.p. 60-62.5' (after solidification and remelting, a t 57-58'). Mercuric Acetate Oxidation of 1-Methyl- 1-azacyclononane.-Oxidation of 4.38 g. (0.031 mole) of l-methyl-lazacyclononane following the directions given above yielded 2.4 g. (37y0)of the trimer of 8-methylaminothiooctanal hydrochloride, or 2,4,6-tris-(7'-methylaminoheptyl)-trithiane trihydrochloride, recrystallized from absolute ethanol, m.p. " : :A 238 mp (log B 3.06), infrared spec234.5236' dec., trum like that of the lower homolog. Anal. Calcd. for C?7H&13N3S3: C, 51.53; H, 9.61; C1, 16.90; N, 6.68; S,15.28. Found: C, 51.29; H, 9.85; C1, 16.79; S , 6.48; S, 14.83. Raney Nickel Desulfurization-Alkylation of 2,4,6-Tris( 7 '-methylaminohepty1)-trithianeTrihydrochloride.-Treatment of tris-( 7'-methylaminohepty1)-trithiane trihydrochloride in aqueous ethanol with Raney nickel gave ethylmethyloctylamine, isolated as the picrolonate, m.p. 101-102' dec., yellow prisms from aqueous methanol, yield 527,. Anal. Calcd. for C21H33NSO5: C, 57.91; H , 7.64; N, 16.08. Found: C,58.13; H,7.71; N, 16.24. Mercuric Acetate Oxidation of I-Methyl-l-azacycloheptane.-Oxidation of 5.70 g. (0.05 mole) of l-methyl-l-azacycloheptane, followed by the isolation procedure described above, gave 1.65 g. (23y0)of the trimer of 6-methylaminothiohexanal hydrochloride, or 2,4,6-tris-(5'-methylaminopentyl)-trithiane trihydrochloride, recrystallized from abso237 mp (lpg e lute ethanol, m.p. 223-225' dec., A",,'"," 3.09), infrared spectrum very similar to those of the higher homologs. Anal. Calcd. for C21H48C13XaS3: C, 46.28; H , 8.88; C1, 19.50; N, 7.71; S, 17.64. Found: C,46.12; H,8.58; C1, 19.59; N, 7.49; S,17.91. Raney Nickel Desulfurization-Alkylation of 2,4,6-Tris(5'-methylaminopenty1)-trithianeTrihydroch1oride.-Treatment of tris-( 5'-methylaminopenty1)-trithiane trihydrochloride in aqueous ethanol with Raney nickel gave ethylmoethylhexylamine, isolated as the picrolonate, m.p. 79.581 , yellow needles from aqueous methanol, yield 41%. Anal. Calcd. for CI0HZ9N605:C, 56.00; H , 7.17; N, 17.09. Found: C,56.09; H,7.02; N, 16.80. Mercuric Acetate Oxidation of 1-Methy1piperidine.When the mercuric acetate oxidation of 1-methylpiperidine, followed by product isolation, was carried out according to the directions described above rather than following the conditions used previously for the oxidation of this substrate,3 which had yielded (677,) 1,l'-dimethyl-A2-tetrahydroanabasine, no product was obtained corresponding to opening of the six-membered ring. (17) N.J. Leonard, S. Swann, Jr., and H. L. D r y d e n , THISJ O U R N A L , 74, 2871 (1952).
URBANA, ILL.
