2
13
3,5-CH2); 2.71 (4H, 3J = 6.0, satellite d, JTe–H = 35.0, 2,6-CH2). C NMR spectrum, , ppm: -4.1 (C-2,6); 28.1
(C-3,5); 29.0 (C-4). 125Te NMR spectrum, , ppm: 200.3. Mass spectrum 130Te, m/z (Irel, % of total ion current):
200 [M]+ (26), 170 [M-CH2]+ (4), 158 [C2H4Te]+ (121), 144 [CH2Te]+ (7), 130 [Te]+ (12), 70 [C5H10]+ (23), 55
[C4H7]+ (8), 42 [C3H6]+ (8). Found, %: C 30.46; H 5.03; Te 64.37. C5H10Te. Calculated, %: C 30.37; H 5.10;
Te 64.53. The spectroscopic parameters for N-aminopiperidine (9) are given below.
N-Aminopyrrolidine (8). 1,4-Dibromobutane 3 (10.9 g, 0.05 mol) was added to a solution of KOH
(7.0 g, 0.12 mol) in hydrazine hydrate (40 ml) at 40ºC. The reaction mixture was stirred for 5 h at 50-55ºC,
cooled, extracted with ether, and the extract was dried over magnesium sulfate. Solvent was evaporated and
vacuum distillation of the residue gave N-aminopyrrolidine 8. Yield 1.3 g (31%); bp 80-81ºC (140 mm Hg) (bp
28-30ºC at 13 mm Hg [14]). IR spectrum (thin film), , cm-1: 3396, 3302, 3146, 2966, 2877, 2799, 1609, 1460,
1
1413, 1354, 1314, 1290, 1191, 1161, 1111, 1050, 977, 942, 897, 870, 782, 646. H NMR spectrum, , ppm (J,
Hz): 1.73 (4H, m, 3,4-CH2); 2.77 (4H, m, 2,5-CH2). 13C NMR spectrum, , ppm: 23.6 (C-3,4); 55.8 (C-2,5).
Mass spectrum, m/z (Irel, %): 86 [M]+ (40), 85 [M-H]+ (60), 68 [M-H-NH3]+ (18), 58 (36), 44 (41), 43 (52),
42(100), 41 (61), 40 (16).
N-Aminopiperidine (9). 1,5-Dibromopentane 4 (26.7 g, 0.12 mol) was added to a solution of KOH
(13.2 g, 0.24 mol) in hydrazine hydrate (100 ml) at room temperature, stirred for 3 h at the same temperature,
and then for 1 h at 45-48ºC. The product was extracted with dichloromethane and then ether and the combined
extract was dried over magnesium sulfate. Solvent was removed and vacuum distillation of the residue gave the
N-aminopiperidine (9). Yield 6.7 g (58% based on the dibromide 4 taken); bp 148-149ºC (bp 146ºC (730 mm
Hg) [15]). IR spectrum (thin film), , cm-1: 3292, 3212, 3135, 2935, 2854, 2781, 2732, 2668, 1601, 1468, 1454,
1
1443, 1376, 1317, 1264, 1151, 1126, 1099, 1037, 1012, 940, 900, 853, 765, 567, 472. H NMR spectrum, ,
ppm: 1.34 (2H, m, 4-CH2); 1.61 (4H, m, 3,5-CH2); 2.52 (4H, m, 2,6-CH2); 3.11 (2H, br. s, NH2). 13C NMR
spectrum, , ppm: 22.5 (C-4); 25.2 (C-3,5); 60.2 (C-2,6). 15N NMR spectrum, , ppm: -300.0. Mass spectrum,
m/z (Irel, %): 100 [M]+ (80), 99 [M-H]+ (100), 84 [M-NH2]+ (22), 82 [M-H-NH3]+ (14), 72 (5), 59 (32), 55 (72),
45 (39), 44 (99), 42 (78). Found, %: C 59.85; H 12.40; N 27.75. C5H12N2. Calculated, %: C 59.96; H 12.08;
N 27.97.
1-Methyltelluranonium Iodide (10). A. MeI (1.1 g, 7.8 mmol) was added dropwise to a solution of
tellurane (7) (1.5 g, 7.6 mmol) in dry ether (3 ml). A white crystalline material was formed. The reaction mixture
was stirred on a magnetic stirrer for 1.5 h and the precipitate formed was filtered off, washed with dry ether, and
dried in vacuo to give the telluronium salt 10. Yield 2.1 g (81%); mp 213-220ºC (decomp.). IR spectrum (KBr),
, cm-1: 3004, 2963, 2941, 2916, 2843, 1444, 1412, 1352, 1334, 1285, 1248, 1234, 1225, 1191, 1119, 1091,
1061, 1010, 964, 950, 931, 890, 795, 778, 536, 515, 465. 1H NMR spectrum, , ppm (J, Hz): 1.93 and 1.64 (4H,
m, 3,5-CH2); 1.82 and 1.64 (2H, m, 4-CH2); 2.39 (3H, s, satellite d, 2JH–Te = 26. 14, CH3Te); 3.20 and 3.54 (4H,
m, 2,6-CH2). 13C NMR spectrum, , ppm: 1.9 (CH3Te); 21.0 (CH2Te); 21.5 (3,5-CH2); 27.3 (4-CH2). 125Te NMR
spectrum, , ppm: 344.3. Found, %: C 21.53; H 3.99; Te 37.54; I 37.15. C6H13ITe. Calculated, %: C 21.22; H 3.86;
Te 37.57; I 37.36.
B. Tellurane (7) (1.0 g, 5 mmol) and MeI (0.7 g, 5 mmol) were added to a solution of KOH (0.6 g,
0.01 mol) in hydrazine hydrate (5 ml). The reaction mixture was stirred on a magnetic stirrer for 2 h and the
precipitate formed was separated, washed with ethanol and dried in vacuo to give the telluronium salt 10. Yield
1.0 g (57%); mp 210-220ºC (decomp.). Elemental composition and spectroscopic data were identical to that
given above.
The telluronium salt 10 was obtained similarly using the system hydrazine hydrate–monoethanolamine
(yield 31%). With the use of hydrazine hydrate only the salt was obtained in 36% yield.
Reaction of the Telluronium Salt 10 with the Hydrazine Hydrate–KOH System. The telluronium
salt 10 (0.2 g, 0.6 mmol) obtained in ether was added to a solution of KOH (34 mg, 0.6 mmol) in hydrazine
hydrate (3 ml), stirred for 2 h on a magnetic stirrer at room temperature, extracted with dichloromethane, and the
extract was dried over magnesium sulfate. Solvent was removed to give the tellurane (7). Yield 0.1 g (80%). The
mass spectrum of compound 7 is given above.
1350