NJC
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35.97, H 4.64, N 53.34%. Crystals of 2 suitable for single crystal 2H, CH2, ethylene spacer), 3.53 (t, JH,H = 5.1 Hz, 2H, CH2,
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X-ray analysis were obtained by dissolving the product (0.02 g) ethylene spacer), 3.69 (t, JH,H = 8.0 Hz, 2H, CH2, oxazolidin-2-
in hot MeOH (2 mL) with further slow evaporation of the one), 4.36 (t, 3JH,H = 8.0 Hz, 2H, CH2, oxazolidin-2-one) ppm. MS
solvent.
5. Yield: 3.64 g (13%). H NMR (DMSO-d6), d: 3.58–4.82 (m, H 5.16, N 35.88. Found: C 38.48, H 5.27, N 35.65%.
12H, CH2, ethylene spacer), 7.63 (s, 1H, CHO), 9.37 (s, 1H, CH, 3-(2-Aminoethyl)oxazolidin-2-one (12). A solution of 11
(m/z): 157.0 [M + H]+. Anal. Calc. for C5H8N4O2 (156.14): C 38.46,
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tetrazole), 9.42 (s, 1H, CH, tetrazole), 11.84 (br. s, 1H, NH) ppm. (0.0064 mol, 1 g) was added drop-wise to a cold solution of
MS (m/z): 281.1 [M + H]+. Anal. Calc. for C9H16N10O (280.29): C PPh3 (2.1 g, 0.008 mol) in MeCN–THF (1 : 1, v/v; 40 mL). The
38.57, H 5.75, N 49.97. Found: C 38.68, H 5.61, N 49.88%.
reaction mixture was stirred for 2 h and water (25 mL) was
added. MeCN and THF were then removed in vacuo and the
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8. Yield: 2.93 g (8%). H NMR (DMSO-d6), d: 3.62 (t, JH,H
=
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5.5 Hz, 4H, CH2, ethylene spacer), 3.85 (t, JH,H = 5.4 Hz, 4H, mixture was filtered. Water was then removed in vacuo. The
CH2, ethylene spacer), 4.26 (t, 3JH,H = 5.6 Hz, 4H, CH2, ethylene product was obtained as a pale yellow liquid. Yield: 0.77 g
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spacer), 4.37 (t, JH,H = 5.6 Hz, 4H, CH2, ethylene spacer), 7.76 (92%). 1H NMR (DMSO-d6), d: 1.80 (br. s, 2H, NH2), 2.72 (t, 3JH,H
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(s, 2H, CHO), 9.32 (s, 1H, CH, tetrazole), 9.34 (s, 1H, CH, = 6.3 Hz, 2H, CH2, ethylene spacer), 3.17 (t, JH,H = 6.3 Hz, 2H,
tetrazole), 12.28 (br. s, 1H, NH) ppm. MS (m/z): 367.3 [M + H]+. CH2, ethylene spacer), 3.44 (t, JH,H = 8.1 Hz, 2H, CH2, oxazo-
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Anal. Calc. for C13H24N11O2 (366.41): C 42.61, H 6.60, N 42.05. lidin-2-one), 4.24 (t, JH,H = 8.1 Hz, 2H, CH2, oxazolidin-2-one)
Found: C 42.74, H 6.54, N 42.13%.
ppm. MS (m/z): 131.1 [M + H]+. Anal. Calc. for C5H10N2O2
Bis(2-(1H-tetrazol-1-yl)ethyl)amine hydrochloride (3ꢁHCl), N1,N2- (130.15): C 46.14, H 7.74, N 21.52. Found: 46.29, 7.68, N 21.60%.
bis(2-(1H-tetrazol-1-yl)ethyl)ethane-1,2-diamine dihydrochloride
3-(2-(1H-tetrazol-1-yl)ethyl)oxazolidin-2-one (13). Acetic acid
(6ꢁ2HCl) and N1-(2-(1H-tetrazol-1-yl)ethyl)-N2-(2-(2-(1H-tetrazol- (38 mL) was slowly added to a mixture of 12 (0.0058 mol,
1-yl)ethylamino)ethyl)ethane-1,2-diamine trihydrochloride (9ꢁ3HCl). 0.75 g), NaN3 (0.46 g, 0.007 mol) and HC(OEt)3 (2.31 g,
HCl (6 M, 10 mL) was added to 2, 5 or 8 (0.22 mmol; 0.052, 0.062 and 0.0156 mol). The reaction mixture was heated at 105 1C for
0.081 g, respectively) and the mixture was refluxed overnight. The 20 h and cooled. The solvent was then removed in vacuo. The
solvent was then removed in vacuo. The product was obtained as obtained yellow oil was dissolved in hot ethyl acetate (3 mL).
pale yellow or pale brown oil.
The resulting solution was kept at ꢀ18 1C until an orange or
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3ꢁHCl. 1H NMR (D2O), d: 3.71 (t, JH,H = 5.9 Hz, 4H, CH2, pale brown powder was precipitated. The product was filtered
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ethylene spacer), 4.93 (t, JH,H = 5.9 Hz, 4H, CH2, ethylene off and dissolved in hot MeOH (3 mL). The resulting solution
spacer), 9.26 (s, 2H, CH, tetrazole) ppm. MS (m/z): 210.0 was kept at 18 1C until a pale orange powder was precipitated.
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[M – Cl]+. Anal. Calc. for C6H12ClN9 (245.67): C 29.33, H 4.92, Yield: 0.93 g (88%). H NMR (CDCl3), d: 3.38 (t, JH,H = 8.0 Hz,
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N 51.31. Found: C 29.14, H 5.17, N 51.42%.
2H, CH2, oxazolidin-2-one), 3.81 (t, JH,H = 5.7 Hz, 2H, CH2,
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6ꢁ2HCl. H NMR (D2O), d: 3.82 (t, JH,H = 5.8 Hz, 4H, CH2, ethylene spacer), 4.28 (t, JH,H = 8.0 Hz, 2H, CH2, oxazolidin-2-
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ethylene spacer), 4.11 (t, JH,H = 5.8 Hz, 4H, CH2, ethylene one), 4.73 (t, JH,H = 5.7 Hz, 2H, CH2, ethylene spacer), 8.97
spacer), 4.87 (t, JH,H = 5.9 Hz, 4H, CH2, ethylene spacer), 9.29 (s, 1H, CH, tetrazole) ppm. MS (m/z): 184.0 [M + H]+. Anal. Calc.
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(s, 2H, CH, tetrazole) ppm. MS (m/z): 289.6 [M – Cl]+. Anal. Calc. for C6H9N5O2 (183.17): C 39.34, H 4.95, N 38.23. Found: C 39.18,
for C8H18Cl2N10 (325.20): C 29.50, H 5.58, N 43.07. Found: C H 4.92, N 38.14%. Crystals suitable for single crystal X-ray
29.37, H 5.51, N 43.14%.
analysis were obtained by dissolving of 13 (0.02 g) in hot MeOH
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9ꢁ3HCl. H NMR (D2O), d: 3.67 (t, JH,H = 5.9 Hz, 4H, CH2, (2 mL) with further slow evaporation of the solvent.
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ethylene spacer), 3.78 (t, JH,H = 5.9 Hz, 4H, CH2, ethylene
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X-Ray crystallography
spacer), 4.16 (t, JH,H = 5.7 Hz, 4H, CH2, ethylene spacer), 5.02
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(t, JH,H = 5.7 Hz, 4H, CH2, ethylene spacer), 9.27 (s, 2H, CH, The X-ray data for 2 and 13 were collected at 293 and 120 K,
tetrazole) ppm. MS (m/z): 369.1 [M – Cl]+. Anal. Calc. for respectively, using an MAR345 image plate and Mo–Ka (l =
C
10H24Cl3N11 (404.73): C 29.68, H 5.98, N 38.07. Found: C 0.71069 Å) radiation. The unit cell parameters were refined
29.82, H 6.08, N 38.19%. using all the collected spots after the integration process. The
3-(2-Azidoethyl)oxazolidin-2-one (11). A solution of 10, 14 or data were not corrected for absorption, but the data collection
15 (0.033 mol; 8.0, 9.4 and 14.1 g, respectively), which were obtained mode partially takes the absorption phenomena into account.
by the similar procedure as described in ref. 20, NaN3 (4.7 g, 0.072 All structures were solved by direct methods using SHELX9726
mol) and KI (5.5 g, 0.033 mol) in DMF (100 mL) was refluxed for 4 h and refined by full-matrix least-squares on F2 using SHELX97.26
and cooled. To the resulting mixture toluene (100 mL) was added All non-hydrogen atoms were refined with anisotropic tempera-
and the solution was filtered. The solvent was then removed ture factors. All H-atoms were localized by Fourier-difference
in vacuo. The obtained orange oil was dissolved in water (20 mL) synthesis. The H-atoms were included in the refinement with a
and extracted with diethyl ether (3 ꢂ 20 mL) and then with ethyl common isotropic temperature factor; when calculated, they
acetate (3 ꢂ 20 mL). The latter fraction was collected and dried with were refined using appropriate riding models. Figures were
MgSO4. The solvent was then removed in vacuo. The product was generated using the program Mercury.27
obtained as dark brown oil or a beige fine crystalline solid.
11. Yield: 2.16 g (42%), using 10; 1.91 g (37%), using 14; clinic, space group P21/a, a = 12.849(3), b = 5.378(2), c = 16.169(5) Å,
2.47 g (48%), using 15. 1H NMR (CDCl3), d: 3.44 (t, 3JH,H = 5.1 Hz, b = 102.50(2)1, V = 1090.8(6) Å3, Z = 4, r = 1.445 g cmꢀ3
Crystal data for 2. C17H11N9O, Mr = 237.25 g molꢀ1, mono-
,
c
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New J. Chem.