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53549092018
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Preparation of cyanogen azide was based on a modified literature method.[7,8a] At 0°C, cyanogen bromide (1.30 g, 12.3 mmol) was dissolved in dry acetonitrile (20 mL) and sodium azide (3.82 g, 58.8 mmol) was added. The reaction mixture was stirred at 0-15°C for 4 h. The inorganic salt was filtered off (Caution! After filtering, the salt must be quickly dissolved in cold water, The solution was added to a suspension containing 3,6-dihydrazinyl-1,2,4,5-tetrazine[10b, 100 mg (0.704 mmol) in water (10 mL) at 0°C. After 4 d[10c] of stirring at ambient temperature, the suspension was filtered to leave an orange filter cake, which was dried in air. Compound 13 was obtained (127 mg, 0.457 mmol, 65, a) The unknown salt which is formed is likely the azidotetrazolate salt, 7
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[7]
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23
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0032444497
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Synthesis of 3,6-dihydrazinyl-1,2,4,5-tetrazine: D. E. Chavez, M. A. Hiskey, J. Heterocycl. Chem. 1998, 35, 1329-1332.
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b) Synthesis of 3,6-dihydrazinyl-1,2,4,5-tetrazine: D. E. Chavez, M. A. Hiskey, J. Heterocycl. Chem. 1998, 35, 1329-1332.
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53549092650
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Each compound required a different reaction time (1: 4 h, 6: 2 h, 7: 2 h, 8: 24 h, 9: 3 d, 10: 2 d, 11: 4 d, 12: 24 h, 13: 4 d).
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c) Each compound required a different reaction time (1: 4 h, 6: 2 h, 7: 2 h, 8: 24 h, 9: 3 d, 10: 2 d, 11: 4 d, 12: 24 h, 13: 4 d).
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Crystallographic data: 8: (C2H6N 8O, Mr, 158.15; crystal size 0.28 x 0.25 x 0.13 mm; monoclinic, space group Cc, a, 11.2323(7, b, 4.6153(3, c, 11.9898(7) Å, β, 91.413(1)°, V, 621.37(7) Å3, Z, 4, 2θmax, 58°, 829 independent reflections, R1, 0.0281 for 814 reflections with I > 2σ(I) and wR2, 0.0766, 100 parameters. 13: (C12H30N16O 4S4, Mr, 590.76; crystal size 0.44 x 0.23 x 0.14 mm; triclinic, space group P1, a, 8.6351(5, b, 9.0007(5, c, 9.5097(6) Å, α, 92.8441(8, β, 111.4645(7, γ, 103.7774(8)°, V, 660.37(7) Å3, Z, 1, 2θmax, 52°, 2606 independent reflections, R1
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2 = 0.0747, 179 parameters. CCDC-684330 and CCDC-684331 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/ data_request/cif.
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53549085583
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Gaussian03 (RevisionD.01): M. J. Frisch et al., see Supporting Information.
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Gaussian03 (RevisionD.01): M. J. Frisch et al., see Supporting Information.
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Classification of impact sensitivities from reference [5] (insensitive: > 40 J; less sensitive: ≥ 35 J; sensitive: ≥ 4 J; very sensitive: ≤ 3 J).
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Classification of impact sensitivities from reference [5] (insensitive: > 40 J; less sensitive: ≥ 35 J; sensitive: ≥ 4 J; very sensitive: ≤ 3 J).
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