Hydrazine → HCID 86750954, compound

HRID 1683435Notes

Reaction equation

HRID 1683435 reaction equation
[N:1]([CH2:4][C:5]([CH2:11][O:12][C:13]([F:23])([F:22])[C:14]([F:21])([F:20])[CH2:15][C:16]([F:19])([F:18])[F:17])([CH3:10])[CH2:6][N:7]=[N+]=[N-])=[N+]=[N-].NN>>[NH2:1][CH2:4][C:5]([CH2:11][O:12][C:13]([F:22])([F:23])[C:14]([F:20])([F:21])[CH2:15][C:16]([F:17])([F:18])[F:19])([CH3:10])[CH2:6][NH2:7]

Participants

3

Reactant 2

HCID 9321Hydrazine2×HCID 86750955HCID 86750955, compound

Product 1

HCID 86750954HCID 86750954, compoundYield 84.7%

Conditions

Temperature
60 °C

Procedure

1,3-Diazido-2-heptafluorobutoxymethyl-2-methyl-propane (50.0 g, 0.142 mole) was weighed into a 1-L, 3-neck flask fitted with a magnetic stir bar, reflux condenser, drying tube and a thermocouple probe. Pearlman's catalyst (4.2 g, 10% Pd on carbon) was slurried in methanol (50 ml) and added to the flask. The mixture was stirred, and additional methanol (200 ml) was added. After heating to 60° C., anhydrous hydrazine (5.0 g, 0.16 mole) was added with a syringe at a rate such that the temperature did not exceed 63° C. Evolution of gas was observed during the addition, and the addition was complete after 20 minutes. 1H NMR analysis indicated that the reaction was 80% complete. A second portion of anhydrous hydrazine (1.27 g, 0.04 mole) was added, and the mixture was stirred overnight at 60° C. The progress of the reaction was also monitored by GC and by following the disappearance of the N3 stretching band in the infrared spectrum. The mixture was cooled to room temperature, filtered, and stripped of solvent on a rotary evaporator. Short path distillation of the crude product (bp 45°-47° C., high vacuum) gave 36.1 g (84.7%) of 1,3-diamino-2-heptafluorobutoxymethyl-2-methyl-propane (9), a clear oil: IR 3400-3370 (NH2), 2925, 2875, 1330, 1225, and 1120 cm-1 ; 1H NMR (CDCl3) 0.84 (s, 3H), 1.20 (s, 4H), 2.63 (s, 4H), 3,46 (s, 2H) and 3.92 (t, J=13.8 Hz, 2H); 13C NMR (CDCl3) 18.36, 40.27, 46.85 68.38 (t, J=25.92 Hz), and 77.72. Anal. Calcd for C9H15F7N2 : C, 36.00; H, 5.05; N, 9.33; Found: C, 34.99; H, 5.08; N, 7.98.

Workup

  1. customfitted with a magnetic stir bar
  2. temperaturereflux condenser
  3. customdrying tube
  4. additionadded to the flask
  5. additionadditional methanol (200 ml) was added
  6. customdid not exceed 63° C
  7. additionEvolution of gas was observed during the addition
  8. additionthe addition
  9. stirringthe mixture was stirred overnight at 60° C
  10. temperatureThe mixture was cooled to room temperature
  11. filtrationfiltered
  12. customstripped of solvent on a rotary evaporator
  13. distillationShort path distillation of the crude product (bp 45°-47° C., high vacuum)

Sources & evidence

ORD record
ord-ffb1252c558e46a9aa4208781efbde11
Source dataset
uspto-grants-1997_06
Patent number
US05637772

Reaction notes

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