Allyl bromide → N'-allyl-N'-cyclobutyl-hydrazinecarboxylic acid tert-butyl ester

HRID 731347Notes

Reaction equation

HRID 731347 reaction equation
[C:1]([O:5][C:6]([NH:8][NH:9][CH:10]1[CH2:13][CH2:12][CH2:11]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH2:14](Br)[CH:15]=[CH2:16].C(=O)([O-])[O-].[K+].[K+].[I-].[Li+]>C(O)C>[C:1]([O:5][C:6]([NH:8][N:9]([CH2:16][CH:15]=[CH2:14])[CH:10]1[CH2:11][CH2:12][CH2:13]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 66321Lithium iodideHCID 45790335tert-Butyl 2-cyclobutylhydrazinecarboxylate

Product 1

HCID 57671220N'-allyl-N'-cyclobutyl-hydrazinecarboxylic acid tert-butyl esterYield 92%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
25 °C

Procedure

N′-cyclobutyl-hydrazinecarboxylic acid tert-butyl ester (0.88 g, 4.72 mmol) was dissolved in ethanol (45 mL). Allyl bromide (0.82 mL, 9.44 mmol), potassium carbonate (0.65 g, 4.72 mmol), and lithium iodide (0.063 g, 0.47 mmol) were added sequentially. The reaction was stirred at reflux for 18 h. The mixture was cooled to 25° C., concentrated in vacuo, taken up in water (20 mL) and extracted with ethyl acetate (3×20 mL). The organic layers were combined, dried over magnesium sulfate, filtered, and concentrated in vacuo to afford a yellow oil. Purification by flash column chromatography (Teledyne Isco RediSep Column; 0-20% ethyl acetate in hexanes) afforded the desired product, N′-allyl-N′-cyclobutyl-hydrazinecarboxylic acid tert-butyl ester (0.98 g, 4.34 mmol, 92%), as a white powder. 1H NMR (400 MHz, DMSO-d6) δ: 1.36 (9H, s), 1.50-1.62 (2H, m), 1.82-1.88 (4H, m), 3.13 (2H, d, J=6.0 Hz), 3.34-3.39 (1H, m), 5.03 (1H, d, J=10.0 Hz), 5.14 (1H, d, J=16.8 Hz), 5.71-5.81 (1H, m), 7.59 (1H, bs). LC-MS (ESI) calcd for C7H14N2 (free hydrazine) 126.20, found 127.0 [M+H+].

Workup

  1. temperatureat reflux for 18 h
  2. concentrationconcentrated in vacuo
  3. extractionextracted with ethyl acetate (3×20 mL)
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto afford a yellow oil
  8. customPurification by flash column chromatography (Teledyne Isco RediSep Column; 0-20% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-47b0e8dab03a451b97a8ddc8faf62b89
Source dataset
uspto-grants-2009_09
Patent number
US07582626B2

Reaction notes

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