Hydrazine → (S)-tert-butyl(1-(4-hydrazinylpyridin-2-yl)but-3-en-1-yl)carbamate

HRID 1481313Notes

Reaction equation

HRID 1481313 reaction equation
Cl[C:2]1[CH:7]=[CH:6][N:5]=[C:4]([C@@H:8]([NH:12][C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16])[CH2:9][CH:10]=[CH2:11])[CH:3]=1.[NH2:20][NH2:21].[Al]>C(O)C>[NH:20]([C:2]1[CH:7]=[CH:6][N:5]=[C:4]([C@@H:8]([NH:12][C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16])[CH2:9][CH:10]=[CH2:11])[CH:3]=1)[NH2:21]

Participants

5

Reactant 3

HCID 9321HydrazineHCID 5359268AluminumHCID 66744734Carbamic acid, N-[(1S)-1-(4-chloro-2-pyridinyl)-3-buten-1-yl]-, 1,1-dimethylethyl ester

Product 1

HCID 131736635(S)-tert-butyl(1-(4-hydrazinylpyridin-2-yl)but-3-en-1-yl)carbamateYield 85.7%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A vial with a Teflon septum cap was charged with a solution of 1C (2 g, 7.0 mmol) and hydrazine (35% in water) (10 mL, 111 mmol, 15.75 equiv) in ethanol (10 mL). The solution was heated by an aluminum block set to 115° C. for 18 hours. The reaction was concentrated to give a pink oil. Purification by normal phase silica gel chromatography yielded 222A (1.67 g, 85%) as a yellow, foaming solid. 1H NMR (400 MHz, CHLOROFORM-d) δ 8.22 (d, J=5.7 Hz, 1H), 6.60 (s, 1H), 6.57 (dd, J=5.5, 2.4 Hz, 1H), 5.79-5.54 (m, 3H), 5.14-4.99 (m, 2H), 4.74-4.62 (m, 1H), 2.59 (t, J=6.7 Hz, 2H), 1.52-1.40 (m, 9H). MS (ESI) m/z: 279.2 (M+H)+.

Workup

  1. concentrationThe reaction was concentrated
  2. customto give a pink oil
  3. customPurification by normal phase silica gel chromatography

Sources & evidence

ORD record
ord-6ff820f5aac94eb5b4aa252a67d9ef46
Source dataset
uspto-grants-2016_08
Patent number
US09409908B2

Reaction notes

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