Oxalyl chloride → Hydrazinecarboxylic acid, 2-[2-[2-(3-buten-1-yloxy)phenyl]acetyl]-, 1,1-dimethylethyl ester

HRID 1481986Notes

Reaction equation

HRID 1481986 reaction equation
[CH2:1]([O:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[CH2:12][C:13]([OH:15])=O)[CH2:2][CH:3]=[CH2:4].C(Cl)(=O)C(Cl)=O.[NH:22]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[NH2:23].CCN(C(C)C)C(C)C>C(Cl)Cl.CN(C=O)C>[CH2:1]([O:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[CH2:12][C:13]([NH:23][NH:22][C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])=[O:15])[CH2:2][CH:3]=[CH2:4]

Participants

7

Reactant 4

HCID 65578Oxalyl chlorideHCID 70091tert-Butyl carbazateHCID 81531DiisopropylethylamineHCID 80741150HCID 80741150, compound

Product 1

HCID 118319911Hydrazinecarboxylic acid, 2-[2-[2-(3-buten-1-yloxy)phenyl]acetyl]-, 1,1-dimethylethyl esterYield 83%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent4×

Procedure

To a solution of 2-(2-(but-3-en-1-yloxy)phenyl)acetic acid (0.22 g, 1.06 mmol, 1 equiv) in DCM (11 mL) was added one drop DMF followed by oxalyl chloride (0.19 mL, 2.11 mmol, 2 equiv). Gas evolution observed. After 1 h, the reaction was concentrated in vacuo to provide the crude acid chloride. The acid chloride was taken up in DCM (5 mL) and added slowly to a solution of tert-butyl hydrazinecarboxylate (168 mg, 1.27 mmol, 1.2 equiv) and DIPEA (0.55 mL, 3.17 mmol, 3 equiv) in DCM (11 mL). After stirring 1 h, the reaction was diluted with DCM, washed with saturated aqueous NaHCO3, dried (MgSO4), and concentrated in vacuo. The crude product was purified via flash column chromatography (0-100% EtOAc/hexane) to provide the product (0.28 g, 83%) as a viscous tan oil. 1H NMR (400 MHz, CDCl3) δ 7.62 (br. s., 1H), 7.31-7.23 (m, 2H), 7.00-6.87 (m, 2H), 6.48-6.26 (m, 1H), 5.99-5.85 (m, 1H), 5.23 (dd, J=17.1, 1.5 Hz, 1H), 5.17 (d, J=10.3 Hz, 1H), 4.14-4.09 (m, 2H), 3.61 (s, 2H), 2.61 (q, J=6.4 Hz, 2H), 1.48-1.36 (m, 9H).

Workup

  1. concentrationthe reaction was concentrated in vacuo
  2. customto provide the crude acid chloride
  3. washwashed with saturated aqueous NaHCO3
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo
  6. customThe crude product was purified via flash column chromatography (0-100% EtOAc/hexane)

Sources & evidence

ORD record
ord-ea5d3fa81e164287a85c606eea346c9a
Source dataset
uspto-grants-2016_08
Patent number
US09409922B2

Reaction notes

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