Triethylamine → HCID 90253578, compound

HRID 1478748Notes

Reaction equation

HRID 1478748 reaction equation
Cl[O-].[Na+].[OH:4][N:5]=[CH:6][CH2:7][O:8][CH:9]([C:13]1([CH3:16])[CH2:15][CH2:14]1)[CH2:10][CH:11]=[CH2:12].C(N(CC)CC)C>ClCCl.O>[CH3:16][C:13]1([C@@H:9]2[O:8][CH2:7][C:6]3=[N:5][O:4][CH2:12][C@@H:11]3[CH2:10]2)[CH2:15][CH2:14]1

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 23665760Sodium HypochloriteHCID 118621171HCID 118621171, compound

Product 1

HCID 90253578HCID 90253578, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

An aqueous solution of sodium hypochlorite (6.15% solution, 65 mL, 51 mmol) was added drop-wise over 24 minutes to a solution of N-hydroxy-2-{[1-(1-methylcyclopropyl)but-3-en-1-yl]oxy}ethanimine (C55) (6.54 g, 36 mmol) and triethylamine (280 mg, 2.7 mmol) in dichloromethane (64 mL) that was immersed in a room temperature water bath. The rate of addition was adjusted to maintain the internal temperature of the reaction between 19.5° C. and 22.8° C. After completion of the addition, the reaction mixture was diluted with water (50 mL) and the aqueous layer was extracted with dichloromethane (3×50 mL). The combined organic layers were washed with saturated aqueous sodium chloride solution (50 mL), dried over sodium sulfate, filtered, and concentrated in vacuo (300 mbar, 40° C.). Silica gel chromatography (Gradient: 0% to 10% ethyl acetate in petroleum ether) provided the product as a white solid. Yield: 3.84 g, 21.2 mmol, 57%. The indicated relative stereochemistry of compound C56 was assigned based on nuclear Overhauser enhancement studies, which revealed an interaction between the methine protons on carbons 3a and 5. LCMS m/z 182 [M+H+]. 1H NMR (400 MHz, CDCl3) δ 4.73 (d, J=13.2 Hz, 1H), 4.64 (dd, J=10.4, 8.0 Hz, 1H), 4.14 (d, J=14.1 Hz, 1H), 3.81 (dd, J=11.6, 8.0 Hz, 1H), 3.44-3.39 (m, 1H), 2.82 (d, J=12.8 Hz, 1H), 2.21-2.15 (m, 1H), 1.76 (q, J=11.9 Hz, 1H), 1.05 (s, 3H), 0.55-0.51 (m, 1H), 0.44-0.41 (m, 2H), 0.40-0.39 (m, 1H).

Workup

  1. customwas immersed in a room temperature
  2. additionThe rate of addition
  3. temperatureto maintain
  4. customthe internal temperature of the reaction between 19.5° C. and 22.8° C
  5. additionAfter completion of the addition
  6. extractionthe aqueous layer was extracted with dichloromethane (3×50 mL)
  7. washThe combined organic layers were washed with saturated aqueous sodium chloride solution (50 mL)
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo (300 mbar, 40° C.)

Sources & evidence

ORD record
ord-ded5261b36cb4e6a9b78d40a20a6db25
Source dataset
uspto-grants-2016_08
Patent number
US09403846B2

Reaction notes

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