Diisopropylamine → HCID 87568163, compound

HRID 2068169Notes

Reaction equation

HRID 2068169 reaction equation
[Br:1]Br.[CH:3]([O:5][CH2:6][CH3:7])=[CH2:4].C(NC(C)C)(C)C.[OH:15][C:16]1[C:17]([O:41][CH3:42])=[CH:18][CH:19]=[C:20]([CH:39]=[O:40])[C:21]=1[C:22]1[CH:27]=[CH:26][C:25]([O:28][Si:29]([CH:36]([CH3:38])[CH3:37])([CH:33]([CH3:35])[CH3:34])[CH:30]([CH3:32])[CH3:31])=[CH:24][CH:23]=1>C(Cl)Cl>[Br:1][CH2:4][CH:3]([O:5][CH2:6][CH3:7])[O:15][C:16]1[C:17]([O:41][CH3:42])=[CH:18][CH:19]=[C:20]([CH:39]=[O:40])[C:21]=1[C:22]1[CH:23]=[CH:24][C:25]([O:28][Si:29]([CH:30]([CH3:31])[CH3:32])([CH:36]([CH3:38])[CH3:37])[CH:33]([CH3:34])[CH3:35])=[CH:26][CH:27]=1

Participants

6

Reactant 4

HCID 7912DiisopropylamineHCID 8023Ethyl vinyl etherHCID 24408BromineHCID 86647715HCID 86647715, compound

Product 1

HCID 87568163HCID 87568163, compoundYield 99%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of bromine (0.91 mL, 17.8 mmol) in CH2Cl2 (50 mL) at 0° C. was added drop-wise ethyl vinyl ether (2.13 mL, 22.2 mmol). The resulting colorless solution was stirred for 20 min at 0° C. and N,N-diisopropylamine (DIEA) (6.23 mL, 35.6 mmol) added drop-wise, followed by a CH2Cl2 (20 mL) solution of 10 (3.55 g, 8.9 mmol). The resulting solution was stirred for 16 h at 23° C., until all starting material was consumed, as determined by TLC. The mixture was poured onto saturated aqueous NaHCO3 (100 mL), and extracted with CH2Cl2 (3×70 mL). The combined extracts were washed with brine (80 mL), dried (Na2SO4), and concentrated in vacuo to yield orange oil. The crude oil was purified via flash column chromatography (SiO2, 10% EtOAc/hexanes) to give 12 (4.84 g, 99% yield) as a thick orange oil. Rf 0.52 (3:1 hexanes/EtOAc). IR (thin film) 2966, 2944, 2892, 2867, 1684 cm−1. 1H NMR (300 MHz, CDCl3) δ 9.64 (1H, s), 7.85 (1H, d, J=8 Hz), 7.25-7.18 (2H, m), 7.03 (1H, d, J=8 Hz), 6.96 (2H, d, J=8 Hz), 5.06-5.02 (1H, m), 3.98 (3H, s), 3.65-3.55 (1H, m), 3.42-3.34 (1H, m), 3.12-3.01 (2H, m), 1.35-1.20 (3H, m), 1.13 (18H, d, J=7 Hz), 1.05 (3H, t, J=7 Hz). 13C NMR (75 MHz, CDCl3) δ 191.1, 156.9, 156.1, 141.5, 140.5, 132.4, 128.4, 125.1, 119.4, 113.6, 111.0, 103.5, 64.5, 55.9, 31.7, 17.8, 14.9, 12.5. HRMS calcd. for C27H40O5SiBr (MH+) 551.1828. Found 551.1821.

Workup

  1. stirringThe resulting solution was stirred for 16 h at 23° C., until all starting material
  2. customwas consumed
  3. additionThe mixture was poured onto saturated aqueous NaHCO3 (100 mL)
  4. extractionextracted with CH2Cl2 (3×70 mL)
  5. washThe combined extracts were washed with brine (80 mL)
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated in vacuo
  8. customto yield orange oil
  9. customThe crude oil was purified via flash column chromatography (SiO2, 10% EtOAc/hexanes)

Sources & evidence

ORD record
ord-4ac30a83af28440b8a303d6a1ff38bb8
Source dataset
uspto-grants-2012_10
Patent number
US08293927B2

Reaction notes

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