Diisopropylamine → HCID 59316984, compound

HRID 1189929Notes

Reaction equation

HRID 1189929 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[CH:3]=1.[CH2:11]([NH:14][C:15](=[O:21])[O:16][C:17]([CH3:20])([CH3:19])[CH3:18])[C:12]#[CH:13].C(NC(C)C)(C)C.P(C(C)(C)C)(C(C)(C)C)C(C)(C)C.O1CCOCC1>C(OCC)(=O)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O1CCOCC1>[N+:8]([C:4]1[CH:3]=[C:2]([C:13]#[C:12][CH2:11][NH:14][C:15](=[O:21])[O:16][C:17]([CH3:19])([CH3:18])[CH3:20])[CH:7]=[CH:6][CH:5]=1)([O-:10])=[O:9]

Participants

9

Reactant 4

HCID 7912DiisopropylamineHCID 11457Benzene, 1-bromo-3-nitro-HCID 11073648tert-butyl N-(prop-2-yn-1-yl)carbamateHCID 131731250HCID 131731250, compound

Product 1

HCID 59316984HCID 59316984, compound

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
45 °C

Procedure

To an oven dried, argon filed, flask was added 1-bromo-3-nitrobenzene (14) (3.09 g, 15.3 mmol), tert-butyl prop-2-ynylcarbamate (15) (2.8 g, 18.0 mmol), diisopropylamine (92.5 ml, 17.8 mmol), CuI (0.054 g, 0.18 mmol), PdCl2(PPh3)2 (0.42 g, 0.6 mmol) and dioxane (17 ml). The resulting mixture was purged with argon three times and then a solution of t-Bu3P-dioxane solution (0.9 ml, 0.9 mmol) was added. The mixture was heated at 45° C. for 15 h, cooled to room temperature, diluted with ethyl acetate, filtered through celite and the filtrate was concentrated under reduced pressure. Purification by flash chromatography (10 to 50% EtOAc-hexanes gradient) gave tert-butyl 3-(3-nitrophenyl)prop-2-ynylcarbamate (16) as colorless oil. Yield (4.98 g, 100%); 1H NMR (400 MHz, CDCl3) δ 8.25 (t, J=1.6 Hz, 1H), 8.15 (ddd, J=8.4, 2.4, 1.2 Hz, 1H), 7.69 (dt, J=7.6, 0.8 Hz, 1H), 4.78 (br s, 1H), 4.16 (d, J=5.6 Hz, 2H), 1.47 (s, 9H).

Workup

  1. customTo an oven dried
  2. customThe resulting mixture was purged with argon three times
  3. temperaturecooled to room temperature
  4. filtrationfiltered through celite
  5. concentrationthe filtrate was concentrated under reduced pressure
  6. customPurification by flash chromatography (10 to 50% EtOAc-hexanes gradient)

Sources & evidence

ORD record
ord-0dafd509476d434b86145f32df4a8f6a
Source dataset
uspto-grants-2014_03
Patent number
US08674137B2

Reaction notes

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