Toluene → HCID 58078877, compound

HRID 532084Notes

Reaction equation

HRID 532084 reaction equation
[N+:1]([C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:5]=1[NH:13][CH2:14][CH2:15][O:16][CH2:17][CH2:18][OH:19])([O-:3])=[O:2].[H-].[Na+].[CH2:22](Br)[C:23]#[CH:24].C1(C)C=CC=CC=1>CN(C=O)C.CCOC(C)=O>[N+:1]([C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:5]=1[NH:13][CH2:14][CH2:15][O:16][CH2:17][CH2:18][O:19][CH2:24][C:23]#[CH:22])([O-:3])=[O:2]

Participants

7

Reactant 4

HCID 1140TolueneHCID 7842Propargyl bromideHCID 24758Sodium hydrideHCID 3918222HCID 3918222, compound

Product 1

HCID 58078877HCID 58078877, compoundYield 45%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent3×

Conditions

Temperature
0 °C

Procedure

2-(2-(2,4-dinitrophenylamino)ethoxy)ethanol (s-1b) (100 mg, 0.369 mmol, 1.0 equiv.) was dissolved in 0.81 mL of DMF and slowly added to a slurry of NaH (17.71 mg, 0.738 mmol, 2.0 equiv.) in 0.81 mL of DMF in a flame dried flask pre-cooled to 0° C. An 80% solution of propargyl bromide in toluene (0.0490 □L, 0.443 mmol, 1.2 equiv.) was added slowly. The ice bath was then removed and the reaction was allowed to stir at room temperature for an additional 2 hours. The reaction was then re-cooled to 0° C., quenched with saturated NH4Cl, and then extracted with diethyl ether (3×50 mL). The organic layers were combined, dried with Na2SO4, concentrated under reduced pressure, and chromatographed (silica gel, 3×25 cm, 0% EtOAc in hexanes, then 10% EtOAc in hexanes, then 20% EtOAc in hexanes, then 30% EtOAc in hexanes) to yield 2,4-dinitro-N-(2-(2-(prop-2-ynyloxy)ethoxy)ethyl)aniline (s-2b) as a dark yellow solid (50 mg, 45% yield). IR (thin film) 3360 (m), 3285 (m), 3107 (w), 2872 (m), 1621 (s), 1588 (m), 1524 (m), 1425 (w), 1335 (s), 1305 (m), 1133 (m), 1101 (m), 920 (w), 832 (w); 1H NMR (500 MHz, CDCl3) δ 9.15 (d, J=2.6 Hz, 1H), 8.81 (bs, 1H), 8.27 (dd, J=9.4, 2.3 Hz, 1H), 6.96 (d, J=9.5 Hz, 1H), 4.21 (d, J=2.3 Hz, 2H), 3.84 (t, J=5.2 Hz, 2H), 3.74 (m, 4H), 3.61 (q, J=5.2 Hz, 2H), 2.44 (t, J=2.3 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 148.6, 136.3, 130.7, 130.4, 124.4, 114.2, 79.6, 74.9, 70.7, 69.3, 68.9, 58.7, 43.4. HRMS (ES+) calc'd for C13H15N3O6 (M+H) m/z 310.0994 Found 310.1033.

Workup

  1. customdried flask
  2. customThe ice bath was then removed
  3. temperatureThe reaction was then re-cooled to 0° C.
  4. customquenched with saturated NH4Cl
  5. extractionextracted with diethyl ether (3×50 mL)
  6. dry with materialdried with Na2SO4
  7. concentrationconcentrated under reduced pressure
  8. customchromatographed (silica gel, 3×25 cm, 0% EtOAc in hexanes

Sources & evidence

ORD record
ord-e42c38ac17aa47dcbef741d4696c5fc7
Source dataset
uspto-grants-2014_10
Patent number
US08852630B2

Reaction notes

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