1-Chloro-2-nitrobenzene → 2-Nitro-N-[2-[2-(2-propyn-1-yloxy)ethoxy]ethyl]benzenamine

HRID 532086Notes

Reaction equation

HRID 532086 reaction equation
Cl[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].[CH2:11]([O:14][CH2:15][CH2:16][O:17][CH2:18][CH2:19][NH2:20])[C:12]#[CH:13]>>[N+:8]([C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[NH:20][CH2:19][CH2:18][O:17][CH2:16][CH2:15][O:14][CH2:11][C:12]#[CH:13])([O-:10])=[O:9]

Participants

3

Reactant 2

HCID 69451-Chloro-2-nitrobenzeneHCID 552192912-[2-(2-Propyn-1-yloxy)ethoxy]ethanamine

Product 1

HCID 580788622-Nitro-N-[2-[2-(2-propyn-1-yloxy)ethoxy]ethyl]benzenamineYield 30%

Conditions

Temperature
100 °C

Procedure

To 1-chloro-2-nitrobenzene (152 mg, 0.97 mmol, 1.0 equiv.) was added neat 2-(2-(prop-2-ynyloxy)ethoxy)ethanamine (s-5) (900 mg, 6.31 mmol, 6.5 equiv.), and the resulting slurry was heated to 100° C. for 6 hours during which time the solid dissolved. At the end of this period, the heating bath was removed, the reaction content was mixed with water (50 mL), and then extracted with CH2Cl2 (3×50 mL). The organic layers were combined, dried with Na2SO4, concentrated under reduced pressure, and chromatographed (silica gel, 1×25 cm, 0% CH3OH in CH2Cl2, then 10% CH3OH in CH2Cl2) to yield 2-nitro-N-(2-(2-(prop-2-ynyloxy)ethoxy)ethyl)aniline (s-6) as a dark yellow oil (76 mg, 30%). IR (thin film) 3378 (m), 3286 (m), 3085 (w), 2875 (m), 2114 (w), 1616 (s), 1570 (s), 1508 (s), 1417 (m), 1349 (m), 1228 (s), 1093 (s), 1034 (m), 740 (m), 670 (s); 1H NMR (500 MHz, CDCl3) δ 8.23 (bs, 1H), 8.18 (dd, J=8.6, 1.6 Hz, 1H), 7.43 (ddd, J=8.6, 7.0, 1.6 Hz, 1H), 6.86 (d, J=8.6 Hz, 1H), 6.65 (ddd, J=8.3, 7.0, 1.2 Hz, 1H), 4.22 (d, J=2.4 Hz, 2H), 3.80 (t, J=5.5 Hz, 2H), 3.73 (d, J=2.4 Hz, 4H), 3.52 (q, J=5.4 Hz, 2H), 2.43 (t, J=2.4 Hz, 1H). 13C NMR (125 MHz, CDCl3) δ 145.45, 136.13, 132.22, 126.94, 115.39, 113.78, 79.56, 74.61, 70.50, 69.20, 69.19, 58.52, 42.75; HRMS (ES+) calc'd for C13H16N2O4 (M+H) m/z 265.1144 Found 265.1181.

Workup

  1. dissolutiondissolved
  2. customAt the end of this period, the heating bath was removed
  3. additionthe reaction content was mixed with water (50 mL)
  4. extractionextracted with CH2Cl2 (3×50 mL)
  5. dry with materialdried with Na2SO4
  6. concentrationconcentrated under reduced pressure
  7. customchromatographed (silica gel, 1×25 cm, 0% CH3OH in CH2Cl2

Sources & evidence

ORD record
ord-c7f8cf7eff534809b3fdd829d72b822e
Source dataset
uspto-grants-2014_10
Patent number
US08852630B2

Reaction notes

Loading…