Diisopropylethylamine → HCID 67403053, compound

HRID 906110Notes

Reaction equation

HRID 906110 reaction equation
C([N:4](CC)C(C)C)(C)C.F[P-](F)(F)(F)(F)F.N1(OC(N(C)C)=[N+](C)C)C2N=CC=CC=2N=N1.[CH3:34][C:35]([O:38][C:39]([C:41]1[CH:49]=[CH:48][C:44]([C:45](O)=[O:46])=[C:43]([N+:50]([O-:52])=[O:51])[CH:42]=1)=[O:40])([CH3:37])[CH3:36]>CN(C)C=O>[NH2:4][C:45]([C:44]1[CH:48]=[CH:49][C:41]([C:39]([O:38][C:35]([CH3:37])([CH3:36])[CH3:34])=[O:40])=[CH:42][C:43]=1[N+:50]([O-:52])=[O:51])=[O:46]

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 190761834-(1,1-Dimethylethyl) 2-nitro-1,4-benzenedicarboxylate

Product 1

HCID 67403053HCID 67403053, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

N,N-Diisopropylethylamine (0.41 mL, 2.30 mmol) was added to a mixture of O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (321 mg, 0.84 mmol) and 4-{[(1,1-dimethylethyl)oxy]carbonyl}-2-nitrobenzoic acid (prepared according to Gao, Y. et. al WO2001070737) (205 mg, 0.77 mmol) in N,N-dimethylformamide (2 mL), and the reaction mixture was stirred at room temperature for 30 minutes. Ammonia was bubbled into the reaction mixture and stirring was continued for 45 minutes. The reaction mixture was quenched with 0.5M aqueous hydrochloric acid solution (20 mL) and extracted with ethyl acetate (3×20 mL), and the combined extract was washed with water (20 mL), then brine (20 mL), dried over sodium sulfate, filtered and concentrated. The residue was purified by silica gel flash chromatography (25 to 75% ethyl acetate in hexanes) to give the 1,1-dimethylethyl 4-(aminocarbonyl)-3-nitrobenzoate (160 mg, 78% yield). 1H NMR (400 MHz, CDCl3): 8.55 (s, 1H), 8.25 (d, 1H), 7.64 (d, 1H), 6.51 (br, 1H), 6.26 (br, 1H), 1.61 (s 9H); MS (EI) for C12H14N2O5: 267 (MH+).

Workup

  1. customAmmonia was bubbled into the reaction mixture
  2. stirringstirring
  3. waitwas continued for 45 minutes
  4. customThe reaction mixture was quenched with 0.5M aqueous hydrochloric acid solution (20 mL)
  5. extractionextracted with ethyl acetate (3×20 mL)
  6. extractionthe combined extract
  7. washwas washed with water (20 mL)
  8. dry with materialbrine (20 mL), dried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by silica gel flash chromatography (25 to 75% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-a3c20a8db8a64bd3988e26aa2d6331d5
Source dataset
uspto-grants-2011_09
Patent number
US08012956B2

Reaction notes

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