3-Amino-1-propanol → HCID 11340964, compound

HRID 1865801Notes

Reaction equation

HRID 1865801 reaction equation
[Br:1][CH2:2][CH2:3][N:4]([CH2:20][CH2:21][Br:22])[C:5]1[C:6]([N+:17]([O-:19])=[O:18])=[CH:7][C:8]([N+:14]([O-:16])=[O:15])=[C:9]([CH:13]=1)[C:10]([OH:12])=O.C(Br)(=O)C(Br)=O.[NH2:29][CH2:30][CH2:31][CH2:32][OH:33].CCOC(C)=O.O(C(C)C)C(C)C>C1C=CC=CC=1.CN(C=O)C.O>[OH:33][CH2:32][CH2:31][CH2:30][NH:29][C:10](=[O:12])[C:9]1[CH:13]=[C:5]([N:4]([CH2:3][CH2:2][Br:1])[CH2:20][CH2:21][Br:22])[C:6]([N+:17]([O-:19])=[O:18])=[CH:7][C:8]=1[N+:14]([O-:16])=[O:15]

Participants

8

Reactant 4

HCID 90863-Amino-1-propanolHCID 84841Ethanedioyl dibromideHCID 16115121HCID 16115121, compoundHCID 22281796Diisopropylether ethyl acetate

Product 1

HCID 11340964HCID 11340964, compound

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 241BenzeneSolventHCID 962WaterSolvent2×

Conditions

Temperature
20 °C

Procedure

A suspension of powdered 5-[bis(2-bromoethyl)amino]-2,4-dinitrobenzoic acid (2) (1.10 g, 2.49 mmol) in benzene (170 mL) was treated at 20° C. with oxalyl bromide (1.10 mL, 11.7 mmol) and DMF (2 drops). The mixture was stirred at 20° C. for 2 h, then concentrated under reduced pressure, and re-evaporated to dryness in the presence of benzene under high vacuum. The resulting acid bromide was dissolved in Me2CO (20 mL) and the solution was treated at −5° C. with a cold solution of 3-amino-1-propanol (0.39 g, 5.19 mmol) in water (10 mL). The mixture was shaken at room temperature for 5 min, then diluted with water and extracted with EtOAc (2×). The organic extract was worked up and the resulting residue was chromatographed on silica gel, eluting with EtOAc, to give IIa-8 (1.06 g, 85%): mp (EtOAc/i-Pr2O) 85-86° C.; 1H NMR [(CD3)2SO] δ 8.64 (t, J=5.6 Hz, 1 H, CONH), 8.53 (s, 1 H, H-3), 7.41 (s, 1 H, H-6), 3.77-3.64 (m, 8 H, N(CH2CH2Cl)2), 4.46 (br s, 1 H, OH), 3.49 (t, J=6.3 Hz, 2 H, CH2OH), 3.33-3.25 (m, partially obscured, 2 H, CONHCH2), 1.68 (pent, J=6.72 Hz, 2 H, CH2CH2CH2). Anal. (C14Hl18Br2N4O6) C, H, N, Br.

Workup

  1. concentrationconcentrated under reduced pressure
  2. customre-evaporated to dryness in the presence of benzene under high vacuum
  3. dissolutionThe resulting acid bromide was dissolved in Me2CO (20 mL)
  4. stirringThe mixture was shaken at room temperature for 5 min
  5. extractionextracted with EtOAc (2×)
  6. extractionThe organic extract
  7. customthe resulting residue was chromatographed on silica gel
  8. washeluting with EtOAc
  9. customto give IIa-8 (1.06 g, 85%)

Sources & evidence

ORD record
ord-a63921771ddf49c5ba56693758ae3b4f
Source dataset
uspto-grants-2009_12
Patent number
US07629332B2

Reaction notes

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