Hydrochloric Acid → HCID 87461051, compound

HRID 1865804Notes

Reaction equation

HRID 1865804 reaction equation
[CH3:1][S:2]([O:5][CH2:6][CH2:7][N:8]([CH2:24][CH2:25][O:26][S:27]([CH3:30])(=[O:29])=[O:28])[C:9]1[C:10]([N+:21]([O-:23])=[O:22])=[CH:11][C:12]([N+:18]([O-:20])=[O:19])=[C:13]([CH:17]=1)[C:14]([OH:16])=O)(=[O:4])=[O:3].CN(C=O)C.[NH2:36][CH2:37][CH2:38][CH2:39][OH:40].Cl>O=S(Cl)Cl>[CH3:1][S:2]([O:5][CH2:6][CH2:7][N:8]([CH2:24][CH2:25][O:26][S:27]([CH3:30])(=[O:29])=[O:28])[C:9]1[CH:17]=[C:13]([C:14]([NH:36][CH2:37][CH2:38][CH2:39][OH:40])=[O:16])[C:12]([N+:18]([O-:20])=[O:19])=[CH:11][C:10]=1[N+:21]([O-:23])=[O:22])(=[O:4])=[O:3]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 90863-Amino-1-propanolHCID 16115119HCID 16115119, compound

Product 1

HCID 87461051HCID 87461051, compoundYield 68%

Reagents, catalysts & solvents 1

HCID 24386Thionyl ChlorideSolvent

Procedure

5-(Bis{2-[(methylsulfonyl)oxy]ethyl}amino)-2,4-dinitrobenzoic acid [A method of preparing this compound is disclosed in co-pending NZ Application No. 521851] (9) was heated under reflux in excess SOCl2 (60 mL) and catalytic DMF for1 h. Evaporation under reduced pressure, followed by azeotroping in benzene, gave the crude acid chloride. This was dissolved in dry Me2CO and treated at 0° C. with 3-amino-1-propanol at 0° C. for 5 min. The mixture was acidified to pH 2-3 with 0.2 N HCl, concentrated to half volume, and then solid NaBr was added, followed by extraction with EtOAc (2×). Evaporation, and chromatography of the residue on silica gel, eluting with EtOAc/MeOH (9:1), gave give 2-(5-{[(3-hydroxypropyl)amino]carbonyl } {2-[(methylsulfonyl)oxy]ethyl}-2,4-dinitroanilino)ethyl methanesulfonate (8) (68%) as a yellow gum; 1H NMR [(CD3)2SO] δ 8.54 (t, J=5.7 Hz, 1 H), 8.53 (s, 1 H), 7.45 (s, 1 H), 4.43 (t, J=5.1 Hz, 1 H), 4.33 (t, J=5.2 Hz, 4 H), 3.69 (t, J=5.2 Hz, 4 H), 3.57 (q, J=5.9 Hz, 2 H), 3.26 (after D2O exchange, t, J=7.0 Hz, 2 H), 3.12 (s, 6 H), 1.66 (pent, J=6.7 Hz, 2 H). HRMS (FAB) calcd. for C16H25N4O12S (MH+) m/z 529.0910; found 529.0904.

Workup

  1. customEvaporation under reduced pressure
  2. customby azeotroping in benzene
  3. customgave the crude acid chloride
  4. dissolutionThis was dissolved in dry Me2CO
  5. concentrationconcentrated to half volume
  6. additionsolid NaBr was added
  7. extractionfollowed by extraction with EtOAc (2×)
  8. customEvaporation, and chromatography of the residue on silica gel
  9. washeluting with EtOAc/MeOH (9:1)
  10. customgave

Sources & evidence

ORD record
ord-9dd22496298241b394c2da727189b508
Source dataset
uspto-grants-2009_12
Patent number
US07629332B2

Reaction notes

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