Diisopropylethylamine → 3,3,9,9-Tetramethyl-1-[2-hydroxy-3-(2-nitro-1H-imidazol-1-yl)propoxy]-4,8-diazaundecane-2,10-dione dioxime

HRID 968166Notes

Reaction equation

HRID 968166 reaction equation
Cl[C:2]([CH3:21])([CH3:20])[CH:3]([N:18]=[O:19])[CH2:4][O:5][CH2:6][CH:7]([OH:17])[CH2:8][N:9]1[CH:13]=[CH:12][N:11]=[C:10]1[N+:14]([O-:16])=[O:15].[NH2:22][CH2:23][CH2:24][CH2:25][NH:26][C:27]([CH3:34])([CH3:33])[C:28](=[N:31][OH:32])[CH2:29]C.C(N(C(C)C)CC)(C)C>C(#N)C>[CH3:20][C:2]([CH3:21])([NH:22][CH2:23][CH2:24][CH2:25][NH:26][C:27]([CH3:34])([CH3:33])[C:28](=[N:31][OH:32])[CH3:29])[C:3](=[N:18][OH:19])[CH2:4][O:5][CH2:6][CH:7]([OH:17])[CH2:8][N:9]1[CH:13]=[CH:12][N:11]=[C:10]1[N+:14]([O-:16])=[O:15]

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 222877343-chloro-1-[2-hydroxy-3-(2-nitro-1H-imidazol-1-yl)propoxy]-3-methyl-2-nitrosobutaneHCID 86585151N-(3-aminopropyl)-1-amino-1,1-dimethyl-2-butanone oxime

Product 1

HCID 850703603,3,9,9-Tetramethyl-1-[2-hydroxy-3-(2-nitro-1H-imidazol-1-yl)propoxy]-4,8-diazaundecane-2,10-dione dioxime

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Conditions

Temperature
40 °C

Procedure

A slurry of 3-chloro-1-[2-hydroxy-3-(2-nitro-1H-imidazol-1-yl)propoxy]-3-methyl-2-nitrosobutane (3.2 g, 0.01 mol) in acetonitrile (35 mL) was maintained at 40° C. for 30 minutes. To this slurry was added a solution of N-(3-aminopropyl)-1-amino-1,1-dimethyl-2-butanoneoxime (1.73 g, 0.01 mol) in acetonitrile (10 mL) and diisopropylethylamine (1.5 g, 0.012 mol) and the mixture was maintained at 40° C. for 48 hrs. The solid which formed was filtered and the acetonitrile solution was evaporated on a rotary evaporator to give a green viscous oil which was dried under vacuum. The foamy solid obtained was triturated with acetonitrile to afford a thick oil which solidified on standing. This was purified by column chromatography (CH2Cl2:CH3OH, 7:3, 50:50)). The fractions containing the product were collected and evaporated to give an oil which was dried under vacuum and triturated with acetonitrile to give a white solid. It was recrystallized from ethyl acetate to yield the title product. Yield: 1.2 g (26%). mp: 134-35° C. MS: (M+H)+=458+. 1H NMR (DMSO) δ 1.05 and 1.16 [s, 12H, C(CH3)2], 1.38 (m, 2H, NHCH2CH2CH2NH), 1.72 (s, 3H, CH3), 2.2 (m, 2H, NHCH2CH2CH2NH), 3.38 (m, 4H, CH2OCH2CHOH), 3.8 (m, 2H, OCH2CHOH), 4.28 and 4.6 (m, 3H, CHOHCH2N<), 7.12 and 7.58 (8, 2H, imi H), 10.4 and 10.85 (s, 2H, NOH). Anal. Calcd for C19H35N7O6: C, 49.88; H, 7.71; N, 21.43. Found: C, 49.80; H, 7.79; N, 21.47.

Workup

  1. customThe solid which formed
  2. filtrationwas filtered
  3. customthe acetonitrile solution was evaporated on a rotary evaporator
  4. customto give a green viscous oil which
  5. customwas dried under vacuum
  6. customThe foamy solid obtained
  7. customwas triturated with acetonitrile
  8. customto afford a thick oil which
  9. customThis was purified by column chromatography (CH2Cl2:CH3OH, 7:3, 50:50))
  10. additionThe fractions containing the product
  11. customwere collected
  12. customevaporated
  13. customto give an oil which
  14. customwas dried under vacuum
  15. customtriturated with acetonitrile
  16. customto give a white solid
  17. customIt was recrystallized from ethyl acetate

Sources & evidence

ORD record
ord-52fcb85ed149477083dfabd81c013faa
Source dataset
uspto-grants-2005_10
Patent number
US06958141B2

Reaction notes

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