Hydrochloric Acid → HCID 56926628, compound

HRID 595341Notes

Reaction equation

HRID 595341 reaction equation
C[C@]12C(C)(C)[C@H](CC1)C[C@H]2NCCN[C@@H]1C[C@@H]2C(C)(C)[C@@]1(C)CC2.[C:25]1([CH2:31][O:32][CH2:33][CH2:34][CH2:35][O:36][C:37]2[CH:38]=[C:39]([CH:42]=[CH:43][CH:44]=2)[CH:40]=[O:41])[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1.[N+:45]([CH3:48])([O-:47])=[O:46].C(N(C(C)C)CC)(C)C.Cl>O.C([O-])(=O)C.[Cu+2].C([O-])(=O)C.COC(C)(C)C.C(O)C>[N+:45]([CH2:48][C@H:40]([C:39]1[CH:42]=[CH:43][CH:44]=[C:37]([O:36][CH2:35][CH2:34][CH2:33][O:32][CH2:31][C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)[CH:38]=1)[OH:41])([O-:47])=[O:46]

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 6375NitromethaneHCID 81531DiisopropylethylamineHCID 44477597HCID 44477597, compoundHCID 866376223-(3-(Benzyloxy)propoxy)benzaldehyde

Product 1

HCID 56926628HCID 56926628, compound

Reagents, catalysts & solvents 3

HCID 165397Cupric acetate monohydrateCatalystHCID 702EthanolSolvent2×HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
55 °C

Procedure

Copper (II) acetate monohydrate (3.70 g, 0.05 eq) and bis-camphorethylenediamine (N1,N2-bis[(1R,2R,4R)-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl]-1,2-ethanediamine) (7.38 g, 0.06 eq) were charged to a reactor, followed by ethanol (200 mL, 2 vol). The contents were heated to 50-60° C. for ˜1 h or until all solids dissolved, then cooled to room temperature and stirred, at which time a solution of 3-({3-[(phenylmethyl)oxy]propyl}oxy)benzaldehyde in ethanol (100 g, 1 eq in 50 mL, 0.5 vol) was charged. The reaction mixture was cooled to −10° C. to −20° C., whereupon nitromethane (112.7 g, 5 eq) was added slowly to the reaction, maintaining a temperature below −10° C., followed by diisopropylethylamine (1.94 mL, 1.44 g, 0.03 eq). The reaction temperature was maintained at −10° C. for ˜22-30 h. When the reaction was complete, a room temperature solution of 1 N HCl (250 mL, 2.5 vol) and t-butyl methyl ether (TBME, 500 mL, 5 vol) were charged to the reaction vessel. Following the addition, the contents were stirred for ˜5 minutes and brought to 20° C. (˜room temperature), and then the layers were allowed to separate and the aqueous phase removed. The organic phase was then washed 2× with water (250 mL, 2.5 vol) and each time the aqueous phase removed. TBME was then distilled off and replaced with absolute ethanol.

Workup

  1. dissolutiondissolved
  2. temperaturecooled to room temperature
  3. additionwas charged
  4. additionwas added slowly to the reaction
  5. temperaturemaintaining a temperature below −10° C.
  6. temperatureThe reaction temperature was maintained at −10° C. for ˜22-30 h
  7. customwas complete, a room temperature
  8. additionwere charged to the reaction vessel
  9. additionthe addition
  10. custombrought to 20° C.
  11. custom(˜room temperature)
  12. customto separate
  13. customthe aqueous phase removed
  14. washThe organic phase was then washed 2× with water (250 mL, 2.5 vol)
  15. customeach time the aqueous phase removed
  16. distillationTBME was then distilled off

Sources & evidence

ORD record
ord-f58648a1b7a54d70bd3e769d3fdacb73
Source dataset
uspto-grants-2016_01
Patent number
US09243003B2

Reaction notes

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