HCID 347846, compound → HCID 57458838, compound

HRID 574755Notes

Reaction equation

HRID 574755 reaction equation
[N+:1]([CH:4]([CH:6]([OH:14])[CH:7]([CH2:12][CH3:13])[CH2:8][CH2:9][CH2:10][CH3:11])[CH3:5])([O-])=O.NO.NC(C(O)C(CC)CCCC)C>[Ni].CO>[NH2:1][CH:4]([CH:6]([OH:14])[CH:7]([CH2:12][CH3:13])[CH2:8][CH2:9][CH2:10][CH3:11])[CH3:5]

Participants

5

Reactant 2

HCID 347846HCID 347846, compound2×HCID 86640811HCID 86640811, compound

Product 1

HCID 57458838HCID 57458838, compound

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 887MethanolSolvent

Conditions

Temperature
40 °C

Procedure

Catalytic hydrogenation of the 2-nitro-4-ethyl-3-octanol to the 2-amino-4-ethyl-3-octanol amino alcohol. A sample of 2-amino-4-ethyl-3-octanol was synthesized by the reduction of the 2-nitro-4-ethyl-3-octanol by a Parr Autoclave unit. The stainless steel, 2 liter autoclave was loaded with Grace 3201 Raney Nickel (RaNi, 70 g wet, 35 g dry, 10 wt %) and methanol (MeOH, 300 g). The autoclave was sealed, assembled, purged with nitrogen then hydrogen, pressurized with hydrogen (750 psig), stirred at 600 RPM, and warmed to 40° C. The nitro-alcohol (362 g) was diluted with methanol MeOH, 380 ml) and pumped into the autoclave (5 ml/min). After 2 h the addition was complete and after another 15 min the reaction was judged complete as no hydrogen uptake was observed. The autoclave was cooled, stirring stopped, vented, and purged with nitrogen. The autoclave was disassembled and the contents were vacuum filtered to remove the RaNi catalyst. This resulted in the isolation of a light yellow liquid (84 area % pure) that was concentrated in vacuo (55° C./full vacuum) before product was taken overhead (122° C./15 mm) using a vacuum jacketed 18″ vigreux column/head assembly. This resulted in the isolation of product as a clear, colorless, solution (182 g, 96.9 area %, 44% overall yield).

Workup

  1. customThe autoclave was sealed
  2. custompurged with nitrogen
  3. additionThe nitro-alcohol (362 g) was diluted with methanol MeOH, 380 ml) and
  4. additionAfter 2 h the addition
  5. temperatureThe autoclave was cooled
  6. stirringstirring
  7. custompurged with nitrogen
  8. filtrationfiltered
  9. customto remove the RaNi catalyst
  10. customThis resulted in the isolation of a light yellow liquid (84 area % pure) that
  11. concentrationwas concentrated in vacuo (55° C./full vacuum) before product
  12. custom(122° C./15 mm)
  13. customThis resulted in the isolation of product as a clear, colorless,
  14. customsolution (182 g, 96.9 area %, 44% overall yield)

Sources & evidence

ORD record
ord-829875288e8e4de9b1dae08c62270eb8
Source dataset
uspto-grants-2015_05
Patent number
US09034929B2

Reaction notes

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