Formamidine acetate → HCID 70926810, compound

HRID 1042394Notes

Reaction equation

HRID 1042394 reaction equation
[CH3:1][C:2]1([CH3:14])[CH:10]2[CH:5]([C:6](=O)[CH2:7][CH2:8][CH2:9]2)[C:4]([CH3:13])([CH3:12])[CH2:3]1.CC1(C)C2CCCC(=O)C=2C(C)(C)C1.[H][H].[C:31](O)(=O)C.[CH:35]([NH2:37])=[NH:36]>[Pd].C(O)CCC>[CH3:12][C:4]1([CH3:13])[CH:5]2[C:6]3[C:7]([CH2:8][CH2:9][CH:10]2[C:2]([CH3:1])([CH3:14])[CH2:3]1)=[CH:31][N:37]=[CH:35][N:36]=3

Participants

7

Reactant 4

HCID 160693Formamidine acetateHCID 86673205HCID 86673205, compoundHCID 86673206HCID 86673206, compound2×HCID 178418361HCID 178418361, compound

Product 1

HCID 70926810HCID 70926810, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 2631-ButanolSolvent

Conditions

Temperature
130 °C

Procedure

1,1,3,3-Tetramethyl-octahydro-inden-4-one is first prepared by hydrogenating 1,1,3,3-tetramethyl-1,2,3,5,6,7-hexahydro-inden-4-one (prepared as described in U.S. Pat. No. 3,927,083) with Pd/C in alcohol in a Parr Hydrogenator at 25-60° C. and under 500 psi of hydrogen gas. A 100 mL reaction flask is the charged with 1,1,3,3-tetramethyl-octahydro-inden-4-one (10 g, 0.05 mol), formamidine acetate (27 g, 0.26 mol), and butanol (50 mL). The reaction mixture is heated to 130° C. and stirred for 24 hours. The crude mass is washed once with aqueous sulfuric acid (10%, 100 mL) followed by twice with brine (30 mL). Butanol is recovered by roto-evaporation. The crude product is further purified with liquid chromatography (Biotage® system) and then crystallized. Product 1,1,3,3-tetramethyl-2,3,3a,4,5,9b-hexahydro-1H-7,9-diaza-cyclopenta[a]naphthalene (˜5 g) is obtained.

Workup

  1. customprepared
  2. customat 25-60° C.
  3. customA 100 mL reaction flask
  4. washThe crude mass is washed once with aqueous sulfuric acid (10%, 100 mL)
  5. customButanol is recovered by roto-evaporation
  6. customThe crude product is further purified with liquid chromatography (Biotage® system)
  7. customcrystallized

Sources & evidence

ORD record
ord-2eca59cdd82a498d8f2088a3229932f5
Source dataset
uspto-grants-2013_10
Patent number
US08557876B2

Reaction notes

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