Ethylenediamine → HCID 70926676, compound

HRID 1042423Notes

Reaction equation

HRID 1042423 reaction equation
[CH3:1][C:2]1([CH3:15])[CH:10]2[CH:5]([C:6](=O)[CH2:7][CH2:8][CH2:9]2)[C:4]([CH3:13])([CH3:12])[CH:3]1[CH3:14].CC1(C)C2CCCC(=O)C=2C(C)(C)C1C.CC1(C)C2C(C(=O)C(=O)CC2)C(C)(C)C1C.[CH2:47]([NH2:50])[CH2:48][NH2:49].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>COCCOCCOC>[CH3:1][C:2]1([CH3:15])[CH:10]2[CH:5]([C:6]3[N:49]=[CH:48][CH:47]=[N:50][C:7]=3[CH2:8][CH2:9]2)[C:4]([CH3:13])([CH3:12])[CH:3]1[CH3:14]

Participants

7

Reactant 5

HCID 3301EthylenediamineHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 92292(+-)-CashmeranHCID 109547844H-Inden-4-one, octahydro-1,1,2,3,3-pentamethyl-2×HCID 70926475HCID 70926475, compound2×

Product 1

HCID 70926676HCID 70926676, compound

Reagents, catalysts & solvents 1

HCID 8150DiglymeSolvent

Conditions

Temperature
130 °C

Procedure

1,1,2,3,3-Pentamethyl-octahydro-inden-4-one is first prepared by the hydrogenation of 1,1,2,3,3-pentamethyl-1,2,3,5,6,7-hexahydro-inden-4-one (Cashmeran®) (commercially available at IFF). 1,1,2,3,3-Pentamethyl-hexahydro-indene-4,5-dione is subsequently prepared with 1,1,2,3,3-pentamethyl-octahydro-inden-4-one (prepared as described by Barton in Tetrahedron Letters, 1984, 25(6), pages: 603-606). A 100 mL reaction flask is charged with 1,1,2,3,3-pentamethyl-hexahydro-indene-4,5-dione (10 g, 0.04 mol), ethylene diamine (NH2CH2CH2NH2) (2.5 g, 0.04 mol), and diglyme (50 mL). The reaction mixture is heated to 130° C. and stirred for 24 hours. The reaction mixture is then cooled to 25° C. and further oxidized with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (10 g, 0.045 mol) for another 8 hours. The crude mass is washed once with aqueous sodium carbonate (10%, 100 mL) followed by twice with brine (30 mL). Diglyme is recovered by roto-evaporation. The crude product is further purified with liquid chromatography (Biotage® system) and then crystallized. Product 7,7,8,9,9-pentamethyl-5,6a,7,8,9,9a-hexahydro-6H-cyclopenta[f]quinoxaline (˜10 g) is obtained.

Workup

  1. customA 100 mL reaction flask
  2. washThe crude mass is washed once with aqueous sodium carbonate (10%, 100 mL)
  3. customDiglyme is recovered by roto-evaporation
  4. customThe crude product is further purified with liquid chromatography (Biotage® system)
  5. customcrystallized

Sources & evidence

ORD record
ord-4ece2dda572341f1a5d5dd3fd2306772
Source dataset
uspto-grants-2013_10
Patent number
US08557876B2

Reaction notes

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