Formamide → HCID 70926103, compound

HRID 1042419Notes

Reaction equation

HRID 1042419 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.[CH:47]([NH2:49])=[O:48]>C1(C)C=CC=CC=1>[CH3:1][C:2]1([CH3:15])[CH:10]2[CH2:9][CH2:8][C:7]3[O:48][CH:47]=[N:49][C:6]=3[CH:5]2[C:4]([CH3:13])([CH3:12])[CH:3]1[CH3:14]

Participants

6

Reactant 4

HCID 713FormamideHCID 92292(+-)-CashmeranHCID 109547844H-Inden-4-one, octahydro-1,1,2,3,3-pentamethyl-2×HCID 70926475HCID 70926475, compound2×

Product 1

HCID 70926103HCID 70926103, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
200 °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) and formamide (50 mL). The reaction mixture is heated to 200° C. and stirred for 24 hours. The crude mass is diluted with toluene (50 mL) and then washed once with aqueous sodium carbonate (10%, 100 mL) followed by twice with brine (30 mL). Toluene is recovered by roto-evaporation. The crude product is further purified with liquid chromatography (Biotage® system) and then crystallized. Product of a mixture of 6,6,7,8,8-pentamethyl-5,5a,6,7,8,8a-hexahydro-4H-1-oxa-3-aza-as-indacene and 6,6,7,8,8-pentamethyl-5,5a,6,7,8,8a-hexahydro-4H-indeno[4,5-d]oxazole (˜10 g) is obtained.

Workup

  1. customA 100 mL reaction flask
  2. washwashed once with aqueous sodium carbonate (10%, 100 mL)
  3. customToluene is recovered by roto-evaporation
  4. customThe crude product is further purified with liquid chromatography (Biotage® system)
  5. customcrystallized
  6. additionProduct of a mixture of 6,6,7,8,8-pentamethyl-5,5a,6,7,8,8a-hexahydro-4H-1-oxa-3-aza-as-indacene

Sources & evidence

ORD record
ord-80444935685f47a5a5a94b8c30676d71
Source dataset
uspto-grants-2013_10
Patent number
US08557876B2

Reaction notes

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