Formamide → HCID 70926266, compound
Reaction equation
[CH3:1][C:2]1([CH3:16])[C:10]2[CH2:9][CH2:8][C:7](=[O:11])[C:6](=O)[C:5]=2[C:4]([CH3:14])([CH3:13])[CH:3]1[CH3:15].CC1(C)C2CCCC(=O)C=2C(C)(C)C1C.[CH:32]([NH2:34])=O>C1(C)C=CC=CC=1>[CH3:1][C:2]1([CH3:16])[C:10]2[CH2:9][CH2:8][C:7]3[O:11][CH:32]=[N:34][C:6]=3[C:5]=2[C:4]([CH3:14])([CH3:13])[CH:3]1[CH3:15]Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 200 °C
Procedure
1,1,2,3,3-Pentamethyl-2,3,6,7-tetrahydro-1H-indene-4,5-dione is first prepared with 1,1,2,3,3-pentamethyl-1,2,3,5,6,7-hexahydro-inden-4-one (Cashmeran®) (commercially available at IFF) via oxidation with (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO) (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-2,3,6,7-tetrahydro-1H-indene-4,5-dione (10 g, 0.04 mol) and formamide (NH2CHO) (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-5,6,7,8-tetrahydro-4H-1-oxa-3-aza-as-indacene and 6,6,7,8,8-pentamethyl-5,6,7,8-tetrahydro-4H-indeno[4,5-d]oxazole (˜10 g) is obtained.
Workup
- customA 100 mL reaction flask
- washwashed once with aqueous sodium carbonate (10%, 100 mL)
- customToluene is recovered by roto-evaporation
- customThe crude product is further purified with liquid chromatography (Biotage® system)
- customcrystallized
- additionProduct of a mixture of 6,6,7,8,8-pentamethyl-5,6,7,8-tetrahydro-4H-1-oxa-3-aza-as-indacene
Sources & evidence
- ORD record
- ord-ca55f678340d4da187ed9b17765d55f6
- Source dataset
- uspto-grants-2013_10
- Patent number
- US08557876B2
Reaction notes
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