Dimethylformamide → N-tert-Butyl-3-(diazenylmethyl)-4,5,6,7-tetrahydrobenzo[b]thiophene-2-carboxamide

HRID 519355Notes

Reaction equation

[C:1]([NH:5][C:6]([C:8]1[S:12][C:11]2[CH2:13][CH2:14][CH2:15][CH2:16][C:10]=2[CH:9]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[Li]CCCC.C[N:23]([CH:25]=O)C.[NH2:27]N.O>C1COCC1>[C:1]([NH:5][C:6]([C:8]1[S:12][C:11]2[CH2:13][CH2:14][CH2:15][CH2:16][C:10]=2[C:9]=1[CH2:25][N:23]=[NH:27])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

Conditions

Temperature: -78 °C

Procedure

To a solution of 117a (100 g, 0.42 mol, 1.0 equiv) in THF (500 mL) was slowly added n-BuLi (672 mL, 2.5M in THF, 1.68 mol, 4.0 equiv) at −78° C. under argon. The mixture was stirred for 2 h. DMF (306 g, 4.2 mol, 10.0 equiv) was added to the mixture while the temperature was maintained at −78° C. After another 2.0 h, the reaction was quenched with methanol (500 mL) at −78° C. It was stirred for 0.50 h at room temperature. 80% aqueous hydrate hydrazine (131 g, 2.1 mol) was added and the mixture was refluxed at 65° C. overnight. The organic solvent was removed under reduced pressure. The residue was filtered and the yellow solid collected was washed with water. The solid was dried in vacuo to afford crude 117b, which was used in the next step without further purification. MS: [M+H]+ 280.

Workup

customat −78° C.
waitAfter another 2.0 h
customthe reaction was quenched with methanol (500 mL) at −78° C
stirringIt was stirred for 0.50 h at room temperature
temperaturethe mixture was refluxed at 65° C. overnight
customThe organic solvent was removed under reduced pressure
filtrationThe residue was filtered
customthe yellow solid collected
washwas washed with water
customThe solid was dried in vacuo

Sources & evidence

ORD record: ord-b7938b5d30c34da68a4f203a9f1f7465
Source dataset: uspto-grants-2015_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09115152B2

Reaction notes

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