Aluminium lithium hydride → (2-amino-9-methyl-6,7-dihydro-5H-benzo[7]annulen-8-yl)methanol

HRID 1911025Notes

Reaction equation

HRID 1911025 reaction equation
[NH2:1][C:2]1[CH:3]=[CH:4][C:5]2[CH2:11][CH2:10][CH2:9][C:8]([C:12](OC)=[O:13])=[C:7]([CH3:16])[C:6]=2[CH:17]=1.[H-].[H-].[H-].[H-].[Li+].[Al+3]>C1COCC1>[NH2:1][C:2]1[CH:3]=[CH:4][C:5]2[CH2:11][CH2:10][CH2:9][C:8]([CH2:12][OH:13])=[C:7]([CH3:16])[C:6]=2[CH:17]=1

Participants

4

Reactant 2

HCID 21226445Aluminium lithium hydrideHCID 86685426methyl 2-amino-9-methyl-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate

Product 1

HCID 86685427(2-amino-9-methyl-6,7-dihydro-5H-benzo[7]annulen-8-yl)methanolYield 96%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirred solution of methyl 2-amino-9-methyl-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate from step J1 (65 mg, 0.281 mmol) in THF (2 mL) was added a solution of LAH in THF (1.0 M, 0.337 mL, 0.337 mmol) at −20° C. The mixture was warmed to rt over 2 h. The reaction was quenched with a couple of drops of 1 N NaOH. EtOAc was added. The mixture was dried over sodium sulfate, filtered, and concentrated in vacuo to afford (2-amino-9-methyl-6,7-dihydro-5H-benzo[7]annulen-8-yl)methanol (55.0 mg, 0.271 mmol, 96% yield). LCMS (M+H)+=204.1. 1H NMR (500 HMz, chloroform-d) δ 6.96 (d, J=7.9 Hz, 1H), 6.63 (d, J=2.4 Hz, 1H), 6.54 (dd, J=7.9, 2.4 Hz, 1H), 4.36 (d, J=3.4 Hz, 2H), 3.59 (br. s., 2H), 2.45 (t, J=6.9 Hz, 2H), 2.19 (d, J=2.9 Hz, 1H), 2.08 (s, 3H), 2.07-2.01 (m, 2H), 1.99-1.94 (m, 2H).

Workup

  1. customThe reaction was quenched with a couple of drops of 1 N NaOH
  2. additionEtOAc was added
  3. dry with materialThe mixture was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-43acad8db1cb44fea823d5f6e15cc1d4
Source dataset
uspto-grants-2013_12
Patent number
US08604024B2

Reaction notes

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