1,2-Dichloroethane → HCID 67263703, compound

HRID 1040699Notes

Reaction equation

HRID 1040699 reaction equation
[N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[CH2:13][CH2:12][C:11](=O)[CH2:10][CH2:9][C:8]=2[CH:15]=1)([O-:3])=[O:2].ClCCCl.[NH:20]1[CH2:25][CH2:24][O:23][CH2:22][CH2:21]1.C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(Cl)Cl>[N+:1]([C:4]1[CH:5]=[CH:6][C:7]2[CH2:13][CH2:12][CH:11]([N:20]3[CH2:25][CH2:24][O:23][CH2:22][CH2:21]3)[CH2:10][CH2:9][C:8]=2[CH:15]=1)([O-:3])=[O:2]

Participants

7

Reactant 5

HCID 111,2-DichloroethaneHCID 176Acetic AcidHCID 8083MorpholineHCID 5049666Sodium triacetoxyborohydrideHCID 457903192-Nitro-8,9-dihydro-5H-benzo[7]annulen-7(6H)-one

Product 1

HCID 67263703HCID 67263703, compoundYield 81.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 2-nitro-5,6,8,9-tetrahydrobenzocyclohepten-7-one (500 mg, 0.002 mol) in 1,2-dichloroethane (20 mL, 0.2 mol) was added morpholine (0.23 mL, 0.0027 mol) and acetic acid (0.15 mL, 0.0027 mol). Sodium triacetoxyborohydride (670 mg, 0.0032 mol) was then added to the reaction mixture and the contents stirred at room temperature overnight. The reaction mixture was cooled to 0° C., diluted with methylene chloride (20 mL), quenched with aqueous ammonium chloride (5 mL) and washed with water and brine. The organic phase was dried over magnesium sulfate, filtered and concentrated in vacuo to a brown residue. The reaction mixture was purified by ISCO chromatography on silica gel (40 g column) using 10-30% ethyl acetate-hexane gradient. The major fractions corresponding to product as confirmed by LCMS were combined and concentrated in vacuo to give a light brown solid, 4-(2-nitro-6,7,8,9-tetrahydro-5H-benzocyclohepten-7-yl)-morpholine (450 mg, 70%). 1HNMR (400 MHz, CDCl3) δ 8.05 (s, 1H), 7.98 (d, 1H, J=8 Hz), 7.44 (d, 1H, J=8 Hz), 3.62 (m, 4H), 3.37 (m, 1H), 3.04 (m, 4H), 2.77 (m, 4H), 2.05 (m, 2H), 1.4 (m, 2H); MS (m/e) 276 (M+1).

Workup

  1. temperatureThe reaction mixture was cooled to 0° C.
  2. customquenched with aqueous ammonium chloride (5 mL)
  3. washwashed with water and brine
  4. dry with materialThe organic phase was dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo to a brown residue
  7. customThe reaction mixture was purified by ISCO chromatography on silica gel (40 g column)
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-1f31e2644da042078b42b7e033369258
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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