Ammonium Acetate → 6-Benzyloxycarbonylamino-5,6,7,8-tetrahydroquinoline

HRID 1765327Notes

Reaction equation

HRID 1765327 reaction equation
[CH2:1]([O:8][C:9]([NH:11][CH:12]1[CH2:17][CH2:16][C:15](=O)[CH2:14][CH2:13]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH2:19][CH:20]=[CH:21][CH:22]=O.C([O-])(=O)C.[NH4+]>C(N(CC)CC)C>[CH2:1]([O:8][C:9]([NH:11][CH:12]1[CH2:17][CH2:16][C:15]2[N:19]=[CH:20][CH:21]=[CH:22][C:14]=2[CH2:13]1)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 517165Ammonium AcetateHCID 14615292Benzyl (4-oxocyclohexyl)carbamateHCID 539779123-Aminoacrolein

Product 1

HCID 211070726-Benzyloxycarbonylamino-5,6,7,8-tetrahydroquinolineYield 10.6%

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent

Conditions

Temperature
115 °C

Procedure

A mixture of 4-benzyloxycarbonylaminocyclohexanone (13.75 g, 55.6 mmol), 3-aminopropenal (5.57 g, 78.4 mmol), and ammonium acetate (0.14 g, 1.78 mmol) in triethylamine (85 mL) was stirred at 115° C. under nitrogen for 3 d. The reaction mixture was then partitioned between chloroform and water. The organic layer was separated, washed sequentially with water, saturated aqueous ammonium chloride solution and brine, dried over anhydrous magnesium sulfate, and evaporated under vacuum to yield a residue. The residue was subjected to silica gel chromatography (eluted with 5% methanol in methylene chloride) to obtain the title compound (1.67 g, 10.5%) as a brown oil. 3C NMR (400 MHz, CDCl3) δ 155.6, 147.5, 137.2, 136.4, 129.2, 128.5, 128.1, 121.2, 66.7, 46.2, 35.2, 30.1, 28.7. 1H NMR (400 MHz, CDCl3) δ 8.31 (d, J=4.4 Hz, 1H), 7.27 (m, 6H), 6.98 (dd, J=4.8, 7.5 Hz, 1H), 5.03 (s, 2H), 4.85 (br s, 1H), 4.00 (br s, 1H), 3.06 (d, J=16.3 Hz, 1H), 2.97 (t, J=6.6 Hz, 2H), 2.62 (dd, J=7.9, 16.0 Hz, 1H), 2.08 (d, J=8.4 Hz, 1H), 1.82 (m, 1H).

Workup

  1. customThe reaction mixture was then partitioned between chloroform and water
  2. customThe organic layer was separated
  3. washwashed sequentially with water, saturated aqueous ammonium chloride solution and brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. customevaporated under vacuum
  6. customto yield a residue
  7. washThe residue was subjected to silica gel chromatography (eluted with 5% methanol in methylene chloride)

Sources & evidence

ORD record
ord-69a01765ec8445e487bc17d86b6da2ed
Source dataset
uspto-grants-2007_06
Patent number
US07226942B2

Reaction notes

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