Calcium Chloride → HCID 87957780, compound

HRID 1278704Notes

Reaction equation

HRID 1278704 reaction equation
[Br-:1].[F:2][C:3]1[CH:8]=[CH:7][C:6]([CH2:9][CH:10]2[CH2:15][CH2:14][N+:13]3([CH2:23][C:22]4[C:17](=[CH:18][CH:19]=[CH:20][C:21]=4[N+:24]([O-])=O)[CH2:16]3)[CH2:12][CH2:11]2)=[CH:5][CH:4]=1.[Cl-].[Ca+2].[Cl-]>[Zn].C(O)C.O>[Br-:1].[NH2:24][C:21]1[CH:20]=[CH:19][CH:18]=[C:17]2[C:22]=1[CH2:23][N+:13]1([CH2:16]2)[CH2:12][CH2:11][CH:10]([CH2:9][C:6]2[CH:7]=[CH:8][C:3]([F:2])=[CH:4][CH:5]=2)[CH2:15][CH2:14]1

Participants

5

Reactant 2

HCID 5284359Calcium ChlorideHCID 87957881HCID 87957881, compound

Product 1

HCID 87957780HCID 87957780, compoundYield 84.1%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 19096565Water ethanolSolvent

Procedure

1,3-Dihydro-4′-[4-fluorophenylmethyl]-4-nitro-spiro[2H-isoindole-2,1′-piperidinium]bromide (1.03 g, 2.46 mmol, 1.0 eq), zinc (5.32 g, 81.5 mmol, 33.0 eq), and calcium chloride (0.18 g, 1.60 mmol, 0.65 eq) were refluxed under N2 in 25 ml of a 78% ethanol/water solution. The reaction was worked up after 5 hours by filtering through Celite® and rinsing the cake with methanol. The filtrate was concentrated in vacuo to a mixture of water and an amber oil. The mixture was dissolved in 50 ml of 2-propanol, and concentrated in vacuo to remove excess water. The resulting yellow foam was dissolved in methanol and applied to a 3.5 cm×5 cm quartz column via silica plug. The product was eluted with 20% MeOH/CHC13 to yield 0.81 g of a yellow foam. NMR (300 MHz, DMSO) δ 7.27-7.05 (m, 5H), 6.61-6.53 (m, 2H), 5.43-5.41 (m, 2H), 4.80 (bs, 1H), 4.74 (bs, 2H), 4.63 (bs, 1H), 3.62-3.43 (m, 4H), 2.60 (bd, 2H, J=7 Hz), 1.98-1.59 (m, 5H).

Workup

  1. filtrationby filtering through Celite®
  2. washrinsing the cake with methanol
  3. concentrationThe filtrate was concentrated in vacuo to a mixture of water
  4. dissolutionThe mixture was dissolved in 50 ml of 2-propanol
  5. concentrationconcentrated in vacuo
  6. customto remove excess water
  7. dissolutionThe resulting yellow foam was dissolved in methanol
  8. washThe product was eluted with 20% MeOH/CHC13

Sources & evidence

ORD record
ord-7cf109993343415ca76beef5509e41e7
Source dataset
uspto-grants-2002_09
Patent number
US06444686B1

Reaction notes

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