Hydrogen Bromide → HCID 58010084, compound

HRID 1854368Notes

Reaction equation

HRID 1854368 reaction equation
[OH-:1].[K+].[CH3:3]N(N=O)C(N[N+]([O-])=O)=N.Cl[C:14]([C@@H:16]1[CH2:21][CH2:20][CH2:19][N:18]([C:22]([O:24][CH2:25][CH:26]2[C:38]3[CH:37]=[CH:36][CH:35]=[CH:34][C:33]=3[C:32]3[C:27]2=[CH:28][CH:29]=[CH:30][CH:31]=3)=[O:23])[CH2:17]1)=O.C1C2C(COC(N3CCC[C@@H](C(O)=O)C3)=O)C3C(=CC=CC=3)C=2C=CC=1.[BrH:65]>C1COCC1.CCOCC>[Br:65][CH2:3][C:14]([C@@H:16]1[CH2:21][CH2:20][CH2:19][N:18]([C:22]([O:24][CH2:25][CH:26]2[C:38]3[CH:37]=[CH:36][CH:35]=[CH:34][C:33]=3[C:32]3[C:27]2=[CH:28][CH:29]=[CH:30][CH:31]=3)=[O:23])[CH2:17]1)=[O:1]

Participants

8

Reactant 5

HCID 260Hydrogen BromideHCID 14797Potassium HydroxideHCID 17040144(3R)-1-{[(9H-Fluoren-9-yl)methoxy]carbonyl}piperidine-3-carboxylic acidHCID 58010181HCID 58010181, compoundHCID 135436526N-Methyl-N'-nitro-N-nitrosoguanidine

Product 1

HCID 58010084HCID 58010084, compoundYield 95.1%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of 45% aqueous KOH (30 mL, 2.70 mmol) and Et2O (100 mL) at about 0° C. 1-methyl-3-nitro-1-nitrosoguanidine (5.0 g, 34 mmol, TCI) was added portion-wise. After about 30 min the layers were separated and the organic layer was added slowly to a solution of (R)-(9H-fluoren-9-yl)methyl 3-(chlorocarbonyl)piperidine-1-carboxylate (1.0 g, 2.7 mmol) prepared using W from (R)-1-(((9H-fluoren-9-yl)methoxy)carbonyl)piperidine-3-carboxylic acid (Fluka) in THF (10 mL). The reaction mixture was slowly stirred for about 30 min at about 0° C. before the drop-wise addition of 48% aqueous HBr (2.0 mL, 37 mmol). After about 15 min, the reaction mixture was washed with brine (2×100 mL). The organic layer was dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure to give (R)-(9H-fluoren-9-yl)methyl 3-(2-bromoacetyl)piperidine-1-carboxylate (1.10 g, 95%) as a clear oil: LC/MS (Table 2, Method a) Rt=2.59 min; MS m/z: 428/430 (M+H)+.

Workup

  1. customAfter about 30 min the layers were separated
  2. customprepared
  3. washthe reaction mixture was washed with brine (2×100 mL)
  4. dry with materialThe organic layer was dried over anhydrous Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-6d3fa20d5bc540cdbbccc8915dc63810
Source dataset
uspto-grants-2015_02
Patent number
US08962629B2

Reaction notes

Loading…