Diethyl Ether → Ethyl 4-(6-azaspiro(2.5)oct-6-yl)benzoate

HRID 1785789Notes

Reaction equation

HRID 1785789 reaction equation
[CH3:1]N(N=O)C(N[N+]([O-])=O)=N.[OH-].[K+].C(OCC)C.[CH2:18]=[C:19]1[CH2:24][CH2:23][N:22]([C:25]2[CH:35]=[CH:34][C:28]([C:29]([O:31][CH2:32][CH3:33])=[O:30])=[CH:27][CH:26]=2)[CH2:21][CH2:20]1>C1COCC1.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH2:1]1[C:19]2([CH2:24][CH2:23][N:22]([C:25]3[CH:35]=[CH:34][C:28]([C:29]([O:31][CH2:32][CH3:33])=[O:30])=[CH:27][CH:26]=3)[CH2:21][CH2:20]2)[CH2:18]1

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 14797Potassium HydroxideHCID 16109082Ethyl 4-(4-methylenepiperidin-1-yl)benzoateHCID 135436526N-Methyl-N'-nitro-N-nitrosoguanidine

Product 1

HCID 22729977Ethyl 4-(6-azaspiro(2.5)oct-6-yl)benzoate

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of methyl-3-nitro-1-nitrosoguanidine (1.18 g, 8.1 mmol), 40% KOH (3.4 mL), and diethyl ether (12 mL) at 0° C. was stirred for 10 minutes. The organic phase was added slowly to a −25° C. solution of Example 158C and Pd(OAc)2 (18 mg, 0.11 mmol) in THF (8.8 mL). The mixture was stirred for 1 hour at −20° C. and concentrated. The concentrate was purified by flash column chromatography on silica gel with 9:1 hexanes/ethyl acetate to provide the desired product. MS (DCI) m/e 260 (M+H)+.

Workup

  1. stirringThe mixture was stirred for 1 hour at −20° C.
  2. concentrationconcentrated
  3. customThe concentrate was purified by flash column chromatography on silica gel with 9:1 hexanes/ethyl acetate

Sources & evidence

ORD record
ord-3c11291137a64cedb891c7563934e936
Source dataset
uspto-grants-2009_03
Patent number
US07504512B2

Reaction notes

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