Ethyl Acetate → 1,7-Diazaspiro[4.4]nonane-1-carboxylic acid, 7-[3-(1-methylethoxy)-4-nitrophenyl]-, 1,1-dimethylethyl ester

HRID 518857Notes

Reaction equation

HRID 518857 reaction equation
[N:1]1([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[C:5]2([CH2:9][CH2:8][NH:7][CH2:6]2)[CH2:4][CH2:3][CH2:2]1.F[C:18]1[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[C:20]([O:27][CH:28]([CH3:30])[CH3:29])[CH:19]=1.C(=O)([O-])[O-].[K+].[K+].C(OCC)(=O)C>CS(C)=O>[N+:24]([C:21]1[CH:22]=[CH:23][C:18]([N:7]2[CH2:8][CH2:9][C:5]3([N:1]([C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11])[CH2:2][CH2:3][CH2:4]3)[CH2:6]2)=[CH:19][C:20]=1[O:27][CH:28]([CH3:30])[CH3:29])([O-:26])=[O:25]

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 106318324-Fluoro-2-isopropoxy-1-nitrobenzeneHCID 426145731,7-Diaza-spiro(4.4)nonane-1-carboxylic acid tert-butyl ester

Product 1

HCID 866980101,7-Diazaspiro[4.4]nonane-1-carboxylic acid, 7-[3-(1-methylethoxy)-4-nitrophenyl]-, 1,1-dimethylethyl esterYield 63.3%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

A mixture of 3.0 g of tert-butyl 1,7-diazaspiro[4.4]nonane-1-carboxylate and 2.64 g of 4-fluoro-1-nitro-2-(propan-2-yloxy)benzene (obtained according to method 6), and 2.75 g of potassium carbonate in DMSO is stirred at ambient temperature overnight. The mixture is taken up with ethyl acetate and washed twice with 10 volumes of water. The organic phase is dried over magnesium sulfate and concentrated under vacuum. The crude product is purified on 120 g of silica, elution being carried out with dichloromethane, so as to obtain 3.40 g of 2-methylpropan-2-yl 7-[4-nitro-3-(propan-2-yloxy)phenyl]-1,7-diazaspiro[4.4]nonane-1-carboxylate in the form of a dark yellow solid.

Workup

  1. washwashed twice with 10 volumes of water
  2. dry with materialThe organic phase is dried over magnesium sulfate
  3. concentrationconcentrated under vacuum
  4. customThe crude product is purified on 120 g of silica, elution

Sources & evidence

ORD record
ord-5cf24f6c4d214560829e5e772a758ab7
Source dataset
uspto-grants-2015_08
Patent number
US09115140B2

Reaction notes

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