4-Chloro-6-methyl-2-nitro-10,10-dioxo-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acid → 2-Amino-4-chloro-6-methyl-10,10-dioxo-10,11-dihydro-5-oxa-10lambda *6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acid

HRID 1927454Notes

Reaction equation

HRID 1927454 reaction equation
[Cl:1][C:2]1[C:7]2[O:8][C:9]3[C:18]([CH3:19])=[CH:17][C:16]([C:20]([OH:22])=[O:21])=[CH:15][C:10]=3[S:11](=[O:14])(=[O:13])[CH2:12][C:6]=2[CH:5]=[C:4]([N+:23]([O-])=O)[CH:3]=1>CN(C=O)C.[Ni]>[NH2:23][C:4]1[CH:3]=[C:2]([Cl:1])[C:7]2[O:8][C:9]3[C:18]([CH3:19])=[CH:17][C:16]([C:20]([OH:22])=[O:21])=[CH:15][C:10]=3[S:11](=[O:13])(=[O:14])[CH2:12][C:6]=2[CH:5]=1

Participants

4

Reactant 1

HCID 1317284344-Chloro-6-methyl-2-nitro-10,10-dioxo-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acid

Product 1

HCID 116317172-Amino-4-chloro-6-methyl-10,10-dioxo-10,11-dihydro-5-oxa-10lambda *6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acidYield 76%

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 6228DimethylformamideSolvent

Procedure

To a solution of the methyl ester of Example 32j (0.280 g, 0.7 mmols) in DMF (10 mL) was added activated Raney-Nickel (100 mg) and the reaction mixture was subjected to reduction in a Parr hydrogenator (20 psi, 2 h). The reaction mixture was filtered (celite bed), and the filtrate was poured onto crushed ice to obtain a solid which was subjected to hydrolysis as described in the synthesis of Example 11 to obtain the title compound. Yield: 76%; 1H NMR (DMSO-d6): δ 2.60 (s, 3H, CH3), 5.10 (s, 2H, CH2), 5.40 (s, 2H, NH2), 6.80 (d, 2H, Ar), 8.10 (s, 1H, Ar), 8.20 (s, 1H, Ar); MS: m/e (EI+) 354 (M+1).

Workup

  1. customwas subjected to reduction in a Parr hydrogenator (20 psi, 2 h)
  2. filtrationThe reaction mixture was filtered (celite bed)
  3. additionthe filtrate was poured
  4. customonto crushed ice
  5. customto obtain a solid which
  6. customwas subjected to hydrolysis
  7. customas described in the synthesis of Example 11

Sources & evidence

ORD record
ord-9b078ac5bca44ac381f96517d597a0a5
Source dataset
uspto-grants-2012_05
Patent number
US08183234B2

Reaction notes

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