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

HRID 1927456Notes

Reaction equation

HRID 1927456 reaction equation
[NH2:1][C:2]1[CH:22]=[C:21]([Cl:23])[C:5]2[O:6][C:7]3[C:16]([CH3:17])=[CH:15][C:14]([C:18]([OH:20])=[O:19])=[CH:13][C:8]=3[S:9](=[O:12])(=[O:11])[CH2:10][C:4]=2[CH:3]=1.[CH3:24][O-].[Na+].C=O.[BH4-].[Na+].[OH-].[K+]>CO>[Cl:23][C:21]1[C:5]2[O:6][C:7]3[C:16]([CH3:17])=[CH:15][C:14]([C:18]([OH:20])=[O:19])=[CH:13][C:8]=3[S:9](=[O:11])(=[O:12])[CH2:10][C:4]=2[CH:3]=[C:2]([NH:1][CH3:24])[CH:22]=1

Participants

7

Reactant 5

HCID 712FormaldehydeHCID 14797Potassium HydroxideHCID 4311764Sodium borohydrideHCID 10942334Sodium MethoxideHCID 116317172-Amino-4-chloro-6-methyl-10,10-dioxo-10,11-dihydro-5-oxa-10lambda *6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acid

Product 1

HCID 1317284374-Chloro-6-methyl-2-methylamino-10,10-dioxo-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acidYield 38.46%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Methyl ester of Example 35j (0.5 g, 1.36 mmol) was added to solution of sodium methoxide [Na (0.156 g, 6.78 mmol) in methanol (6 mL)], which in turn was added to a solution of paraformaldehyde (0.057 g, 1.90 mmol) in MeOH (5 mL). The reaction mixture was stirred for 5 h at room temperature, treated with sodium borohydride (0.051 g, 1.36 mmol), refluxed for 1 h, cooled, treated with 1M aqueous KOH (1.5 mL) and stirred for 15 mins. It was extracted with ethyl acetate and the aqueous portion was neutralized to pH 5 with 10% aqueous HCl to obtain the title compound (J. Chem. Soc. Chem. Commun, 1334, (1984)). Yield: 38.46%; 1H NMR (DMSO-d6): δ 2.60 (s, 3H, N—CH3), 2.70 (s, 3H, CH3), 5.10 (s, 2H, CH2), 6.30 (d, 1H, NH), 6.65 (d, 1H, Ar), 7.50 (d, 1H, Ar), 8.08 (s, 1H, Ar), 8.20 (s, 1H, Ar); MS: m/e (EI+) 367 (M+).

Workup

  1. temperaturerefluxed for 1 h
  2. temperaturecooled
  3. stirringstirred for 15 mins
  4. extractionIt was extracted with ethyl acetate

Sources & evidence

ORD record
ord-032bae0774ff4ea6b96910ac034dd4ad
Source dataset
uspto-grants-2012_05
Patent number
US08183234B2

Reaction notes

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