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

HRID 1927458Notes

Reaction equation

HRID 1927458 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.[CH:24](=O)[CH:25]([CH3:27])[CH3:26].FC(F)(F)C(O)=O.C([BH3-])#N.[Na+].C([O-])(O)=O.[Na+]>O.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][CH2:24][CH:25]([CH3:27])[CH3:26])[CH:22]=1

Participants

8

Reactant 5

HCID 6422Trifluoroacetic acidHCID 6561IsobutyraldehydeHCID 516892Sodium BicarbonateHCID 5003444Sodium cyanoborohydrideHCID 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 1317284394-Chloro-2-isobutylamino-6-methyl-10,10-dioxo-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acidYield 64.74%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

To a mixture of the methyl ester of Example 35j (0.1 g, 0.27 mmol), isobutyraldehyde (0.098 g, 1.35 mmol)), trifluoro acetic acid (0.27 mmol) and sodium cyanoborohydride (0.67 mmol) was added MeOH (15 mL) at 0-5° C. The reaction mixture was stirred overnight at room temperature, treated with chilled water, neutralized with 10% aqueous NaHCO3, extracted with EtOAc, concentrated and subjected to hydrolysis as described in Example 11 to obtain the title compound (Tet. Lett. 38, 5831-5834, (1997)). Yield: 64.74%; 1H NMR (DMSO-d6): δ 0.90 (d, 6H, 2CH3), 1.80 (m, 1H, CH), 2.60 (s, 3H, CH3), 2.90 (d, 2H, N—CH2), 5.10 (s, 2H, CH2), 6.70 (s, 2H, Ar), 8.10 (d, 2H, Ar); MS: m/e (EI+) 409 (M+).

Workup

  1. extractionextracted with EtOAc
  2. concentrationconcentrated
  3. customsubjected to hydrolysis

Sources & evidence

ORD record
ord-abba03748c094bfd90c8a0ba9e018add
Source dataset
uspto-grants-2012_05
Patent number
US08183234B2

Reaction notes

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