HCID 10339855, compound → HCID 10450661, compound

HRID 1884030Notes

Reaction equation

HRID 1884030 reaction equation
[N+:1]([C:4]1[CH:26]=[CH:25][C:7]2[C:8](=[O:24])[N:9]([C@@H:11]([CH2:17][CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:12]([O:14][CH2:15][CH3:16])=[O:13])[S:10][C:6]=2[CH:5]=1)([O-])=O>C(O)(=O)C.[Fe]>[NH2:1][C:4]1[CH:26]=[CH:25][C:7]2[C:8](=[O:24])[N:9]([C@@H:11]([CH2:17][CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:12]([O:14][CH2:15][CH3:16])=[O:13])[S:10][C:6]=2[CH:5]=1

Participants

4

Reactant 1

HCID 10339855HCID 10339855, compound

Product 1

HCID 10450661HCID 10450661, compoundYield 93.6%

Reagents, catalysts & solvents 2

HCID 23925IronCatalyst2×HCID 176Acetic AcidSolvent

Conditions

Temperature
550 °C

Procedure

A solution of diethyl (S)-2-(2,3-dihydro-6-nitro-3-oxo-1,2-benzisothiazol-2-yl)glutarate (4.0 g, 10 mmol) and suspended iron (1.0 g, 18 mmol) in acetic acid (100 ml) was stirred under nitrogen for 1 hour at 550° C. Additional iron (3×0.25 g, 13 mmol) was added at intervals of 1, 1.25, and 1.75 hours. The reaction mixture was stirred 30 minutes after the last addition, filtered, concentrated in vacuo, and the residue absorbed onto silica gel (20 g) from a methylene chloride solution. Purification by chromatography on silica gel (150 g) eluting with ethyl acetate:hexane (1:1→2:1) gave diethyl (S)-2-(6-amino-2,3-dihydro-3-oxo-1,2-benzisothiazol-2-yl)glutarate (3.3 g) as an oil. 1H NMR (DMSO-d6, 300 MHz) δ: 1.15 (t, J=7 Hz, 3H, esterCH3), 1.17 (t, J=7 Hz, 3H, esterCH3), 1.95-2.38 (m, 4H, gluCH2CH2), 4.02 (q, J=7 Hz, 2H, esterCH2), 4.13 (q, J=7 Hz, 2H, esterCH2), 5.08-5.15 (m, 1H, gluCH), 6.09 (br s, 2H, NH2), 6.62 (dd, J=9, 2 Hz, 1H, Ar), 6.84 (d, J=2 Hz, 1H, Ar), 7.50 (d, J=9 Hz, 1H, Ar). Mass spectrum (CI-CH4): 353 (M+1, 100%). Anal. Calculated for C16H20N2O5S: C, 54.53; H, 5.72; N, 7.95; S, 9.10. Found: C, 54.34; H, 5.73; N, 7.87; S, 9.00.

Workup

  1. stirringThe reaction mixture was stirred 30 minutes
  2. additionafter the last addition
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customthe residue absorbed onto silica gel (20 g) from a methylene chloride solution
  6. customPurification by chromatography on silica gel (150 g)
  7. washeluting with ethyl acetate:hexane (1:1→2:1)

Sources & evidence

ORD record
ord-f1a6eeb0884146e6818171c7b9f27bd2
Source dataset
uspto-grants-2004_07
Patent number
US06762188B1

Reaction notes

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