HCID 10339855, compound → HCID 10450661, compound

HRID 1654378Notes

Reaction equation

HRID 1654378 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
55 °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 55° 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, ester CH3), 1.17 (t, J=7 Hz, 3H, ester CH3 ), 1.95-2.38 (m, 4H, glu CH2CH2), 4.02 (q, J=7 Hz, 2H, ester CH2), 4.13 (q, J=7 Hz, 2H, ester CH2), 5.08-5.15 (m, 1H, glu CH), 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-739b46a1654646479d15381de7ffd482
Source dataset
uspto-grants-1995_04
Patent number
US05405851

Reaction notes

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