Dimethylformamide → Dimethylsulfamic acid 5-tert-butyl-4-{4-hydroxy-6,6-bis-[2-(4-hydroxyphenyl)ethyl]-2-oxo-5,6-dihydro-2H-pyran-3-ylsulfanyl}-2-methylphenyl ester

HRID 356556Notes

Reaction equation

HRID 356556 reaction equation
[C:1]([C:5]1[CH:10]=[C:9]([O:11][S:12](=[O:17])(=[O:16])[NH:13][CH2:14][CH3:15])[C:8]([CH3:18])=[CH:7][C:6]=1[S:19]S(C1C=CC(C)=CC=1)(=O)=O)([CH3:4])([CH3:3])[CH3:2].[OH:30][C:31]1[CH2:32][C:33]([CH2:50][CH2:51][C:52]2[CH:57]=[CH:56][C:55]([NH:58]C(=O)[O-])=[CH:54][CH:53]=2)([CH2:38][CH2:39][C:40]2[CH:45]=[CH:44][C:43]([NH:46]C(=O)[O-])=[CH:42][CH:41]=2)[O:34][C:35](=[O:37])[CH:36]=1.C([O-])([O-])=O.[K+].[K+].CN(C=O)C>CCOC(C)=O>[C:1]([C:5]1[C:6]([S:19][C:36]2[C:35](=[O:37])[O:34][C:33]([CH2:38][CH2:39][C:40]3[CH:41]=[CH:42][C:43]([NH2:46])=[CH:44][CH:45]=3)([CH2:50][CH2:51][C:52]3[CH:53]=[CH:54][C:55]([NH2:58])=[CH:56][CH:57]=3)[CH2:32][C:31]=2[OH:30])=[CH:7][C:8]([CH3:18])=[C:9]([O:11][S:12](=[O:16])(=[O:17])[NH:13][CH2:14][CH3:15])[CH:10]=1)([CH3:2])([CH3:3])[CH3:4]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 10551814toluene-4-thiosulfonic acid S-(2-tert-butyl-4-ethylsulfamoyloxy-5-methyl-phenyl) esterHCID 86753329(3,6-dihydro-4-hydroxy-6-oxo-2H-pyran-2,2-diyl)bis[2, 1-ethanediyl-(4,1-phenylene)]biscarbamate

Product 1

HCID 54713187Dimethylsulfamic acid 5-tert-butyl-4-{4-hydroxy-6,6-bis-[2-(4-hydroxyphenyl)ethyl]-2-oxo-5,6-dihydro-2H-pyran-3-ylsulfanyl}-2-methylphenyl ester

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent2×

Procedure

To a round bottom flask equipped with a magnetic stirrer were added toluene-4-thiosulfonic acid S-(2-tert-butyl-4-ethylsulfamoyloxy-5-methyl-phenyl) ester (prepared in Example VVV; 0.218 g, 0.470 mmol), (1,1-dimethylethyl)[(3,6-dihydro-4-hydroxy-6-oxo-2H-pyran-2,2-diyl)bis[2,1-ethanediyl-(4,1-phenylene)]-biscarbamate (prepared in Example OO; 0.200 g, 0.380 mmol), K2CO3 (0.260 g, 1.88 mmol), and DMF (8 mL), as described in General Method 9. The reaction was stirred at room temperature for 3 hours and then worked up in the usual fashion. The residue was submitted to flash chromatography (100% EtOAc). The product form chromatography was taken up in EtOAc, triturated with hexane, filtered, and then taken up in CH2Cl2 (20 mL). Gaseous HCl was bubbled into this solution for 30 minutes. The solids that formed were filtered, washed with Et2O and dried under high vacuum to yield the title compound, m.p. 194° C. 1H NMR (DMSO-d6) δ 1.14 (t, 3 H), 1.49 (s, 9 H), 1.88 (s, 3 H), 2.09 (br m, 4 H), 2.70 (br m, 4 H), 3.12 (s, 2 H) 3.13 (m, 2 H), 6.79 (s, 1 H), 7.11 (s, 1 H), 7.27 (d, 4 H), 7.33 (d, 4 H), 8.40 (t, 1 H).

Workup

  1. customTo a round bottom flask equipped with a magnetic stirrer
  2. customtriturated with hexane
  3. filtrationfiltered
  4. customGaseous HCl was bubbled into this solution for 30 minutes
  5. customThe solids that formed
  6. filtrationwere filtered
  7. washwashed with Et2O
  8. customdried under high vacuum

Sources & evidence

ORD record
ord-8b33c1a199b64b32bd159dd4fa0b4440
Source dataset
uspto-grants-1998_11
Patent number
US05834506

Reaction notes

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