4-Methoxybenzenethiol → HCID 13689101, compound

HRID 364195Notes

Reaction equation

HRID 364195 reaction equation
[H-].[Na+].Cl[C:4]1[C:12]([N+:13]([O-:15])=[O:14])=[CH:11][CH:10]=[C:9]([Cl:16])[C:5]=1[C:6]([OH:8])=[O:7].[CH3:17][O:18][C:19]1[CH:24]=[CH:23][C:22]([SH:25])=[CH:21][CH:20]=1>O1CCCC1>[Cl:16][C:9]1[C:5]([C:6]([OH:8])=[O:7])=[C:4]([S:25][C:22]2[CH:23]=[CH:24][C:19]([O:18][CH3:17])=[CH:20][CH:21]=2)[C:12]([N+:13]([O-:15])=[O:14])=[CH:11][CH:10]=1

Participants

5

Reactant 3

HCID 127654-MethoxybenzenethiolHCID 24758Sodium hydrideHCID 3506232,6-Dichloro-3-nitrobenzoic acid

Product 1

HCID 13689101HCID 13689101, compoundYield 70.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
25 °C

Procedure

An ice-cooled suspension of 3.0 g (0.125 mol) of oil-free sodium hydride in 100 ml of tetrahydrofuran was treated portionwise during ten minutes with 12.2 g (0.052 mol) of 2,6-dichloro-3-nitrobenzoic acid [Lehmstedt and Schrader, Ber. 70B, 1526 (1937)]. After stirring for ten minutes, the suspension was treated dropwise with 7.0 g (0.05 mol) of 4-methoxybenzenethiol [C. M. Suter and H. L. Hansen, J. Am. Chem. Soc., 54, 4100 (1934)] in 50 ml of tetrahydrofuran. After stirring for 30 minutes at 0° C., the cooling bath was removed and the mixture was maintained at 25° C. for 12 hours. The mixture was acidified with 150 ml of 10% aqueous HCl, then treated with 200 ml of ethyl acetate. The organic layer was separated and the aqueous phase was extracted with 100 ml of ethyl acetate. The combined organic phases were dried (MgSO4), and concentrated to a yellow solid which was purified by flash chromatography on silica gel, utilizing dichloromethane:methanol (8:1) as eluting solvent, to give 11.9 g of 6-chloro-2-[(4-methoxyphenyl)thio]-3-nitrobenzoic acid, mp 154°-157° C., following crystallization from toluene.

Workup

  1. stirringAfter stirring for 30 minutes at 0° C.
  2. customthe cooling bath was removed
  3. additiontreated with 200 ml of ethyl acetate
  4. customThe organic layer was separated
  5. extractionthe aqueous phase was extracted with 100 ml of ethyl acetate
  6. dry with materialThe combined organic phases were dried (MgSO4)
  7. concentrationconcentrated to a yellow solid which
  8. customwas purified by flash chromatography on silica gel
  9. washas eluting solvent

Sources & evidence

ORD record
ord-add72c009a2347cfac287085da1a83c0
Source dataset
uspto-grants-1986_08
Patent number
US04604390

Reaction notes

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