Hydrochloric Acid → HCID 13590117, compound

HRID 1380620Notes

Reaction equation

HRID 1380620 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:12]=[CH:11][C:10]([N+:13]([O-:15])=[O:14])=[C:9](Cl)[C:5]=1[C:6]([OH:8])=O.[CH3:17][O:18][C:19]1[CH:20]=[C:21]([SH:25])[CH:22]=[CH:23][CH:24]=1.Cl>O1CCCC1.CCCCC>[Cl:3][C:4]1[C:5]2[C:6](=[O:8])[C:22]3[C:21](=[CH:20][C:19]([O:18][CH3:17])=[CH:24][CH:23]=3)[S:25][C:9]=2[C:10]([N+:13]([O-:15])=[O:14])=[CH:11][CH:12]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 849893-MethoxybenzenethiolHCID 3506232,6-Dichloro-3-nitrobenzoic acid

Product 1

HCID 13590117HCID 13590117, compound

Reagents, catalysts & solvents 2

HCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

The requisite 1-chloro-6-methoxy-4-nitrothioxanthone was prepared as follows: To a prewashed (pentane) suspension of NaH in 500 ml of tetrahydrofuran cooled to 0° was added dropwise over about 25 minutes a solution of 35.4 g of 2,6dichloro-5-nitrobenzoic acid in 200 ml of tetrahydrofuran. After about five minutes a solution of 20 g of m-methoxybenzenethiol in 50 ml of tetrahydrofuran was added, and the mixture was stirred for 20 hours as it gradually came to ambient temperature. The mixture was treated with a 10% aqueous hydrochloric acid solution, extracted into ethyl acetate, dried, and the solvent was removed in vacuo. The orange gum was purified by flash chromatography on SiO2 with a 90:5:0.5 mixture of methylene chloride:methanol:acetic acid. The resulting oil was sufficiently pure for use in the next step. A solution of this material (24.8 g) in 120 ml of trifluoroacetic acid was treated with 60 ml of trifluoroacetic anhydride and allowed to stir at room temperature for 30 minutes. The solution was diluted with acetonitrile, and the precipitate was collected and triturated with boiling acetonitrile to give 15.8 g of the product, mp 254°-258°.

Workup

  1. temperaturecooled to 0°
  2. customgradually came to ambient temperature
  3. extractionextracted into ethyl acetate
  4. customdried
  5. customthe solvent was removed in vacuo
  6. customThe orange gum was purified by flash chromatography on SiO2 with a 90:5:0.5 mixture of methylene chloride
  7. additionA solution of this material (24.8 g) in 120 ml of trifluoroacetic acid was treated with 60 ml of trifluoroacetic anhydride
  8. stirringto stir at room temperature for 30 minutes
  9. additionThe solution was diluted with acetonitrile
  10. customthe precipitate was collected
  11. customtriturated with boiling acetonitrile

Sources & evidence

ORD record
ord-5c7eeb63dc104646a0231843b3cfb115
Source dataset
uspto-grants-1986_04
Patent number
US04582851

Reaction notes

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