Sodium Dithionite → 6,7-Dichlorothieno[3,4-b](1,5]benzoxazepine-10(9H)-one

HRID 614221Notes

Reaction equation

HRID 614221 reaction equation
S(S([O-])=O)([O-])=O.[Na+].[Na+].NC1C=C(Cl)C(Cl)=CC=1O.C(OC1C(C(Cl)=O)=CSC=1)C.[Cl:30][C:31]1[C:47]([Cl:48])=[CH:46][C:34]([NH:35][C:36]([C:38]2[C:42](OCC)=[CH:41][S:40][CH:39]=2)=[O:37])=[C:33]([OH:49])[CH:32]=1>C(Cl)Cl.C(N(CC)CC)C.O.CC(C)=O>[Cl:30][C:31]1[C:47]([Cl:48])=[CH:46][C:34]2[NH:35][C:36](=[O:37])[C:38]3[C:42](=[CH:41][S:40][CH:39]=3)[O:49][C:33]=2[CH:32]=1

Participants

9

Reactant 4

HCID 24489Sodium DithioniteHCID 30154152-Amino-4,5-dichlorophenolHCID 125737274-Ethoxy-3-thiophenecarbonyl chlorideHCID 213288054',5'-Dichloro-4-ethoxy-2'-hydroxy-3-thiophenecarboxanilide

Product 1

HCID 213288086,7-Dichlorothieno[3,4-b](1,5]benzoxazepine-10(9H)-one

Reagents, catalysts & solvents 4

HCID 180AcetoneSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×HCID 8471TriethylamineSolvent

Procedure

A 20.87 g. portion of the preceding product (prepared as described above) is stirred in 210 ml. of acetone and 210 ml. of water, then 87.0 g. of sodium dithionite is added portionwise with stirring at room temperature as described in J. Chem. Soc., 4727 (1956). The resulting colorless mixture is heated on a steam bath for 1/2 hour, then is cooled and extracted four times with ether. The ether layer is washed 3 times with brine, then is dried over anhydrous sodium sulfate and evaporated to provide yellow crystals. This material is recrystallized from methylene chloride/hexane to yield 3.63 g. of 2-amino-4,5-dichlorophenol as buff colored crystals. A 4.81 g. amount of this product (prepared as described) is dissolved in 35 ml. of methylene chloride then a 3.51 ml. portion of triethylamine is added and the mixture is stirred. To this is added dropwise with stirring 48 ml. of a solution of 9.90 g. of 4-ethoxy-3-thiophenecarbonyl chloride (prepared as described in Example 1 ) dissolved in 100 ml. of methylene chloride. The mixture is allowed to stir overnight then the precipitate is collected, air dried, triturated with water, collected and dried to yield 4.95 g. of 4',5'-dichloro-4-ethoxy-2'-hydroxy-3-thiophenecarboxanilide.

Workup

  1. customportion of the preceding product (prepared as described above)
  2. stirringwith stirring at room temperature
  3. temperatureThe resulting colorless mixture is heated on a steam bath for 1/2 hour
  4. temperatureis cooled
  5. extractionextracted four times with ether
  6. washThe ether layer is washed 3 times with brine
  7. dry with materialis dried over anhydrous sodium sulfate
  8. customevaporated
  9. customto provide yellow crystals
  10. customThis material is recrystallized from methylene chloride/hexane
  11. customto yield 3.63 g
  12. customamount of this product (prepared as described)
  13. dissolutionis dissolved in 35 ml
  14. stirringthe mixture is stirred
  15. additionTo this is added dropwise
  16. stirringwith stirring 48 ml
  17. stirringto stir overnight
  18. customthe precipitate is collected
  19. customair dried
  20. customtriturated with water
  21. customcollected
  22. customdried
  23. customto yield 4.95 g

Sources & evidence

ORD record
ord-3923b0d3d2324a2cb9f0ff815762c4e8
Source dataset
uspto-grants-1979_03
Patent number
US04144235

Reaction notes

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