Aniline → HCID 21530396, compound

HRID 1657813Notes

Reaction equation

HRID 1657813 reaction equation
[C:1](Cl)(Cl)=[O:2].[N:5]1([C:10]2[C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=3[S:14](=[O:22])(=[O:21])[CH2:13][CH2:12][CH:11]=2)[CH2:9][CH2:8][CH2:7][CH2:6]1.C(N(CC)CC)C.[NH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1>C1C=CC=CC=1.O1CCCC1>[N:5]1([C:10]2[C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=3[S:14](=[O:22])(=[O:21])[CH2:13][CH2:12][C:11]=2[C:1]([NH:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)=[O:2])[CH2:9][CH2:8][CH2:7][CH2:6]1

Participants

7

Reactant 4

HCID 6115AnilineHCID 6371PhosgeneHCID 8471Triethylamine2×HCID 21530393HCID 21530393, compound

Product 1

HCID 21530396HCID 21530396, compound

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

A mixture of 80 ml (contg 0.084 mol of COCl2) of a 12.5% solution of phosgene in benzene and 80 ml of tetrahydrofuran was cooled to -50° and a solution of 22.0 g (0.08 mol) of crude 2,3-dihydro-5-(1-pyrrolidinyl)-1-benzothiepin 1,1-dioxide and 8.8 g of triethylamine in 400 ml of tetrahydrofuran was added. The mixture was stirred at room temperature for 3 hours, cooled to -60°, and a solution of 8.0 g (0.088 mol) of aniline and 11 g of triethylamine in 200 ml of tetrahydrofuran was added. The mixture was stirred at room temperature for 18 hours, refluxed for 3 hours, and part of the tetrahydrofuran was removed by distillation under reduced pressure. The residue was treated with ice water and extracted with dichloromethane. The organic phase was washed with water, dried over sodium sulfate, and evaporated. The residue was redissolved in dichloromethane and ether was added until the solution became turbid. On standing there was collected 22.4 g of a solid precipitate. This was recrystallized from a mixture of 200 ml of tetrahydrofuran and 300 ml of isopropyl ether to give 15.6 g of product, mp 160°-163° dec. Recrystallization from a mixture of 200 ml of dichloromethane and 1600 ml of ether gave 10.4 g of material mp 167°-169° dec.

Workup

  1. temperaturewas cooled to -50°
  2. temperaturecooled to -60°
  3. stirringThe mixture was stirred at room temperature for 18 hours
  4. temperaturerefluxed for 3 hours
  5. custompart of the tetrahydrofuran was removed by distillation under reduced pressure
  6. additionThe residue was treated with ice water
  7. extractionextracted with dichloromethane
  8. washThe organic phase was washed with water
  9. dry with materialdried over sodium sulfate
  10. customevaporated
  11. dissolutionThe residue was redissolved in dichloromethane
  12. additionether was added until the solution
  13. customOn standing there was collected 22.4 g of a solid precipitate
  14. customThis was recrystallized from a mixture of 200 ml of tetrahydrofuran and 300 ml of isopropyl ether

Sources & evidence

ORD record
ord-3730c7f74d3f4ba4996f431d7381823e
Source dataset
uspto-grants-1976_06
Patent number
US03962261

Reaction notes

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