Water → 3-(Phenylsulfonyl)-8-quinolinamine

HRID 271134Notes

Reaction equation

HRID 271134 reaction equation
[N+:1]([C:4]1[CH:5]=[CH:6][CH:7]=[C:8]2[C:13]=1[N:12]=[CH:11][C:10]([S:14]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)(=[O:16])=[O:15])=[CH:9]2)([O-])=O.O.C(=O)([O-])[O-].[K+].[K+].C(N(CC(O)=O)CC(O)=O)CN(CC(O)=O)CC(O)=O>O1CCCC1.Cl.[Cl-].[Ti+3].[Cl-].[Cl-]>[NH2:1][C:4]1[CH:5]=[CH:6][CH:7]=[C:8]2[C:13]=1[N:12]=[CH:11][C:10]([S:14]([C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)(=[O:16])=[O:15])=[CH:9]2

Participants

8

Reactant 4

HCID 962WaterHCID 6049Ethylenediaminetetraacetic AcidHCID 11430Potassium Carbonate2×HCID 534255033-(Benzenesulfonyl)-8-nitroquinoline

Product 1

HCID 534255023-(Phenylsulfonyl)-8-quinolinamineYield 72%

Reagents, catalysts & solvents 3

HCID 10313229titanium(III) trichlorideCatalystHCID 313Hydrochloric AcidSolventHCID 8028TetrahydrofuranSolvent

Procedure

A slurry of 8-nitro-3-phenylsulfonylquinoline (D4) (46.7 g, 172 mmol), in tetrahydrofuran (750 ml) was added to a stirred solution of 30% titanium (III) chloride in aqueous HCl (470 ml) [Supplied by BDH] cooled in an ice bath, at such a rate that the temperature was maintained below 35° C. Once the addition was completed, the solution was stirred for a further 10 minutes then water (1.5 L) was introduced and the mixture poured into a 5 L beaker. The rapidly stirred solution was treated by portionwise addition of solid potassium carbonate in order to attain pH ˜8.5. EDTA (250 g, 0.86 mol) was added and followed by further potassium carbonate to maintain pH ˜8.5. The mixture was extracted with dichloromethane (3×1 L) and the combined organic phase passed through a silica plug (500 g) eluting with further dichloromethane (1 L) and 10% ethyl acetate in dichloromethane (1 L). The combined organic phases were evaporated and the residue subjected to purification using Biotage Flash-75 chromatography apparatus (2 kg silica gel), eluting with dichloromethane and increasing proportions of ether to give the title compound (D5) (34.5 g, 72%) as a pale brown solid;

Workup

  1. temperaturecooled in an ice bath
  2. temperatureat such a rate that the temperature was maintained below 35° C
  3. additionOnce the addition
  4. additionthe mixture poured into a 5 L beaker
  5. temperatureto maintain pH ˜8.5
  6. extractionThe mixture was extracted with dichloromethane (3×1 L)
  7. washeluting with further dichloromethane (1 L) and 10% ethyl acetate in dichloromethane (1 L)
  8. customThe combined organic phases were evaporated
  9. customthe residue subjected to purification
  10. washchromatography apparatus (2 kg silica gel), eluting with dichloromethane
  11. temperatureincreasing proportions of ether

Sources & evidence

ORD record
ord-ee734b8bf497401c941132deac6010ba
Source dataset
uspto-grants-2008_11
Patent number
US07452888B2

Reaction notes

Loading…