Water → HCID 387497, compound

HRID 1420558Notes

Reaction equation

HRID 1420558 reaction equation
[Cl:1][CH2:2][CH:3]1[C:11]2[C:6](=[CH:7][C:8]([N:12]([CH3:23])[CH2:13][C:14]3[CH:19]=[CH:18][C:17]([N+:20]([O-:22])=[O:21])=[CH:16][CH:15]=3)=[CH:9][CH:10]=2)[N:5]([S:24]([CH3:27])(=[O:26])=[O:25])[CH2:4]1.F[B-](F)(F)F.[CH3:33][O+](C)C.O>C(Cl)Cl>[Cl-:1].[Cl:1][CH2:2][CH:3]1[C:11]2[C:6](=[CH:7][C:8]([N+:12]([CH3:33])([CH3:23])[CH2:13][C:14]3[CH:15]=[CH:16][C:17]([N+:20]([O-:22])=[O:21])=[CH:18][CH:19]=3)=[CH:9][CH:10]=2)[N:5]([S:24]([CH3:27])(=[O:26])=[O:25])[CH2:4]1

Participants

5

Reactant 3

HCID 962WaterHCID 2735153Oxonium, trimethyl-, tetrafluoroborate(1-) (1:1)HCID 18782137HCID 18782137, compound

Product 1

HCID 387497HCID 387497, compoundYield 198.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of 31 (79 mg, 0.19 mmol) and trimethyloxonium tetrafluoroborate (105 mg, 0.71 mmol) in CH2Cl2 (5 mL) was stoppered and stirred at 20 C for 4 days. Water was added and the mixture stirred until most of the oily solid dissolved. The separated organic layer was dried (Na2SO4) and evaporated, dry column chromatography, eluting with EtOAc/petroleum ether (1:2), gave recovered starting material (24 mg, 30%). The aqueous phase was combined with the remaining oily solid, evaporated, and the residue extracted with MeOH. The resulting crude ammonium salt was converted to the chloride form by ion exchange chromatography on Dowex 50 WX8 resin (1.5 mL), loading the sample in MeOH:water (1:1) and washing until the eluate was neutral, then eluting with 1:1 MeOH:2N HCl (10 mL) followed by MeOH.backslash.4N HCl (1:1) (10 mL). The combined eluate was evaporated to give 3-(chloromethyl)-6-[N,N-dimethyl-N-(4-nitrobenzyl)-ammonio]-1-(methanesulfonyl)indoline chloride (11) as a white foam (87 mg). 1H NMR (CD3OD) a 8.17 (d, J=8.2 Hz, 2 H, ArH), 7.63 (br d, J=8.3 Hz, 1 H, H-4 or 5), 7.57 (br d, J=8.3 Hz, 1 H, H-4 or 5), 7.51 (s, 1 H, H-7), 7.41 (d, J=8.2 Hz, 2 H, ArH), 5.22 (s, 2 H, NCH2Ar), 4.32-4.25 (m, 1 H), 4.06-4.01 (m, 2 H), 3.96-3.93 (m, 2 H), 3.75 (s, 6 H, NMe2), 3.02 (s, 3 H, NSO2CH3). 13C NMR a 150.7, 146.0, 145.8, 136.1, 135.7 (C-6,8,9,1,4), 135.3, 124.8 (C-2 and 6, 3 and 5), 128.2, 117.9, 107.6 (C-4,5,7), 73.1 (NCH2Ar), 55.3 (C-2), 54.6 (NMe2), 47.8 (CH2Cl), 42.8 (C-3), 36.4 (SO2CH3).

Workup

  1. stirringthe mixture stirred until most of the oily solid
  2. dissolutiondissolved
  3. dry with materialThe separated organic layer was dried (Na2SO4)
  4. customevaporated
  5. customdry column chromatography
  6. washeluting with EtOAc/petroleum ether (1:2)
  7. customgave
  8. customrecovered
  9. customevaporated
  10. extractionthe residue extracted with MeOH
  11. washwashing until the eluate
  12. washeluting with 1:1 MeOH
  13. customThe combined eluate was evaporated

Sources & evidence

ORD record
ord-7c01a34fd59444188e4354607ff3b06d
Source dataset
uspto-grants-2000_06
Patent number
US06071908

Reaction notes

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