Dimethylformamide → HCID 86691695, compound

HRID 1427541Notes

Reaction equation

HRID 1427541 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([C:9](=O)[CH2:10][O:11][C:12]2[CH:25]=[CH:24][C:15](/[CH:16]=[C:17]3/[C:18](=[O:23])[NH:19][C:20](=[O:22])[S:21]/3)=[CH:14][CH:13]=2)[CH:6]=[CH:7][CH:8]=1.CN(C=O)C.Cl.[NH2:33][OH:34]>C1COCC1>[OH:34][N:33]=[C:9]([C:5]1[CH:6]=[CH:7][CH:8]=[C:3]([O:2][CH3:1])[CH:4]=1)[CH2:10][O:11][C:12]1[CH:25]=[CH:24][C:15](/[CH:16]=[C:17]2/[C:18](=[O:23])[NH:19][C:20](=[O:22])[S:21]/2)=[CH:14][CH:13]=1

Participants

5

Reactant 3

HCID 6228Dimethylformamide2×HCID 443297Hydroxyamine hydrochloride4×HCID 86691696HCID 86691696, compound

Product 1

HCID 86691695HCID 86691695, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A stirring suspension of (5Z)-5-{4-[2-(3-methoxyphenyl)-2-oxoethoxy]benzylidene}-1,3-thiazolidine-2,4-dione (1.42 g, 3.84 mmol; Supplier=Kalexsyn; Lot=1003-TTP-149) in THF (15 ml) was heated with a heat gun—no solution. Added DMF (5 ml) and heated—no solution. Added another 5 ml DMF and heated until all solids dissolved. The hydroxylamine hydrochloride was added portionwise. Added HONH2.HCl (100 mg) and allowed to sit at RT overnight. HPLC showed a ratio of ca. 2:1 SM:pdt. Added 100 mg HONH2.HCl. After 4 hours there was little change in HPLC. Added 100 mg HONH2.HCl and left to stir over the weekend. The reaction was complete. The reaction mixture was partitioned between EtOAc (30 ml) and 1M KHSO4 (30 ml). The aqueous phase was extracted with EtOAc (30 ml). The combined organic phases were washed with saturated NaHCO3 (30 ml), brine (30 ml), dried (Na2SO4), filtered and evaporated in vacuo to give 1.34 g yellow solid. 1H-NMR (DMSO-d6): δ 12.53(brs, 1H), 12.02(brs, 1H), 7.73(s, 1H), 7.54(d, J=8.9 Hz, 2H), 7.30(t, J=7.9 Hz, 1H), 7.20(m, 2H), 7.10(d, J=8.9 Hz, 2H), 6.95(dd, J=8.1, 2.5 Hz, 1H), 5.31(s, 2H), 3.74(s, 3H). HPLC: 3.690 min., 10 area %, and 3.788 min., 89 area % @ 210 nm; 3.690 min., 6 area %, and 3.789 min., 94 area % @ 254 nm. MS (ESI−) for C19H16N2O5S m/z 383.3 (M−H)−.

Workup

  1. temperaturewas heated with a heat gun—no solution
  2. temperatureheated until all solids
  3. dissolutiondissolved
  4. waitAfter 4 hours there was little
  5. waitleft
  6. customThe reaction mixture was partitioned between EtOAc (30 ml) and 1M KHSO4 (30 ml)
  7. extractionThe aqueous phase was extracted with EtOAc (30 ml)
  8. washThe combined organic phases were washed with saturated NaHCO3 (30 ml), brine (30 ml)
  9. dry with materialdried (Na2SO4)
  10. filtrationfiltered
  11. customevaporated in vacuo

Sources & evidence

ORD record
ord-365599994fb340aab082ddde801b57ae
Source dataset
uspto-grants-2015_01
Patent number
US08933240B2

Reaction notes

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