Water → HCID 16203589, compound

HRID 2212884Notes

Reaction equation

HRID 2212884 reaction equation
[Li+].CC([N-]C(C)C)C.[Br:9][C:10]1[CH:11]=[C:12]([C:16](=O)[CH2:17][C:18](=[O:20])[CH3:19])[CH:13]=[CH:14][CH:15]=1.[C:22](=[S:24])=[S:23].O>C1COCC1>[Br:9][C:10]1[CH:11]=[C:12]([C:16]2[S:23][C:22]([SH:24])=[CH:19][C:18](=[O:20])[CH:17]=2)[CH:13]=[CH:14][CH:15]=1

Participants

6

Reactant 4

HCID 962WaterHCID 6348Carbon DisulfideHCID 2724682Lithium diisopropylamideHCID 21955999HCID 21955999, compound

Product 1

HCID 16203589HCID 16203589, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a stirred solution of LDA (20 mL, 40 mmol) in 40 mL anhydrous THF under an atmosphere of nitrogen was added slowly a solution of 1-(3-Bromophenyl)-butane-1,3-dione (4.84 g, 20 mmol) dissolved in THF (30 mL). After addition was complete the mixture was allowed to warm slowly to ambient temperature and stir for 10 minutes. The solution was re-cooled to −78° C. for the addition of a solution of carbon disulfide (1.2 mL, 20 mmol) in THF (20 mL). This temperature was maintained for 2 hours, before warm warmed slowly to ambient temperature and stirred for 18 hours. Cold water (150 mL) was added and mixture was heated to 60° C. with good stirring for 3 hours. The volatiles were removed in vacuo and the aqueous solution was washed with diethyl ether (2×100 mL). The aqueous solution was acidified to pH 1 with 2N HCl, and the orange precipitate was filtered from the acid, washed with water, and dried by vacuum desiccation. Orange solid (4.28 g, 72%); m.p. 188° C. (decomp); LCMS m/z 299, 301 ([M+1]+) 298, 300 ([M−1]−), 1H-NMR (D6-DMSO): 7.07 (d, 1H, J=1.4 Hz, H-3), 7.36 (d, 1H, J=1.4 Hz, H-5), 7.47–7.52 (dd, 1H, J1=J2=7.9 Hz, Ar-5), 7.69–7.72 (d, 1H, J=7.9 Hz, Ar-4/6), 7.76–7.78 (d, 1H, J=7.9 Hz, Ar-4/6), 7.92 (s, 1H, Ar-2); infrared spectrum (cm−1): 815, 950, 1008, 1072, 1202, 1451, 1364, 1451, 1487, 1508, 1584.

Workup

  1. additionAfter addition
  2. temperatureThis temperature was maintained for 2 hours
  3. temperaturebefore warm
  4. temperaturewarmed slowly to ambient temperature
  5. stirringstirred for 18 hours
  6. temperaturemixture was heated to 60° C.
  7. stirringwith good stirring for 3 hours
  8. customThe volatiles were removed in vacuo
  9. washthe aqueous solution was washed with diethyl ether (2×100 mL)
  10. filtrationthe orange precipitate was filtered from the acid
  11. washwashed with water
  12. customdried by vacuum desiccation

Sources & evidence

ORD record
ord-e2b47bde0f2c4d88b6ed0b22621b3d9a
Source dataset
uspto-grants-2006_09
Patent number
US07105518B2

Reaction notes

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