Hydrochloric Acid → HCID 69415058, compound

HRID 1295882Notes

Reaction equation

HRID 1295882 reaction equation
[CH:1]1[C:14]2[C:13](=[O:15])[C:12]3[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=3)[O:6][C:5]=2[CH:4]=[CH:3][CH:2]=1.C[O:17][CH3:18].Cl[C:20]([CH3:24])([CH3:23])[C:21]#C.[C:25]([O-:28])([O-])=O.[Cs+].[Cs+].Cl.CN([CH:35]=[O:36])C>>[CH3:35][O:36][C:11]1[C:12]2[C:13](=[O:15])[C:14]3[C:5](=[C:4]([O:28][CH3:25])[CH:3]=[CH:2][CH:1]=3)[O:6][C:7]=2[CH:8]=[C:9]([O:17][C:18]#[C:21][CH:20]([CH3:24])[CH3:23])[CH:10]=1

Participants

6

Reactant 5

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 10796Cesium carbonateHCID 706791-Butyne, 3-chloro-3-methyl-HCID 69411640HCID 69411640, compound

Product 1

HCID 69415058HCID 69415058, compoundYield 75%

Conditions

Temperature
50 °C

Procedure

To the crude dimethyl ether xanthone (3.27 g, 12.0 mmol) in DMF (60 mL) was added 3-chloro-3-methyl-1-butyne (11.8 g, 36.1 mmol), KI (1.0 g, 6.01 mmol) and Cs2CO3 (11.8 g, 36.1 mmol). The reaction was heated at 50° C. for 19 h, cooled to rt, and then placed in an ice-bath. 2M HCl was added until the reaction had been quenched and no more foaming was observed. The mixture was then diluted with CH2Cl2 (200 mL) and the layers were separated. The organic layer was washed with sat. NaCl (50 mL), dried (Na2SO4), and concentrated under reduced pressure. The crude product was purified by column chromatography (60% EtOAc/hex) to yield 3.50 g (75%) of a yellow solid. (LH-63-16) 1H NMR (250 MHz, CDCl3) δ 7.88 (d, 1H, J=5.12 Hz), 7.20-7.02 (m, 3H), 4.00 (s, 3H), 3.98 (s, 3H), 2.78 (s, 1H), 1.80 (s, 6H; 13C NMR (62.5 MHz) δ 175.1, 161.4, 161.2, 158.7, 147.8, 145.2, 123.1, 117.6, 115.5, 114.5, 107.6, 98.7, 98.6, 84.6, 76.9, 72.6, 56.2, 29.4; mass spectrum (CI) m/z+1 339.1233 [C20H19O5 (M+1) requires 339.1232] 339 (base), 273.

Workup

  1. temperaturecooled to rt
  2. customplaced in an ice-bath
  3. customhad been quenched
  4. additionThe mixture was then diluted with CH2Cl2 (200 mL)
  5. customthe layers were separated
  6. washThe organic layer was washed with sat. NaCl (50 mL)
  7. dry with materialdried (Na2SO4)
  8. concentrationconcentrated under reduced pressure
  9. customThe crude product was purified by column chromatography (60% EtOAc/hex)

Sources & evidence

ORD record
ord-469d869e23424212a680f652c3a25376
Source dataset
uspto-grants-2007_07
Patent number
US07244760B2

Reaction notes

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