3-(Trifluoromethyl)benzoyl chloride → HCID 14697449, compound

HRID 1649880Notes

Reaction equation

HRID 1649880 reaction equation
[S:1]([O:5][C@H:6]1[C@@H:12]([CH2:13][O:14][C:15]([O:17][CH3:18])=[O:16])[O:11][CH:8]([O:9][CH3:10])[C@@H:7]1[OH:19])([CH3:4])(=[O:3])=[O:2].[F:20][C:21]([F:32])([F:31])[C:22]1[CH:23]=[C:24]([CH:28]=[CH:29][CH:30]=1)[C:25](Cl)=[O:26]>N1C=CC=CC=1>[S:1]([O:5][C@H:6]1[C@@H:12]([CH2:13][O:14][C:15]([O:17][CH3:18])=[O:16])[O:11][CH:8]([O:9][CH3:10])[C@@H:7]1[O:19][C:25](=[O:26])[C:24]1[CH:28]=[CH:29][CH:30]=[C:22]([C:21]([F:20])([F:31])[F:32])[CH:23]=1)([CH3:4])(=[O:3])=[O:2]

Participants

4

Reactant 2

HCID 752573-(Trifluoromethyl)benzoyl chlorideHCID 14697447HCID 14697447, compound

Product 1

HCID 14697449HCID 14697449, compoundYield 97.3%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

A flame dried 250 ml flask equipped with an addition funnel, magnetic stirrer and nitrogen inlet was charged with methyl 3-O-mesyl-5-O-(methoxycarbonyl)-D-xylofuranoside (5.84 g, 19.4 mmoles) (C. D. Anderson, L. Goodman and B. R. Baker, J. Am. Chem. Soc. 1958, 80, 5247) and anhydrous pyridine. The solution was cooled in an ice bath and 3-(trifluoromethyl)-benzoyl chloride (5.27 g, 25.3 mmoles) was added dropwise over 10 min. After the addition was complete the ice bath was removed and the reaction was continued 24 hours at ambient temperature. The mixture was poured into ice water (400 mL) and the aqueous solution extracted with ether (2×250 mL). The combined ether extracts were washed with 400 mL. of 1.2NHCl and 400 mL of 10% aqueous NaHCO3. The solvent was removed by rotary evaporation and the residual oil was purified by flash chromatography (3-inch diameter column containing 18 inches of flash silica gel). The column was eluted with 1:1/ethyl acetate:hexanes while collecting 200 mL fractions. Fractions 12-15 contained pure product and these fractions were concentrated in vacuo to afford 8.92 g (97.3%) of methyl 3-O-mesyl-5-O-(methoxycarbonyl)-2-O-(m-trifluoromethylbenzoyl)-D-xylofuranoside as a colourless oil containing an approximately equal mixture of α and β anomers. 1H NMR (CDCl3) δ3.09 and 3.19(s, 3H, OCH3), 3.34 and 3.37(s, 3H, SO2CH3), 3.79(s, 3H, OCO2CH3), 4.4-4.9(m, 3H, C-4H and C-5H), 5.1-5.6(m, 3H, C-1H, C-2H and C-3H) and 7.5-8.5 (m, 4H, ArH); TLC Rf =0.77 and 0.84, silica gel, CHCl3 :CH3OH/90:10.

Workup

  1. customA flame dried 250 ml flask
  2. customequipped with an addition funnel, magnetic stirrer and nitrogen inlet
  3. temperatureThe solution was cooled in an ice bath
  4. additionAfter the addition
  5. customwas removed
  6. additionThe mixture was poured into ice water (400 mL)
  7. extractionthe aqueous solution extracted with ether (2×250 mL)
  8. washThe combined ether extracts were washed with 400 mL
  9. customThe solvent was removed by rotary evaporation
  10. customthe residual oil was purified by flash chromatography (3-inch diameter column containing 18 inches of flash silica gel)
  11. washThe column was eluted with 1:1/ethyl acetate
  12. customhexanes while collecting 200 mL fractions
  13. concentrationFractions 12-15 contained pure product and these fractions were concentrated in vacuo

Sources & evidence

ORD record
ord-647a73401a274fe4aaa900d995924990
Source dataset
uspto-grants-1990_05
Patent number
US04921950

Reaction notes

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