Carbon Dioxide → HCID 66973666, compound

HRID 628476Notes

Reaction equation

HRID 628476 reaction equation
[C:1]1([O:7][C:8](=[O:20])[CH2:9][C:10]2[CH:15]=[C:14]([O:16][CH3:17])[CH:13]=[C:12]([O:18][CH3:19])[CH:11]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(=O)=O.Cl[C:25]([O:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)=[O:26].CCCCCC>O1CCCC1>[CH3:17][O:16][C:14]1[CH:15]=[C:10]([CH:9]([C:25]([O:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[O:26])[C:8]([O:7][C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)=[O:20])[CH:11]=[C:12]([O:18][CH3:19])[CH:13]=1

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 8058HexaneHCID 15891Phenyl chloroformateHCID 66973723HCID 66973723, compound

Product 1

HCID 66973666HCID 66973666, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-70 °C

Procedure

To a solution of lithium bis(trimethylsilyl)amide (400 mL, 1M in tetrahydrofuran obtained commercially from Aldrich Chem. Co.) was added a solution of 3,5-dimethoxybenzeneacetic acid phenyl ester (53.1 g) in tetrahydrofuran (65 mL) dropwise over 20 min while cooling in a dry ice bath at −70° C. The resulting slurry was stirred at dry ice temperature for 45 min. Phenyl chloroformate (26 mL) was added all at once followed by 50 mL of tetrahydrofuran. The resulting thick slurry was stirred for 2.5 h at 0° C. while cooling in an ice bath before quenching with diluted aqueous HCl (50 mL of conc. HCl diluted to 150 mL with water). The bulk of tetrahydrofuran was removed under vacuum and diethyl ether (550 mL) and water (80 mL) were added. The aqueous layer was separated and extracted with diethyl ether (50 mL). The combined ether layers were dried over magnesium sulfate and concentrated under vacuum to yield a crude solid which was stirred with hexane (250 mL) for 24 h. The solid was then collected by filtration, washed with hexane (100 mL), and vacuum dried to yield 62 g of the title compound. 1H NMR (CDCl3) δ 7.37 (t, 2H), 7.26 (q, 1H), 7.13 (d, 2H), 6.73 (s, 2H), 6.45 (s, 1H), 5.02 (s, 1H), 3.82 (s, 6H).

Workup

  1. temperaturewhile cooling in an ice bath
  2. custombefore quenching with diluted aqueous HCl (50 mL of conc. HCl diluted to 150 mL with water)
  3. customThe bulk of tetrahydrofuran was removed under vacuum and diethyl ether (550 mL) and water (80 mL)
  4. additionwere added
  5. customThe aqueous layer was separated
  6. extractionextracted with diethyl ether (50 mL)
  7. dry with materialThe combined ether layers were dried over magnesium sulfate
  8. concentrationconcentrated under vacuum
  9. customto yield a crude solid which
  10. filtrationThe solid was then collected by filtration
  11. washwashed with hexane (100 mL), and vacuum
  12. customdried

Sources & evidence

ORD record
ord-766e2dcad9df49c0a2a808812033fbd1
Source dataset
uspto-grants-2016_04
Patent number
US09314025B2

Reaction notes

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