Chloroacetamide → methyl 9H-fluorene-9-carboxylate

HRID 1607430Notes

Reaction equation

HRID 1607430 reaction equation
C1C2C(C(O)=O)C3C(=CC=CC=3)C=2C=CC=1.Cl.CO.[Na].ClCC(N)=O.[CH3:26][O:27][C:28]([C:30]1(O)[C:42]2[CH:41]=[C:40](F)[CH:39]=[CH:38][C:37]=2[C:36]2[C:31]1=[CH:32][C:33](F)=[CH:34][CH:35]=2)=[O:29].[OH-].[Na+]>CO>[CH3:26][O:27][C:28]([CH:30]1[C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][C:36]=2[C:37]2[C:42]1=[CH:41][CH:40]=[CH:39][CH:38]=2)=[O:29]

Participants

8

Reactant 6

HCID 6580ChloroacetamideHCID 14798Sodium HydroxideHCID 748099-CarboxyfluoreneHCID 5360545SodiumHCID 14075053Methyl 2,7-difluoro-9-hydroxy-9H-fluorene-9-carboxylateHCID 21893726Hydrochloride methanol

Product 1

HCID 232396methyl 9H-fluorene-9-carboxylate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

9H-fluoren-9-carboxylic acid methyl ester (19), which was prepared by refluxing 9H-fluoren-9-carboxylic acid (Aldrich Chemical, Inc.) in HCl/MeOH, (10.0 g, 44.6 mmol) was added to a solution of sodium (1.2 eq, 53.5 mmol, 1.23 g) in 100 mL methanol. After 15 min., 2-chloroacetamide (1.1 eq, 49.1 mmol, 4.59 g) was added and the mixture was allowed to stir at room temperature under nitrogen for two (2) days. The reaction mixture was poured into 400 mL of cold 2.5% w/v aqueous sodium hydroxide and the insoluble material was removed by filtration. The filtrate was chilled and acidified with concentrated hydrochloric acid to precipitate the spiro-succinimide which was collected and air dried to provide 6.7 g (60%). Recrystallization from methanol gave purified (20), 4.28 g (39%). m.p. 237°-239° C. Calc. %C 77.09, %H 4.45, %N 5.62: meas. %C 77.17, %H 4.55, %N 5.58.

Workup

  1. additionThe reaction mixture was poured into 400 mL of cold 2.5%
  2. customthe insoluble material was removed by filtration
  3. temperatureThe filtrate was chilled
  4. customto precipitate the spiro-succinimide which
  5. customwas collected
  6. customair dried
  7. customto provide 6.7 g (60%)
  8. customRecrystallization from methanol
  9. customgave
  10. custompurified (20), 4.28 g (39%)

Sources & evidence

ORD record
ord-809d66d1256a4b01a8f60228758739be
Source dataset
uspto-grants-1989_09
Patent number
US04864028

Reaction notes

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