HCID 23293613, compound → HCID 70133496, compound

HRID 862765Notes

Reaction equation

HRID 862765 reaction equation
Br[CH:2]([CH:8]1[C:17]2[C:12](=[CH:13][CH:14]=[C:15]([F:18])[CH:16]=2)[CH2:11][CH2:10][CH2:9]1)[C:3]([O:5]CC)=[O:4].CC(C)([O-])C.[K+]>O1CCCC1.C(O)(C)(C)C>[F:18][C:15]1[CH:16]=[C:17]2[C:12]([CH2:11][CH2:10][CH2:9]/[C:8]/2=[CH:2]\[C:3]([OH:5])=[O:4])=[CH:13][CH:14]=1

Participants

5

Reactant 2

HCID 23293613HCID 23293613, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 70133496HCID 70133496, compoundYield 55.4%

Reagents, catalysts & solvents 2

HCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A mixture of ethyl 2-bromo-2-(7-fluoro-1,2,3,4-tetrahydro-1-naphthyl)acetate (2.2 g, 7.0 mmol), 1N potassium tert-butoxide in tetrahydrofuran (14 mL, Aldrich) and tert-butanol (140 mL) was stirred for 5h at room temperature. The resulting suspension was concentrated in vacuo, diluted with water (200 mL) and washed with diethyl ether. The aqueous layer was acidified by adding 1N hydrochloric acid (14 mL) and extracted with diethyl ether. The ether extract was dried over anhydrous sodium sulfate, filtered, concentrated in vacuo and chromatographed on Silica Gel 60 using ethyl acetate-hexane (1:1) as eluent. The fractions containing only (E)-2-(7-fluoro-1,2,3,4-tetrahydro-1-naphthylidene)acetic acid were combined and concentrated in vacuo to give a white solid (0.8 g, 55%); NMR (DMSO-d6): d 12.22 (br s, 1H, COOH), 7.57 (d of d, Jm =2.6 Hz, Jo =11.0 Hz, 1H, Ar), 7.12-7.28 (m, 2H, Ar), 6.36 (s, 1H, =CH, E), 3.04 (t, 2H, ArCH2), 2.74 (t, 2H, CH2), 1.74 (m, 2H, CH2); steady-state nOe: irradiation at 6.36, observed 25% nOe at 7.57.

Workup

  1. concentrationThe resulting suspension was concentrated in vacuo
  2. additiondiluted with water (200 mL)
  3. washwashed with diethyl ether
  4. additionby adding 1N hydrochloric acid (14 mL)
  5. extractionextracted with diethyl ether
  6. extractionThe ether extract
  7. dry with materialwas dried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customchromatographed on Silica Gel 60 using ethyl acetate-hexane (1:1) as eluent
  11. additionThe fractions containing only (E)-2-(7-fluoro-1,2,3,4-tetrahydro-1-naphthylidene)acetic acid
  12. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-463eb59dddf74242b53f617b13290f6d
Source dataset
uspto-grants-1998_02
Patent number
US05719186

Reaction notes

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