Acetate → HCID 53838877, compound

HRID 1284880Notes

Reaction equation

HRID 1284880 reaction equation
C([O:4][C@H:5]1[CH2:32][CH2:31][C@@:30]2([CH3:33])[C:7](=[CH:8][CH2:9][C@@H:10]3[C@@H:29]2[CH2:28][CH2:27][C@@:26]2([CH3:34])[C@H:11]3[CH2:12][CH2:13][C@@H:14]2[C@H:15]([CH3:25])[CH2:16][C:17]([F:24])([F:23])[CH2:18][C:19]([OH:22])([CH3:21])[CH3:20])[CH2:6]1)(=O)C.C(Cl)(Cl)(Cl)Cl.CC1C=C(C)N=C(C)C=1.CC1C=CC(S(O)(=O)=O)=CC=1.C([O-])(=O)C.[OH-].[K+].CO>C1(C)C(C)=CC=CC=1.CC(C)=O.C1COCC1.C1C=CC=CC=1.C(OCC)(=O)C>[F:23][C:17]([F:24])([CH2:16][C@H:15]([C@@H:14]1[C@:26]2([CH3:34])[C@H:11]([C:10]3[C@H:29]([CH2:28][CH2:27]2)[C@:30]2([CH3:33])[C:7]([CH2:6][CH:5]([OH:4])[CH2:32][CH2:31]2)=[CH:8][CH:9]=3)[CH2:12][CH2:13]1)[CH3:25])[CH2:18][C:19]([OH:22])([CH3:21])[CH3:20]

Participants

11

Reactant 6

HCID 175AcetateHCID 5943Carbon TetrachlorideHCID 6101p-Toluenesulfonic acidHCID 79532,4,6-TrimethylpyridineHCID 23689386Potassium hydroxide methanolHCID 70465999HCID 70465999, compound

Product 1

HCID 53838877HCID 53838877, compoundYield 21.7%

Reagents, catalysts & solvents 4

HCID 180AcetoneSolventHCID 7237O-XyleneSolvent2×HCID 8028TetrahydrofuranSolventHCID 21583983Benzene ethyl acetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of the acetate (14) (19 mg, 0.0396 mmol) in carbontetrachloride (2 ml) N-bromosuccinimide (10 mg, 0.0571 mmol) was added and this mixture was refluxed under argon atmosphere for 20 min. After cooling to 0° C., the resulting precipitate was filtered off. The filtrate was concentrated below 40° C. to leave the residue. This residue in xylene (2 ml) was added dropwise to a refluxing solution of S-collidine (0.5) and xylene (1.5 ml) and refluxing was continued for 20 min. The usual work-up (ethyl acetate for extraction) gave the crude diene. This diene in acetone (10 ml) was treated with a catalytic amount of TsOH at room temperature under argon atmosphere in the dark for 14 hr. The usual work-up (ethyl acetate for extraction) gave the crude 5,7-diene acetate. This acetate in THF (5 ml) was treated with 5% KOH-MeOH (1.0 ml) at room temperature under argon atmosphere in the dark for 30 min. The usual work-up (ethyl acetate for extraction) gave a crude product, which was submitted to preparative TLC (benzene-ethyl acetate 2:1, developed twice). The band of Rf value 0.47 was scraped off and eluted with ethyl acetate. Removal of the solvent provided the 5,7-diene (15) (3.75 mg, 21.7%). UV λmax mm: 294, 282, 272.

Workup

  1. temperaturethis mixture was refluxed under argon atmosphere for 20 min
  2. filtrationthe resulting precipitate was filtered off
  3. concentrationThe filtrate was concentrated below 40° C.
  4. customto leave the residue
  5. temperaturerefluxing
  6. extractionThe usual work-up (ethyl acetate for extraction)
  7. customgave the crude diene
  8. extractionThe usual work-up (ethyl acetate for extraction)
  9. customgave the crude 5,7-diene acetate
  10. extractionThe usual work-up (ethyl acetate for extraction)
  11. customgave a crude product, which
  12. washeluted with ethyl acetate
  13. customRemoval of the solvent

Sources & evidence

ORD record
ord-7db5d66095b54088a1f2322128159e0f
Source dataset
uspto-grants-1986_01
Patent number
US04564474

Reaction notes

Loading…