4-Toluenesulfonyl chloride → HCID 14088496, compound

HRID 704115Notes

Reaction equation

HRID 704115 reaction equation
[2H]C(C(O)(C([2H])([2H])[2H])[C@H](/C=C/[C@H]([C@@H]1[C@@]2(C)CCC/C(=C\[CH:22]=[C:23]3\[CH2:24][C@@H:25](O)[CH2:26][C@H:27]([OH:30])[C:28]\3=[CH2:29])/[C@@H]2CC1)C)C)([2H])[2H].C([Li])CCC.C1(C)C=CC(S(Cl)(=O)=O)=CC=1>C1COCC1>[CH2:26]([CH:27]1[CH:28]([CH2:23][CH3:22])[CH2:29][O:30]1)[CH2:25][CH3:24]

Participants

5

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 66577026(1S,3R,5Z,7E,22E)-(26,26,26,27,27,27-~2~H_6_)-9,10-Secoergosta-5,7,10,22-tetraene-1,3,25-triolHCID 178418339Butyllithium2×

Product 1

HCID 14088496HCID 14088496, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

This compound was prepared after the method of Moulines et al, Synthesis, (1981), 550. 18 g 2-ethylhexa e-1, 3-diol (Aldrich Chemical Co.) was dissolved in dry THF (350 ml) and the solution was chilled to -3° C. (ice-salt bath). n-Butyllithium solution (1.6M in hexane, 94 ml, 0.15 mol) was added dropwise with stirring over 45 minutes (temperature 5°±5° C.). Stirring was continued for a further 1 hour at room temperature, then p-toluenesulphonyl chloride (28.6 g, 0.15 mol) in dry THF (75 ml) was added dropwise over 45 minutes with cooling in an ice-bath. After a further period of stirring of 1 hour a second portion of n-butyl lithium (94 ml) was added over 30 minutes at 5°-10° C. (ice-bath cooling), and the mixture was stirred overnight at room temperature. Finally, the mixture was heated at 60°-65° C. for 2.5 hours (thick white suspension forms), prior to concentration in vacuo, addition of water (750 ml) and continuous extraction with ether for 4 hours. After removal of the ether the resulting pale yellow oil was distilled to give 5.25 g (33%) of (CXXIII), bp 70.4°-71.8° C./100 mbar.

Workup

  1. customThis compound was prepared
  2. customafter the method of Moulines et al, Synthesis, (1981), 550
  3. stirringStirring
  4. waitwas continued for a further 1 hour at room temperature
  5. temperaturewith cooling in an ice-bath
  6. additionwas added over 30 minutes at 5°-10° C.
  7. temperature(ice-bath cooling)
  8. stirringthe mixture was stirred overnight at room temperature
  9. temperatureFinally, the mixture was heated at 60°-65° C. for 2.5 hours (thick white suspension forms)
  10. concentrationto concentration
  11. additionin vacuo, addition of water (750 ml) and continuous extraction with ether for 4 hours
  12. customAfter removal of the ether the resulting pale yellow oil
  13. distillationwas distilled
  14. customto give 5.25 g (33%) of (CXXIII), bp 70.4°-71.8° C./100 mbar

Sources & evidence

ORD record
ord-201afbc1790b4b7698afc7ba3b370f8d
Source dataset
uspto-grants-1991_01
Patent number
US04985584

Reaction notes

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