Pyridine → HCID 67794269, compound

HRID 1651069Notes

Reaction equation

HRID 1651069 reaction equation
[Cl:1][C:2]1[C:12]2[CH:11]=[CH:10][C:9]3[CH:13]=[CH:14][CH:15]=[CH:16][C:8]=3[CH:7]([CH2:17][OH:18])[C:6]=2[CH:5]=[CH:4][CH:3]=1.C1(C)C=CC(S(Cl)(=O)=O)=CC=1.N1C=CC=CC=1.[OH-].[K+]>ClCCl.CN(C)C1C=CN=CC=1.CO>[Cl:1][C:2]1[C:12]2[CH:11]=[CH:10][C:9]3[CH:13]=[CH:14][CH:15]=[CH:16][C:8]=3[CH:7]=[C:17]([OH:18])[C:6]=2[CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 1049PyridineHCID 73974-Toluenesulfonyl chlorideHCID 14797Potassium HydroxideHCID 67794699HCID 67794699, compound

Product 1

HCID 67794269HCID 67794269, compoundYield 18.2%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 1-chloro-5-hydroxymethyl-dibenzo [a,d]cycloheptene (8.3 g) in dichloromethane (80 ml) was added p-toluenesulphonyl chloride (6.3 g), pyridine (5.11 g), and 4-dimethylamino pyridine (150 mg). The reaction mixture was refluxed for 15h, cooled washed with water (2×80 ml), dried (Na2SO4), filtered and concentrated in vacuo to leave an oil which was purified by chromatography on flash silica with 15% ethyl acetate in hexane as eluent. The purified tosylate was dissolved in glacial acetic acid (100 ml) with anhydrous sodium acetate (4.4 g) and the solution refluxed for 15h. The mixture was concentrated in vacuo to leave a residue which was partitioned between dichloromethane (3×100 ml) and water (100 ml). The combined organic layers were dried (Na2SO4), filtered and concentrated in vacuo to leave a residue which was dissolved in 75% aqueous methanol (160 ml) and treated at 0° C. with potassium hydroxide (10 g). After 14h the reaction mixture was concentrated in vacuo. Chromatography of the residue on flash silica with 15% ethyl acetate in hexane as eluent gave the less polar isomer, 1-chloro-5-hydroxydibenzo[a,e]cyclooctene (1.5 g), m.p. 158°-160° C. δ(360 MHz, CDCl3) 3.12 (1H, dd, J =1.51 and 10.2 Hz, CHAHB --CHOH), 3.63 (1H, dd, J=15.1 and 6.9 Hz, CHAHB --CHOH), 5.57 (1H, dd, J=10.2 and 6.9 Hz, CHAHB --CHOH), 6.74 (1H, d, J=11.9 Hz, ArCHD =CHE --Ar), 7.03 (1H, d, J=11.9 Hz, ArCHD =CHEAr) and 7.07-7.46 (7H, m, aromatics). m/e 256 (M+). i.r.(νmax, nujol) 3350-3100 cm-1 (br, OH). Found: C, 74.5; H, 5.1. C16H13C10 requires: C, 74.9; H, 5.1%. Further elution gave the more polar isomer, 1-chloro-6-hydroxy-dibenzo[a,e]cyclooctene (0.47 g), m.p. 144°-146° C. δ(360 MHz, CDCl3) 3.39 (2H, m, CH--CHOH), 5.13 (1H, m, CH2 --CHOH), 6.77 (1H, d, J=11.9 Hz, Ar--CHA =CHB), 7.02 (1H, d, J=11.9 Hz, ArCHA =CHB) and 7.07-7.38 (7H, m, aromatics). m/e 256 (M+). i.r (νmax, nujol) 3300-3100 cm-1 (br, OH). Found: C, 74.8; H, 5.2. C16H13C10 requires: C, 74.9; H, 5.1%.

Workup

  1. temperaturecooled
  2. washwashed with water (2×80 ml)
  3. dry with materialdried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customto leave an oil which
  7. customwas purified by chromatography on flash silica with 15% ethyl acetate in hexane as eluent
  8. dissolutionThe purified tosylate was dissolved in glacial acetic acid (100 ml) with anhydrous sodium acetate (4.4 g)
  9. temperaturethe solution refluxed for 15h
  10. concentrationThe mixture was concentrated in vacuo
  11. customto leave a residue which
  12. customwas partitioned between dichloromethane (3×100 ml) and water (100 ml)
  13. dry with materialThe combined organic layers were dried (Na2SO4)
  14. filtrationfiltered
  15. concentrationconcentrated in vacuo
  16. customto leave a residue which
  17. concentrationAfter 14h the reaction mixture was concentrated in vacuo

Sources & evidence

ORD record
ord-5abfac9e72744f418d50a86ba46b16be
Source dataset
uspto-grants-1990_05
Patent number
US04927819

Reaction notes

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