Hydrochloric Acid → HCID 10811027, compound

HRID 2255847Notes

Reaction equation

HRID 2255847 reaction equation
C([Li])CCC.[Br:6][C:7]1[CH:12]=[C:11]([O:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[C:10](Br)=[CH:9][C:8]=1[O:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27].[B:28](OC)([O:31]C)[O:29]C.Cl.[K+].[Br-]>CCOCC>[Br:6][C:7]1[CH:12]=[C:11]([O:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])[C:10]([B:28]([OH:31])[OH:29])=[CH:9][C:8]=1[O:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH3:27]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 8470Trimethyl borateHCID 253877Potassium BromideHCID 167262041,4-Dibromo-2,5-bis(hexyloxy)benzeneHCID 178418339Butyllithium

Product 1

HCID 10811027HCID 10811027, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

Butyllithium (48.2 mmol, 30.2 ml, 15% in hexane) was added into a solution of 1,4-dibromo-2,5-dihexyloxybenzene (48.2 mmol, 21.0 g) in ether (195 ml) under argon at between -10° to -30° C. over 15 min. The mixture was allowed to warm to room temperature and was stirred for further 2 h. It was then transferred into a solution of freshly distilled trimethyl borate (145 mmol, 16.4 ml) in ether (390 ml) under argon at -60° C. The mixture was allowed to warm to room temperature and was stirred for further 15 h. Aqueous hydrochloric acid (2M, 300ml) was added into the mixture, and the aqueous layer was separated and extracted with ether (100 ml×2). The combined organic layer was evaporated and 40/60 petroleum ether (200 ml) was added. A colourless solid was recovered by filtration and dried under vacuum. Further purification was carried out by column chromatography over silica (60 g), with toluene (200 ml) as an eluent to remove by-products. Elution with ether (300 ml) produced a pure product. (8.9 g, 46%); m.p. 102°-103° C.; Rf (ether), 0.71; γmax (KBr, cm-1) 3360 (OH), 2940 (C--H), 1200 (Ph), 1040 (C--O), 810 (Ph); δH (400 MHz, CDCl3) 0.91 (67H, m, Me), 1.33 (8H, m), 1.44 (4H, m) 1.80 (4H, m) 4.00 (4H, m), 6.48 (2H, s, OH), 7.09 (1H, s, Ph), 7.36 (ill, s, Ph); t δc (100 MHz, CDCl3) 13.9, 22.5, 25.5, 29.1, 31.4, 69.6, 116.3, 116.4 (PhC--H), 118 (br, C--B), 120.5 (PhC--H), 149.6 (PhC--O), 158.0 (PhC--O).

Workup

  1. temperatureto warm to room temperature
  2. stirringwas stirred for further 15 h
  3. customthe aqueous layer was separated
  4. extractionextracted with ether (100 ml×2)
  5. customThe combined organic layer was evaporated
  6. addition40/60 petroleum ether (200 ml) was added
  7. filtrationA colourless solid was recovered by filtration
  8. customdried under vacuum
  9. customFurther purification
  10. customto remove by-products
  11. washElution with ether (300 ml)
  12. customproduced a pure product

Sources & evidence

ORD record
ord-3ee98af4fb6f437fbfde3111bb6c2017
Source dataset
uspto-grants-1997_08
Patent number
US05653914

Reaction notes

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