Sulfuric Acid → HCID 19920648, compound

HRID 1648676Notes

Reaction equation

HRID 1648676 reaction equation
I[C:2]1C=C(O)C=CC=1.C12(O)CC3CC(CC(C3)C1)C2.S(=O)(=O)(O)O.[CH:25]12[CH2:34][CH:29]3[CH2:30][CH:31]([CH2:33][CH:27]([CH2:28]3)[CH:26]1[C:35]1[CH:40]=[CH:39][C:38]([I:41])=[CH:37][C:36]=1[OH:42])[CH2:32]2.COS(OC)(=O)=O.C(=O)([O-])[O-].[K+].[K+]>C(Cl)Cl.CC(C)=O>[CH:27]12[CH2:28][CH:29]3[CH2:30][CH:31]([CH2:32][CH:25]([CH2:34]3)[CH:26]1[C:35]1[CH:40]=[CH:39][C:38]([I:41])=[CH:37][C:36]=1[O:42][CH3:2])[CH2:33]2

Participants

9

Reactant 6

HCID 1118Sulfuric AcidHCID 6497Dimethyl SulfateHCID 11430Potassium CarbonateHCID 122723-IodophenolHCID 641521-AdamantanolHCID 19920657HCID 19920657, compound

Product 1

HCID 19920648HCID 19920648, compoundYield 81%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 6344DichloromethaneSolvent

Procedure

For 4-(1-Adamantyl)-3-methoxybenzaldehyde (3c): scale=3.51 mmol, yield=43%: The precursor aryl halide, 2-adamantyl-5-iodoanisole, was obtained in two steps from 3-iodophenol via the following procedure. 3-Iodophenol was treated with 1-adamantanol and sulfuric acid in methylene chloride following the general procedure of Shreet et al. U.S. Pat. No. 4,717,720, January 1988. This gave, without recrystallization, pure 2-adamantyl-5-iodophenol: scale=114 mmol, yield=91%; mp 142°-44° C.; 1H NMR (300 MHz, DMSO-d6) δ7.08 (d, J=2 Hz, 1H, ArH), 7.04 (dd, J=2, 8 Hz, 1H, ArH), 6.80 (d, J=8 Hz, 1H, ArH), 3.36 (s, 1H, OH), 1.99 (s, 9 H, adamantyl), and 1.68 (s, 6H, adamantyl); 13C NMR (75 MHz, CDCl3) δ157.26, 135.66, 128.32, 127.54, 124.50, 91.23, 39.61, 36.56, 36.12, and 28.32; IR (KBr) 3480 (OH), 2900, 2845, 1490, 1395, 1210, and 875 cm-1 ; MS (DCI) m/e 355 (MH+), 354 (M+), 353 (M--H)+, 135 (C10H15+). Anal. Calcd for C16H19OI: C, 54.25; H, 5.41. Found: C, 54.32; H, 5.37. A solution of 2-adamantyl-5-iodophenol (7.70 g, 21.7 mmol) in acetone (100 mL) was treated with dimethylsulfate (4.11 g, 32.6 mmol) and potassium carbonate (4.50 g, 32.6 mmol). The reaction mixture was stirred at reflux for 24 h, cooled, and concentrated in vacuo. The crude product was partitioned between methylene chloride and water. The organic phase was dried over anhydrous magnesium sulfate, filtered, and concentrated to provide 6.5 g (81%) of 2-adamantyl-5-iodoanisole; 1H NMR (300 MHz, CDCl3) δ7.22 (dd, J=2, 8 Hz, 1H, ArH), 7.10 (d, J=2 Hz, 1H, ArH), 6.89 (d, J=8 Hz, 1H, ArH), 3.79 (s, 3H, OCH3), 2.02 (s, 9H, adamantyl), and 1.73 (s, 6H, adamantyl); 13C NMR (75 MHz, CDCl3) δ159.35, 138.43, 129.63, 128.25, 120.75, 91.20, 55.22 (OCH3), 40.35, 37.02, 36.92, and 28.97; MS (DCI) m/e 369 (MH+), 368 (M+), 367 (M--H)+, 135 (C10H15+). Anal. Calcd for C17H21OI: C, 55.45; H, 5.75. Found: C, 55.51; H, 5.81. Reaction of 2-adamantyl-5-iodoanisole according to general procedure A gave 3c: 1H NMR (300 MHz, CDCl3) δ9.92 (s, 1H, CHO), 7.35-7.41 (m, 3H, ArH), 3.88 (s, 3H, OCH3), 2.08 (s, 9H, adamantyl), and 1.76 (s, 6H, adamantyl); 13C NMR (75 MHz, CDCl3) δ192.04 (C=O), 159.38, 146.00, 135.36, 127.06, 124.45, 109.54, 55.09 (OCH3), 40.15, 37.79, 36.95, and 28.90; IR (KBr) 2965, 2900, 2850, 1690 (C=O), 1250, 1160, 1135, 1035, and 1025 cm-1 ; MS (DCI) m/e 271(MH+), 135 (C10H15 +). Anal. Calcd for C18H22O2.0.02H2O: C, 79.86; H, 8.21. Found: C, 79.48; H, 8.34.

Workup

  1. customThis gave, without recrystallization, pure 2-adamantyl-5-iodophenol
  2. temperatureat reflux for 24 h
  3. temperaturecooled
  4. concentrationconcentrated in vacuo
  5. customThe crude product was partitioned between methylene chloride and water
  6. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-d4d057cfd73b47699c3a0ee9060521fb
Source dataset
uspto-grants-1995_07
Patent number
US05436369

Reaction notes

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