Hydrochloric Acid → HCID 20239856, compound

HRID 1632457Notes

Reaction equation

HRID 1632457 reaction equation
[CH:1]([C:3]1[CH:12]=[C:11]([CH3:13])[C:10]2[C:9]([CH3:15])([CH3:14])[CH2:8][CH2:7][C:6]([CH3:17])([CH3:16])[C:5]=2[C:4]=1[OH:18])=[O:2].[OH-].[K+].S(OC)(O[CH3:25])(=O)=O.Cl>C1(C)C=CC=CC=1>[CH:1]([C:3]1[CH:12]=[C:11]([CH3:13])[C:10]2[C:9]([CH3:14])([CH3:15])[CH2:8][CH2:7][C:6]([CH3:17])([CH3:16])[C:5]=2[C:4]=1[O:18][CH3:25])=[O:2]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6497Dimethyl SulfateHCID 14797Potassium HydroxideHCID 20239854HCID 20239854, compound

Product 1

HCID 20239856HCID 20239856, compoundYield 81.3%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
40 °C

Procedure

Methylation. 2-Formyl-1-hydroxy-4,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (42 g, 0.17 mol) was stirred with toluene (656 mL), and potassium hydroxide 85% (16.8 g, 0.255 mol) was added in one portion. The mixture was heated to 40° C., dimethyl sulfate (32.13 g, 0.255 mol) added at 40°-45° C. during 0.5 h, and the heating continued at 50° C. for an additional 1.5 h. The mixture was cooled to 20° C., neutralized with 5% HCl solution, then washed with water (20 mL), and finally washed with brine (25 mL). The solvent was removed by distillation and the residue distilled to give 2-formyl-1-methoxy-4,5,5,8,8- pentamethyl-5,6,7,8-tetrahydronaphthalene (36 g), bp 140°-142° C./1.5 mm, GLC purity 95%. Crystallization from hexane gave 28 g material, GLC purity 99%. 1H-NMR (CDCl3) δ10.23 (2 H, s), 7.41 (1H, s), 3.89 (3H, s), 2.52 (3H, s), 1.63 (4H, s), 1.42 (6H, s), 1.40 (6H, s). 13C-NMR (CDCl3) δ189.9 (1C, d), 162.3 (1C, s), 153.1 (1C, s), 139.9 (1C, s), 132.7 (1C, s), 131.3 (1C, d), 126.5 (1C, s), 66.0 (1C, q), 39.4 (1C, t), 38.2 (1C, t), 36.4 (1C, s), 35.6 (1C, s), 30.0 (2C, q), 28.9 (2C, q), 23.7 (1C, q). IR (KBr) 1683, 1235 cm-1, MS (m/e) 260.3 (M+, 46.3), 245.2 (100.0), 175 (38.5), 128 (31.1).

Workup

  1. additionwas added in one portion
  2. temperatureThe mixture was cooled to 20° C.
  3. washwashed with water (20 mL)
  4. washfinally washed with brine (25 mL)
  5. customThe solvent was removed by distillation
  6. distillationthe residue distilled

Sources & evidence

ORD record
ord-f194249442b04cbf8c2572a4c86fd160
Source dataset
uspto-grants-1984_10
Patent number
US04476040

Reaction notes

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