Acetic Acid → HCID 20239855, compound

HRID 364770Notes

Reaction equation

HRID 364770 reaction equation
[OH:1][C:2]1[C:11]2[C:10]([CH3:13])([CH3:12])[CH2:9][CH2:8][C:7]([CH3:15])([CH3:14])[C:6]=2[C:5]([CH3:16])=[C:4]([CH3:17])[CH:3]=1.[C:18](O)(=[O:20])C.C1N2CN3CN(C2)CN1C3.O>C1(C)C=CC=CC=1>[CH:18]([C:3]1[C:4]([CH3:17])=[C:5]([CH3:16])[C:6]2[C:7]([CH3:15])([CH3:14])[CH2:8][CH2:9][C:10]([CH3:12])([CH3:13])[C:11]=2[C:2]=1[OH:1])=[O:20]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 4101HexamethylenetetramineHCID 20239857HCID 20239857, compound

Product 1

HCID 20239855HCID 20239855, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

Formylation. 1-Hydroxy-3,4,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene (15 g, 0.0646 mol) was stirred with glacial acetic acid (100 mL), and hexamethylenetetramine (15 g, 0.107 mol) was added in one portion. The mixture was heated at 100° C. for 2 h. Hot water (100 mL) was added and the heating continued for an additional 0.5 h at 100° C. The mixture was cooled to 20° C., toluene (25 mL) was added, and the mixture was stirred vigorously. The organic layer was separated, washed with water (2×10 mL), then neutralized with 5% NaHCO3 solution and finally washed with brine (10 mL). The solvent was removed by distillation, and the residue crystallized from hexane, to give 2-formyl-1-hydroxy-3,4,5,5,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalene (8.8 g), GLC purity 94%. 1H-NMR (CDCl3) δ12.94 (1H, s), 10.36 (1H, s), 2.43 (3H, s), 2.36 (3H, s), 1.65 (4H, s), 1.48 (6H, s), 1.46 (6H, s). 13C-NMR (CDCl3) δ195.4 (1C, d), 161.4 (1C, s), 156.0 (1C, s), 138.0 (1C, s), 131.9 (1C, s), 126.6 (1C, s), 116.7 (1C, s), 40.2 (1C, t), 37.9 (1C, t), 36.5 (1C, s), 35.1 (1C, s), 29.5 (2C, q), 28.1 (2C, q), 19.3 (1C, q), 14.1 (1C, q). IR (KBr) 1628 cm-1, MS (m/e) 260.3 (M+, 38.6), 245.2 (100.0), 175.1 (28.7), 189.1 (20.1).

Workup

  1. additionwas added in one portion
  2. temperatureThe mixture was cooled to 20° C.
  3. customThe organic layer was separated
  4. washwashed with water (2×10 mL)
  5. washfinally washed with brine (10 mL)
  6. customThe solvent was removed by distillation
  7. customthe residue crystallized from hexane

Sources & evidence

ORD record
ord-65130e0e55864b7fa36fd04eeaa13316
Source dataset
uspto-grants-1986_08
Patent number
US04605778

Reaction notes

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