Acetic Acid → HCID 20239854, compound

HRID 364764Notes

Reaction equation

HRID 364764 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])=[CH:4][CH:3]=1.[C:17](O)(=[O:19])C.C1N2CN3CN(C2)CN1C3.O>C1(C)C=CC=CC=1>[CH:17]([C:3]1[CH:4]=[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:19]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 962WaterHCID 4101HexamethylenetetramineHCID 202398584,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydronaphthalen-1-ol

Product 1

HCID 20239854HCID 20239854, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
20 °C

Procedure

Formylation. 1-Hydroxy-4,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (78 g, 0.358 mol) was stirred with glacial acetic acid (632 mL) and hexamethylenetetramine (93.6 g, 0.669 mol). The mixture was heated at 105°-110° C. for 10 h. Hot water (632 mL) was added and the heating was continued for an additional 2.5 h at 100° C. The mixture was cooled to 20° C., toluene (250 mL) was added, and the mixture was stirred vigorously. The organic layer was separated, washed with water (2×50 mL), then neutralized with 5% NaHCO3 solution, and finally washed with brine (50 mL). The solvent was removed by distillation and the residue distilled to yield 2-formyl-1-hydroxy-4,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (45 g), bp 138°-146° C./1 mm, GLC purity 95%. 1H-NMR (CDCl3) δ11.63 (1H, s), 9.73 (1H, s), 7.09 (1H, s), 2.52 (3H, s), 1.66 (3H, s), 1.47 (6H, s), 1.42 (6H, s). 13C-NMR (CDCl3) δ196 (1C, d), 159 (1C, s), 155 (1C, s), 134.7 (1C, d), 134.1 (1C, s), 128 (1C, s), 118.1 (1C, s), 39.3 (1C, t), 37.8 (1C, t), 36.5 (1C, s), 35.2 (1C, s), 28.7 (2C, q), 27.9 (2C, q), 23.5 (1C, q). IR (KBr) 1637 cm- 1, MS (m/e) 246.2 (M+, 36.1), 231.2 (100.0), 161.2 (41.6), 189.1 (27.9).

Workup

  1. temperatureThe mixture was heated at 105°-110° C. for 10 h
  2. customThe organic layer was separated
  3. washwashed with water (2×50 mL)
  4. washfinally washed with brine (50 mL)
  5. customThe solvent was removed by distillation
  6. distillationthe residue distilled

Sources & evidence

ORD record
ord-9ce9776af54d4943850ab63303173f9b
Source dataset
uspto-grants-1986_08
Patent number
US04605778

Reaction notes

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