Acetic Acid → 2-Formyl-1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene

HRID 364762

Reaction equation

HRID 364762 reaction equation
C1N2CN3CN(C2)CN1C3.[OH:11][C:12]1[C:21]2[C:20]([CH3:23])([CH3:22])[CH2:19][CH2:18][C:17]([CH3:25])([CH3:24])[C:16]=2[CH:15]=[C:14]([CH3:26])[CH:13]=1.[C:27](O)(=[O:29])C.Cl>C(OCC)C.O>[CH:27]([C:13]1[C:14]([CH3:26])=[CH:15][C:16]2[C:17]([CH3:25])([CH3:24])[CH2:18][CH2:19][C:20]([CH3:22])([CH3:23])[C:21]=2[C:12]=1[OH:11])=[O:29]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 313Hydrochloric AcidHCID 4101HexamethylenetetramineHCID 216784833,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydronaphthalen-1-ol

Product 1

HCID 190951662-Formyl-1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
20 °C

Procedure

Formylation. Hexamethylenetetramine (21 g, 0.15 mol) and 1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene were added in one portion with stirring to acetic acid (250 mL) and the mixture was heated at 95°-100° C. for 2 h. After cooling to 80°-85° C., water (250 mL) and concentrated hydrochloric acid (60 mL) were added and the mixture was heated at 95°-100° C. for a further 2 h. The reaction product was then cooled to 20° C., diethyl ether (150 mL) was added and the mixture was stirred vigorously. The organic layer was separated, washed with brine (2×50 mL), neutralized with 5% sodium bicarbonate solution (100 mL), and dried (Na2SO4). The solvent was removed by distillation and the residue was distilled to yield 2-formyl-1-hydroxy-3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene (4a) (18 g), mp 91°-92° C., GLC purity 99%+. 1H-NMR (CDCl3) δ12.92 (1H, s), 10.21 (1H, s), 6.73 (1H, s), 1.68 (3H, s), 1.67 (4H, s), 1.48 (6H, s), 1.32 (6H, s). 13C-NMR (CDCl3) δ194.4 (1C, d), 163.5 (1C, s), 156.5 (1C, s), 138.0 (1C, s), 130.8 (1C, s), 120.1 (1C, d), 116.2 (1C, s), 37.7 (1C, t), 35.3 (1C, s), 34.6 (1C, t), 33.9 (1C, s), 31.0 (2C, q), 27.7 (2C, q), 17.8 (1C, q). IR (KBr) 1615, 1628 cm-1, MS (m/e) 246.2 (M+, 23.9) 231.2 (100.0), 189.1 (19.9), 161.2 (19.2).

Workup

  1. temperaturethe mixture was heated at 95°-100° C. for 2 h
  2. temperatureAfter cooling to 80°-85° C.
  3. temperaturethe mixture was heated at 95°-100° C. for a further 2 h
  4. customThe organic layer was separated
  5. washwashed with brine (2×50 mL)
  6. dry with materialdried (Na2SO4)
  7. customThe solvent was removed by distillation
  8. distillationthe residue was distilled

Sources & evidence

ORD record
ord-caec32583f9c4391a84f5d83b5b14185
Source dataset
uspto-grants-1986_08
Patent number
US04605778

Linked notes

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