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

HRID 1632454

반응식

HRID 1632454 반응식
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]

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 962Water용매HCID 3283Diethyl Ether용매

반응 조건

온도
20 °C

실험 절차

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)67194.4 (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).

후처리

  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

출처 및 근거

ORD 기록
ord-1367049ccce94c0696d33bcfee26110f
출처 데이터셋
uspto-grants-1984_10
특허 번호
US04476040

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