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

HRID 364762ノート

反応式

HRID 364762 の反応式
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]

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒

反応条件

温度
20 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-caec32583f9c4391a84f5d83b5b14185
出典データセット
uspto-grants-1986_08
特許番号
US04605778

反応ノート

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