Triethylamine → [(3-Hydroxyphenyl)methoxymethylene]adamantane

HRID 974439

反応式

HRID 974439 の反応式
[H-].[H-].[H-].[H-].[Li+].[Al+3].C(N(CC)CC)C.[OH:14][C:15]1[CH:16]=[C:17]([CH:22]=[CH:23][CH:24]=1)[C:18]([O:20][CH3:21])=O.[CH:25]12[CH2:34][CH:29]3[CH2:30][CH:31]([CH2:33][CH:27]([CH2:28]3)[C:26]1=O)[CH2:32]2>C1COCC1.O>[OH:14][C:15]1[CH:16]=[C:17]([CH2:18][O:20][CH:21]=[C:26]2[CH:27]3[CH2:33][CH:31]4[CH2:30][CH:29]([CH2:34][CH:25]2[CH2:32]4)[CH2:28]3)[CH:22]=[CH:23][CH:24]=1

参加物

7

反応物 4

HCID 8471TriethylamineHCID 64151AdamantanoneHCID 88068Methyl 3-HydroxybenzoateHCID 21226445Aluminium lithium hydride

生成物 1

HCID 53971236[(3-Hydroxyphenyl)methoxymethylene]adamantane収率 89%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

[(3-Hydroxyphenyl)methoxymethylene]adamantane (1a) was prepared as described in my previous application Ser. No. 224,681, filed July 27, 1988. A 500-mL flask was fitted with a reflux condenser, a 125-mL addition funnel, and nitrogen line. The apparatus was dried by means of a hot air gun and nitrogen purging. Dry THF (40 mL) was added and the flask cooled in an ice bath. TiCl3 (1.5 g, 10 mmol) was added rapidly followed by LAH (0.19 g, 5 mmol) in portions with stirring. The cooling bath was removed and the black mixture was allowed to warm to room temperature. Triethylamine (0.7 mL, 5 mmol) was added to the stirred suspension and refluxed for 15 min. After this period, a solution of methyl 3-hydroxybenzoate (152 mg, 1 mmol) and 2-adamantanone (300 mg, 2 mmol) in 20 mL of dry THF was added dropwise to the refluxing mixture over 15 min. Refluxing was continued for an additional 15 min after which the reaction was cooled to room temperature and diluted with 100 mL of distilled water. The aqueous solution was extracted with 3×50 mL portions of ethyl acetate. The combined organic layer was washed with water, dried over MgSO4, and concentrated. Chromatography over silica with 15% ethyl acetate/hexane gave 240 mg (89%) of 1a as a white solid: mp 133°-4° C.; 1H NMR (CDCl3) δ1.64-1.96 (m, 12H), 2.65 (s, 1H), 3.24 (s, 1H), 3.32 (s, 3H), 5.25 (s, 1H, OH exchange with D2O), 6.70-7.30 (m, 4H); 13C NMR (CDCl3) δ28.45, 30.36, 32.36, 37.30, 39.18, 39.33, 57.82, 114.60, 116.16, 122.19, 129.24, 137.24, 155.62; MS m/e (rel intensity) 271 (20, M+1), 270 (100, M), 253 (7.3), 213 (35.1 ), 121 (41.7), 93 (9.4); Exact mass: calcd 270.1619, found 270.1616. ##STR21##

後処理

  1. custom[(3-Hydroxyphenyl)methoxymethylene]adamantane (1a) was prepared
  2. customA 500-mL flask was fitted with a reflux condenser, a 125-mL addition funnel
  3. customThe apparatus was dried by means of a hot air gun and nitrogen purging
  4. additionDry THF (40 mL) was added
  5. temperaturethe flask cooled in an ice bath
  6. customThe cooling bath was removed
  7. temperaturerefluxed for 15 min
  8. waitAfter this period
  9. temperatureRefluxing
  10. temperatureafter which the reaction was cooled to room temperature
  11. extractionThe aqueous solution was extracted with 3×50 mL portions of ethyl acetate
  12. washThe combined organic layer was washed with water
  13. dry with materialdried over MgSO4
  14. concentrationconcentrated

出典と根拠

ORDレコード
ord-d77d067845f541b0b0d94cb1575e1d9b
出典データセット
uspto-grants-1991_11
特許番号
US05068339

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