Iodine → 2-Iodo-5-isopropoxy-4-methoxybenzaldehyde

HRID 225515

反応式

HRID 225515 の反応式
[CH:1]([O:4][C:5]1[CH:6]=[C:7]([CH:10]=[CH:11][C:12]=1[O:13][CH3:14])[CH:8]=[O:9])([CH3:3])[CH3:2].[I:15]I>C(Cl)(Cl)Cl.FC(F)(F)C([O-])=O.[Ag+]>[I:15][C:10]1[CH:11]=[C:12]([O:13][CH3:14])[C:5]([O:4][CH:1]([CH3:3])[CH3:2])=[CH:6][C:7]=1[CH:8]=[O:9]

参加物

5

反応物 2

HCID 807IodineHCID 5920923-Isopropoxy-4-methoxybenzaldehyde

生成物 1

HCID 111099932-Iodo-5-isopropoxy-4-methoxybenzaldehyde収率 93%

試薬・触媒・溶媒 2

HCID 76299Silver trifluoroacetate触媒HCID 6212Chloroform溶媒

反応条件

温度
61 °C

実験手順

Silver trifluoroacetate (12.3 g, 56.7 mmol) was added to a solution of isovanillin isopropyl ether (10.0 g, 51.5 mmol) in dry chloroform (120 mL) under nitrogen and the resultant slurry stirred and heated to 61° C. Iodine (14.4 g, 56.7 mmol) was then added portionwise (6 portions) over 0.6 h and the reaction allowed to reflux for a futher 6.5 h. The reaction mixture was then cooled and filtered, rinsing with chloroform (50 mL). The filtrate was washed with Na2S2O5 (10% solution in water, 150 mL), NaHCO3 (sat. in water, 150 mL) and water (150 mL) dried (MgSO4) and concentrated under vacuum. The solid residue was suspended in hexane (200 mL) and stirred vigoursly for 1 h, cooled in an ice bath for 1 h and filtered rinsing with ice cold hexane (200 mL) to give the title compound as a cream solid (15.3 g, 93%) mp 75-6° C. IR (KBr disc, cm−1) 3072, 2978, 2932, 1673, 1581, 1503, 1438, 1385, 1332, 1260, 1215, 1174, 1157, 1133, 1105, 1024, 939. 1H NMR (300 MHz, CDCl3) δ 9.77 (s, 1H,), 7.34 (s, 1H), 7.24 (s, 1H), 4.57 (septet, J=6.0 Hz, 1H), 3.86 (s, 3H), 1.31 (d, J=6.0 Hz, 6H). 13C NMR+APT (75.5 MHz, CDCl3) δ 194.7 (−), 155.5 (+), 147.9 (+), 128.2 (+), 122.2 (−), 114.1 (−), 110.8 (+), 92.4 (+), 71.3 (−), 56.4 (−), 21.77 (−). MS (70 eV) m/z (%): 320 (M+·, 43), 278 (100), 249 (17), 207 (12), 150 (40). Anal. Calcd for C11H13O3I: C, 41.27; H, 4.09; I, 39.64. Found: C, 41.06; H, 3.80; I, 39.59.

後処理

  1. temperatureto reflux for a futher 6.5 h
  2. temperatureThe reaction mixture was then cooled
  3. filtrationfiltered
  4. washrinsing with chloroform (50 mL)
  5. washThe filtrate was washed with Na2S2O5 (10% solution in water, 150 mL), NaHCO3 (sat. in water, 150 mL) and water (150 mL)
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated under vacuum
  8. stirringstirred vigoursly for 1 h
  9. temperaturecooled in an ice bath for 1 h
  10. filtrationfiltered
  11. washrinsing with ice cold hexane (200 mL)

出典と根拠

ORDレコード
ord-018b2414a42e4e40a79f7f5c99872d9b
出典データセット
uspto-grants-2009_07
特許番号
US07557118B2

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