Methanol → [6-Ethyl-7-methyl-3-oxo-4-(2-trimethylsilanyl-ethoxy)-1,3-dihydro isobenzofuran-5-yl]-acetaldehyde

HRID 33004

反応式

HRID 33004 の反応式
[CH2:1]([C:4]1[C:12]([O:13][CH2:14][CH2:15][Si:16]([CH3:19])([CH3:18])[CH3:17])=[C:11]2[C:7]([CH2:8][O:9][C:10]2=[O:20])=[C:6]([CH3:21])[C:5]=1[CH2:22][CH3:23])[CH:2]=C.NC(N)=S.C[OH:29]>C(Cl)Cl.N1C=CC=CC=1>[CH2:22]([C:5]1[C:6]([CH3:21])=[C:7]2[C:11]([C:10](=[O:20])[O:9][CH2:8]2)=[C:12]([O:13][CH2:14][CH2:15][Si:16]([CH3:18])([CH3:19])[CH3:17])[C:4]=1[CH2:1][CH:2]=[O:29])[CH3:23]

参加物

6

反応物 3

HCID 887MethanolHCID 2723790ThioureaHCID 574598636-Allyl-5-ethyl-4-methyl-7-(2-trimethylsilanyl-ethoxy)3H-isobenzofuran-1-one

生成物 1

HCID 59794521[6-Ethyl-7-methyl-3-oxo-4-(2-trimethylsilanyl-ethoxy)-1,3-dihydro isobenzofuran-5-yl]-acetaldehyde収率 69%

試薬・触媒・溶媒 2

HCID 1049Pyridine溶媒HCID 6344Dichloromethane溶媒

実験手順

A solution of 6-allyl-5-ethyl-4-methyl-7-(2-trimethylsilanyl-ethoxy)-3H-isobenzofuran-1-one (261 mg, 0.788 mmol) in MeOH (5 mL), CH2Cl2 (5 mL) and pyridine (50 μL) was cooled to −78° C. using a dry ice/acetone bath according to the procedure of Smith, D. B. et al., J. Org. Chem., 1996, 61, 6, 2236. A stream of ozone was bubbled through the reaction via a gas dispersion tube until the reaction became blue in color (15 minutes). The ozone line was replaced with a stream of nitrogen and bubbling continued for another 15 minutes, by which time the blue color had disappeared. To this solution, at −78° C., was added thiourea (59.9 mg, 0.788 mmol) in one portion, and the cooling bath was removed. The reaction was allowed to warm to room temperature and stirred for 15 hours. The reaction mixture was filtered and then partitioned between CH2Cl2 and water. The aqueous layer was extracted with CH2Cl2 one more time and the organic extracts were combined, washed with aqueous 1N HCl, saturated NaHCO3 and brine and dried over sodium sulfate. Filtration and evaporation of solvents in vacuo yielded the crude product, which was purified by silica gel chromatography to afford 181 mg (69%) of the product as a white solid. 1H NMR (300 MHz, CDCl3): δ=0.04 (s, 9H), 1.11 (t, J=7.5 Hz, 3H), 1.19 (m, 2H), 2.21 (s, 3H), 2.66 (q, J=7.5 Hz, 2H), 3.90 (s, 2H), 4.36 (m, 2H), 5.18 (s, 2H), 9.71 (s, 1H) ppm.

後処理

  1. customA stream of ozone was bubbled through the reaction via a gas dispersion tube until the reaction
  2. custombecame blue in color (15 minutes)
  3. custombubbling
  4. customthe cooling bath was removed
  5. filtrationThe reaction mixture was filtered
  6. custompartitioned between CH2Cl2 and water
  7. extractionThe aqueous layer was extracted with CH2Cl2 one more time
  8. washwashed with aqueous 1N HCl, saturated NaHCO3 and brine
  9. dry with materialdried over sodium sulfate
  10. filtrationFiltration and evaporation of solvents in vacuo
  11. customyielded the crude product, which
  12. customwas purified by silica gel chromatography

出典と根拠

ORDレコード
ord-ed958c6406a14b04871577b52366a706
出典データセット
uspto-grants-2008_09
特許番号
US07427636B2

関連ノート

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