Tributylphosphine → 3-(4-[2-(6,11-Dihydrodibenzo[b,e]oxepin-11-yloxy)-ethoxy]-phenyl)-2-ethoxy-propionic acid ethyl ester

HRID 1060849ノート

反応式

HRID 1060849 の反応式
[CH:1]1[C:11]2[CH:10]([O:12][CH2:13][CH2:14][OH:15])[C:9]3[CH:16]=[CH:17][CH:18]=[CH:19][C:8]=3[CH2:7][O:6][C:5]=2[CH:4]=[CH:3][CH:2]=1.C(P(CCCC)CCCC)CCC.[CH2:33]([O:35][C:36](=[O:49])[CH:37]([O:46][CH2:47][CH3:48])[CH2:38][C:39]1[CH:44]=[CH:43][C:42](O)=[CH:41][CH:40]=1)[CH3:34].C1CCN(C(N=NC(N2CCCCC2)=O)=O)CC1>C1C=CC=CC=1.CCCCCCC>[CH2:33]([O:35][C:36](=[O:49])[CH:37]([O:46][CH2:47][CH3:48])[CH2:38][C:39]1[CH:44]=[CH:43][C:42]([O:15][CH2:14][CH2:13][O:12][CH:10]2[C:9]3[CH:16]=[CH:17][CH:18]=[CH:19][C:8]=3[CH2:7][O:6][C:5]3[CH:4]=[CH:3][CH:2]=[CH:1][C:11]2=3)=[CH:41][CH:40]=1)[CH3:34]

参加物

7

反応物 4

HCID 13831TributylphosphineHCID 730421,1'-(Azodicarbonyl)dipiperidineHCID 11791243Ethyl 2-ethoxy-3-(4-hydroxyphenyl)propanoateHCID 227276792-(6,11-Dihydrodibenzo[b,e]oxepin-11-yloxy)-ethanol

生成物 1

HCID 99346953-(4-[2-(6,11-Dihydrodibenzo[b,e]oxepin-11-yloxy)-ethoxy]-phenyl)-2-ethoxy-propionic acid ethyl ester収率 37%

試薬・触媒・溶媒 2

HCID 241Benzene溶媒HCID 8900Heptane溶媒

反応条件

温度
0 °C

実験手順

Under a nitrogen atmosphere, 2-(6,11-dihydrodibenzo[b,e]oxepin-11-yloxy)-ethanol (256 mg, 1.0 mmol), tributylphosphine (223 mg, 1.1 mmol) and 2-ethoxy-3-(4-hydroxy-phenyl)-propionic acid ethyl ester (262 mg, 1.1 mmol) were successively dissolved in dry benzene (10 mL). Solid azodicarboxylic dipiperidine (ADDP) (278 mg, 1.1 mmol) was added under stirring at 0° C. to the solution. After 10 min, the reaction mixture was brought to room temperature and the stirring was continued for 16 h. Heptane (10 mL) was added to the reaction mixture and dihydro-ADDP separated out was filtered off. After evaporation of the solvent the product was purified chromatography eluting with ethyl acetate/heptane (1:4) to give 175 mg (37%) of the title compound: 1H NMR (300 MHz, CDCl3)δ1.15 (t, 3H), 1.25 (t, 3H), 2.93 (d, 2H), 3.30-3.40 (m, 1H), 3.55-3.65 (m, 1H), 3.65-3.75 (m, 1H),3.78-3.88 (m,1 H), 3.95 (t, 1H), 4.10 (t, 2H), 4.15 (q, 2H), 4.85 (d, 1H), 5.25 (s, 1H), 6.15 (d, 1H), 6.75 (d,2H), 6.85-6.95 (m, 2H), 7.10 (d, 2H), 7.15-7.40 (m, 6H).

後処理

  1. customwas brought to room temperature
  2. waitthe stirring was continued for 16 h
  3. customseparated out
  4. filtrationwas filtered off
  5. customAfter evaporation of the solvent the product
  6. customwas purified chromatography
  7. washeluting with ethyl acetate/heptane (1:4)

出典と根拠

ORDレコード
ord-3866af5879364970a738f6be70900c3e
出典データセット
uspto-grants-2003_02
特許番号
US06525086B2

反応ノート

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