Hydrochloric Acid → HCID 178420267、化合物

HRID 263808ノート

反応式

HRID 263808 の反応式
[C:1]1([C:7]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH2:8][CH2:9][OH:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.O[C:24]1[CH:29]=[CH:28][C:27]([CH2:30][CH2:31][C:32]#[N:33])=[CH:26][CH:25]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O.C[Al](C)C.[N:69]([Si](C)(C)C)=[N+:70]=[N-:71].Cl>C1COCC1.C1(C)C=CC=CC=1.CCOC(C)=O>[C:17]1([C:7]([C:1]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)([C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=2)[CH2:8][CH2:9][O:10][C:24]2[CH:29]=[CH:28][C:27]([CH2:30][CH2:31][C:32]3[NH:33][N:71]=[N:70][N:69]=3)=[CH:26][CH:25]=2)[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

参加物

11

反応物 7

HCID 313Hydrochloric AcidHCID 11776TriphenylphosphineHCID 78378AzidotrimethylsilaneHCID 870793-(p-Hydroxyphenyl)propiononitrileHCID 2986573,3,3-Triphenylpropan-1-olHCID 5462977Diethyl azodicarboxylateHCID 16682925Trimethylaluminum

生成物 1

HCID 178420267HCID 178420267、化合物収率 30%

試薬・触媒・溶媒 3

HCID 1140Toluene溶媒2 回HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
80 °C

実験手順

To 3,3,3-triphenylpropanol (8.70 mmol), 3-(4-hydroxyphenyl)propionitrile (9.40 mmol) and triphenylphosphine (2.42 g, 9.23 mmol) in dry THF (25 mL) under a nitrogen atmosphere at room temperature, was added dropwise DEAD (1.50 mL, 9.52 mmol) in dry THF (20 mL) over approximately 30 minutes. The reaction was heated to reflux overnight. After cooling, the THF was evaporated and the residue chromatographed on a silica column, with 15-20% EtOAc/hexanes. White solid, mp=98°-100° C. (ether), 60% yield. 1H NMR δ 7.18-7.35 (m, 15H), 7.06 (d, J=8.6 Hz, 2H), 6.67 (d, J=8.6 Hz, 2H), 3.72 (t, J=7.8 Hz, 2H), 3.13 (t, J=7.8 Hz, 2H), 2.85 (t, J=7.3 Hz, 2H), 2.54 (t, J=7.3 Hz, 2H). IR 2243, 1540 cm-1. MS 418 (MH+), 243. Anal. calcd. for C30H27NO: C, 86.30; H, 6.52; N, 3.35. Found: C, 86.07; H, 6.39; N, 3.24. To a solution of trimethyl aluminum (1M in hexanes, 0.57 mL), in toluene (3 mL) at ~2° C., was added azidotrimethylsilane (0.569 mmol). A solution of nitrile (0.474 mmol) in toluene (2 mL) was slowly added. The reaction was stirred at 80° C. for 72 h. The cooled (0° C.) reaction was added dropwise to HCl (6M, 10 mL) and EtOAc (10 mL). The resulting mixture was extracted with EtOAc (2×50 mL). The combined organic layers were dried (MgSO4), filtered and evaporated. The crude material was triturated with dichloromethane to remove unreacted starting nitrile leaving behind the title compound as a hydrate, a white solid (mp=193°-195° C., 30% yield). 1H NMR (DMSO-d6) δ 7.19-7.35 (m, 15H), 7.02 (d, J=8.5 Hz, 2H), 6.58 (d, J=8.5 Hz, 2H), 3.60 (t, J=7.4 Hz, 2H), 3.04-3.12 (m, 4H), 2.91 (t, J=7.6 Hz, 2H). IR 3300-3450 (br), 1586, 1511 cm-1. MS 461 (MH+), 243. Anal. calcd. for C30H28N4O.0.25H2O: C, 77.48; H, 6.18; N, 12.05. Found: C, 77.18; H, 5.96; N, 11.71.

後処理

  1. temperatureThe reaction was heated
  2. temperatureto reflux overnight
  3. temperatureAfter cooling
  4. customthe THF was evaporated
  5. customthe residue chromatographed on a silica column, with 15-20% EtOAc/hexanes
  6. temperatureThe cooled
  7. custom(0° C.) reaction
  8. extractionThe resulting mixture was extracted with EtOAc (2×50 mL)
  9. dry with materialThe combined organic layers were dried (MgSO4)
  10. filtrationfiltered
  11. customevaporated
  12. customThe crude material was triturated with dichloromethane
  13. customto remove unreacted

出典と根拠

ORDレコード
ord-5962dd71f1304d1a81e7f98f0a9ff223
出典データセット
uspto-grants-1997_07
特許番号
US05643950

反応ノート

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