Trityl chloride → 1-(Triphenylmethoxy)but-3-en-2-ol

HRID 707700

反応式

HRID 707700 の反応式
[C:1]1([C:7](Cl)([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:21]([OH:26])[CH:22]([OH:25])[CH:23]=[CH2:24].C(N(CC)CC)C>C1(C)C=CC=CC=1.CN(C)C1C=CN=CC=1.CCCCCCC.CCOC(C)=O>[C:7]([O:26][CH2:21][CH:22]([OH:25])[CH:23]=[CH2:24])([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

参加物

7

反応物 3

HCID 6456Trityl chlorideHCID 8471TriethylamineHCID 103383-Butene-1,2-diol

生成物 1

HCID 132073271-(Triphenylmethoxy)but-3-en-2-ol収率 100.7%

試薬・触媒・溶媒 3

HCID 142844-(Dimethylamino)pyridine触媒HCID 1140Toluene溶媒HCID 21899848Ethylacetate heptane溶媒

反応条件

温度
0 °C

実験手順

To a solution of triphenylmethyl chloride (3.31 kg, 11.87 mol, 0.99 equiv) in toluene (6.74 kg) at RT, was added but-3-ene-1,2-diol (1.06 kg, 12.02 mol, 1.0 equiv.). The reaction mixture was cooled down to 0° C. Triethylamine (2.72 kg, 26.91 mol, 2.24 equiv.) was slowly added to the reaction mixture while maintaining temperature below 5° C., followed by 4-dimethylaminopyridine (8.38 g, 0.068 mol, 5.71 mmol). The reaction mixture was allowed to warm up to 10° C. then heated to 40° C. The reaction mixture was stirred at 40° C. overnight. The reaction was followed by TLC (Rf 0.45 in Heptane/EtOAc 20%). The reaction mixture was cooled down to 26.5° C., filtered and the solids were rinsed with toluene (2.72 kg). The filtrate was successively washed with 28% aq. NH4Cl solution (3.38 kg) and saturated aq NaCl solution (1.26 kg). The organic phase was then concentrated under reduced pressure to afford an oil as a crude mixture 3.95 kg). 1H NMR (500 MHz, DMSO) δ ppm 7.42 (dd, J=8.3, 1.0 Hz, 6H), 7.33 (dd, J=10.5, 4.8 Hz, 6H), 7.30-7.19 (m, 3H), 5.94-5.83 (m, 1H), 5.25 (td, J=17.3, 1.8 Hz, 1H), 5.08 (td, J=10.9, 1.8 Hz, 1H), 2.99 (dd, J=8.9, 6.3 Hz, 1H), 2.84 (dd, J=8.9, 5.7 Hz, 1H); 13C NMR (125 MHz, DMSO) δ 144.35, 140.07, 128.78, 128.26, 127.39, 115.04, 86.25, 70.88, 68.27.

後処理

  1. temperaturewhile maintaining temperature below 5° C.
  2. temperatureto warm up to 10° C.
  3. temperaturethen heated to 40° C
  4. temperatureThe reaction mixture was cooled down to 26.5° C.
  5. filtrationfiltered
  6. washthe solids were rinsed with toluene (2.72 kg)
  7. washThe filtrate was successively washed with 28% aq. NH4Cl solution (3.38 kg) and saturated aq NaCl solution (1.26 kg)
  8. concentrationThe organic phase was then concentrated under reduced pressure

出典と根拠

ORDレコード
ord-566d1f168aae4612895f71d0b9628ddd
出典データセット
uspto-grants-2015_11
特許番号
US09175013B2

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