Water → Tert-butyl 2-((1-(trityloxy)but-3-en-2-yl)oxy)acetate

HRID 707701ノート

反応式

HRID 707701 の反応式
[OH-].[Na+].[C:3]([O:22][CH2:23][CH:24]([OH:27])[CH:25]=[CH2:26])([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.Br[CH2:29][C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31].O>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1.CCCCCCC.CCOC(C)=O.COC(C)(C)C>[C:3]([O:22][CH2:23][CH:24]([O:27][CH2:29][C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[CH:25]=[CH2:26])([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)([C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

参加物

9

反応物 4

HCID 962Water2 回HCID 14798Sodium HydroxideHCID 79177tert-Butyl bromoacetate2 回HCID 132073271-(Triphenylmethoxy)but-3-en-2-ol

生成物 1

HCID 70557162Tert-butyl 2-((1-(trityloxy)but-3-en-2-yl)oxy)acetate

試薬・触媒・溶媒 4

HCID 94433Tetrabutylammonium hydrogen sulfate触媒HCID 1140Toluene溶媒2 回HCID 15413tert-Butyl methyl ether溶媒HCID 21899848Ethylacetate heptane溶媒

反応条件

温度
0 °C

実験手順

A suspension of tetrabutylammonium hydrogen sulfate (367 g, 1.08 mol, 0.1 equiv.) in toluene (4.63 kg) under nitrogen atmosphere was prepared and cooled down to 0° C. 50% aq. NaOH solution (9.09 kg) was slowly added with the temperature kept under 50° C. Crude mixture from Step 4-(2) (3.95 kg of 1-(trityloxy)but-3-en-2-ol in toluene, total weight 6.34 kg) was slowly added with temperature kept under 15° C. The reaction mixture was stirred for 15 min. tert-Butyl bromoacetate (1.01 kg, 5.19 mol, 0.43 equiv.) was added leading to the formation of a slurry. Water (1 kg) was added then tert-butyl bromoacetate (1.55 kg, 7.95 mol, 0.66 equiv) while maintaining temperature below 30° C. The reaction was left to stir overnight. The reaction was followed by TLC (Rf 0.60 in Heptane/EtOAc 20%). Water (9.72 kg) and 2-methoxy-2-methylpropane (10.4 kg) were added then the reaction mixture was successively washed with water (3.90 kg) and with saturated aq NaCl solution (0.63 kg). The organic phase was then concentrated under reduced pressure to generate a crude mixture (4.70 kg). 1H NMR (500 MHz, CDCl3) δ ppm 7.47 (dt, J=7.9, 3.9 Hz, 6H), 7.27-7.19 (m, 6H), 7.14 (dd, J=14.2, 6.9 Hz, 3H), 5.81-5.70 (m, 1H), 5.28 (d, J=17.2 Hz, 1H), 5.21 (d, J=9.9 Hz, 1H), 4.10-3.94 (m, 3H), 3.34 (dt, J=17.7, 8.8 Hz, 1H), 3.18 (dd, J=9.6, 5.3 Hz, 1H), 1.43 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 169.48, 143.95, 135.69, 128.69, 127.67, 126.86, 118.47, 86.62, 81.07, 80.74, 66.75, 66.41, 28.05.

後処理

  1. customwas prepared
  2. customkept under 50° C
  3. customkept under 15° C
  4. additionwas added
  5. waitThe reaction was left
  6. washthe reaction mixture was successively washed with water (3.90 kg) and with saturated aq NaCl solution (0.63 kg)
  7. concentrationThe organic phase was then concentrated under reduced pressure

出典と根拠

ORDレコード
ord-8912ae067ba34d199f7305d7bd94796f
出典データセット
uspto-grants-2015_11
特許番号
US09175013B2

反応ノート

読み込み中…