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

HRID 707701Notes

Reaction equation

HRID 707701 reaction equation
[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

Participants

9

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 4

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 1140TolueneSolvent2×HCID 15413tert-Butyl methyl etherSolventHCID 21899848Ethylacetate heptaneSolvent

Conditions

Temperature
0 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-8912ae067ba34d199f7305d7bd94796f
Source dataset
uspto-grants-2015_11
Patent number
US09175013B2

Reaction notes

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