Water → HCID 46941502, compound

HRID 1491563Notes

Reaction equation

HRID 1491563 reaction equation
[C:1]([C@@H:6]([C@H:8]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[OH:9])[OH:7])([O:3][CH2:4][CH3:5])=[O:2].O=[CH:16][C:17]1[CH:26]=[CH:25][C:23]([OH:24])=[C:19]([O:20][CH2:21][CH3:22])[CH:18]=1.C1(C)C=CC=CC=1.O>C1(C)C=CC(S(O)(=O)=O)=CC=1.CO>[CH2:21]([O:20][C:19]1[CH:18]=[C:17]([CH:16]2[O:9][C@@H:8]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C@H:6]([C:1]([O:3][CH2:4][CH3:5])=[O:2])[O:7]2)[CH:26]=[CH:25][C:23]=1[OH:24])[CH3:22]

Participants

7

Reactant 4

HCID 962WaterHCID 1140TolueneHCID 8467EthylvanillinHCID 6993580Diethyl tartrate

Product 1

HCID 46941502HCID 46941502, compoundYield 34%

Reagents, catalysts & solvents 2

HCID 6101p-Toluenesulfonic acidCatalystHCID 887MethanolSolvent

Procedure

A mixture of diethyl L-tartrate (309 g, 1.5 mol), ethyl vanillin (166 g, 1 mol), toluene (2 L) and p-toluenesulfonic acid (5 g, 0.026 mol) was heated at 115°-116° C. for 24 hours under a nitrogen atmosphere. During the reaction, water was removed by azeotropic distillation via a Dean-Stark trap. The mixture was washed sequentially with saturated sodium bicarbonate solution (500 mL), brine (2×1 L) and dried over sodium sulfate. The solvent was evaporated under reduced pressure and the solid obtained was recrystallized from isopropanol to provide 120 g (34% yield) of (4R,5R)-2-(3-ethoxy-4-hydroxy-phenyl)4,5-dicarboethoxy-1,3-dioxolane, mp 78°-80° C., [α]D25 -38° (c,1.0, methanol). 1H-HMR (CDCl3)δ 7.17 (1H,d,J=1.8 Hz), 7.06 (1H,dd,J=1.8 Hz and 8.10 Hz), 6.91 (1H,d,J= 8.2 Hz), 6.07 (1H,s), 5.83 (1H,s), 4.91, (1H,d,J=4.0 Hz), 4.80 (1H,d,J=4.0 Hz), 4.37-4.25 (4H, 2 q, overlapping, J=7.2 Hz), 4.15 (2H,q,J=7.0 Hz), 1.45 (3H,t,J=7.0 Hz), 1.38-1.29 (6H,2 t, overlapping J=7.2 Hz). IR (KBr) 3390, 2980, 2930, 1735, 1600 cm-1. MS m/e (% abundance) 354 (55), 326 (3), 281 (40), 182 (85), 167 (85), 154 (100), 137 (70), 110 (30), 93 (10), 81 (10), 53 (5).

Workup

  1. temperaturewas heated at 115°-116° C. for 24 hours under a nitrogen atmosphere
  2. customwas removed by azeotropic distillation via a Dean-Stark trap
  3. washThe mixture was washed sequentially with saturated sodium bicarbonate solution (500 mL), brine (2×1 L)
  4. dry with materialdried over sodium sulfate
  5. customThe solvent was evaporated under reduced pressure
  6. customthe solid obtained
  7. customwas recrystallized from isopropanol

Sources & evidence

ORD record
ord-6c6c53cdd2824447bc5fea85e7b44189
Source dataset
uspto-grants-1994_12
Patent number
US05371069

Reaction notes

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