Toluene → HCID 54450011, compound

HRID 1885395Notes

Reaction equation

HRID 1885395 reaction equation
[CH:1]1[C:6]([CH:7]=[O:8])=[CH:5][C:4]2[O:9][CH2:10][O:11][C:3]=2[CH:2]=1.C(OCC)(OCC)OCC.C1(C)C=CC=CC=1.[C:29]([C@@H:34]([C@H:36]([C:38]([O:40][CH2:41][CH3:42])=[O:39])[OH:37])O)([O:31][CH2:32][CH3:33])=[O:30]>C1(C)C=CC(S(O)(=O)=O)=CC=1.CO>[CH2:10]1[O:11][C:3]2[CH:2]=[CH:1][C:6]([CH:7]3[O:37][C@@H:36]([C:38]([O:40][CH2:41][CH3:42])=[O:39])[C@H:34]([C:29]([O:31][CH2:32][CH3:33])=[O:30])[O:8]3)=[CH:5][C:4]=2[O:9]1

Participants

7

Reactant 4

HCID 1140TolueneHCID 8438PiperonalHCID 31214Ethyl orthoformateHCID 6993580Diethyl tartrate

Product 1

HCID 54450011HCID 54450011, compoundYield 67%

Reagents, catalysts & solvents 2

HCID 6101p-Toluenesulfonic acidCatalystHCID 887MethanolSolvent

Conditions

Temperature
25 °C

Procedure

A mixture of piperonal (60 g, 0.4 mol), triethyl orthoformate (59.2 g, 0.4 mol), toluene (250 mL) and p-toluenesulfonic acid (2 g, 0.01 mol) was heated at 100°-110° C. for 0.5 h. Diethyl L-tartrate (103 g, 0.5 mol) was added to the hot solution over a 10 min. period. The mixture was then heated at reflux for 2 h. Subsequently over a 3 hour period, distillate (150 mL) was collected (pot temperature 84° C. to 110° C.). The mixture was cooled (25° C.) and washed with sodium bicarbonate solution (2×50 mL) and brine (1×50 mL). Evaporation of solvents under reduced pressure provided 130.7 g of crude product. Recrystallization from methanol provided 90 g (67% yield) of (4R,5R)-2-(3,4-methylenedioxyphenyl)-4,5-dicarboethoxy-1,3-dioxolane, mp 39°-40° C., [α]D -34.8° (c, 1.0 methanol). 1H-NMR (CDCl3) δ7.12 (1H, d, J=1.5 Hz), 7.03 (1 H, dd, J=1.5 Hz and 7.9 Hz), 6.80 (1H, d, J=7.9 Hz), 6.06 (1H, s), 5.97 (2H, s), 4.91 (1H, d, J=4.0 Hz), 4.80 (1H, d, J=4.0 Hz), 4.36-4.26 (4H, 2 q, overlapping, J=7.0 Hz), 1.38-1.30 (6H, 2 t, overlapping, J=7.0 Hz). IR (KBr) 2980, 2900, 1735, 1490, 1445, 1415 cm-1. MS m/e (% abundance) 338 (3), 265 (16), 166 (100), 149 (96), 135 (54), 121 (35), 93 (10), 65 (12), 43 (8).

Workup

  1. temperaturewas heated at 100°-110° C. for 0.5 h
  2. temperatureThe mixture was then heated
  3. temperatureat reflux for 2 h
  4. distillationSubsequently over a 3 hour period, distillate (150 mL) was collected (pot temperature 84° C. to 110° C.)
  5. washwashed with sodium bicarbonate solution (2×50 mL) and brine (1×50 mL)
  6. customEvaporation of solvents under reduced pressure
  7. customprovided 130.7 g of crude product
  8. customRecrystallization from methanol

Sources & evidence

ORD record
ord-11706bf246824d748a1c922f073b66ff
Source dataset
uspto-grants-1992_09
Patent number
US05144048

Reaction notes

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