O-Xylene → methyl E-4-[5-[4-(dimethylamino)-4-oxobut-1-enyl]-1-propylindol-3-ylmethyl]-3-methoxybenzoate

HRID 330199Notes

Reaction equation

HRID 330199 reaction equation
OC([C:5]1[CH:6]=[C:7]2[C:11](=[CH:12][CH:13]=1)[N:10]([CH2:14][CH2:15][CH3:16])[CH:9]=[C:8]2[CH2:17][C:18]1[CH:27]=[CH:26][C:21]([C:22]([O:24][CH3:25])=[O:23])=[CH:20][C:19]=1[O:28][CH3:29])C=C.C(O[CH:35]([O:39]C(C)(C)C)[N:36]([CH3:38])[CH3:37])(C)(C)C.[C:44]1(C)[C:45](C)=CC=C[CH:49]=1>>[CH3:38][N:36]([CH3:37])[C:35](=[O:39])[CH2:45]/[CH:44]=[CH:49]/[C:5]1[CH:6]=[C:7]2[C:11](=[CH:12][CH:13]=1)[N:10]([CH2:14][CH2:15][CH3:16])[CH:9]=[C:8]2[CH2:17][C:18]1[CH:27]=[CH:26][C:21]([C:22]([O:24][CH3:25])=[O:23])=[CH:20][C:19]=1[O:28][CH3:29]

Participants

4

Reactant 3

HCID 7237O-XyleneHCID 5477121,1-bis(1,1-dimethylethoxy)-N,N,N-trimethylamineHCID 19870651Methyl 4-[5-(1-hydroxyallyl)-1-propylindol-3-ylmethyl]-3-methoxybenzoate

Product 1

HCID 14882660methyl E-4-[5-[4-(dimethylamino)-4-oxobut-1-enyl]-1-propylindol-3-ylmethyl]-3-methoxybenzoateYield 40%

Procedure

A mixture of methyl 4-[5-(1-hydroxyallyl)-1-propylindol-3-ylmethyl]-3-methoxybenzoate (1.57 g, prepared as described in Example 87, part a), N,N-dimethylformamide di-tert-butylacetal (1.63 g, redistilled) in dry xylene (15 ml), under an atmosphere of nitrogen, was stirred and heated under reflux for 2 hr. A further portion of the acetal (1.63 g) was added, and refluxing continued for a further 3.5 hr. The cooled solution was introduced directly into a column of silica gel and the product purified by flash chromatography, eluting with 7:3 ethyl acetate:hexane, to give methyl E-4-[5-[4-(dimethylamino)-4-oxobut-1-enyl]-1-propylindol-3-ylmethyl]-3-methoxybenzoate (0.71 g, 40%) as an off-white solid: mp 122.5°-123.5°; partial NMR (300 MHz, DMSO-d6): 0.81(t, 3H, CH2CH3), 1.75(m, 2H, CH2CH3), 2.83(s, 3H, NCH3), 3.01(s, 3H, NCH3), 3.24(d, 2H, --COCH2CH=), 3.83(s, 3H, OCH3), 3.92(s, 3H, OCH3), 4.05(s, 4H, ArCH2Ar', NCH2CH2), 6.15(d of t, 1H, CH2CH=CH), 6.45(d, 1H, CH2CH=CH).

Workup

  1. customprepared
  2. temperatureheated
  3. temperatureunder reflux for 2 hr
  4. temperaturerefluxing
  5. additionThe cooled solution was introduced directly into a column of silica gel
  6. customthe product purified by flash chromatography
  7. washeluting with 7:3 ethyl acetate

Sources & evidence

ORD record
ord-82fdc9d98743446ebdf867ebdb0dfed2
Source dataset
uspto-grants-1990_01
Patent number
US04894386

Reaction notes

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