Ethyl Acetate → (E)-Methyl 3-[3-[4-(4-methoxyphenyl)butyloxy]-6-[(2,6-dichlorophenylthio)methyl]-2-pyridinyl]-2-propenoate

HRID 263410Notes

Reaction equation

HRID 263410 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Cl:8])[C:3]=1[SH:9].Cl.C(C/C=[CH:16]/[C:17]1[C:22]([O:23][CH2:24][CH2:25][CH2:26][CH2:27][C:28]2[CH:33]=[CH:32][C:31]([O:34][CH3:35])=[CH:30][CH:29]=2)=[CH:21][CH:20]=[C:19]([CH2:36]Cl)[N:18]=1)(O)=O.N12CCCN=C1CCCCC2.C[CH2:50][O:51][C:52]([CH3:54])=[O:53]>CC#N>[CH3:35][O:34][C:31]1[CH:30]=[CH:29][C:28]([CH2:27][CH2:26][CH2:25][CH2:24][O:23][C:22]2[C:17](/[CH:16]=[CH:54]/[C:52]([O:51][CH3:50])=[O:53])=[N:18][C:19]([CH2:36][S:9][C:3]3[C:2]([Cl:1])=[CH:7][CH:6]=[CH:5][C:4]=3[Cl:8])=[CH:20][CH:21]=2)=[CH:33][CH:32]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 90671Benzenethiol, 2,6-dichloro-HCID 196068312-(E-2-Carboxymethylethenyl)-3-[4-(4-methoxyphenyl)butyloxy]-6-chloromethylpyridine hydrochloride

Product 1

HCID 10673813(E)-Methyl 3-[3-[4-(4-methoxyphenyl)butyloxy]-6-[(2,6-dichlorophenylthio)methyl]-2-pyridinyl]-2-propenoate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
50 °C

Procedure

2,6-Dichlorothiophenol (53 mg, 0.297 mmol, Aldrich) was dissolved in dry MeCN (0.60 mL,) and treated with 2-(E-2-carboxymethylethenyl)-3-[4-(4-methoxyphenyl)butyloxy]-6-chloromethylpyridine hydrochloride (115 mg, 0.270 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 0.142 mL, 0.949 mmol). The reaction was stirred under an atmosphere of argon at 50° C. for 3 h. The reaction solution was diluted with EtOAc and washed with H2O and brine and dried (MgSO4). Purification by flash column chromatography (silica, EtOAc: CH2Cl2 : hexane, 10:15:75) gave a colorless waxy solid: 1H NMR (250 MHz, CDCl3) δ7.94 (d, J=15.7 Hz, 1H, vinyl), 7.31 (d, J=7.6 Hz, 2H, aryl), 7.13 (m, 4H, aryl, pyridyl), 7.11 (d, J=8.4 Hz, 1H, pyridyl), 6.86 (d, J=8.7 Hz, 2H, phenyl), 6.69 (d, J=15.7 Hz, 1H, vinyl), 4.14 (s, 2H, CH2 -S), 3.97 (t, J=6.1 Hz, 2H, CH2 -O), 3.80 (s, 3H, OMe), 3.78 (s, 3H, methyl ester), 2.63 (t, J=7.2 Hz, 2H, benzylic), 1.81 (m, 4H, CH2CH2); analysis calcd. for C27H27Cl2NO4S: C, 60.90; H, 5.11; N, 2.63; found: C, 60.61; H, 5.01; N, 2.57; MS (ES+): 532.0 (M+H).

Workup

  1. washwashed with H2O and brine
  2. dry with materialdried (MgSO4)
  3. customPurification by flash column chromatography (silica, EtOAc: CH2Cl2 : hexane, 10:15:75)
  4. customgave a colorless waxy solid

Sources & evidence

ORD record
ord-27164e97bfc446a19ba7c13c516ff771
Source dataset
uspto-grants-1997_07
Patent number
US05643914

Reaction notes

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