Cesium carbonate → HCID 86750839, compound

HRID 1780781Notes

Reaction equation

HRID 1780781 reaction equation
O=S(Cl)Cl.[C:5]([CH2:8]/[CH:9]=[CH:10]/[C:11]1[C:16]([O:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]2[CH:31]=[CH:30][C:29]([O:32][CH3:33])=[CH:28][CH:27]=2)=[CH:15][CH:14]=[C:13]([CH2:34][OH:35])[N:12]=1)([OH:7])=[O:6].[C:36]([NH:40][C:41]([O:43][C:44]1[CH:49]=[CH:48][CH:47]=[C:46]([NH2:50])[CH:45]=1)=[O:42])([CH3:39])([CH3:38])[CH3:37].C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.CCOC(C)=O.CN(C=O)C>[C:36]([NH:40][C:41](=[O:42])[OH:43])([CH3:39])([CH3:38])[CH3:37].[C:5]([CH2:8]/[CH:9]=[CH:10]/[C:11]1[C:16]([O:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][C:26]2[CH:27]=[CH:28][C:29]([O:32][CH3:33])=[CH:30][CH:31]=2)=[CH:15][CH:14]=[C:13]([CH2:34][O:35][C:44]2[CH:49]=[CH:48][CH:47]=[C:46]([NH2:50])[CH:45]=2)[N:12]=1)([OH:7])=[O:6]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 24386Thionyl ChlorideHCID 19433728HCID 19433728, compoundHCID 19692717HCID 19692717, compound

Product 1

HCID 86750839HCID 86750839, compound

Reagents, catalysts & solvents 3

HCID 1140TolueneSolvent2×HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a cooled (0° C.) solution of SOCl2 (0.51 mL, 7.0 mmol) in dry toluene (2 mL) under an argon atmosphere was added a solution of 2-(E-2-carboxymethylethenyl)-3-[8-(4-methoxyphenyl)octyloxy]-6-hydroxymethylpyridine (300 mg, 0.70 mmol) in toluene (5 mL). After 5 minutes the cooling bath was removed and the reaction was stirred for 2 hours at room temperature. The toluene and excess SOCl2 were evaporated. To this was added dry DMF (0.90 mL), 3-aminophenol t butylcarbamate (209 mg, 1.0 mmol), and anhydrous Cs2CO3 (1.63 g, 5.0 mmol). The reaction was heated at 90° C. under an atmosphere of argon for 2 hours. Upon cooling to room temperature the reaction was diluted with EtOAc and washed with H2O, 10% NaOH, H2O, and brine and dried (MgSO4). Purification by flash column chromatography (silica, EtOAc:hexane:CH2Cl2, 7:63:30) yielded a colorless oil: 1H NMR (250 MHz, CDCl3) δ 8.09 (d, J=15.7 Hz, 1H, olefin), 7.44 (d, J=8.6 Hz, 1H, aryl), 7.15 (m, 5H, aryl), 7.05 (d, J=15.7 Hz, 1H, olefin), 6.90 (m, 1H, aryl), 6.82 (d, J=8.6 Hz, 2H, aryl), 6.65 (m, 1H, aryl), 6.51 (s, 1H, NH), 5.12 (s, 2H, CH2 --O), 4.0 (t, J=6.5 Hz, 2H, O--CH2), 3.81 (s, 3H, methyl ester), 3.78 (s, 3H, OMe), 2.54 (t, J=7.6 Hz, 2H, benzylic), 1.88 (m, 2H, CH2), 1.51 (s, 9H, t butyl), 1.46 (m, 10H, aliphatic).

Workup

  1. customAfter 5 minutes the cooling bath was removed
  2. customThe toluene and excess SOCl2 were evaporated
  3. temperatureThe reaction was heated at 90° C. under an atmosphere of argon for 2 hours
  4. temperatureUpon cooling to room temperature the reaction
  5. washwashed with H2O, 10% NaOH, H2O, and brine
  6. dry with materialdried (MgSO4)
  7. customPurification by flash column chromatography (silica, EtOAc:hexane:CH2Cl2, 7:63:30)
  8. customyielded a colorless oil

Sources & evidence

ORD record
ord-3e00061d05f742f89b585d9476b78f3c
Source dataset
uspto-grants-1997_05
Patent number
US05631262

Reaction notes

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