Oxalyl chloride → HCID 178436308, compound

HRID 2233766Notes

Reaction equation

HRID 2233766 reaction equation
C(Cl)(=O)C(Cl)=O.[CH:7]([C:9]1[CH:10]=[C:11]([CH:15]=[CH:16][CH:17]=1)[C:12]([OH:14])=O)=[CH2:8].C(C1C=C(C=CC=1)C(Cl)=O)=C.[F:29][C:30]1[CH:31]=[C:32]([C:37](=[O:48])[CH:38]=[C:39]2[NH:43][C:42]3[CH:44]=[CH:45][CH:46]=[CH:47][C:41]=3[NH:40]2)[CH:33]=[C:34]([F:36])[CH:35]=1.C(=O)(O)[O-].[Na+]>COCCOCCOC.O.CN(C=O)C.C(Cl)Cl>[F:29][C:30]1[CH:31]=[C:32]([C:37](=[O:48])[C:38](=[C:39]2[NH:40][C:41]3[CH:47]=[CH:46][CH:45]=[CH:44][C:42]=3[NH:43]2)[C:12]([C:11]2[CH:15]=[CH:16][CH:17]=[C:9]([CH:7]=[CH2:8])[CH:10]=2)=[O:14])[CH:33]=[C:34]([F:36])[CH:35]=1

Participants

10

Reactant 5

HCID 65578Oxalyl chlorideHCID 516892Sodium BicarbonateHCID 44382313-Vinylbenzoic AcidHCID 125414943-Vinylbenzoyl chlorideHCID 1785203801-(3,5-difluorophenyl)-2-(1,3-dihydrobenzimidazol-2-ylidene)ethanone

Product 1

HCID 178436308HCID 178436308, compoundYield 68.5%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolventHCID 8150DiglymeSolvent2×

Conditions

Temperature
70 °C

Procedure

A 3.8 g portion of oxalic acid chloride was gradually added dropwise to 30 ml of methylene chloride solution containing 1.54 g of 3-vinylbenzoic acid and a catalytically effective amount of DMF and stirred at room temperature for about 2 hours, and then an appropriate amount of Tol was poured into the mixture and evaporation was carried out under a reduced pressure, thereby preparing 3-vinylbenzoic acid chloride. This was dissolved in a small amount of Diglyme and gradually added dropwise to 5 ml of Diglyme solution containing 0.82 g of 1-(3,5-difluorophenyl)-2-(1,3-dihydro-2H-benzimidazol-2-ylidene)ethanone which had been separately prepare in advance and 1.4 ml of TEA, under heating at 70° C. After completion of the dropwise addition, this was risen to 100° C. and heated for about 25 minutes, mixed with 0.1 ml of purified water, and further risen to 175° C. and heated for about 25 minutes. This was mixed with sodium bicarbonate aqueous solution, extracted several times with ethyl acetate, dried with anhydrous magnesium sulfate and concentrated, and then the thus formed residue was purified by a silica gel column chromatography to obtain 0.83 g (Reference Example 2-1) (68%) of 1-(3,5-difluorophenyl)-2-(1,3-dihydro-2H-benzimidazol-2-ylidene)-3-(3-vinylphenyl)propane-1,3-dione as a yellow foam compound from an ethyl acetate-hexane (1:3) eluate. FA: 403

Workup

  1. additionan appropriate amount of Tol was poured into the mixture and evaporation
  2. additionAfter completion of the dropwise addition
  3. customthis was risen to 100° C.
  4. temperatureheated for about 25 minutes
  5. customfurther risen to 175° C.
  6. temperatureheated for about 25 minutes
  7. extractionextracted several times with ethyl acetate
  8. dry with materialdried with anhydrous magnesium sulfate
  9. concentrationconcentrated
  10. customthe thus formed residue was purified by a silica gel column chromatography

Sources & evidence

ORD record
ord-e3c706d6c660467a97c415a32f52336b
Source dataset
uspto-grants-2010_05
Patent number
US07709519B2

Reaction notes

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