Oxalyl chloride → HCID 14877952, compound

HRID 1085743Notes

Reaction equation

HRID 1085743 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:18]2[CH:23]=[CH:22][C:21]([F:24])=[CH:20][CH:19]=2)=[C:9]([N:13]2[CH:17]=[N:16][N:15]=[N:14]2)[C:10](O)=[O:11])=[CH:4][CH:3]=1.C(Cl)(=O)C(Cl)=O.[H-].[Al+3].[Li+].[H-].[H-].[H-]>C1C=CC=CC=1.N1C=CC=CC=1>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:18]2[CH:19]=[CH:20][C:21]([F:24])=[CH:22][CH:23]=2)=[C:9]([N:13]2[CH:17]=[N:16][N:15]=[N:14]2)[CH2:10][OH:11])=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 65578Oxalyl chlorideHCID 14877951HCID 14877951, compoundHCID 21226445Aluminium lithium hydride

Product 1

HCID 14877952HCID 14877952, compoundYield 88.7%

Reagents, catalysts & solvents 2

HCID 1049PyridineCatalystHCID 241BenzeneSolvent

Conditions

Temperature
-80 °C

Procedure

The crude acid from Step A was suspended in 12 mL of dry benzene and the mixture was treated with 350 mL of oxalyl chloride. To this suspension was added one drop of pyridine and a very vigorous reaction was apparent The clear homogenous solution was warmed to reflux temperature for 10 minutes then kept at about 70° C. for 2 days under an argon atmosphere. Most of the solvents were evaporated under high vacuum and the semi-solid was dissolved in 6 mL of tetrahydrofuran. To this chilled (-80° C., dry ice-acetone) solution under argon was added dropwise 0.5 mL (0.5 mmole, 1.OM in tetrahydrofuran) of lithium aluminum hydride and the reduction was complete in one hour. The crude reaction mixture was quenched with 2.OM HCl and the organic residue was extracted with ethyl acetate, dried and evaporated to give 0.21 g (88.7%) of the title compound which was pure enough to be used in the next step.

Workup

  1. customa very vigorous reaction
  2. temperaturewas warmed
  3. temperatureto reflux temperature for 10 minutes
  4. customMost of the solvents were evaporated under high vacuum
  5. dissolutionthe semi-solid was dissolved in 6 mL of tetrahydrofuran
  6. waitthe reduction was complete in one hour
  7. customThe crude reaction mixture
  8. customwas quenched with 2.OM HCl
  9. extractionthe organic residue was extracted with ethyl acetate
  10. customdried
  11. customevaporated

Sources & evidence

ORD record
ord-137e19fb48e84508a9b31fba01a561cb
Source dataset
uspto-grants-1991_04
Patent number
US05010205

Reaction notes

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