Oxalyl chloride → HCID 54059945, compound

HRID 612054Notes

Reaction equation

HRID 612054 reaction equation
[Br:1][CH2:2]/[CH:3]=[CH:4]/[C:5]([OH:7])=O.C(Cl)(=O)C(Cl)=O.[NH2:14][C:15]1[CH:16]=[C:17]2[C:22](=[CH:23][CH:24]=1)[N:21]=[CH:20][C:19]([C:25]#[N:26])=[C:18]2[NH:27][C:28]1[CH:33]=[CH:32][CH:31]=[C:30]([Br:34])[CH:29]=1.C(N(C(C)C)CC)(C)C>ClCCl.CN(C)C=O.O1CCCC1.C(OCC)(=O)C.O>[Br:34][C:30]1[CH:29]=[C:28]([NH:27][C:18]2[C:17]3[C:22](=[CH:23][CH:24]=[C:15]([NH:14][C:5](=[O:7])[CH:4]=[CH:3][CH2:2][Br:1])[CH:16]=3)[N:21]=[CH:20][C:19]=2[C:25]#[N:26])[CH:33]=[CH:32][CH:31]=1

Participants

10

Reactant 4

HCID 65578Oxalyl chlorideHCID 81531DiisopropylethylamineHCID 64364114-Bromocrotonic acidHCID 99677126-Amino-4-(3-bromophenylamino)quinoline-3-carbonitrile

Product 1

HCID 54059945HCID 54059945, compoundYield 68.1%

Reagents, catalysts & solvents 5

HCID 6228DimethylformamideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A solution of 1.65 grams (0.01 mole) of 4-bromo crotonic acid (Giza Braun, J. Am. Chem. Soc. 52, 3167 1930) in 15 ml of dichloromethane was treated with 1.74 ml (0.02 moles) of oxalyl chloride and 1 drop of N,N-dimethylformamide. After an hour the solvents were removed on the rotary evaporator. The residual oil was taken up in ml of tetrahydrofuran, and 3.39 grams of 6-Amino-4-(3-bromo-phenylamino)-quinoline-3-carbonitrile in 25 ml of tetrahydrofuran was added dropwise. This was followed by the dropwise addition of 1.92 ml (0.011 moles) of diisopropylethylamine. After the addition of 25 ml of water and 50 ml of ethyl acetate, the layers were separated. The organic layer was dried over anhydrous sodium sulfate, and taken to a solid in vacuo. This solid was digested for an hour with refluxing ethyl acetate then filtered from the ethyl acetate while still hot. Thus was obtained 3.31 grams (68%) of 4-bromo-but-2-enoic acid [4-(3-bromo-phenylamino)-3-cyano-quinolin-6-yl]-amide.

Workup

  1. customAfter an hour the solvents were removed on the rotary evaporator
  2. customthe layers were separated
  3. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  4. waitThis solid was digested for an hour with refluxing ethyl acetate
  5. filtrationthen filtered from the ethyl acetate while still hot

Sources & evidence

ORD record
ord-22e8c43321954b42a105ee47fb58717e
Source dataset
uspto-grants-1999_12
Patent number
US06002008

Reaction notes

Loading…