Toluene → HCID 54466218, compound

HRID 1387416Notes

Reaction equation

HRID 1387416 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:17]=[C:18]([Br:21])[C:19]=1[OH:20])[CH:5]=[C:6]1[C:14]2[C:9](=[CH:10][CH:11]=[C:12]([I:15])[CH:13]=2)[NH:8][C:7]1=[O:16].CC(C)([O-])C.[K+].[C:28](Cl)(Cl)=[O:29].C1(C)C=CC=CC=1.[NH2:39][CH2:40][CH2:41][O:42][CH2:43][CH2:44][OH:45].CN1CCOCC1>C1COCC1.CCOCC>[OH:45][CH2:44][CH2:43][O:42][CH2:41][CH2:40][NH:39][C:28](=[O:29])[O:20][C:19]1[C:18]([Br:21])=[CH:17][C:4]([CH:5]=[C:6]2[C:14]3[C:9](=[CH:10][CH:11]=[C:12]([I:15])[CH:13]=3)[NH:8][C:7]2=[O:16])=[CH:3][C:2]=1[Br:1]

Participants

9

Reactant 6

HCID 1140TolueneHCID 5034220904-83-6HCID 6371PhosgeneHCID 79724-MethylmorpholineHCID 13578DiglycolamineHCID 23665647Potassium tert-butoxide

Product 1

HCID 54466218HCID 54466218, compoundYield 79%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of 3-(3,5-Dibromo-4-hydroxy-benzylidene)-5-iodo-1,3-dihydro-indol-2-one (210 mg, 0.40 mmol) in 20 ml of THF under nitrogen was added 1M potassium t-butoxide in THF (0.40 ml, 0.40 mmol) dropwise via syringe. The solution was cooled to 0° C. and 1.97M phosgene in toluene (0.21 ml, 0.41 mmol) was added dropwise via syringe and the reaction mixture was stirred 10 minutes. 2-(2-Aminoethoxy)ethanol (40 μl, 0.40 mmol) was then added via syringe followed by N-methyl morpholine (˜45 mg, ˜45 mmol). The reaction mixture was stirred 10 minutes at 0° C. and then allowed to warm to room temperature. The solution was diluted with an equal volume of ether, filtered through a fine frit to clarify, and further diluted with 10 ml of ether. The product was then precipitated by the addition of ˜80 ml of hexanes and was filtered and washed with more hexanes to give 0.21 g (79%) of the title compound as a yellow solid. 1H NMR (400 MHz, DMSO-d6) 6: 10.77 (s, 1H), 8.24 (t, J=5.6 Hz, 1H), 8.02 (s, 2H), 7.6 (s, 1H), 7.57 (s, 1H), 7.55 (dd, J=8.2, 1.6 Hz, 1H), 6.71 (d, J=8.2 Hz, 1H), 4.58 (br t, 1H), 3.52-3.42 (m, 6H), 3.27-3.20 (m, 2H). ESI-MS m/z 673, 675, 677 (M+23). Anal. Calcd. for C20H17Br2IN2O5: C, 36.84; H, 2.63; N, 4.30. Found: C, 36.75; H, 2.60; N, 4.22.

Workup

  1. stirringThe reaction mixture was stirred 10 minutes at 0° C.
  2. temperatureto warm to room temperature
  3. filtrationfiltered through a fine frit
  4. additionfurther diluted with 10 ml of ether
  5. customThe product was then precipitated by the addition of ˜80 ml of hexanes
  6. filtrationwas filtered
  7. washwashed with more hexanes

Sources & evidence

ORD record
ord-caed062bc4cd45cab2912497a94c56a4
Source dataset
uspto-grants-2001_07
Patent number
US06268391B1

Reaction notes

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