Bromoacetic Acid → HCID 85804820, compound

HRID 1591532Notes

Reaction equation

HRID 1591532 reaction equation
[Cl:1][C:2]1[S:10][C:5]2[N:6]=[C:7]([CH3:9])[S:8][C:4]=2[CH:3]=1.[Br:11][CH2:12][C:13]([OH:15])=[O:14].C1(C(C)C)C=CC=CC=1>CC(C)=O>[Br-:11].[C:13]([CH2:12][N+:6]1[C:5]2[S:10][C:2]([Cl:1])=[CH:3][C:4]=2[S:8][C:7]=1[CH3:9])([OH:15])=[O:14]

Participants

5

Reactant 3

HCID 6227Bromoacetic AcidHCID 7406CumeneHCID 68446708HCID 68446708, compound

Product 1

HCID 85804820HCID 85804820, compoundYield 59.2%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Conditions

Temperature
135 °C

Procedure

5- Chloro-2-methylthieno[2,3-d]thiazole (15.2 g), 13.3 g of bromoacetic acid and 24 ml of cumene were mixed and stirred with heating at outer temperature of 135° C. for 8 hours. After cooling the reaction mixture, 100 ml of acetone was added thereto. The crystals precipitated were filtered out by suction, washed with 50 ml of acetone, dried under reduced pressure, thereby 15.6 g of 3-carboxymethyl-5-chloro-2-methylthieno[2,3-d]thiazolium bromide (A) was obtained as yellow powder. To 7.4 g of (A), 18.5 g of 3-[5-chloro-2-(2-ethoxy-1-butenyl)-3-benzoxazolio]propanesulfonate and 70 ml of benzyl alcohol were added and stirred at room temperature. After that, 10.1 ml of 1,8-diazabicyclo[5.4.0]-7-undecene was added to the above mixture and stirred at outer temperature of 50° C. for 20 minutes, 1,000 ml of ethyl acetate was then added thereto, a supernatant was removed by decantation to obtain a residue. The residue was dissolved in methanol and refined by Sephadex column chromatography. The refined product was dissolved in 150 ml of methanol, 3 g of potassium acetate was added thereto, after heating under reflux for 10 minutes, the mixture was allowed to be cooled, and the crystals precipitated were filtered out by suction. Methanol (300 ml) was added to the above-obtained powder, and the solution was heated under reflux for 50 minutes, then the solution was concentrated by distilling off 100 ml of the solvent. After cooling, the obtained crystals were recoveredby suction filtration, the filtrate was washed with 50 ml of methanol and dried under reduced pressure, thereby 2.65 g of orange powder of S-96 was obtained. The structure of S-96 was confirmed by 1H-NMR, FAB-MS, and elemental analysis. λmax (MeOH)=535 nm (ε=8.3×104)

Workup

  1. additionwas added
  2. customThe crystals precipitated
  3. filtrationwere filtered out by suction
  4. washwashed with 50 ml of acetone
  5. customdried under reduced pressure

Sources & evidence

ORD record
ord-33951757949a4fa9965b8bacd93f1507
Source dataset
uspto-grants-2007_11
Patent number
US07291449B2

Reaction notes

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