Triethylamine → HCID 70982646, compound

HRID 1468698Notes

Reaction equation

HRID 1468698 reaction equation
[Br:1][C:2]1[S:3][C:4]2[C:10]([OH:11])=[CH:9][C:8]([CH3:12])=[CH:7][C:5]=2[N:6]=1.C(N(CC)CC)C.[C:20]([O:24][CH2:25][CH3:26])(=[O:23])[CH:21]=[O:22].C(C(C(C([O-])=O)O)O)([O-])=O.[Na+].[K+]>C(Cl)Cl.[Ti](Cl)(Cl)(Cl)Cl.O>[Br:1][C:2]1[S:3][C:4]2[C:10]([OH:11])=[C:9]([CH:21]([OH:22])[C:20]([O:24][CH2:25][CH3:26])=[O:23])[C:8]([CH3:12])=[CH:7][C:5]=2[N:6]=1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 70211Ethyl oxoacetateHCID 9855836Potassium sodium tartarateHCID 70981527HCID 70981527, compound

Product 1

HCID 70982646HCID 70982646, compoundYield 44.8%

Reagents, catalysts & solvents 3

HCID 24193Titanium TetrachlorideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of 27 (3.90 g, 16.0 mmol) in CH2Cl2 (80 mL) at 0° C. was added triethylamine (2.45 mL, 16.8 mmol) then a solution of titanium tetrachloride in CH2Cl2 (1.0 M, 16.8 mL, 16.8 mmol). After 15 min, ethyl glyoxalate (50% in toluene, 3.49 mL, 17.6 mmol) was added. The reaction mixture was stirred for 2 h while warming to room temperature. Water (50 mL) and a saturated solution of potassium sodium tartrate (50 mL) were added. The mixture was stirred vigorously for 2 h. The layers were separated, and the aqueous layer was extracted with CH2Cl2. The combined organic layers were dried, filtered, and concentrated in vacuo. The crude material was purified by column chromatography to give 2.48 g of 28 and recovered ˜500 mg of 27. 1H-NMR: 400 MHz, (CD3OH) δ: 7.33 (s, 1H), 5.69 (s, 1H), 4.17 (m, 2H), 2.50 (s, 3H), 1.18 (t, 3H, J=7 Hz). LCMS-ESI+: calc'd for C12H13BrNO4S: 346.0 (M+H+). Found: 346.1 (M+H+).

Workup

  1. stirringThe mixture was stirred vigorously for 2 h
  2. customThe layers were separated
  3. extractionthe aqueous layer was extracted with CH2Cl2
  4. customThe combined organic layers were dried
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe crude material was purified by column chromatography

Sources & evidence

ORD record
ord-c38000ffcd8a40bdb018731f8d76fb42
Source dataset
uspto-grants-2015_04
Patent number
US09006229B2

Reaction notes

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