Oxalyl chloride → HCID 68773723, compound

HRID 1174891Notes

Reaction equation

HRID 1174891 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:10]=[CH:11][CH:12]=1)[CH:5]=[CH:6][C:7]([OH:9])=O.C(Cl)(=O)C(Cl)=O.[CH3:19][N:20]([CH3:36])[CH:21]1[CH2:25][CH2:24][N:23]([C:26]2[S:27][C:28]3[CH:34]=[C:33]([NH2:35])[CH:32]=[CH:31][C:29]=3[N:30]=2)[CH2:22]1>CN(C=O)C.C(Cl)Cl>[Cl:1][C:2]1[CH:3]=[C:4]([CH:5]=[CH:6][C:7]([NH:35][C:33]2[CH:32]=[CH:31][C:29]3[N:30]=[C:26]([N:23]4[CH2:24][CH2:25][CH:21]([N:20]([CH3:36])[CH3:19])[CH2:22]4)[S:27][C:28]=3[CH:34]=2)=[O:9])[CH:10]=[CH:11][CH:12]=1

Participants

6

Reactant 3

HCID 65578Oxalyl chlorideHCID 746313-(3-Chlorophenyl)prop-2-enoic acidHCID 632315072-(3-Dimethylamino-pyrrolidin-1-yl)-benzothiazol-6-ylamine

Product 1

HCID 68773723HCID 68773723, compoundYield 49.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent3×

Procedure

Combine 3-chlorocinnamic acid (0.104 g, 0.572 mmol), CH2Cl2 (13 mL), and DMF (3 drops) with stirring. Add oxalyl chloride (0.17 mL, 1.91 mmol) and stir the mixture for 2.5 h at room temperature. Concentrate the mixture in vacuo, add hexane (approximately 10 mL), re-concentrate in vacuo, and add CH2Cl2 (4.0 mL). Transfer the mixture to a 40 mL reaction vial and add a mixture of 2-(3-dimethylamino-pyrrolidin-1-yl)-benzothiazol-6-ylamine (0.100 g, 0.381 mmol) (Example 1, step 3) in CH2Cl2 (5.0 mL). Shake the reaction vial for 1 h at room temperature. Dilute the reaction mixture with CH2Cl2 (25 mL), wash with 1.0 M NaOH (aqueous) (4×25 mL), dry over sodium sulfate, filter, and concentrate in vacuo. Purify the residue using silica gel chromatography (12 g column, 10-20% MeOH(CH2Cl2) to afford the title compound as a yellow solid (80 mg, 49%). mass spectrum (m/e): 427.2 [M+1], 425.2 [M−1]. 1H NMR (400 MHz, CDCl3 (spiked with CD3OD)): δ 8.28 (s, 1H), 7.61 (d, 1H, J=15.6 Hz), 7.47-7.43 (m, 2H), 7.32 (d, 1H, J=7.2 Hz), 7.30-7.23 (m, 2H), 7.19 (dd, 1H, J=8.8, 2.0 Hz), 6.57 (d, 1H, J=15.6 Hz), 3.78 (t, 1H, J=8.8 Hz), 3.68 (t, 1H, J=10.0 Hz), 3.50 (m, 1H), 3.36 (t, 1H, J=9.2 Hz), 2.88 (m, 1H), 2.29 (s, 6H), 2.23 (m, 1H), 1.97 (m, 1H).

Workup

  1. concentrationConcentrate the mixture in vacuo
  2. additionadd hexane (approximately 10 mL)
  3. concentrationre-concentrate in vacuo
  4. additionadd CH2Cl2 (4.0 mL)
  5. customTransfer the mixture to a 40 mL reaction vial
  6. additionadd
  7. customShake the reaction vial for 1 h at room temperature
  8. washwash with 1.0 M NaOH (aqueous) (4×25 mL)
  9. dry with materialdry over sodium sulfate
  10. filtrationfilter
  11. concentrationconcentrate in vacuo
  12. customPurify the residue

Sources & evidence

ORD record
ord-dd2a35c035704521a9c3f4af390d5294
Source dataset
uspto-grants-2010_11
Patent number
US07838543B2

Reaction notes

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