Pivaloyl chloride → HCID 25130825, compound

HRID 1942993Notes

Reaction equation

HRID 1942993 reaction equation
[NH2:1][C:2]1[S:3][C:4]([C:9]2[N:10]=[C:11]([NH:15][C:16]3[CH:21]=[C:20]([Cl:22])[CH:19]=[CH:18][C:17]=3[O:23][CH3:24])[S:12][C:13]=2[CH3:14])=[C:5]([CH2:7][CH3:8])[N:6]=1.[C:25](Cl)(=[O:30])[C:26]([CH3:29])([CH3:28])[CH3:27]>C(Cl)Cl>[Cl:22][C:20]1[CH:19]=[CH:18][C:17]([O:23][CH3:24])=[C:16]([NH:15][C:11]2[S:12][C:13]([CH3:14])=[C:9]([C:4]3[S:3][C:2]([NH:1][C:25](=[O:30])[C:26]([CH3:29])([CH3:28])[CH3:27])=[N:6][C:5]=3[CH2:7][CH3:8])[N:10]=2)[CH:21]=1

Participants

4

Reactant 2

HCID 62493Pivaloyl chlorideHCID 25130142HCID 25130142, compound

Product 1

HCID 25130825HCID 25130825, compoundYield 66.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a suspension of 16z (0.50 g, 1.1 mmol) in DCM (55 mL) was added TEA (395 μL, 2.84 mmol). Pivaloyl chloride (174 μL, 1.42 mmol) was then added to the suspension in one portion and the reaction mixture was stirred at room temperature for 10 min at which time TLC indicated reaction completion. The reaction mixture was washed with cold water and extracted with DCM (2×). The organic layer was dried over anhydrous sodium sulfate and filtered and DCM was removed in vacuo. The resulting solid was purified by silica gel column chromatography (hexane:ethyl acetate=4:1 eluent) to yield 17z as a light orange powder (0.34 g, 66%). Mp decomposition at 192° C. 1H NMR (400 MHz, CDCl3): δ 7.72 (d, J=2.8 Hz, 1H), 7.13 (dd, J=8.8 Hz, 2.8 Hz, 1H), 6.88 (d, J=8.8 Hz, 1H), 3.90 (s, 3H), 2.79 (q, J=7.6 Hz, 2H), 2.30 (s, 3H), 1.39 (s, 9H), 1.34 (t, J=7.6 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 178.6, 164.6, 164.2, 163.8, 162.2, 149.1, 144.9, 128.9, 125.5, 120.5, 113.8, 112.3, 104.9, 56.3, 40.1, 26.7, 21.4, 13.5, 12.2. HRMS m/z (ESI) calcd. for C21H25ClN4O2S2 (M+H)+ 465.1180. Found 465.1181.

Workup

  1. customreaction completion
  2. washThe reaction mixture was washed with cold water
  3. extractionextracted with DCM (2×)
  4. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. customDCM was removed in vacuo
  7. customThe resulting solid was purified by silica gel column chromatography (hexane:ethyl acetate=4:1 eluent)

Sources & evidence

ORD record
ord-87e0c7effae9493080d2f57b4e319b6c
Source dataset
uspto-grants-2013_03
Patent number
US08389736B2

Reaction notes

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