Dimethylformamide → HCID 86684913, compound

HRID 2402908Notes

Reaction equation

HRID 2402908 reaction equation
F[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][N:11]=[C:10]([CH3:14])[CH:9]=2)=[CH:4][C:3]=1[C:15]([F:18])([F:17])[F:16].[CH3:19][C:20]([SH:23])([CH3:22])[CH3:21].CN(C=O)C.CC(C)([O-])C.[Na+]>C1COCC1.CC(OC)(C)C>[C:20]([S:23][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][N:11]=[C:10]([CH3:14])[CH:9]=2)=[CH:4][C:3]=1[C:15]([F:18])([F:17])[F:16])([CH3:22])([CH3:21])[CH3:19]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 6387tert-Butyl mercaptanHCID 23676156Sodium t-butoxideHCID 86684912HCID 86684912, compound

Product 1

HCID 86684913HCID 86684913, compoundYield 100.6%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
50 °C

Procedure

To a solution of 4-(4-Fluoro-3-trifluoromethyl-phenyl)-2-methyl-pyridine (51.0 g, ˜200 mmol) in THF (100 mL) were carefully added at room temperature 2-methyl-2-propanethiol (23.5 g, 260 mmol) and DMF (29.2 g, 400 mmol). Sodium-tert-butoxide solution 25% in THF (96.1 g=106 mL, 250 mmol, Chemetall) was added over 50 min and the beige suspension was stirred at 50° C. for 17 h. The brownish suspension was transferred into a separatory funnel, filled with TBME (500 mL), and washed with water (500 mL) and with 10% brine (500 mL). The two aqueous layers were extracted with TBME (300 mL) and the combined organic layers were dried (Na2SO4). Filtration and evaporation (45° C./≧10 mbar) afforded crude title product (65.5 g, 100.6%) as a brown oil which was used without purification in the next step. 1H NMR (CDCl3, 400 MHz) δ 1.39 (s, 9H), 2.65 (s, 3H), 7.33 (d, J=5.1 Hz, 1H), 7.39 (s, 1H), 7.73 (dd, J1=8.1 Hz, J2=1.9 Hz, 1H), 7.83 (d, J=8.1 Hz, 1H), 7.96 (d, J=1.9, 1H), 8.60 (d, J=5.4, 1H). ESI-MS (m/z) [M+H]+326 (100).

Workup

  1. customThe brownish suspension was transferred into a separatory funnel
  2. washwashed with water (500 mL) and with 10% brine (500 mL)
  3. extractionThe two aqueous layers were extracted with TBME (300 mL)
  4. dry with materialthe combined organic layers were dried (Na2SO4)
  5. filtrationFiltration and evaporation (45° C./≧10 mbar)

Sources & evidence

ORD record
ord-a14f6429b5354030aef5e75dc312c4bd
Source dataset
uspto-grants-2014_08
Patent number
US08796471B2

Reaction notes

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