Tin tetrachloride → HCID 178489077, compound

HRID 2173951Notes

Reaction equation

HRID 2173951 reaction equation
[C:1]([C:3]1[CH:51]=[CH:50][C:6]2[N:7](COCC[Si](C)(C)C)[C:8]([C:10]([C:23]3[C:31]([O:32][CH3:33])=[CH:30][C:29]([CH3:34])=[C:28]4[C:24]=3[CH:25]=[CH:26][N:27]4C(OC(C)(C)C)=O)([O:15][CH2:16][C:17]3[O:18][C:19]([CH3:22])=[N:20][N:21]=3)[C:11]([F:14])([F:13])[F:12])=[N:9][C:5]=2[CH:4]=1)#[N:2].C(C1C=CC2N=C(C(C3C(OC)=CC(C)=C4C=3C=CN4C(OC(C)(C)C)=O)(OCC3OC(C)=NN=3)C(F)(F)F)N(COCC[Si](C)(C)C)C=2C=1)#N.Cl[Sn](Cl)(Cl)Cl.C(=O)(O)[O-].[Na+]>ClCCl.C(OCC)(=O)C>[F:14][C:11]([F:12])([F:13])[C:10]([C:8]1[NH:7][C:6]2[CH:50]=[CH:51][C:3]([C:1]#[N:2])=[CH:4][C:5]=2[N:9]=1)([C:23]1[C:31]([O:32][CH3:33])=[CH:30][C:29]([CH3:34])=[C:28]2[C:24]=1[CH:25]=[CH:26][NH:27]2)[O:15][CH2:16][C:17]1[O:18][C:19]([CH3:22])=[N:20][N:21]=1

Participants

7

Reactant 4

HCID 24287Tin tetrachlorideHCID 516892Sodium BicarbonateHCID 86701513HCID 86701513, compoundHCID 86701514HCID 86701514, compound

Product 1

HCID 178489077HCID 178489077, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of (±)-tert-butyl 4-(1-(5-cyano-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-benzo[d]imidazol-2-yl)-2,2,2-trifluoro-1-((5-methyl-1,3,4-oxadiazol-2-yl)methoxy)ethyl)-5-methoxy-7-methyl-1H-indole-1-carboxylate compound and (±)-tert-butyl 4-(1-(6-cyano-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-benzo[d]imidazol-2-yl)-2,2,2-trifluoro-1-((5-methyl-1,3,4-oxadiazol-2-yl)methoxy)ethyl)-5-methoxy-7-methyl-1H-indole-1-carboxylate (Example 35-K) (38 mg, 0.051 mmol) in dichloromethane (1.0 mL) at 0° C. was added a 1.0M solution of SnCl4 in dichloromethane (0.51 mL, 0.51 mmol). This mixture was stirred at 0° C. for 30 min and then warmed to room temperature and stirred for an additional 1.0 hr. The crude reaction mixture was diluted with ethyl acetate and a saturated sodium bicarbonate solution and the layers were passed over Celite® and then separated. The organic phase was washed with brine solution, dried over sodium sulfate, and concentrated in vacuo. The crude product was purified using FCC eluting with ethyl acetate/heptane (0-100%) to afford the title compound. 1H NMR (400 MHz, DMSO-d6) δ ppm 13.00 (br.s., 1H) 11.10 (br. s., 1H) 8.30 (s, 1H) 7.82-7.93 (m, 1H) 7.49-7.64 (m, 1H) 7.36 (t, J=2.91 Hz, 1H) 6.76 (s, 1H) 6.68 (br. s., 1H) 4.47-4.82 (m, 2H) 3.11 (s, 3H) 2.40 (s, 3H) 1.24 (s, 3H). HRMS calcd. for C24H19F3N6O3 (M+H)+ 497.1535. found 497.1504.

Workup

  1. temperaturewarmed to room temperature
  2. stirringstirred for an additional 1.0 hr
  3. customThe crude reaction mixture
  4. customseparated
  5. washThe organic phase was washed with brine solution
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe crude product was purified
  9. washeluting with ethyl acetate/heptane (0-100%)

Sources & evidence

ORD record
ord-1191d930afad4165b530a5a3414782b4
Source dataset
uspto-grants-2015_06
Patent number
US09056874B2

Reaction notes

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