Tributyltin Chloride → Hydrochloric Acid

HRID 1628259Notes

Reaction equation

HRID 1628259 reaction equation
C([Sn]([Cl:14])(CCCC)CCCC)CCC.[N-:15]=[N+:16]=[N-:17].[Na+].[C:19]([CH2:21][NH:22][C@@H:23]([CH2:41][C:42]1[CH:47]=[CH:46][C:45]([F:48])=[CH:44][CH:43]=1)[C:24]([NH:26][C:27]1[N:31]([CH3:32])[N:30]=[C:29]([C:33]2[CH:38]=[CH:37][N:36]=[C:35]([NH:39][CH3:40])[CH:34]=2)[CH:28]=1)=[O:25])#[N:20]>CN(C=O)C.O>[NH:15]1[C:19]([CH2:21][NH:22][C@@H:23]([CH2:41][C:42]2[CH:43]=[CH:44][C:45]([F:48])=[CH:46][CH:47]=2)[C:24]([NH:26][C:27]2[N:31]([CH3:32])[N:30]=[C:29]([C:33]3[CH:38]=[CH:37][N:36]=[C:35]([NH:39][CH3:40])[CH:34]=3)[CH:28]=2)=[O:25])=[N:20][N:17]=[N:16]1.[ClH:14]

Participants

7

Reactant 3

HCID 15096Tributyltin ChlorideHCID 33557Sodium AzideHCID 86664830HCID 86664830, compound

Product 2

HCID 313Hydrochloric AcidHCID 178482067HCID 178482067, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
160 °C

Procedure

To neat tributyltin chloride (1250 μl, 4608 μmol) was added sodium azide (271 μl, 7691 μmol). After sting at 80° C. for 30 mins, to the mixture was added a solution of 23.E (178 mg, 437 μmol) in DMF. The resulting mixture was stirred at 160° C. under N2 for 1.5 hr, cooled and diluted with water. The resulting mixture was extracted with 30% iPrOH/CHCl3 (3×10 mL), and organic solvents was removed under reduced pressure. After purification of the residue by preparative HPLC (10-90% CH3CN/water, 30 min), the combined product fractions were treated with 1.0 N HCl (0.50 ml) and concentrated to provide 23.11 HCl salt colorless solid (121 mg, 57%) as. MS ESI (positve.) m/e: 451.1 (M+H), 1H NMR (400 MHz, CD3OD) δ ppm 7.82 (d, J=6.65 Hz, 1H), 7.23-7.45 (m, 4H), 7.11 (t, J=8.61 Hz, 2H), 6.88 (s, 1H), 4.71 (s, 2H), 4.60 (br. s., 1H) 3.63 (s, 3H) 3.42-3.54 (m, 1H), 3.20-3.29 (m, 1H), 3.01-3.11 (m, 4H).

Workup

  1. temperaturecooled
  2. extractionThe resulting mixture was extracted with 30% iPrOH/CHCl3 (3×10 mL), and organic solvents
  3. customwas removed under reduced pressure
  4. customAfter purification of the residue by preparative HPLC (10-90% CH3CN/water, 30 min)
  5. additionthe combined product fractions were treated with 1.0 N HCl (0.50 ml)
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-f3c5067ae6cd47e3a7973ce893dd9ef0
Source dataset
uspto-grants-2014_07
Patent number
US08785468B2

Reaction notes

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