Diisopropylamine → HCID 86638418, compound

HRID 1662889Notes

Reaction equation

HRID 1662889 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3][CH3:4].C(N[CH:10]([CH3:12])[CH3:11])(C)C.[CH2:13]([O:17][P:18]([C:25]1[CH:29]=[CH:28][S:27][CH:26]=1)([O:20][CH2:21][CH2:22][CH2:23][CH3:24])=[O:19])[CH2:14][CH2:15][CH3:16].[CH2:30]([Sn:34](Cl)([CH2:39][CH2:40][CH2:41][CH3:42])[CH2:35][CH2:36][CH2:37][CH3:38])[CH2:31][CH2:32][CH3:33].P([O-])([O-])(O)=O.[Na+].[Na+].P([O-])(O)(O)=O.[Na+]>C1COCC1>[CH2:13]([O:17][P:18]([C:25]1[CH:29]=[C:28]([Sn:34]([CH2:39][CH2:40][CH2:41][CH3:42])([CH2:35][CH2:36][CH2:37][CH3:38])[CH2:30][CH2:31][CH2:32][CH3:33])[S:27][C:26]=1[Sn:34]([CH2:35][CH2:12][CH2:10][CH3:11])([CH2:30][CH2:31][CH2:32][CH3:33])[CH2:1][CH2:2][CH2:3][CH3:4])([O:20][CH2:21][CH2:22][CH2:23][CH3:24])=[O:19])[CH2:14][CH2:15][CH3:16]

Participants

7

Reactant 5

HCID 7912DiisopropylamineHCID 15096Tributyltin ChlorideHCID 59155845HCID 59155845, compoundHCID 86630341Sodium phosphate (Na3(PO4)2)HCID 178418339Butyllithium

Product 1

HCID 86638418HCID 86638418, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Commercially available n-butyl lithium (1.59 M hexane solution, 45.0 mmols) was slowly dropped in a THF solution of 4.55 g (45.0 mmols) of commercially available diisopropylamine, cooled to −78° C. After stirring for 1 hour, this solution was slowly dropped in a separately prepared solution, cooled to −78° C., of 4.97 g (18.0 mmols) of 3-(dibutoxyphosphoryl)thiophene dissolved in THF, followed by stirring for 2 hours at a standing temperature. Thereafter, 14.6 g (45.0 mmols) of commercially available tributylstannyl chloride was dropped, followed by stirring for 4.5 hours. After completion of the reaction, a disodium hydrogen phosphate/sodium dihydrogen phosphate buffer solution, adjusted to pH=7, was added so as to complete the reaction, followed by extraction with ethyl acetate. The organic phase was washed with a saturated saline solution and dried over anhydrous sodium sulfate. The solvent was removed by distilling off under reduced pressure, and the resulting crude product was purified with a silica gel column (gradiated from hexane with ethyl acetate:hexane=1:10) to obtain the specified substance in the form of a transparent oil at a yield of 12.35 g (yield: 80%). The thus obtained substance was used as it is for reaction in Example 12(17).

Workup

  1. additionthis solution was slowly dropped in a separately prepared solution
  2. stirringby stirring for 2 hours at a standing temperature
  3. stirringby stirring for 4.5 hours
  4. customAfter completion of the reaction
  5. additionwas added so as
  6. customthe reaction
  7. extractionfollowed by extraction with ethyl acetate
  8. washThe organic phase was washed with a saturated saline solution
  9. dry with materialdried over anhydrous sodium sulfate
  10. customThe solvent was removed
  11. distillationby distilling off under reduced pressure
  12. customthe resulting crude product was purified with a silica gel column (gradiated from hexane with ethyl acetate:hexane=1:10)
  13. customto obtain the specified substance in the form of a transparent oil at a yield of 12.35 g (yield: 80%)
  14. customis for reaction in Example 12(17)

Sources & evidence

ORD record
ord-0caad54657064151bd18907429552b31
Source dataset
uspto-grants-2011_10
Patent number
US08030438B2

Reaction notes

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