Tributylstannane → 3-(4-Chlorophenyl)-3-methyl-1-tributylstannylbutanol

HRID 1441006Notes

Reaction equation

HRID 1441006 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH2:13]([SnH:17]([CH2:22][CH2:23][CH2:24][CH3:25])[CH2:18][CH2:19][CH2:20][CH3:21])[CH2:14][CH2:15][CH3:16].[Cl:26][C:27]1[CH:32]=[CH:31][C:30]([C:33]([CH3:38])([CH3:37])[CH2:34][CH:35]=[O:36])=[CH:29][CH:28]=1>O1CCCC1>[Cl:26][C:27]1[CH:28]=[CH:29][C:30]([C:33]([CH3:38])([CH3:37])[CH2:34][CH:35]([Sn:17]([CH2:18][CH2:19][CH2:20][CH3:21])([CH2:22][CH2:23][CH2:24][CH3:25])[CH2:13][CH2:14][CH2:15][CH3:16])[OH:36])=[CH:31][CH:32]=1

Participants

6

Reactant 4

HCID 5948TributylstannaneHCID 7912DiisopropylamineHCID 153325663-(4-Chlorophenyl)-3-methylbutyraldehydeHCID 178418339Butyllithium

Product 1

HCID 153325673-(4-Chlorophenyl)-3-methyl-1-tributylstannylbutanolYield 99.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A stirred solution of 5.0 mL (0.036 mole) of diisopropylamine in 100 mL of tetrahydrofuran was cooled to 0° C., and 14.3 mL (0.036 mole) of n-butyllithium (2.5M in hexanes) was added dropwise. Upon completion of addition, 9.6 grams (0.036 mole) of tributyltin hydride was added dropwise during a 15 minute period. The reaction mixture was then stirred at 0° C. for 15 minutes. After this time the reaction mixture was cooled to -78° C., and a solution of 7.0 grams (0.036 mole) of 3-(4-chlorophenyl)-3-methylbutyraldehyde in 10 mL of tetrahydrofuran was added dropwise, while maintaining the reaction mixture temperature below -70° C. The complete addition required about 20 minutes. After this time the reaction mixture was stirred at below -70° C. for ten minutes. The reaction was then quenched by the dropwise addition of about 300 mL of aqueous dilute ammonium chloride solution to the cold reaction mixture. The complete addition required about 10 minutes. The cooling bath was removed, and the reaction mixture was extracted with two 200 mL portions of diethyl ether. The combined extracts were dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure, at a temperature of less than 30° C., yielding 17.4 grams of 3-(4-chlorophenyl)-3-methyl-1-tributylstannylbutanol.

Workup

  1. additionwas added dropwise during a 15 minute period
  2. temperatureAfter this time the reaction mixture was cooled to -78° C.
  3. temperaturewhile maintaining the reaction mixture temperature below -70° C
  4. additionThe complete addition required about 20 minutes
  5. stirringAfter this time the reaction mixture was stirred at below -70° C. for ten minutes
  6. customThe reaction was then quenched by the dropwise addition of about 300 mL of aqueous dilute ammonium chloride solution to the cold reaction mixture
  7. additionThe complete addition required about 10 minutes
  8. customThe cooling bath was removed
  9. extractionthe reaction mixture was extracted with two 200 mL portions of diethyl ether
  10. dry with materialThe combined extracts were dried with magnesium sulfate
  11. filtrationfiltered
  12. concentrationThe filtrate was concentrated under reduced pressure, at a temperature of less than 30° C.

Sources & evidence

ORD record
ord-8fdddaded83644bab1b4b6c3efe45e00
Source dataset
uspto-grants-1996_03
Patent number
US05502054

Reaction notes

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