Tin tetrachloride → 2-Allyl-4-(5-hexynoyl)-6-t-butylphenol

HRID 231611Notes

Reaction equation

HRID 231611 reaction equation
[CH2:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([C:10]([CH3:13])([CH3:12])[CH3:11])[C:5]=1[OH:14])[CH:2]=[CH2:3].[C:15](Cl)(=[O:21])[CH2:16][CH2:17][CH2:18][C:19]#[CH:20].Cl[Sn](Cl)(Cl)Cl>C(Cl)Cl>[CH2:1]([C:4]1[CH:9]=[C:8]([C:15](=[O:21])[CH2:16][CH2:17][CH2:18][C:19]#[CH:20])[CH:7]=[C:6]([C:10]([CH3:13])([CH3:12])[CH3:11])[C:5]=1[OH:14])[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 24287Tin tetrachlorideHCID 5206412-Allyl-6-t-butylphenolHCID 2759284Hex-5-ynoyl chloride

Product 1

HCID 146720422-Allyl-4-(5-hexynoyl)-6-t-butylphenolYield 77%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 2-allyl-6-t-butylphenol (0.57 g; 3 mmol) in dry CH2Cl2 (12 ml) is cooled to -78° C., and 5-hexynoyl chloride (0.43 g; 3.3 mmol) is added via syringe, followed by SnCl4 (0.375 ml) added dropwise via syringe, with stirring under Argon. After 30 min the reaction is allowed to warm to 0° C. and is stirred at that temperature for 5 min; it is then quenched with ca 1 ml of 3N HCl. The reaction is poured into 100 ml water and extracted with 3×50 ml portions of ether. The combined ether layers are washed with 150 ml portions of water until the aqueous layer is neutral (pH test). The ether layer is dried (MgSO4), filtered, and concentrated in vacuo to give crude product, which is chromatographed with 20:1 hexane/EtOAc, giving 0.64 g 2-allyl-4-(5-hexynoyl)-6-t-butylphenol (77% yield). The product is recrystallized from hexane at 0° C. to give crystals melting at 62°-63° C.

Workup

  1. additionadded dropwise via syringe
  2. stirringis stirred at that temperature for 5 min
  3. customit is then quenched with ca 1 ml of 3N HCl
  4. additionThe reaction is poured into 100 ml water
  5. extractionextracted with 3×50 ml portions of ether
  6. washThe combined ether layers are washed with 150 ml portions of water until the aqueous layer
  7. dry with materialThe ether layer is dried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customto give crude product, which
  11. customis chromatographed with 20:1 hexane/EtOAc

Sources & evidence

ORD record
ord-11f37d7ece0f4a3cbfa2555f329168ee
Source dataset
uspto-grants-1989_07
Patent number
US04847303

Reaction notes

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