2,6-Di-tert-butyl-4-methylphenol → Tributyl-[2-(2,2-dimethyl-2H-chromen-6-yl)-3-(3,4,5-trimethoxy-phenyl)-propenyl]-stannane

HRID 1723978Notes

Reaction equation

HRID 1723978 reaction equation
I[CH:2]=[C:3]([C:17]1[CH:18]=[C:19]2[C:24](=[CH:25][CH:26]=1)[O:23][C:22]([CH3:28])([CH3:27])[CH:21]=[CH:20]2)[CH2:4][C:5]1[CH:10]=[C:9]([O:11][CH3:12])[C:8]([O:13][CH3:14])=[C:7]([O:15][CH3:16])[CH:6]=1.[CH2:29]([Sn:33]([CH2:40][CH2:41][CH2:42][CH3:43])([CH2:36][CH2:37][CH2:38][CH3:39])C=C)[CH2:30][CH2:31][CH3:32].[Li+].[Cl-].C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C.[F-].[NH+]1C=CC=CC=1>O1CCOCC1.C(OCC)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.N1C=CC=CC=1>[CH2:40]([Sn:33]([CH2:29][CH2:30][CH2:31][CH3:32])([CH2:36][CH2:37][CH2:38][CH3:39])[CH:2]=[C:3]([C:17]1[CH:18]=[C:19]2[C:24](=[CH:25][CH:26]=1)[O:23][C:22]([CH3:28])([CH3:27])[CH:21]=[CH:20]2)[CH2:4][C:5]1[CH:10]=[C:9]([O:11][CH3:12])[C:8]([O:13][CH3:14])=[C:7]([O:15][CH3:16])[CH:6]=1)[CH2:41][CH2:42][CH3:43]

Participants

10

Reactant 5

HCID 314042,6-Di-tert-butyl-4-methylphenolHCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 13989026HF-PyridineHCID 765654756-[2-iodo-1-(3,4,5-trimethoxy-benzyl)-vinyl]-2,2-dimethyl-2H-chromene

Product 1

HCID 68649596Tributyl-[2-(2,2-dimethyl-2H-chromen-6-yl)-3-(3,4,5-trimethoxy-phenyl)-propenyl]-stannane

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 1049PyridineSolventHCID 3283Diethyl EtherSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 6-[2-iodo-1-(3,4,5-trimethoxy-benyl)-vinyl]-2,2-dimethyl-2H-chromene (974 mg, 1.98 mmol) in 1,4-dioxane (9 mL) is added tri-n-butylethenyl-stannane (650 mg, 2.05 mmol), LiCl (252 mg, 594 mmol), Pd(PPh3)4 (46 mg, 0.04 mmol), and a few crystals of 2,6-di-tert-butyl-4-methyl phenol. The resulting suspension is heated to reflux for 4 hours, cooled to room temperature and treated with pyridine (1 mL) and pyridinium fluoride (2 mL, 1.4 M solution in THF, 2.8 mmol). The resulting mixture is stirred at room temperature for 16 hours and then diluted with diethyl ether and filtered through a small pad of diatomaceous earth (Celite®). The filtrate is washed with water, 10% HCl, water, brine, and dried over sodium sulfate, filtered, and concentrated. Crude material is used in the next step without further purification.

Workup

  1. temperatureThe resulting suspension is heated
  2. temperatureto reflux for 4 hours
  3. filtrationfiltered through a small pad of diatomaceous earth (Celite®)
  4. washThe filtrate is washed with water, 10% HCl, water, brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customCrude material is used in the next step without further purification

Sources & evidence

ORD record
ord-0b23a91aded240708622800080ec3fe2
Source dataset
uspto-grants-2009_02
Patent number
US07485283B2

Reaction notes

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