Iodine → HCID 18991841, compound

HRID 376083Notes

Reaction equation

HRID 376083 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([P:9](=[O:24])([C:17]2[CH:22]=[CH:21][C:20]([CH3:23])=[CH:19][CH:18]=2)[C:10]2[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=2)[CH:6]=[CH:7][CH:8]=1.C([Li])CCC.CCCCCC.CC1(C)CCCC(C)(C)N1.[I:46]I.S(S([O-])=O)([O-])(=O)=O.[Na+].[Na+]>C1COCC1>[I:46][C:4]1[C:3]([O:2][CH3:1])=[CH:8][CH:7]=[CH:6][C:5]=1[P:9](=[O:24])([C:17]1[CH:18]=[CH:19][C:20]([CH3:23])=[CH:21][CH:22]=1)[C:10]1[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][CH:11]=1

Participants

8

Reactant 6

HCID 807IodineHCID 8058HexaneHCID 130352,2,6,6-TetramethylpiperidineHCID 656671Sodium PyrosulfiteHCID 18991845HCID 18991845, compound2×HCID 178418339Butyllithium

Product 1

HCID 18991841HCID 18991841, compoundYield 66.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
0 °C

Procedure

dc) 16.8 g (50 mmol) of (3-methoxyphenyl)-di-p-tolylphosphine oxide were dissolved in 100 ml of dry THF in a 1 l four-necked sulphonation flask provided with a stirrer, dropping funnel, thermometer and argon gasification. In a separate Schlenk tube 34.0 ml of 1.6N n-butyllithium solution in hexane (54.4 mmol) were added dropwise under argon and while stirring at -78° C. to a solution of 9.98 g (70.6 mmol) of 2,2,6,6-tetramethylpiperidine in 50 ml of THF. The solution was warmed to 0° C. for a short period, then again cooled to -78° C. and then added dropwise via a canula at ≤-70° C. to the solution of the phosphine oxide in THF. The resulting red-brown solution was stirred at -78° C. for a further 30 minutes and then treated dropwise with a solution of 15.0 g (59.1 mmol) of iodine in 50 ml of THF, whereby a beige precipitate formed. The reaction mixture was left to warm to 0° C., treated with aqueous sodium pyrosulphite solution and extracted with ethyl acetate. The extracts were washed with sat. NaHCO3 solution and sat. NaCl solution, dried over Na2SO4, filtered and evaporated. The residue was chromatographed on silica gel (200 g, ethyl acetate), whereby 15.3 g of (2-iodo-3-methoxyphenyl)-di-p-tolylphosphine oxide were obtained. After recrystallization from t-butyl methyl ether there was obtained a white powder with a m.p. of 146°-148° C.

Workup

  1. customprovided with a stirrer
  2. temperatureagain cooled to -78° C.
  3. customformed
  4. waitThe reaction mixture was left
  5. temperatureto warm to 0° C.
  6. extractionextracted with ethyl acetate
  7. washThe extracts were washed with sat. NaHCO3 solution and sat. NaCl solution
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. customevaporated
  11. customThe residue was chromatographed on silica gel (200 g, ethyl acetate)

Sources & evidence

ORD record
ord-51fe6709ae2740d489c4537626016f06
Source dataset
uspto-grants-1996_01
Patent number
US05488172

Reaction notes

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