Hydrogen Peroxide → (2,4,6-Trimethylbenzoyl)bis(o-tolyl)phosphine oxide

HRID 10931

반응식

HRID 10931 반응식
[Na].[Cl-].[C:3]1([CH3:17])[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[PH:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[CH3:16].[CH3:18][C:19]1[CH:27]=[C:26]([CH3:28])[CH:25]=[C:24]([CH3:29])[C:20]=1[C:21](Cl)=[O:22].[OH:30]O>O1CCCC1>[CH3:18][C:19]1[CH:27]=[C:26]([CH3:28])[CH:25]=[C:24]([CH3:29])[C:20]=1[C:21]([P:9](=[O:30])([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[CH3:16])[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=1[CH3:17])=[O:22]

참가 물질

6

반응물 4

HCID 784Hydrogen PeroxideHCID 970382,4,6-Trimethylbenzoyl chlorideHCID 5360545SodiumHCID 86595293Ditolylphosphine chloride

생성물 1

HCID 20201894(2,4,6-Trimethylbenzoyl)bis(o-tolyl)phosphine oxide

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

Under argon and with exclusion of moisture, 4.6 g of chopped sodium (0.20 mol) are placed at room temperature in 100 ml of tetrahydrofuran. Stirring slowly, 24.9 g (0.10 mol) of ditolylphosphine chloride (isomeric mixture of di-ortho, di-para and ortho-para) are added dropwise at 20–25° C. After stirring for 12 h, the red solution is filtered via a glass frit (G2 porosity) into a sulfonation flask with exclusion of moisture and using argon as protective gas. With stirring and cooling, 19.0 g (0.105 mol; 5% excess) of 2,4,6-trimethylbenzoyl chloride are added dropwise over 30 minutes at room temperature. After stirring for another 2 hours, the brownish-red reaction suspension is poured on water and extracted with toluene. The organic phase is dried over magnesium sulfate, filtered and concentrated by evaporation in a rotary evaporator (Rotavap). The resulting phosphine has a 23.24 ppm shift in the 31P-NMR spectrum. The residue is taken up in 100 ml of toluene and charged with 11.5 g (0.10 mol) of hydrogen peroxide (30%). The reaction is complete after stirring for 2 hours at a temperature from 50–60° C. The reaction emulsion is poured on water and washed with an aqueous saturated sodium hydrogencarbonate solution and then dried over magnesium sulfate and filtered. The filtrate is concentrated by evaporation in a Rotavap. The residue is purified over silica gel and dried under high vacuum, yielding 33.8 g (90% of theory) of the title compound in the form of a yellow viscous oil. The 31P-NMR shift is 14.54 ppm.

후처리

  1. stirringAfter stirring for 12 h
  2. filtrationthe red solution is filtered via a glass frit (G2 porosity) into a sulfonation flask with exclusion of moisture and
  3. stirringWith stirring
  4. temperaturecooling
  5. stirringAfter stirring for another 2 hours
  6. additionthe brownish-red reaction suspension is poured on water
  7. extractionextracted with toluene
  8. dry with materialThe organic phase is dried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated by evaporation in a rotary evaporator (Rotavap)
  11. stirringafter stirring for 2 hours at a temperature from 50–60° C
  12. additionThe reaction emulsion is poured on water
  13. washwashed with an aqueous saturated sodium hydrogencarbonate solution
  14. dry with materialdried over magnesium sulfate
  15. filtrationfiltered
  16. concentrationThe filtrate is concentrated by evaporation in a Rotavap
  17. customThe residue is purified over silica gel
  18. customdried under high vacuum

출처 및 근거

ORD 기록
ord-180b7cd0d66e453baf7dc0724e4d95f7
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07094931B2

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