Triphenylphosphine → HCID 89907088, compound

HRID 931693Notes

Reaction equation

HRID 931693 reaction equation
[OH:1][C:2]1[CH:15]=[CH:14][C:5]([C:6]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[O:7])=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH2:35]([C:37]1([CH2:45]O)[CH2:42][O:41]C(C)(C)[O:39][CH2:38]1)[CH3:36].N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1.O.ClCCl.CC(C)=O>[C:6]([C:5]1[CH:4]=[CH:3][C:2]([O:1][CH2:45][C:37]([CH2:35][CH3:36])([CH2:42][OH:41])[CH2:38][OH:39])=[CH:15][CH:14]=1)(=[O:7])[C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 143474-Hydroxybenzophenone2×HCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 118161521,3-Dioxane-5-methanol, 5-ethyl-2,2-dimethyl-

Product 1

HCID 89907088HCID 89907088, compoundYield 66.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 21584124Propan-2-one--dichloromethane (1/1)Solvent

Procedure

To a solution of 4-hydroxybenzophenone (2.00 g; 10.1 mmol), triphenylphosphine (4.234 g; 16.1 mmol) and (5-ethyl-2,2-dimethyl-1,3-dioxan-5-yl)methanol (2.813 g; 16.14 mmol) in anhydrous tetrahydrofuran (50 mL) at 0° C. was added diisopropyl azodicarboxylate (3.264 g; 16.14 mmol) dropwise over 10 min. The reaction mixture was stirred for 16 h at ambient temperature. TLC (eluent dichloromethane/acetone 10:1) confirmed ca 50° A) conversion. The reaction was warmed to 35-40° C. for 12 h and the conversion was monitored until ca 95° A) of 4-hydroxybenzophenone had reacted. The bright orange reaction mixture was evaporated to dryness, dissolved in dichloromethane and passed through a plug of silica. The eluent was again evaporated to dryness, redissolved in methanol (80 mL) and 1M HCl (22 mL) was added. The colourless reaction mixture was stirred for 1 h at ambient temperature, complete ketal cleavage was confirmed by TLC (eluent hexane/2-butanone 1:1). The methanol was evaporated to leave an aqueous residue. Water (150 mL) was added and the mixture was extracted with ethyl acetate (2×100 mL). The organic phase was separated, dried, evaporated and the oily crude product was purified by chromatography (eluent hexane/2-butanone 2:1→1:1). This provided the desired 2-(4-benzoylphenoxymethyl)-2-ethylpropane-1,3-diol (2.11 g; 66%) as a viscous colourless oil.

Workup

  1. customconfirmed ca 50°
  2. temperatureThe reaction was warmed to 35-40° C. for 12 h
  3. customwas monitored until ca 95°
  4. customhad reacted
  5. customThe bright orange reaction mixture was evaporated to dryness
  6. dissolutiondissolved in dichloromethane
  7. customThe eluent was again evaporated to dryness
  8. dissolutionredissolved in methanol (80 mL)
  9. addition1M HCl (22 mL) was added
  10. stirringThe colourless reaction mixture was stirred for 1 h at ambient temperature
  11. customThe methanol was evaporated
  12. customto leave an aqueous residue
  13. extractionthe mixture was extracted with ethyl acetate (2×100 mL)
  14. customThe organic phase was separated
  15. customdried
  16. customevaporated
  17. customthe oily crude product was purified by chromatography (eluent hexane/2-butanone 2:1→1:1)

Sources & evidence

ORD record
ord-8659af3816384e04b796a8d4156b7efb
Source dataset
uspto-grants-2016_03
Patent number
US09296835B2

Reaction notes

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