2,6-Di-tert-butyl-4-methylphenol → HCID 86759483, compound

HRID 1883309Notes

Reaction equation

HRID 1883309 reaction equation
Cl.[C:2]1([P:8]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:9]2[CH:23]=[CH:22][CH:21]=[CH:20][C:10]=2[CH2:11][NH:12][C@@H:13]2[CH2:18][CH2:17][CH2:16][CH2:15][C@H:14]2[NH2:19])[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)([O-])O.[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2CN[C@@H]2CCCC[C@H]2N)C=CC=CC=1.[C:63]1([P:69]([C:88]2[CH:93]=[CH:92][CH:91]=[CH:90][CH:89]=2)[C:70]2[CH:77]=[CH:76][C:75]([O:78][CH2:79][C:80]3[CH:85]=[CH:84][C:83]([CH:86]=[CH2:87])=[CH:82][CH:81]=3)=[CH:74][C:71]=2[CH:72]=O)[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=1.C(C1C(O)=C(C(C)(C)C)C=C(C)C=1)(C)(C)C>C(O)C.C(Cl)Cl>[C:2]1([P:8]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:9]2[CH:23]=[CH:22][CH:21]=[CH:20][C:10]=2[CH2:11][N:12]([CH2:72][C:71]2[CH:74]=[C:75]([O:78][CH2:79][C:80]3[CH:85]=[CH:84][C:83]([CH:86]=[CH2:87])=[CH:82][CH:81]=3)[CH:76]=[CH:77][C:70]=2[P:69]([C:88]2[CH:93]=[CH:92][CH:91]=[CH:90][CH:89]=2)[C:63]2[CH:64]=[CH:65][CH:66]=[CH:67][CH:68]=2)[C@@H:13]2[CH2:18][CH2:17][CH2:16][CH2:15][C@H:14]2[NH2:19])[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 5

HCID 314042,6-Di-tert-butyl-4-methylphenolHCID 516892Sodium BicarbonateHCID 15965747HCID 15965747, compoundHCID 23510930HCID 23510930, compoundHCID 86759484HCID 86759484, compound

Product 1

HCID 86759483HCID 86759483, compoundYield 79%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Procedure

2.54 g of (1R,2R)-N-(2-diphenylphosphanylbenzyl)cyclohexane-1,2-diamine hydrochloride (6 mmol) are combined with 100 ml of methylene chloride and 100 ml of saturated sodium hydrogen carbonate solution. Once the phases have separated, the aqueous phase is extracted twice more with methylene chloride and the combined organic phases are washed with saturated sodium chloride solution. Drying is then performed with magnesium sulfate and the solvent removed in a rotary evaporator. After drying under a high vacuum, 1.71 g of (1R,2R)-N-(2-diphenylphosphanylbenzyl)cyclohexane-1,2-diamine (4.4 mmol) are obtained as an air-sensitive clear oil. This is dissolved in 250 ml of absolute ethanol under a protective gas atmosphere in a three-necked flask equipped with a reflux condenser. Once combined with 1.85 g of 2-diphenylphosphanyl-5-(4-vinylbenzyloxy)benzaldehyde (4.4 mmol) and 96 mg of 2,6-di-tert.-butyl-p-cresol (0.4 mmol), the reaction solution is refluxed for 1 hour under protective gas. The reaction mixture is then left to cool and combined with 1.66 g (44 mmol) of sodium hydridoborate. After 3 hours, the reaction is quenched by adding 50 ml of acetone and the solvent is completely removed in a rotary evaporator. The resultant residue is stirred with 100 ml of saturated ammonium hydrochloride solution and 100 ml of methylene chloride until completely dissolved. The aqueous phase is extracted twice more with methylene chloride and the combined organic phases are washed with water and saturated sodium chloride solution. Drying is then performed with magnesium sulfate and the solvent removed. After drying under a high vacuum, 2.83 g of the product, corresponding to a yield of 79%, are obtained as a white mass (stabiliser content according to NMR 9.4%).

Workup

  1. customOnce the phases have separated
  2. extractionthe aqueous phase is extracted twice more with methylene chloride
  3. washthe combined organic phases are washed with saturated sodium chloride solution
  4. customDrying
  5. customthe solvent removed in a rotary evaporator
  6. customare obtained as an air-sensitive clear oil
  7. customequipped with a reflux condenser
  8. temperaturethe reaction solution is refluxed for 1 hour under protective gas
  9. waitThe reaction mixture is then left
  10. temperatureto cool
  11. customthe reaction is quenched
  12. additionby adding 50 ml of acetone
  13. customthe solvent is completely removed in a rotary evaporator
  14. dissolutionuntil completely dissolved
  15. extractionThe aqueous phase is extracted twice more with methylene chloride
  16. washthe combined organic phases are washed with water and saturated sodium chloride solution
  17. customDrying
  18. customthe solvent removed
  19. dry with materialAfter drying under a high vacuum, 2.83 g of the product, corresponding to a yield of 79%
  20. customare obtained as a white mass (stabiliser content according to NMR 9.4%)

Sources & evidence

ORD record
ord-1f640c3a0be84292a9e1484d63f1adb0
Source dataset
uspto-grants-2004_07
Patent number
US06759559B2

Reaction notes

Loading…