Sodium Hydroxide → HCID 86762311, compound

HRID 2362360Notes

Reaction equation

HRID 2362360 reaction equation
[C:1](=[O:8])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])[NH2:2].[OH-].[Na+].ClOC(C)(C)C.CC[C@@H]1[C@@H]2C[C@H]([C@@H](OC3C4C(=CC=CC=4)C(O[C@@H](C4C=CN=C5C=4C=C(OC)C=C5)[C@@H]4N5C[C@H](CC)[C@@H](CC5)C4)=NN=3)C3C=CN=C4C=3C=C(OC)C=C4)N(CC2)C1.[Br:75][C:76]1[CH:77]=[N:78][CH:79]=[C:80](/[CH:82]=[C:83](\[C:85]2[CH:90]=[CH:89][CH:88]=[CH:87][CH:86]=2)/[CH3:84])[CH:81]=1.BrC1C=NC=C(/C=C(/C2C=CC=CC=2)\C)C=1>C(O)CC.O>[Br:75][C:76]1[CH:81]=[C:80]([C@H:82]([NH:2][C:1](=[O:8])[O:3][C:4]([CH3:7])([CH3:6])[CH3:5])[C@@H:83]([C:85]2[CH:90]=[CH:89][CH:88]=[CH:87][CH:86]=2)[CH3:84])[CH:79]=[N:78][CH:77]=1

Participants

9

Reactant 6

HCID 14798Sodium HydroxideHCID 77922tert-Butyl carbamateHCID 521297Tert-Butyl hypochloriteHCID 112172021,4-Bis(dihydroquinidine)phthalazineHCID 69082897HCID 69082897, compoundHCID 69084765HCID 69084765, compound

Product 1

HCID 86762311HCID 86762311, compoundYield 55%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 10311-PropanolSolvent3×

Conditions

Temperature
0 °C

Procedure

To a solution of tert-butyl carbamate (1.907 g, 16.28 mmol) in propanol (4.6 mL) was added sodium hydroxide (0.641 g, 16.02 mmol) in water (8 mL) followed by tert-butyl hypochlorite (1.808 ml, 16.02 mmol). After 5 minutes, the solution was cooled to 0° C. and treated with a solution of (DHQD)2PHAL (0.245 g, 0.315 mmol) in propanol (4.6 mL). To this was added a solution of (Z)-3-bromo-5-(2-phenylprop-1-enyl)pyridine and (E)-3-bromo-5-(2-phenylprop-1-enyl)pyridine (1.440 g, 5.25 mmol) in propanol (7.8 mL), and potassium osmate dihydrate (0.077 g, 0.210 mmol) as a solid in one portion. The ice bath was removed and stirring continued overnight. The reaction was quenched by addition of a solution of sodium thiosulfate (1.84 g) in water (23 mL). After 30 minutes, the reaction was diluted with ether, washed with water, then brine, dried over MgSO4, and concentrated. Biotage purification (20%-50% EtOAc/Hex) gave title compound (1.18 g, 2.90 mmol, 55% yield) as colored semi-solid. Mass spec.: 407.0 (MH)+.

Workup

  1. customThe ice bath was removed
  2. customThe reaction was quenched by addition of a solution of sodium thiosulfate (1.84 g) in water (23 mL)
  3. waitAfter 30 minutes
  4. additionthe reaction was diluted with ether
  5. washwashed with water
  6. dry with materialbrine, dried over MgSO4
  7. concentrationconcentrated
  8. customBiotage purification (20%-50% EtOAc/Hex)

Sources & evidence

ORD record
ord-a533d47eba36453d961cd2db342fd06c
Source dataset
uspto-grants-2014_04
Patent number
US08691821B2

Reaction notes

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