m-Chloroperbenzoic acid → HCID 57310697, compound

HRID 1006662Notes

Reaction equation

HRID 1006662 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[C@:9]([OH:30])([C@H:16]([C:18]1[CH:23]=[CH:22][C:21]([C:24]2[N:28]([CH3:29])[N:27]=[CH:26][CH:25]=2)=[CH:20][CH:19]=1)[CH3:17])[CH2:10][N:11]1[CH:15]=[N:14][CH:13]=[N:12]1.C(N(C(C)C)[P:35]([O:44][CH2:45][C:46]1[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=1)[O:36][CH2:37][C:38]1[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=1)(C)C.N1C=NN=N1.ClC1C=CC=C(C(OO)=[O:68])C=1>CN(C)C1C=CN=CC=1.ClCCl>[P:35]([O:30][C@@:9]([C:3]1[CH:4]=[CH:5][C:6]([F:8])=[CH:7][C:2]=1[F:1])([C@H:16]([C:18]1[CH:23]=[CH:22][C:21]([C:24]2[N:28]([CH3:29])[N:27]=[CH:26][CH:25]=2)=[CH:20][CH:19]=1)[CH3:17])[CH2:10][N:11]1[CH:15]=[N:14][CH:13]=[N:12]1)([O:36][CH2:37][C:38]1[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=1)([O:44][CH2:45][C:46]1[CH:47]=[CH:48][CH:49]=[CH:50][CH:51]=1)=[O:68]

Participants

7

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 196621Bis(benzyloxy)(diisopropylamino)phosphineHCID 18396914HCID 18396914, compoundHCID 178418441HCID 178418441, compound

Product 1

HCID 57310697HCID 57310697, compoundYield 27.2%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of the product of step (j) (2.0 g, 4.4 mmol), dibenzyl diisopropylphosphoramidite (2.28 g, 6.6 mmol), tetrazole (0.92 g, 13.2 mmol) and 4-dimethylaminopyridine (50 mg) in dichloromethane (30 ml) was heated under reflux for 13 hours. The reaction mixture was cooled (0° C.) and m-chloroperbenzoic acid (1.52 g, 8.8 mmol) added. The solution was stirred at 0° C. for a further hour then allowed to warm to room temperature. The reaction mixture was washed with aqueous sodium sulphite solution (10%, 30 ml), saturated sodium bicarbonate solution (30 ml) and brine (30 ml). The organic layer was dried (Na2SO4) and solvent was evaporated in vacuo to give an oil. Purification by column chromatography (silica gel, 45 g, eluting with toluene to 3.5% diethylamine in toluene gradient) gave the required product as a colourless oil (0.8 g, 27%), m/z 671 (M++1). 1H N.M.R. (CDCl3) δ=1.3 (d, 3H); 3.8 (s, 3H); 3.85 (q, 1H); 4.8 (m, 2H); 4.9 (m, 2H), 5.2 (s, 2H); 6.25 (s, 1H); 6.6 (m, 1H); 6.8 (m, 1H); 7.05 (m, 1H); 7.15 (m, 2H); 7.2-7.35 (m, 12H); 7.5 (s,1H); 7.8 (s,1H); 8.23 (s,1H).

Workup

  1. temperatureunder reflux for 13 hours
  2. additionadded
  3. temperatureto warm to room temperature
  4. washThe reaction mixture was washed with aqueous sodium sulphite solution (10%, 30 ml), saturated sodium bicarbonate solution (30 ml) and brine (30 ml)
  5. dry with materialThe organic layer was dried (Na2SO4) and solvent
  6. customwas evaporated in vacuo
  7. customto give an oil
  8. customPurification
  9. washby column chromatography (silica gel, 45 g, eluting with toluene to 3.5% diethylamine in toluene gradient)

Sources & evidence

ORD record
ord-8bdded26417d4cdda0f715a2d93f2908
Source dataset
uspto-grants-2004_09
Patent number
US06790957B2

Reaction notes

Loading…