Toluene → Diethyl thiophosphate

HRID 611798Notes

Reaction equation

HRID 611798 reaction equation
[CH3:1][CH2:2][C@@H:3]1[O:26][C:24](=[O:25])[CH2:23][C@@H:22]2[C:11](=[CH:12][C@@H:13]3[C@H:21]2[CH:20]=[CH:19][C@H:18]2[C@H:14]3[CH2:15][C@H:16]([O:27][C@@H:28]3[O:33][C@@H:32]([CH3:34])[C@H:31]([O:35][CH3:36])[C@@H:30]([O:37][CH3:38])[C@H:29]3[OH:39])[CH2:17]2)[C:9](=[O:10])[C@H:8]([CH3:40])[C@@H:7]([O:41][C@@H:42]2[O:47][C@H:46]([CH3:48])[C@@H:45]([N:49]([CH3:51])[CH3:50])[CH2:44][CH2:43]2)[CH2:6][CH2:5][CH2:4]1.[P:52](Cl)([O:57]CC)([O:54][CH2:55][CH3:56])=[S:53].C1(C)C=CC=CC=1.CCOC(C)=O>N1C=CC=CC=1.CN(C1C=CN=CC=1)C>[CH2:55]([O:54][P:52]([O-:57])([O:47][CH2:46][CH3:48])=[S:53])[CH3:56].[CH3:1][CH2:2][C@@H:3]1[O:26][C:24](=[O:25])[CH2:23][C@@H:22]2[C:11](=[CH:12][C@@H:13]3[C@H:21]2[CH:20]=[CH:19][C@H:18]2[C@H:14]3[CH2:15][C@H:16]([O:27][C@@H:28]3[O:33][C@@H:32]([CH3:34])[C@H:31]([O:35][CH3:36])[C@@H:30]([O:37][CH3:38])[C@H:29]3[OH:39])[CH2:17]2)[C:9](=[O:10])[C@H:8]([CH3:40])[C@@H:7]([O:41][C@@H:42]2[O:47][C@H:46]([CH3:48])[C@@H:45]([N:49]([CH3:51])[CH3:50])[CH2:44][CH2:43]2)[CH2:6][CH2:5][CH2:4]1

Participants

8

Reactant 4

HCID 1140TolueneHCID 8857Ethyl AcetateHCID 17305O,O-diethyl phosphorochloridothioateHCID 23724546Spinosyn H

Product 2

HCID 3683036Diethyl thiophosphateHCID 23724546Spinosyn H

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolvent

Procedure

Compound Spinosyn H (261 mg, 0.364 mmol) was dissolved in dry pyridine (3 ml). DMAP (60 mg) was added, followed by diethyl chlorothiophosphate (152 mg, 125 μl, 0.80 mmol). The reaction mixture was stirred at RT under nitrogen. After 12 hrs. toluene (50 ml) and EtOAc (50 ml) were added. The solution was extracted with brine, then with 5% aq. NaHCO3. The organic layer was dried over and Na2SO4 and concentrated in vacuo. The residue was purified over a flash SiO2 column (30 g/EtOAc) to give compound 2'R)-(diethyl)thiophosphate of Spinosyn H; 84 mg, 27%) CI MS m/z 870 (M+1); 1H-NMR (CDCl3) δ 6.74 (1H, bs), 4.80 (1H, m), 4.22 (4H, 2× CH2, m), 1.30 (6H, 2× CH3, m).

Workup

  1. extractionThe solution was extracted with brine
  2. dry with materialThe organic layer was dried over and Na2SO4
  3. concentrationconcentrated in vacuo
  4. customThe residue was purified over a flash SiO2 column (30 g/EtOAc)

Sources & evidence

ORD record
ord-7c9b22b4a40448e086216b9b12eddd7b
Source dataset
uspto-grants-1999_12
Patent number
US06001981

Reaction notes

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