Toluene → Diethylphosphite

HRID 611797Notes

Reaction equation

HRID 611797 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:56]CC)[O:53][CH2:54][CH3:55].C1(C)C=CC=CC=1.CCOC(C)=O>N1C=CC=CC=1.CN(C1C=CN=CC=1)C>[CH2:54]([O:53][P:52]([O-:56])[O:47][CH2:46][CH3:48])[CH3:55].[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 68530Ethyl phosphorochloriditeHCID 23724546Spinosyn H

Product 2

HCID 3780918DiethylphosphiteHCID 23724546Spinosyn H

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 1049PyridineSolvent

Procedure

Compound Spinosyn H (351 mg, 0.489 mmol) was dissolved in dry pyridine (5 ml). DMAP (62 mg, 0.51 mmol) was added and stirring at RT under nitrogen was continued for 5 min. Diethyl chlorophosphite (157 mg, 0.145 ml, 1.0 mmol) was added. After 30 min. toluene (50 ml) and EtOAc (50 ml) were added. The solution was washed successively with brine (2×) and 5% aq. NaHCO3. The organic layer was dried over Na2SO4 and concentrated. The residue was separated over a flash SiO2 column (100 g/EtOAc) to give compound 2'R)-(diethyl)phosphite of Spinosyn H; 306 mg, 75% CI MS m/z 838 (M+1); 1H-NMR (CDCl3) δ 6.69 (1H, bs), 4.40 (1H, m), 3.83 (4H, 2× CH2, m), 1.18 (6H, 2× CH3, m); Elemental Analysis: for C44H72NO12P calc. C 63.06, H 8.66, N 1.67 found: C 62.94, H 8.88, N 1.71.

Workup

  1. washThe solution was washed successively with brine (2×) and 5% aq. NaHCO3
  2. dry with materialThe organic layer was dried over Na2SO4
  3. concentrationconcentrated
  4. customThe residue was separated over a flash SiO2 column (100 g/EtOAc)

Sources & evidence

ORD record
ord-b04d0b67754c4fa0962e1e5b64105954
Source dataset
uspto-grants-1999_12
Patent number
US06001981

Reaction notes

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