Diethyl (cyanomethyl)phosphonate → 1,1-Dimethylethyl cyclopropyl({2,3-dichloro-5-[(2E)-3-cyano-2-propen-1-yl]phenyl}methyl)carbamate

HRID 337560Notes

Reaction equation

HRID 337560 reaction equation
[Cl-].[Li+].C(OP([CH2:11][C:12]#[N:13])(=O)OCC)C.C1CCN2C(=NCCC2)CC1.[CH:25]1([N:28]([CH2:36][C:37]2[CH:42]=[C:41]([CH2:43][CH:44]=O)[CH:40]=[C:39]([Cl:46])[C:38]=2[Cl:47])[C:29](=[O:35])[O:30][C:31]([CH3:34])([CH3:33])[CH3:32])[CH2:27][CH2:26]1>C1COCC1>[CH:25]1([N:28]([CH2:36][C:37]2[CH:42]=[C:41]([CH2:43]/[CH:44]=[CH:11]/[C:12]#[N:13])[CH:40]=[C:39]([Cl:46])[C:38]=2[Cl:47])[C:29](=[O:35])[O:30][C:31]([CH3:32])([CH3:34])[CH3:33])[CH2:27][CH2:26]1

Participants

6

Reactant 4

HCID 75676Diethyl (cyanomethyl)phosphonateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 433294Lithium ChlorideHCID 866516621,1-Dimethylethyl cyclopropyl{[2,3-dichloro-5-(2-oxoethyl)phenyl]methyl}carbamate

Product 1

HCID 669007271,1-Dimethylethyl cyclopropyl({2,3-dichloro-5-[(2E)-3-cyano-2-propen-1-yl]phenyl}methyl)carbamate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a THF (0.1 M) suspension of anhydrous lithium chloride (1.2 eq.) was added sequentially diethyl(cyanomethyl)phosphonate (1.2 eq.) and DBU (1 eq.). The resulting suspension was stirred at RT for 15 min before 1,1-dimethylethyl cyclopropyl{[2,3-dichloro-5-(2-oxoethyl)phenyl]methyl}carbamate (1 eq.) from the previous step was added dropwise as a THF (0.1 M) solution. The resulting pink suspension was allowed to stir at RT for 12 h before it was carefully quenched with 1 N aq. HCl and then extracted with ether. The combined organic extracts were washed further with water and brine, dried over Na2SO4, filtered and the filtrate concentrated in vacuo. Purification of the crude product thus obtained by way of flash chromatography (SiO2, Hex→3:7 (v/v) Hex:EtOAc) afforded the title compound as a colorless oil.

Workup

  1. customwas carefully quenched with 1 N aq. HCl
  2. extractionextracted with ether
  3. washThe combined organic extracts were washed further with water and brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationthe filtrate concentrated in vacuo
  7. customPurification of the crude product
  8. customthus obtained by way of flash chromatography (SiO2, Hex→3:7 (v/v) Hex:EtOAc)

Sources & evidence

ORD record
ord-de89a8e8d71942059782bc7910a9135e
Source dataset
uspto-grants-2014_11
Patent number
US08889714B2

Reaction notes

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