Tetraethyl methylenediphosphonate → HCID 145857658, compound

HRID 2216139Notes

Reaction equation

HRID 2216139 reaction equation
[C:1]([O:5][C:6](=[O:35])[NH:7][C:8]([C:10]1[S:11][C:12]([S:33][CH3:34])=[C:13]([S:15]([C:18]2[CH:19]=[C:20]([C:24]3[C:29]([CH3:30])=[CH:28][CH:27]=[CH:26][C:25]=3[CH2:31]O)[CH:21]=[CH:22][CH:23]=2)(=[O:17])=[O:16])[CH:14]=1)=[NH:9])([CH3:4])([CH3:3])[CH3:2].[CH2:36]([O:38][P:39]([CH2:44]P(OCC)(OCC)=O)(=[O:43])[O:40][CH2:41][CH3:42])[CH3:37].[H-].[Na+].C(Cl)(Cl)Cl.FC(F)(F)C(O)=O>ClCCl.C1COCC1.[O-2].[O-2].[Mn+4]>[CH2:36]([O:38][P:39](/[CH:44]=[CH:31]\[C:25]1[CH:26]=[CH:27][CH:28]=[C:29]([CH3:30])[C:24]=1[C:20]1[CH:21]=[CH:22][CH:23]=[C:18]([S:15]([C:13]2[CH:14]=[C:10]([C:8]([NH:7][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:35])=[NH:9])[S:11][C:12]=2[S:33][CH3:34])(=[O:16])=[O:17])[CH:19]=1)(=[O:43])[O:40][CH2:41][CH3:42])[CH3:37]

Participants

8

Reactant 4

HCID 15455Tetraethyl methylenediphosphonateHCID 24758Sodium hydrideHCID 19978452Chloroform trifluoroacetic acidHCID 145857676tert-butyl N-[4-[3-[2-(hydroxymethyl)-6-methylphenyl]phenyl]sulfonyl-5-methylsulfanylthiophene-2-carboximidoyl]carbamate

Product 1

HCID 145857658HCID 145857658, compoundYield 60.8%

Reagents, catalysts & solvents 3

HCID 178418406HCID 178418406, compoundCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

Manganese dioxide (0.041 g, 0.470 mmol) was added to a solution of ({[4-(2′-hydroxymethyl-6′-methyl-biphenyl-3-sulfonyl)-5-methylsulfanyl-thiophen-2-yl]-imino-methyl}-carbamic acid tert-butyl ester (0.025 g, 0.047 mmol) [example 213, step b] in dichloromethane [5 mL] and refluxed for 3 hours. The reaction was filtered through Celite and evaporated. The crude residue was dissolved in anhydrous THF [2 mL] and added to a solution of (diethoxy-phosphorylmethyl)-phosphonic acid diethyl ester (0.011 g, 0.061 mmol) and sodium hydride (0.003 g, 0.056 mmol) in THF [2 mL] at room temperature and stirred for 0.5 hours. A solution of 1N NaOH/MeOH (1/1) [10 mL] was added and the crude product was extracted with ether, dried with magnesium sulfate and evaporated. Column chromatography (50% EtOAc in hexanes) of the residue yielded the title compound (0.019 g, 57%) as a solid. ESI-MS (m/z): Calcd. for C30H37N2O7PS3: 664.15; found: 664.8.

Workup

  1. temperaturerefluxed for 3 hours
  2. filtrationThe reaction was filtered through Celite
  3. customevaporated
  4. dissolutionThe crude residue was dissolved in anhydrous THF [2 mL]
  5. extractionthe crude product was extracted with ether
  6. dry with materialdried with magnesium sulfate
  7. customevaporated

Sources & evidence

ORD record
ord-11aa722c388441d0a6f050b7128305b7
Source dataset
uspto-grants-2006_09
Patent number
US07109354B2

Reaction notes

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