Methane → HCID 86734121, compound

HRID 1729785Notes

Reaction equation

HRID 1729785 reaction equation
[H][H].[Cu:3][I:4].C.[CH3:6][N:7]([CH3:15])[P:8]([N:12]([CH3:14])[CH3:13])[N:9]([CH3:11])[CH3:10]>O>[Cu:3][I:4].[CH3:6][N:7]([CH3:15])[P:8]([N:12]([CH3:14])[CH3:13])[N:9]([CH3:11])[CH3:10]

Participants

6

Reactant 4

HCID 297MethaneHCID 15355Hexamethylphosphorous triamideHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)HCID 178418361HCID 178418361, compound

Product 1

HCID 86734121HCID 86734121, compoundYield 44%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

In the above reaction scheme, the starting material IV is readily prepared from the corresponding bromo- or iodo-derivatives which are commercially available; in IV, R1 can be hydrogen, loweralkyl of 1 to 3 carbon atoms, loweralkoxy of 1 to 3 carbon atoms, fluoro, chloro, trifluoromethyl, phenyl or phenoxy. Intermediate V is prepared by reacting cuprious-n-propyl acetylide (prepared according to Castro et al., J. Org. Chem., 31: 4071 [1966]) and hexamethylphosphorus triamide copper iodide, VI. Compound VI is prepared as follows: (1) add 18.39 g of purified CuI (Inorg. Synth., 7: 9 [ 1963]) to 177 g KI in 135 ml. H2O and stir with activated charcoal (Norite); (2) filter the solution through infusorial earth (Celite) and add 14.5 g (0.089 mole) of hexamethylphosphorous triamide (commercially available) under argon atmosphere; (3) filter, wash with aqueous KI and H2O; (4) dissolve product in dry ether, filter, remove ether in vacuo to obtain 13.85 g hexamethylphosphorous triamide copper (I) iodide:NMR (COCl3): singlet, δ 2.65. Compound VII, 15α-ethoxyethoxy-PGA-methyl ester is prepared from 15-α-hydroxy-PGA, which is available from coral extracts or which can be synthesized according to the Corey or Sih procedures (Corey et al., J. Am. Chem. Soc., 91: 5675 [1969]; Sih et al., J. Am. Chem. Soc., 95: 1676 [1973]).

Workup

  1. customIn the above reaction scheme
  2. customIntermediate V is prepared
  3. filtration(2) filter the solution through infusorial earth (Celite)
  4. filtration(3) filter
  5. washwash with aqueous KI and H2O
  6. dissolution(4) dissolve product in dry ether
  7. filtrationfilter
  8. customremove ether in vacuo

Sources & evidence

ORD record
ord-667bcdc4161f43ac861953e36b96b2b6
Source dataset
uspto-grants-1976_11
Patent number
US03989744

Reaction notes

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