Sodium Iodide → HCID 20331740, compound

HRID 2057621Notes

Reaction equation

HRID 2057621 reaction equation
[OH:1][CH:2]([CH2:11][CH2:12][CH2:13][CH2:14][CH3:15])[CH2:3][CH2:4][N:5]1[C:9](=[O:10])[CH2:8][CH2:7][NH:6]1.[C:16]([NH:20][C:21](=[O:30])[CH:22](Cl)[CH2:23][CH2:24][CH2:25][CH2:26][CH2:27]Br)([CH3:19])([CH3:18])[CH3:17].C([O-])(O)=O.[Na+].[Na+].[I-].[OH-].[Na+]>C1S(=O)(=O)CCC1.O>[C:16]([NH:20][C:21](=[O:30])[CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][N:6]1[CH2:7][CH2:8][C:9](=[O:10])[N:5]1[CH2:4][CH2:3][CH:2]([OH:1])[CH2:11][CH2:12][CH2:13][CH2:14][CH3:15])([CH3:19])([CH3:18])[CH3:17]

Participants

8

Reactant 5

HCID 5238Sodium IodideHCID 14798Sodium HydroxideHCID 516892Sodium BicarbonateHCID 20331732HCID 20331732, compoundHCID 20331737HCID 20331737, compound2×

Product 1

HCID 20331740HCID 20331740, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 31347SulfolaneSolvent

Procedure

The 2(3-hydroxy-n-octyl)-3-pyrazolidinone (6) used in this and subsequent examples is prepared according to the General Synthetic Scheme (Ic) shown above and described in more detail in U.S. Pat. No. 3,873,566. A mixture of 3.85 g (18 mmoles) of pyrazolidinone alcohol 6 and 4.90 g (about 18 mmoles) of the N(tert-butyl)-7-bromo(chloro)heptanamide (Example 1a), 5.0g NaHCO3, and 0.25 g NaI in 25 ml of tetramethylene sulfone was heated at 70° for about 56 hrs. The mixture was cooled, poured into 300 ml of H2O and 5% NaOH was added to adjust the pH to 9. The mixture was extracted with ether twice. The combined ether extracts were washed with water and with saturated NaCl solution and dried over anhy. Na2SO4. The dry solution was filtered and treated with HCl gas until no more of the hydrochloride salt (8) separated (as a oil). The oil 8 was run into a separatory funnel, mixed with 50 ml of 5% Na2CO3 solution and extracted into ether. Evaporation of the ether after drying over Na2SO4 gave 3.01 g of N(tert-butyl)7[3-oxo-2(3-hydroxy-n-octyl)pyrazolidin-1-yl]heptanamide 7 which, according to TLC on silica gel (2:1 acetone-toluene; iodine; Rf 0.37) was about 95% pure. The pmr spectrum (CDCl3, TMS) agreed with the assigned structure (tert-butyl 1.33 ppm), as did the IR spectrum [λmax 3320, 3070 (weak, sharp), 1670-1650 (broad, strong) cm-1 ]. A portion of this sample was further purified by preparative scale HPLC (6% MeOH/EtOAc) and analyzed by HRMS:

Workup

  1. customis prepared
  2. temperaturewas heated at 70° for about 56 hrs
  3. temperatureThe mixture was cooled
  4. additionwas added
  5. extractionThe mixture was extracted with ether twice
  6. washThe combined ether extracts were washed with water and with saturated NaCl solution
  7. customdried over anhy
  8. filtrationThe dry solution was filtered
  9. additiontreated with HCl gas until no more of the hydrochloride salt (8)
  10. customseparated (as a oil)
  11. customThe oil 8 was run into a separatory funnel
  12. additionmixed with 50 ml of 5% Na2CO3 solution
  13. extractionextracted into ether
  14. customEvaporation of the ether
  15. dry with materialafter drying over Na2SO4

Sources & evidence

ORD record
ord-aca74d6919ae4b18809b25a8942f6a3f
Source dataset
uspto-grants-1980_07
Patent number
US04211876

Reaction notes

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