Pyridine → HCID 18977332, compound

HRID 2393873Notes

Reaction equation

HRID 2393873 reaction equation
[OH:1][CH2:2][C:3]1([CH3:17])[CH2:8][O:7][C:6]2([O:13][CH2:12][C:11]([CH2:15][OH:16])([CH3:14])[CH2:10][O:9]2)[O:5][CH2:4]1.N1C=CC=CC=1.[C:24](OC(=O)C)(=[O:26])[CH3:25].[CH3:31][CH2:32][O:33]C(C)=O>>[C:24]([O:16][CH2:15][C:11]1([CH3:14])[CH2:10][O:9][C:6]2([O:5][CH2:4][C:3]([CH2:2][O:1][C:32](=[O:33])[CH3:31])([CH3:17])[CH2:8][O:7]2)[O:13][CH2:12]1)(=[O:26])[CH3:25]

Participants

5

Reactant 4

HCID 1049PyridineHCID 7918Acetic AnhydrideHCID 8857Ethyl AcetateHCID 18977335HCID 18977335, compound

Product 1

HCID 18977332HCID 18977332, compound

Procedure

A 100 mL one-neck round-bottom flask was charged with 3,9-dihydroxymethyl-3,9-dimethyl-1,5,7,11-tetraoxaspiro[5.5]undecane prepared as in Example 2 (DHMDM-SOC, 4.6 g, 0.0185 mol) and pyridine (25 mL) under N2. After DHMDM-SOC was dissolved, acetic anhydride (26.2 mL, 0.28 mole) was added. The mixture was stirred at room temperature for 4 h. TLC (1:3 Hexanes:EtOAc) revealed the disappearance of DHMDM-SOC and a new product spot (Rf~0.6). Pyridine and unreacted acetic anhydride were removed under reduced pressure using rotary evaporator. The residue was off-white solid as crude product. It was purified by recrystallization from cyclohexane. The solid was dissolved in ~300 mL of cyclohexane, and the solution was cooled to room temperature, kept in refrigerator overnight to crystallize. The crystals were collected by filtration, washed with cyclohexane (3×20 mL), and dried in vacuo, giving 5.7 g of white crystals as product (93.4 % of theory). m.p. (DSC): 137.4° C.; 1H NMR (CDCl3, 75 Mhz) δ0.87 (s, 6H), 2.05 (s, 6H); 3.65-3.80 (m, 8H), 4.12 (s, 4H); 13C NMR (CDCl3, 75 MHz) δ1711, 20.73, 32.88, 66.17, 67.87, 68.26, 114,20, 170.78. Anal. calcd. for C15H24O8 ; C, 54.21; H, 7.28. Found: C, 54.31; H, 7.48.

Workup

  1. dissolutionAfter DHMDM-SOC was dissolved
  2. customPyridine and unreacted acetic anhydride were removed under reduced pressure
  3. customevaporator
  4. customIt was purified by recrystallization from cyclohexane
  5. dissolutionThe solid was dissolved in ~300 mL of cyclohexane
  6. temperaturethe solution was cooled to room temperature
  7. customkept in refrigerator overnight
  8. customto crystallize
  9. filtrationThe crystals were collected by filtration
  10. washwashed with cyclohexane (3×20 mL)
  11. customdried in vacuo

Sources & evidence

ORD record
ord-d353da8e1b0549d1b5d08554a7f4ed88
Source dataset
uspto-grants-1998_09
Patent number
US05808108

Reaction notes

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