Water → HCID 18705602, compound

HRID 363416Notes

Reaction equation

HRID 363416 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH:7]12[NH:24][CH:20]([CH2:21][CH2:22][CH2:23]1)[C:19](=O)[NH:18][CH2:17][CH2:16][NH:15][CH2:14][CH2:13][NH:12][CH2:11][CH2:10][NH:9][C:8]2=O.O.[OH-].[Na+]>O1CCCC1>[CH:20]12[NH:24][CH:7]([CH2:23][CH2:22][CH2:21]1)[CH2:8][NH:9][CH2:10][CH2:11][NH:12][CH2:13][CH2:14][NH:15][CH2:16][CH2:17][NH:18][CH2:19]2

Participants

6

Reactant 4

HCID 962Water2×HCID 14798Sodium HydroxideHCID 18705606HCID 18705606, compoundHCID 21226445Aluminium lithium hydride2×

Product 1

HCID 18705602HCID 18705602, compoundYield 58%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent5×

Procedure

Lithium aluminum hydride in tetrahydrofuran (thf, 1.0M, 25 ml, 25.0 mmol) was added to anhydrous thf (25 ml) in a 250 ml flask under argon containing a stir bar. A slurry of 3,6,9,12,18-pentaazabicyclo[12.3.1]octadecan-2,13-dione prepared as in Example 38B (1.196 g, 4.326 mmol) in thf (50 ml) was added to the stirred lithium aluminum hydride solution (over about 10 min), and about 35 ml more thf was added to this to aid the addition. Gas evolved as the slurry went in; the color was beige and the reaction mixture was heterogeneous. After about 10 min of stirring, a reflux condenser was connected to the flask, and the reaction mixture was heated to reflux. The reaction mixture became yellow. Heating was stopped after 16 h, and the reaction mixture was cooled to room temperature. Water (0.95 ml) was added slowly with water bath cooling. Gas evolution occurred, and the reaction was exothermic. Next, 15% aqueous sodium hydroxide (0.95 ml) was added, and then 2.85 ml more water. After stirring for about an hour, thf (60 ml) was added and the stirring was continued. The mixture was filtered 1 h later under a strong flow of nitrogen from an inverted funnel, and the filtrate was stripped and placed on the vacuum line. The solid was recrystallized from hot acetonitrile under argon to give 631 mg (58% yield) of long white needles: mp 90°-90.5° C. (under nitrogen); 1H NMR (CDCl3) δ 1.05 (m, 2 H), 1.26 and 1.36 (br s and quart. t, J=13.0, 4.0 Hz, 3 H), 1.50 (m, 2 H), 1.80 (br m, 3 H), 2.40-3.05 (several m, 19 H): Exact mass (M+H)+ : calcd, 256.2501; found, 256.2513 (C13H30N5).

Workup

  1. additionwas added to
  2. additionthe addition
  3. customa reflux condenser was connected to the flask
  4. temperaturethe reaction mixture was heated to reflux
  5. temperatureHeating
  6. waitwas stopped after 16 h
  7. temperaturecooling
  8. stirringAfter stirring for about an hour
  9. filtrationThe mixture was filtered 1 h later under a strong flow of nitrogen from an inverted funnel
  10. customThe solid was recrystallized from hot acetonitrile under argon

Sources & evidence

ORD record
ord-65f952d362de40b391270b93cb192353
Source dataset
uspto-grants-1999_02
Patent number
US05874421

Reaction notes

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