1,5-Di(4-toluenesulfonamido)-3,7-bismethylenediazacyclooctane → 1,5-Dimethyl-3,7-diazabicyclooctane

HRID 355540Notes

Reaction equation

HRID 355540 reaction equation
C1(C)C=CC(S(N[N:11]2[CH2:18][C:17](=[CH2:19])[CH2:16][CH:15](NS(C3C=CC(C)=CC=3)(=O)=O)[CH2:14][C:13](=[CH2:31])N2)(=O)=O)=CC=1.[H-].[Al+3].[Li+].[H-].[H-].[H-]>O1CCCC1>[CH3:15][C:17]1([CH:16]2[CH2:15][CH2:14][CH2:13][CH2:31][CH2:14][CH2:13][CH2:31]2)[CH2:18][NH:11][CH2:19][CH:17]([CH3:16])[CH2:18][NH:11][CH2:19]1

Participants

4

Reactant 2

HCID 189428561,5-Di(4-toluenesulfonamido)-3,7-bismethylenediazacyclooctaneHCID 21226445Aluminium lithium hydride

Product 1

HCID 189428581,5-Dimethyl-3,7-diazabicyclooctaneYield 91.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A suspension of 1,5-di(4-toluenesulfonamido)-3,7-bismethylenediazacyclooctane 1a (2.22 g, 4.98 mmol) in tetrahydrofuran (75 mL) containing lithium aluminum hydride (1.90 g, 50 mmol) was stirred under a nitrogen atmosphere for 42 h. The reaction mixture was quenched by the dropwise addition of 20% sodium hydroxide solution (4.5 mL) with external cooling. Stirring was continued at room temperature for 3 h and the white granular precipitate that formed was removed by filtration and washed with anhydrous ether (3×50 mL). The combined organic extracts were concentrated on a rotary evaporator to give 0.574 g (82%) of 5 as a colorless solid, mp XX° C. 1H NMR (CDCl3) δ0.99 (s, 6H), δ2.71 (d, J=11.2 Hz, 4H), δ2.92 (d, J=11.2 Hz, 4H), δ2.61 (s, 2H. br); 13C NMR (CDCl3) δ20.4, δ51.7, δ62.6. LRMS (EI) calc. for C8H16N2 140.1; found m/z, 140. Treatment of an ethanolic solution of 5 with picric acid afforded the picrate as a yellow solid, mp 258° C.

Workup

  1. customThe reaction mixture was quenched by the dropwise addition of 20% sodium hydroxide solution (4.5 mL) with external cooling
  2. stirringStirring
  3. waitwas continued at room temperature for 3 h
  4. customthe white granular precipitate that formed
  5. customwas removed by filtration
  6. washwashed with anhydrous ether (3×50 mL)
  7. concentrationThe combined organic extracts were concentrated on a rotary evaporator

Sources & evidence

ORD record
ord-8f5aca694a614d1e8eba974e0f341c85
Source dataset
uspto-grants-1998_11
Patent number
US05831099

Reaction notes

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