Cyanogen azide ((CN)(N3)) → HCID 13496666, compound

HRID 358452Notes

Reaction equation

HRID 358452 reaction equation
[CH3:1][N:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH2:3]1.[N:9]#[C:10][N:11]=[N+]=[N-]>CCOCC>[C:10]([N:11]1[CH:3]2[CH:4]1[C:5]([CH3:8])=[CH:6][CH2:7][N:2]2[CH3:1])#[N:9]

Participants

4

Reactant 2

HCID 136583Cyanogen azide ((CN)(N3))HCID 13496664HCID 13496664, compound

Product 1

HCID 13496666HCID 13496666, compoundYield 76.2%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A solution of 1,4-dimethyl-1,2-dihydropyridine (9.69 g, 65 mmol) in ether (10 ml) was added slowly with stirring at 0° C. to a solution of cyanogen azide (5.1 g, 75 mmol). The reaction mixture was allowed to return to 25° C. and the solvent was removed in vacuo to give a reddish-brown product which was partitioned between 200 ml methylene chloride-water (1:1 v/v). The methylene chloride extract was dried (MgSo4) and the solvent removed in vacuo to give 7-cyano-2,5-dimethyl-2,7-diazabicyclo [4.1.0]hept-4-ene (7.39 g, 76.2%) as a tan solid with mp 117° C. 10% palladium on charcoal (400 mg) was added to a solution of 7-cyano-2,5-dimethyl-2,7-diazabicyclo[4.1.0]hept-4-ene (2.23 g, 15 mmol) in 50 ml methanol and the reduction was effected using 10% palladium on charcoal and hydrogen gas at 35 psi for 24 hours. Filtration and then removal of the solvent in vacuo gave 1,4-dimethylpiperidylidene-2-cyanamide as a white solid (2.26 g, 99.8%) with mp 94° C; IR (KBr) 2180 (C≡N) and 1598 cm-` (C=N); NMR (CDCl3) 3.44 (m, 2H, H-6), 3.05 (s, 3H, N--Me), 2.9 (m, 1H, H-3), 2.35 (m, 1H, H-3), 2.15-1.2 (m, 3H, H-4, H-5), 1.04 (d, J=5Hz, 3H, C-4 Me). Mass spectra (70 ev): Mass calc'd for C8H13N3 : 151,1109; found: 151.1107.

Workup

  1. customto return to 25° C.
  2. customthe solvent was removed in vacuo
  3. customto give a reddish-brown product which
  4. customwas partitioned between 200 ml methylene chloride-water (1:1 v/v)
  5. extractionThe methylene chloride extract
  6. customwas dried (MgSo4)
  7. customthe solvent removed in vacuo

Sources & evidence

ORD record
ord-695365c30ef54fbfb6872fb869e1534a
Source dataset
uspto-grants-1984_08
Patent number
US04468403

Reaction notes

Loading…