Formic Acid → 2,6,9-Tribenzyl-4,8-dinitro-2,6,9-triaza-bicyclo[3.3.1]nona-3,7-diene

HRID 341111Notes

Reaction equation

HRID 341111 reaction equation
[OH2:1].[N+:2]([CH:5]([CH:8]=O)[CH:6]=O)([O-:4])=[O:3].[Na].C(O)=O.[CH2:14]([NH2:21])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>CO.O>[CH2:14]([N:21]1[CH:8]=[C:5]([N+:2]([O-:4])=[O:3])[CH:6]2[N:21]([CH2:14][C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[CH:8]1[C:5]([N+:2]([O-:3])=[O:1])=[CH:6][N:21]2[CH2:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

6

Reactant 3

HCID 284Formic AcidHCID 7504BenzylamineHCID 71317419Sodium nitromalonaldehyde hydrate

Product 1

HCID 863043902,6,9-Tribenzyl-4,8-dinitro-2,6,9-triaza-bicyclo[3.3.1]nona-3,7-dieneYield 65.1%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent

Procedure

A yellow-orange suspension of sodium nitromalonaldehyde monohydrate (63 mg, 0.40 mmol) in methanol (760 uL), water (32 uL) and 96% formic acid (3.2 uL, 0.084 mmol) was stirred at room-temperature and benzylamine (91.7 uL, 0.84 mmol) was added dropwise over a 5 min period during which the reaction solids dissolved, subsequently the crude product then quickly crystallized. The orange reaction mixture was stirred about 2 days at room-temperature. Filtration gave a yellow powder (63 mg) of which 59 mg was recrystallized from absolute ethanol (˜10 mL) yielding 25 mg (26%) of the title compound BC1 as a yellow, microcrystalline solid: mp 184-185° C.; HRMS calcd for C27H26N5O4 (M+H+) 484.1985, obsd 484.18924; 1H NMR (300 MHz, DMSO-d6) δ 3.004 (s, 2H), 4.789-5.002 (q, 4H), 5.350 (s, 2H), 6.631-6.659 (d, 2H), 7.035-7.136 (m, 3H), 7.36-7.37 (br s, 10H), 8.800 (s, 2H); 1H NMR (300 MHz, CDCl3) δ 2.948, 2.955 (d, 2H), 4.581, 4.630 (d, 2H), 4.974, 5.023 (d, 2H), 5.308 (s, 2H), 6.714, 6.737 (d, 2H), 7.090, 7.116, 7.170-7.20 (m, 3H), 7.289, 7.298, 7.310, 7.321, 7.335, 7.342, 7.353, 7.363, 7.375 (complex m, 10H), 8.358 (s, 2H); 13C NMR (75 MHz, DMSO-d6) δ 145.704, 135.410, 135.380, 128.787, 128.382, 128.199, 127.879, 127.230, 120.561, 64.383, 57.309, 52.166; Anal. Calcd for C27H25N5O4 (483.52): C, 67.07; H, 5.21; N, 14.48. Found: C, 66.80; H, 5.13; N, 14.45.

Workup

  1. additionwas added dropwise over a 5 min period during which
  2. customthe reaction solids
  3. dissolutiondissolved
  4. customsubsequently the crude product then quickly crystallized
  5. filtrationFiltration

Sources & evidence

ORD record
ord-0af12551e7cf445493ad3f0944a0f3d3
Source dataset
uspto-grants-2014_11
Patent number
US08895736B1

Reaction notes

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