Tert-Butyl nitrite → HCID 178458180, compound

HRID 2306570Notes

Reaction equation

HRID 2306570 reaction equation
N(OC(C)(C)C)=O.[CH2:8]([O:11][C:12]1[CH:24]=[CH:23][C:15]2[N+:16]([O-:22])=[C:17](N)[N:18]=[N+:19]([O-:20])[C:14]=2[CH:13]=1)[CH:9]=[CH2:10]>CN(C=O)C>[CH2:8]([O:11][C:12]1[CH:24]=[CH:23][C:15]2[N+:16]([O-:22])=[CH:17][N:18]=[N+:19]([O-:20])[C:14]=2[CH:13]=1)[CH:9]=[CH2:10]

Participants

4

Reactant 2

HCID 10906Tert-Butyl nitrite2×HCID 135624029121135-28-2

Product 1

HCID 178458180HCID 178458180, compoundYield 38%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred solution of t-butyl nitrite (271 mg, 0.312 ml, 2.63 mmol) in DMF (15 ml) at 60-65° C. was added 7-allyloxy-3-amino-1,2,4-benzotriazine-1,4-dioxide 23 (205 mg, 0.875 mmol) in small portions over 5 min. After 30 min additional t-butyl nitrite (271 mg, 0.312 ml, 2.63 mmol) was added, and shortly thereafter the deep red solution effervesced and lightened appreciably in color over a period of a few minutes. After an additional 30 min the resultant orange solution was reduced under vacuum to a brown solid which was sequentially flash chromatographed (10% EtOAc/CH2Cl2) and crystallized (CH2Cl2/petroleum ether) to give 72 mg (38% yield) of the product 24 as light orange crystals, mp 147-148° C. NMR: δ (400 MHz, d6-acetone) 4.89 (2H, ddd, H-1′, J1′,2′=5.5, J1′,3′cis=J1′,3′trans=1.5 Hz), 5.36 (1H, ddd, H-3′, J3′,2′cis=10.5, J3′,3′=3 J3′,1′=1.5 Hz), 5.52 (1H, ddd, H-3′, J3′,2′trans=17.5, J3′,3′=3, J3′1′=1.5 Hz), 6.14 (1H, ddt, H-2′, J2′,3′cis=10.5, J2′,1′=5.5 Hz), 7.70 (1H, d, H-8, J8,6=2.5 Hz), 7.74 (1H, dd, H-6, J6,5=9.5, J6,8=2.5 Hz), 8.33 (1H, d, H-5, J5,6=9.5 Hz), 8.93 (1H, s, H-3). UV: λ 425, 410, 365, 355, 320, 245, 200. MS m/z/(relative intensity) 220(4), 219(34, M+), 103(4), 77(4), 75(4), 63(13), 62(4), 42(3), 41(100), 39(16). Anal. Calc'd. for C10H9N3O3: C, 54.79; H, 4.14; N, 19.17. Found: C, 54.73; H, 4.16; N, 19.15.

Workup

  1. waitlightened appreciably in color over a period of a few minutes
  2. customchromatographed (10% EtOAc/CH2Cl2)
  3. customcrystallized (CH2Cl2/petroleum ether)

Sources & evidence

ORD record
ord-87d9957e945b4e008dfd669b008cb943
Source dataset
uspto-grants-2004_12
Patent number
US06828321B2

Reaction notes

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