Tert-Butyl nitrite → HCID 178458180, compound

HRID 1954017Notes

Reaction equation

HRID 1954017 reaction equation
[CH2:1]([O:4][C:5]1[CH:17]=[CH:16][C:8]2[N+:9]([O-:15])=[C:10](N)[N:11]=[N+:12]([O-:13])[C:7]=2[CH:6]=1)[CH:2]=[CH2:3].N(OC(C)(C)C)=O>CN(C=O)C>[CH2:1]([O:4][C:5]1[CH:17]=[CH:16][C:8]2[N+:9]([O-:15])=[CH:10][N:11]=[N+:12]([O-:13])[C:7]=2[CH:6]=1)[CH:2]=[CH2:3]

Participants

4

Reactant 2

HCID 10906Tert-Butyl nitriteHCID 135624029121135-28-2

Product 1

HCID 178458180HCID 178458180, compoundYield 38%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a stirred solution of t-butyl nitride (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, m.p. 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(1 H, ddd, H-3', J3'.2'cis =10.5, J3'.3' =1.5 Hz), 5.52 (1 H, ddd, H-3', J3'.2'trans =17.5, J3'.3' =3, J3'1' =1.5 Hz), 6.14 (1 H, ddd, H-2', J2',3'cis =10.5, J2'.1' --5.5 Hz), 7.70 (1 H, d, H-8, J8.6 =2.5 Hz), 7.74 (1 H, dd, H-6, J6.5 =9.5, J6.8 --2.5 Hz), 8.33 (1 H, d, H-5, J5.6 =9.5 Hz), 8.93 (1 H,s, H-3). UV: λmax 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-ccd41f8a6dde490a9d2897c623f2d794
Source dataset
uspto-grants-2000_09
Patent number
US06121263

Reaction notes

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