Acetic Acid → HCID 136017418, compound

HRID 2262325Notes

Reaction equation

HRID 2262325 reaction equation
[NH2:1][C:2]1[N:6]([CH2:7][CH2:8][OH:9])[N:5]=[C:4]([Br:10])[C:3]=1[N+:11]([O-:13])=[O:12].C=O.[C:16](O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(O)(=O)C>ClC(Cl)C>[Br:10][C:4]1[C:3]([N+:11]([O-:13])=[O:12])=[C:2]2[NH:1][CH2:16][O:9][CH2:8][CH2:7][N:6]2[N:5]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 712FormaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 57957908HCID 57957908, compound

Product 1

HCID 136017418HCID 136017418, compound

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent

Procedure

Treatment of 2-(5-amino-3-bromo-4-nitro-1H-pyrazol-1-yl)ethanol 1 with paraformaldehyde and sodium triacetoxyborohydride in dichloroethane containing acetic acid affords 8-bromo-9-nitro-1,2,4,5-tetrahydropyrazolo[5,1-d][1,3,5]oxadiazepine 2. The reaction of the compound 2 with KOH in the presence of Pd2dba3 and 2-di-tert-butylphosphino-2′,4′,6′-triisopropylbiphenyl in 1,4-dioxane, water provides 9-nitro-1,2,4,5-tetrahydropyrazolo[5,1-d][1,3,5]oxadiazepin-8-ol 3, which upon treatment with MeI and cetylammonium bromide in 1,4-dioxane/water/KOH affords compound 8-methoxy-9-nitro-1,2,4,5-tetrahydropyrazolo[5,1-d][1,3,5]oxadiazepine 4 (J. Am. Chem. Soc. 2006, 128, 10694). Hydrogenation of 4 with Pd/C at 60 psi of hydrogen yields 8-methoxy-1,2,4,5-tetrahydropyrazolo[5,1-d][1,3,5]oxadiazepin-9-amine 5.

Sources & evidence

ORD record
ord-a1c0bee3490f40f490016250cdeb5392
Source dataset
uspto-grants-2010_12
Patent number
US07850742B2

Reaction notes

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