2-Bromoaniline → HCID 66718653, compound

HRID 1430357Notes

Reaction equation

HRID 1430357 reaction equation
[Br:1][C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH2:4].[N:9]([O-])=O.[Na+].[CH3:13][C:14]1([CH3:23])[CH2:19][CH:18]([OH:20])[CH2:17][C:16]([CH3:22])([CH3:21])[NH:15]1.[OH-].[Na+]>C1COCC1.Cl.O>[Br:1][C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[N:4]=[N:9][N:15]1[C:16]([CH3:22])([CH3:21])[CH2:17][CH:18]([OH:20])[CH2:19][C:14]1([CH3:23])[CH3:13]

Participants

8

Reactant 4

HCID 119922-BromoanilineHCID 14798Sodium HydroxideHCID 754714-Hydroxy-2,2,6,6-tetramethylpiperidineHCID 23668193Sodium Nitrite

Product 1

HCID 66718653HCID 66718653, compound

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolvent2×HCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent3×

Procedure

50 g crushed ice are added to a solution of 2-bromoaniline in 4 ml THF and 4 ml aqueous HCl (32% w/w). The yellow suspension is diazotized at −5° C. by treatment with a solution of 1.1 g sodium nitrite in 10 ml water. After 3 h, a solution of 2.76 g 2,2,6,6-tetramethyl-4-hydroxypiperidine in 1.5 ml aqueous HCl (32% w/w) and 1 ml THF are added dropwise to the thick yellow suspension at −3° C. Addition of water (ca. 20 ml) is necessary to keep the mixture well stirrable. The reaction mixture is then neutralized by adding dropwise 8.8 ml of aqueous sodium hydroxide (30% w/w) and 4 ml THF between 0 and 2° C. The brownish mixture is extracted with ethyl acetate. The organic phase is separated, evaporated and chromatographed on silica gel with hexane-ethylacetate (3:1), yielding 1.11 g of 1-(2-bromophenyl-diazenyl)-2,2,6,6-tetramethyl-piperidin-4-ol as a red-brown solid, m.p. 81° C.

Workup

  1. custom50 g crushed ice
  2. extractionThe brownish mixture is extracted with ethyl acetate
  3. customThe organic phase is separated
  4. customevaporated
  5. customchromatographed on silica gel with hexane-ethylacetate (3:1)

Sources & evidence

ORD record
ord-f43d87d5e6a44401adb6133a3b80f0ac
Source dataset
uspto-grants-2015_01
Patent number
US08940806B2

Reaction notes

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