Acetic Acid → N-(3-nitrophenyl)-3-(1,1,2,2-tetrafluoroethoxy)benzenemethanamine

HRID 1840076Notes

Reaction equation

HRID 1840076 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:8]=[CH:9][CH:10]=1)[NH2:7])([O-:3])=[O:2].[F:11][C:12]([F:25])([O:16][C:17]1[CH:18]=[C:19]([CH:22]=[CH:23][CH:24]=1)[CH:20]=O)[CH:13]([F:15])[F:14].C(O)(=O)C.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>ClC(Cl)C>[N+:1]([C:4]1[CH:5]=[C:6]([NH:7][CH2:20][C:19]2[CH:22]=[CH:23][CH:24]=[C:17]([O:16][C:12]([F:11])([F:25])[CH:13]([F:14])[F:15])[CH:18]=2)[CH:8]=[CH:9][CH:10]=1)([O-:3])=[O:2]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 74233-NitroanilineHCID 118803Benzaldehyde, 3-(1,1,2,2-tetrafluoroethoxy)-HCID 5049666Sodium triacetoxyborohydride

Product 1

HCID 23506093N-(3-nitrophenyl)-3-(1,1,2,2-tetrafluoroethoxy)benzenemethanamineYield 70%

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent

Procedure

EX-528A) 3-nitroaniline (1.87 g, 13.51 mmol) and 3-(1,1,2,2-tetrafluoroethoxy)-benzaldehyde (3 g, 13.5 mmol) were dissolved in 25 mL of dichloroethane and acetic acid (0.85 mL, 14.9 mmol), then solid NaBH(OAc)3 (3.73 g, 17.6 mmol) was added. The mixture was stirred at room temperature for 48 hours, then quenched with aqueous saturated sodium bicarbonate and diluted with ethyl acetate. The organic layer was dried over MgSO4, and concentrated in vacuo. The crude product was purified by flash column chromatography on silica gel eluting with ethyl acetate:hexane 1:7 to give 3.25 g (70%) of the desired N-(3-nitrophenyl)-3-(1,1,2,2-tetrafluoroethoxy) benzenemethan-amine product as a brown oil. HRMS calcd. for C15H13F4N2O3: 345.0862 [M+H]+, found: 345.0864. 1H NMR (CDCl3) δ 4.4 (s, 2H), 4.5 (s, 1H), 5.9 (tt, 1H), 6.9 (d, 1H), 7.1 (d, 1H), 7.2-7.3 (m, 3H), 7.4 (m, 2H), 7.5 (d, 1H).

Workup

  1. customquenched with aqueous saturated sodium bicarbonate
  2. additiondiluted with ethyl acetate
  3. dry with materialThe organic layer was dried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customThe crude product was purified by flash column chromatography on silica gel eluting with ethyl acetate:hexane 1:7

Sources & evidence

ORD record
ord-82ee627304604bd39be108c45b79fa5f
Source dataset
uspto-grants-2004_01
Patent number
US06677353B2

Reaction notes

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