Sodium Hydroxide → HCID 67264226、化合物

HRID 1040604

反応式

HRID 1040604 の反応式
[CH3:1][O:2][C:3]1[CH:13]=[CH:12][C:6]2[CH2:7][CH2:8][NH:9][CH2:10][CH2:11][C:5]=2[CH:4]=1.FC(F)(F)C([NH-])=O.N1C2C=CC=CC=2C=CC=C1.[N+:32]([O-:35])([O-:34])=[O:33].[K+].[OH-].[Na+]>C(#N)C.FC(F)(F)C(OC(=O)C(F)(F)F)=O>[CH3:1][O:2][C:3]1[C:13]([N+:32]([O-:34])=[O:33])=[CH:12][C:6]2[CH2:7][CH2:8][NH:9][CH2:10][CH2:11][C:5]=2[CH:4]=1.[CH3:1][O:2][C:3]1[CH:13]=[C:12]([N+:32]([O-:35])=[O:33])[C:6]2[CH2:7][CH2:8][NH:9][CH2:10][CH2:11][C:5]=2[CH:4]=1

参加物

9

反応物 5

HCID 14798Sodium HydroxideHCID 24434Potassium NitrateHCID 138533487-Methoxy-2,3,4,5-tetrahydro-1h-3-benzazepineHCID 155596581H-1-BenzazepineHCID 178514236HCID 178514236、化合物

生成物 2

HCID 67264226HCID 67264226、化合物HCID 672643517-Methoxy-8-nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒HCID 9845Trifluoroacetic anhydride溶媒

反応条件

温度
0 °C

実験手順

7-Methoxy-2,3,4,5-tetrahydro-1H-benzo[d]azepine (750 mg/4.2 mmol) was dissolved in a mixture of dry acetonitrile (3 mL) and trifluoroacetic anhydride (3 mL) and cooled to 0° C. (ice bath). The trifluoroacetyl amide of the benzazepine forms immediately (observed by HPLC). Potassium nitrate (450 mg/4.2 mmol) was added in one portion and the mixture allowed to warm to room temperature. After one hour the reaction was complete (HPLC); 33% sodium hydroxide (1 mL) was added via pipette (exotherm) and the mixture stirred for an additional two hours (to hydrolyze the TFA amide). The resulting mixture was partitioned between water (20 mL) and methylene chloride (20 mL). The aqueous layer was extracted with an additional portion of methylene chloride (20 mL) and the combined organics were dried over magnesium sulfate, filtered and concentrated to afford a 1.7:1 ratio of 7-Methoxy-8-nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine and 7-Methoxy-9-nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine as a yellow oil (770 mg/82%). The material was used without further purification. 1H NMR (400 MHz, CDCl3) major isomer: δ 7.66 (s, 1H), 6.82 (s 1H); minor isomer: 7.14 (d, J=8.3 Hz, 1H), 6.76 (d, J=8.3 Hz, 1H).

後処理

  1. temperatureto warm to room temperature
  2. customThe resulting mixture was partitioned between water (20 mL) and methylene chloride (20 mL)
  3. extractionThe aqueous layer was extracted with an additional portion of methylene chloride (20 mL)
  4. dry with materialthe combined organics were dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated

出典と根拠

ORDレコード
ord-a5235457eceb45c7b9d4ab36eea368bf
出典データセット
uspto-grants-2013_10
特許番号
US08552186B2

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