Sodium Carbonate → N-cyclopropyl-3-(4,4-diethoxybutyl)-4-fluorobenzamide

HRID 1985756

反応式

HRID 1985756 の反応式
[CH2:1]([O:3][CH:4]([O:8][CH2:9][CH3:10])[CH2:5][CH:6]=[CH2:7])[CH3:2].B1C2CCCC1CCC2.C([O-])([O-])=O.[Na+].[Na+].Br[C:27]1[CH:28]=[C:29]([CH:36]=[CH:37][C:38]=1[F:39])[C:30]([NH:32][CH:33]1[CH2:35][CH2:34]1)=[O:31]>C(OCC)(=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCO.C1C=CC=CC=1>[CH:33]1([NH:32][C:30](=[O:31])[C:29]2[CH:36]=[CH:37][C:38]([F:39])=[C:27]([CH2:7][CH2:6][CH2:5][CH:4]([O:8][CH2:9][CH3:10])[O:3][CH2:1][CH3:2])[CH:28]=2)[CH2:34][CH2:35]1

参加物

9

反応物 4

HCID 10340Sodium CarbonateHCID 789669-Borabicyclo(3.3.1)nonaneHCID 2564264,4-Diethoxybut-1-eneHCID 220190903-Bromo-N-cyclopropyl-4-fluorobenzamide

生成物 1

HCID 22019163N-cyclopropyl-3-(4,4-diethoxybutyl)-4-fluorobenzamide収率 93.4%

試薬・触媒・溶媒 4

HCID 178418397HCID 178418397、化合物触媒HCID 241Benzene溶媒HCID 702Ethanol溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
80 °C

実験手順

A solution of 3-butenal diethyl acetal (144 mg, 1 mmol) and 9-BBN (0.5 M in THF, 2.2 mL, 1.1 mmol) was stirred at RT for 1 h. The mixture was concentrated and to the residue were added benzene (2 mL), EtOH (1 mL), aqueous Na2CO3 solution (2M, 1 mL), 3-bromo-4-fluoro-N-cyclopropylbenzamide (127 mg, 0.5 mmol) and Pd(Ph3P)4 (40 mg). The resulting mixture was stirred at 80° C. for 2 h. The mixture was then cooled to RT and diluted with ethyl acetate (10 mL) and washed with water. The organic layer was separated and concentrated. The residue was purified by column chromatography (SiO2; EtOAc/hexane 1:3) to afford N-cyclopropyl-3-(4,4-diethoxybutyl)-4-fluorobenzamide (151 mg, 93%). This material was dissolved in acetone (1 mL) and 3 N HCl solution (0.2 mL) and stirred at RT for 1 h. The mixture was neutralized with NaHCO3 solution and extracted with ethyl acetate (3×5 mL). The organic layer was dried and concentrated to afford N-cyclopropyl-4-fluoro-3-(4-oxo-butyl)-benzamide (110 mg, 94%). 1H NMR (CDCl3) δ 9.76 (s, 1H), 7.63 (dd, 1H, J=7.5 and 2.2 Hz,), 7.58 (m, 1H), 7.03 (t, 1H, J=9.0 Hz,), 6.47 (s, NH, 1H), 2.87 (m, 1H), 2.69 (t, 2H, J=7.5 Hz,), 2.48 (m, 2H), 1.95 (m, 2H), 0.86 (m, 2H) and 0.62 (m, 2H).

後処理

  1. concentrationThe mixture was concentrated and to the residue
  2. temperatureThe mixture was then cooled to RT
  3. washwashed with water
  4. customThe organic layer was separated
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography (SiO2; EtOAc/hexane 1:3)

出典と根拠

ORDレコード
ord-6acb1d04a85546bfb4027103cf1e03b9
出典データセット
uspto-grants-2009_06
特許番号
US07547711B2

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