Diphenylmethylidenehydrazine → HCID 57635766、化合物

HRID 2109921ノート

反応式

HRID 2109921 の反応式
I[C:2]1[CH:3]=[C:4]([CH3:10])[CH:5]=[CH:6][C:7]=1[O:8][CH3:9].[C:11](=[N:24][NH2:25])([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CC([O-])(C)C.[Na+]>C1(C)C=CC=CC=1.CCOC(C)=O.O.CC([O-])=O.CC([O-])=O.[Pd+2].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[CH3:9][O:8][C:7]1[CH:6]=[CH:5][C:4]([CH3:10])=[CH:3][C:2]=1[NH:25][N:24]=[C:11]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

参加物

9

反応物 3

HCID 79304DiphenylmethylidenehydrazineHCID 1427263-Iodo-4-methoxytolueneHCID 23676156Sodium t-butoxide

生成物 1

HCID 57635766HCID 57635766、化合物収率 95.4%

試薬・触媒・溶媒 5

HCID 167845palladium(II) acetate触媒HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)触媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
85 °C

実験手順

To a stirred, degassed suspension of 3-iodo-4-methoxytoluene (19.84 g, 80 mmol, 1 equiv), benzophenone hydrazone (17.99 g, 88 mmol, 1.1 equiv), Xantphos (93 mg, 0.16 mmol, 0.2 mol %), and Pd(OAc)2 (36 mg, 0.16 mmol, 0.2 mol %) in anhydrous toluene (96 mL) was added NaOtBu (11.09 g, 112 mmol, 1.4 equiv) in one portion at rt. The mixture was heated to 85° C. and stirred for 12 h. The reaction mixture was cooled, diluted with 200 mL EtOAc and 100 mL water, then the layers separated. The insoluble Pd residues were separated as the aqueous layer was removed. The organic phase was washed 2×100 mL water, then brine, and dried over Na2SO4. The solution was concentrated under reduced pressure, giving an orange-yellow solid. The solid was triturated in 50 mL MeOH, collected via filtration, and washed with 50 mL MeOH. Drying under suction gave the title compound as a yellow solid (24.16 g, 95% yield). 1H NMR (400 MHz, DMSO-d6) δ 2.25 (s, 3H), 3.56 (s, 3H), 6.53 (dd, 1H), 6.72 (d, 1H), 7.30 (m, 6H), 7.46 (d, 2H), 7.56 (m, 1H), 7.62 (m, 2H), 7.79 (s, 1H). ES-MS m/z 317.1 (MH+); HPLC RT (min) 4.26.

後処理

  1. customTo a stirred, degassed
  2. temperatureThe reaction mixture was cooled
  3. customthe layers separated
  4. customThe insoluble Pd residues were separated as the aqueous layer
  5. customwas removed
  6. washThe organic phase was washed 2×100 mL water
  7. dry with materialbrine, and dried over Na2SO4
  8. concentrationThe solution was concentrated under reduced pressure
  9. customgiving an orange-yellow solid
  10. customThe solid was triturated in 50 mL MeOH
  11. filtrationcollected via filtration
  12. washwashed with 50 mL MeOH
  13. customDrying under suction

出典と根拠

ORDレコード
ord-7a6d5602b77c4a5893d8a76a188eeb0d
出典データセット
uspto-grants-2009_04
特許番号
US07517878B2

反応ノート

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