1-(Chloromethyl)-3,5-bis(trifluoromethyl)benzene → HCID 86677030、化合物

HRID 927109

反応式

HRID 927109 の反応式
[CH2:1]([O:8][C:9]1[N:10]=[N:11][C:12](Cl)=[CH:13][C:14]=1[O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(P(C2CCCCC2)C2C=CC=CC=2C2C(C(C)C)=CC(C(C)C)=CC=2C(C)C)CCCCC1.Cl[CH2:59][C:60]1[CH:65]=[C:64]([C:66]([F:69])([F:68])[F:67])[CH:63]=[C:62]([C:70]([F:73])([F:72])[F:71])[CH:61]=1.[Mg].[Cl-].[Li+]>O1CCCC1.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Zn].[Cl-].[Zn+2].[Cl-]>[CH2:1]([O:8][C:9]1[N:10]=[N:11][C:12]([CH2:59][C:60]2[CH:61]=[C:62]([C:70]([F:72])([F:73])[F:71])[CH:63]=[C:64]([C:66]([F:67])([F:68])[F:69])[CH:65]=2)=[CH:13][C:14]=1[O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

11

反応物 5

HCID 1235761-(Chloromethyl)-3,5-bis(trifluoromethyl)benzeneHCID 433294Lithium ChlorideHCID 5462224MagnesiumHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 122134743,4-Bis(benzyloxy)-6-chloropyridazine2 回

生成物 1

HCID 86677030HCID 86677030、化合物収率 33%

試薬・触媒・溶媒 5

HCID 23994Zinc触媒HCID 167845palladium(II) acetate触媒HCID 3007855Zincchloride触媒HCID 8028Tetrahydrofuran溶媒3 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
65 °C

実験手順

To a solution of 3,4-bis(benzyloxy)-6-chloropyridazine (Intermediate 1) (1 g, 3.06 mmol)dicyclohexyl(2′,4′,6′-triisopropylbiphenyl-2-yl)phosphine (0.143 g, 0.3 mmol) and palladium (II) acetate (0.034 g, 0.15 mmol) in tetrahydrofuran (10 ml) under nitrogen was added the supernatant zinc reagent [generated from the addition of 1-(chloromethyl)-3,5-bis(trifluoromethyl)benzene (3 g, 11.43 mmol) to a suspension of magnesium (0.694 g, 28.6 mmol) in lithium chloride (28.6 ml, 14.28 mmol) in tetrahydrofuran (1M) and zinc(II) chloride (12.57 ml, 12.57 mmol) in tetrahydrofuran, warmed to 30° C. to initiate and stirred for one hour to complete] and the resulting red/brown mixture was heated at 65° C. for 16 hours. The reaction mixture was cooled, diluted with ethyl acetate and washed with saturated aqueous sodium bicarbonate solution, saturated aqueous ammonium chloride solution and brine. The organics were dried (MgSO4), filtered and solvent removed in vacuo to give a brown oil. The oil was purified by silica chromatography eluting with 0-40% ethyl acetate in petrol to yield the title compound (520 mg 33%).

後処理

  1. temperatureThe reaction mixture was cooled
  2. washwashed with saturated aqueous sodium bicarbonate solution, saturated aqueous ammonium chloride solution and brine
  3. dry with materialThe organics were dried (MgSO4)
  4. filtrationfiltered
  5. customsolvent removed in vacuo
  6. customto give a brown oil
  7. customThe oil was purified by silica chromatography
  8. washeluting with 0-40% ethyl acetate in petrol

出典と根拠

ORDレコード
ord-7419e22dd563442d9aeb0827d96f65fa
出典データセット
uspto-grants-2016_03
特許番号
US09290456B2

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