1-(Chloromethyl)-3,5-bis(trifluoromethyl)benzene → HCID 86677030, 화합물

HRID 927109

반응식

HRID 927109 반응식
[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

참가 물질

11

반응물 5

HCID 1235761-(Chloromethyl)-3,5-bis(trifluoromethyl)benzeneHCID 433294Lithium ChlorideHCID 5462224MagnesiumHCID 111557942-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenylHCID 122134743,4-Bis(benzyloxy)-6-chloropyridazine2회

생성물 1

HCID 86677030HCID 86677030, 화합물수율 33%

시약·촉매·용매 5

HCID 23994Zinc촉매HCID 167845palladium(II) acetate촉매HCID 3007855Zincchloride촉매HCID 8028Tetrahydrofuran용매3회HCID 8857Ethyl Acetate용매

반응 조건

온도
65 °C

실험 절차

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%).

후처리

  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

출처 및 근거

ORD 기록
ord-7419e22dd563442d9aeb0827d96f65fa
출처 데이터셋
uspto-grants-2016_03
특허 번호
US09290456B2

연결된 노트

불러오는 중…