4-Bromotoluene → Ethyl (E)-4-[2-(5,6-dihydro-5,5-dimethyl-8-(4-methylphenyl)-2-naphthalenyl)ethenyl]-benzoate

HRID 613330

반응식

HRID 613330 반응식
[C:1]([Li:5])([CH3:4])([CH3:3])[CH3:2].Br[C:7]1[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][CH:8]=1.[CH3:14][C:15]1(C)CC=C(OS(C(F)(F)F)(=O)=O)[C:21]2[CH:20]=[C:19](/[CH:33]=[CH:34]/[C:35]3[CH:45]=[CH:44][C:38]([C:39]([O:41][CH2:42][CH3:43])=[O:40])=[CH:37][CH:36]=3)[CH:18]=[CH:17][C:16]1=2>CCCCC.C1COCC1.[Cl-].[Cl-].[Zn+2].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>[Li:5][C:7]1[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][CH:8]=1.[CH3:2][C:1]1([CH3:4])[CH2:14][CH:15]=[C:16]([C:7]2[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][CH:8]=2)[C:17]2[CH:18]=[C:19](/[CH:33]=[CH:34]/[C:35]3[CH:45]=[CH:44][C:38]([C:39]([O:41][CH2:42][CH3:43])=[O:40])=[CH:37][CH:36]=3)[CH:20]=[CH:21][C:3]1=2

참가 물질

9

반응물 3

HCID 78054-BromotolueneHCID 19695065ethyl (E)-4-[2-(5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-5,6-dihydronaphthalen-2-yl)ethenyl]benzoate2회HCID 178418306HCID 178418306, 화합물

생성물 2

HCID 22323752Ethyl (E)-4-[2-(5,6-dihydro-5,5-dimethyl-8-(4-methylphenyl)-2-naphthalenyl)ethenyl]-benzoateHCID 178506695HCID 178506695, 화합물

시약·촉매·용매 4

HCID 3007855Zincchloride촉매HCID 178418397HCID 178418397, 화합물촉매HCID 8003Pentane용매HCID 8028Tetrahydrofuran용매3회

실험 절차

A solution of 4-lithiotoluene was prepared at -78° C. by the addition of 130.7 mg of t-butyllithium (2.04 mmol; 1.20 ml of a 1.7M solution in pentane) to a solution of 374.5 mg (2.20 mmol) of 4-bromotoluene in 2.5 ml of THF. After 30 minutes a solution of 313.4 mg (2.30 mmol) of ZnCl2 in 2.0 ml of THF was added. The resulting solution was warmed to room temperature, stirred for 1.25 hour and then added via canula to a solution of 285.0 mg (0.590 mmol) of ethyl (E)-4-[2-(5,6-dihydro-5,5-dimethyl-8-(trifluoromethylsulfonyl)oxy-2-naphthalenyl)ethenyl]-benzoate (Compound P) and 29.0 mg (0.025 mmol) of tetrakis(triphenylphosphine)palladium(0) in 2.0 ml of THF. The resulting solution was stirred at room temperature for 1 hour and then at 55° C. for 2 hours. Upon cooling to room temperature the reaction was quenched by the addition of saturated aqueous NH4Cl. The mixture was extracted with EtOAc, and the combined extracts were washed with 5% aqueous NaOH, saturated aqueous NaCl, and dried over Na2SO4 before being concentrated under reduced pressure. The title compound was isolated by column chromatography (10% EtOAC/hexanes) as a colorless solid. 1H NMR (CDCl3): δ 7.96 (2H, d, J=8.1 Hz), 7.47 (2H, d, J=8.1 Hz), 7.43-7.16 (7H, m), 7.07 (1H, d, J=16.3 Hz), 6.93 (1H, d, J=16.3 Hz), 5.97 (1H, t, J=4.7 Hz), 4.39 (2H, q, J=7.0 Hz), 2.41 (3H, s), 2.33 (1H, d, J=4.7 Hz), 1.38 (3H, t, J=7.0 Hz), 1.33 (6H, s).

후처리

  1. stirringThe resulting solution was stirred at room temperature for 1 hour
  2. waitat 55° C. for 2 hours
  3. temperatureUpon cooling to room temperature the reaction
  4. customwas quenched by the addition of saturated aqueous NH4Cl
  5. extractionThe mixture was extracted with EtOAc
  6. washthe combined extracts were washed with 5% aqueous NaOH, saturated aqueous NaCl
  7. dry with materialdried over Na2SO4
  8. concentrationbefore being concentrated under reduced pressure

출처 및 근거

ORD 기록
ord-08a8d6a24f184e398a737ca97c00e970
출처 데이터셋
uspto-grants-1999_12
특허 번호
US06008204

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