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Triphenylphosphine → Ethyl 5',6'-dihydro-5',5'-dimethyl-8'-(4-methylphenyl)-[2,2'-binaphthalene]-6-carboxylate

HRID 495956
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HRID 495956 반응식
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:17]3[C:12](=[CH:13][CH:14]=[C:15](Br)[CH:16]=3)[C:11]([CH3:20])([CH3:19])[CH2:10][CH:9]=2)=[CH:4][CH:3]=1.[Mg].Br[C:23]1[CH:24]=[C:25]2[C:30](=[CH:31][CH:32]=1)[CH:29]=[C:28]([C:33]([O:35][CH2:36][CH3:37])=[O:34])[CH:27]=[CH:26]2.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[H-].C([Al+]CC(C)C)C(C)C>C(Br)CBr.C1COCC1.[Cl-].[Zn+2].[Cl-].C1C=CC([P]([Ni]([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>[CH3:19][C:11]1([CH3:20])[CH2:10][CH:9]=[C:8]([C:5]2[CH:4]=[CH:3][C:2]([CH3:1])=[CH:7][CH:6]=2)[C:17]2[CH:16]=[C:15]([C:23]3[CH:32]=[CH:31][C:30]4[C:25](=[CH:26][CH:27]=[C:28]([C:33]([O:35][CH2:36][CH3:37])=[O:34])[CH:29]=4)[CH:24]=3)[CH:14]=[CH:13][C:12]1=2
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

10

반응물 5

HCID 11776TriphenylphosphineHCID 1249959Ethyl 6-bromonaphthalene-2-carboxylate2회HCID 5462224MagnesiumHCID 106876226-Bromo-1,1-dimethyl-4-p-tolyl-1,2-dihydronaphthaleneHCID 21225700Diisobutylaluminumhydride

생성물 1

HCID 15870725
Ethyl 5',6'-dihydro-5',5'-dimethyl-8'-(4-methylphenyl)-[2,2'-binaphthalene]-6-carboxylate

시약·촉매·용매 4

HCID 78391,2-Dibromoethane촉매HCID 3007855Zincchloride촉매HCID 178420538HCID 178420538, 화합물촉매2회HCID 8028Tetrahydrofuran용매6회

실험 절차

A solution of 3,4-dihydro-1-(4-methylphenyl)-4,4-dimethyl-7-bromonaphthalene Compound D) 0.45 g, 1.40 mmol) and THF (2.1 ml) was added to magnesium turnings (0.044 g, 1.82 mmol) at room temperature under argon. Two drops of ethylene dibromide were added, and the solution, which slowly became cloudy and yellow, was heated to reflux for 1.5 hours. In a second flask was added zinc chloride (0.210 g, 1.54 mmol), which was melted under high vacuum, cooled to room temperature and dissolved in THF (3 ml). The Grignard reagent was added to the second flask and, after 30 minutes at room temperature, a solution of ethyl 6-bromo-2-naphthalinecarboxylate (Compound N) 0.293 g, (1.05 mmol) and THF (2 ml) were added. In a third flask was prepared a solution of Ni(PPh3)4 and THF as follows: To a solution of NiCl2(Ph3)2 (0.82 g, 1.25 mmol) and PPh3 (0.66 g, 2.5 mmol) in THF (3.5 ml) was added a 1M solution of diisobutylaluminum hydride and hexanes (2.5 ml, 2.5 mmol), and the resulting solution diluted with THF to a total volume of 15 ml and stirred at room temperature for 15 minute. Three 0.60 ml aliquots of the Ni(PPh3)4 solution were added at 15 minutes intervals to the second flask. The resulting suspension was stirred at room temperature for 2 hours. The reaction was quenched by the addition of 5 ml 1N aqueous HCl and stirred for 1 hour before extracting the products with ethyl acetate. The organic layers were combined, washed with brine, dried (MgSO4), filtered and the solvent removed in-vacuo. The residue was crystalized from hexanes to give 130 mg of pure material. The mother liquor was concentrated under reduced pressure and the residue purified by silica gel chromatography (95:5-hexanes:ethyl acetate) to give an additional 170 mg of the title compound (overall yield=300 mg, 64%) as a colorless solid. 1H NMR (CDCl3) δ 8.57 (s, 1H), 8.05 (dd, 1H, J=1.7, 8.0 Hz), 7.84-7.95 (overlapping d's, 3H), 7.66 (dd, 1H, J=1.7, 8.5 Hz), 7.58 (dd, 1H, J=2.0, 8.0 Hz), 7.48 (d, 1H, J=8.0 Hz), 7.43 (d, 1H, J=2.0 Hz), 7.32 (d, 2H, J=8.0 Hz), 7.21 (d, 2H, J=8.0 Hz), 6.04 (t, 1H, J=4.8 Hz), 4.44 (q, 2H, J=7.1 Hz), 2.40 (s, 3H), 2.39 (d, 2H, J=4.8 Hz), 1.45 (t, 3H, J=7.1 Hz), 1.39 (s, 6H).

후처리

  1. temperaturethe solution, which slowly became cloudy and yellow, was heated
  2. temperatureto reflux for 1.5 hours
  3. stirringThe resulting suspension was stirred at room temperature for 2 hours
  4. customThe reaction was quenched by the addition of 5 ml 1N aqueous HCl
  5. stirringstirred for 1 hour
  6. extractionbefore extracting the products with ethyl acetate
  7. washwashed with brine
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. customthe solvent removed in-vacuo
  11. customThe residue was crystalized from hexanes

출처 및 근거

ORD 기록
ord-21a90acd257b4eac895b674387e07256
출처 데이터셋
uspto-grants-2005_09
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US06942980B1

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