3-Methoxypropyne → 4-Chloro-3-(3-methoxyprop-1-yn-1-yl)benzoic acid

HRID 219835노트

반응식

HRID 219835 반응식
[CH2:1]([O:4][CH3:5])[C:2]#[CH:3].[Cl:6][C:7]1[CH:15]=[CH:14][C:10]([C:11]([OH:13])=[O:12])=[CH:9][C:8]=1I>C1COCC1.C(N(CC)CC)C.CCOC(C)=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:6][C:7]1[CH:15]=[CH:14][C:10]([C:11]([OH:13])=[O:12])=[CH:9][C:8]=1[C:3]#[C:2][CH2:1][O:4][CH3:5]

참가 물질

7

반응물 2

HCID 693933-MethoxypropyneHCID 27576164-Chloro-3-iodobenzoic acid

생성물 1

HCID 675293394-Chloro-3-(3-methoxyprop-1-yn-1-yl)benzoic acid

시약·촉매·용매 4

HCID 178418476HCID 178418476, 화합물촉매HCID 8028Tetrahydrofuran용매HCID 8471Triethylamine용매HCID 8857Ethyl Acetate용매

실험 절차

Methyl propargyl ether (Fluka; 68898; 1.27 mL; 15 mmol; 1.50 eq.) was added dropwise to a suspension of 4-chloro-3-iodobenzoic acid (ABCR; TWC2211-D1; 2 824.60 mg; 10 mmol; 1 eq.), dichlorobis(triphenylphosphine)palladium(II) (701.91 mg; 1 mmol; 0.10 eq.) and cuprous iodide (190.45 mg; 1 mmol; 0.10 eq.) in a mixture of THF (20 mL) and triethylamine (10 mL). The reaction was stirred at RT for 2 h. The reaction mixture was quenched with saturated aqueous NH4Cl, and extracted twice with EtOAc. The combined extract were evaporated under vacuo to afford an orange solid. The latter was dissolved in EtOAc and extracted 4 times with NaOH 0.1M. Then the aqueous layer was filtered, acidified to pH=3-4 with HCl 1M, and extracted with EtOAc. The combined organic layers were dried over magnesium sulfate, filtered and concentrated to afford the title compound as a slightly orange powder. 1H NMR (DMSO-d6, 300 MHz) δ 13.42 (br. s., 1H), 8.03 (d, J=2.07 Hz, 1H), 7.92 (dd, J=2.17, 8.38 Hz, 1H), 7.71 (d, J=8.48 Hz, 1H), 4.41 (s, 2H), 3.19-3.37 (m, 3H). LC/MS (Method B): 223.0 (M−H)−. HPLC (Method A) Rt 3.51 min (Purity: 98.8%).

후처리

  1. customThe reaction mixture was quenched with saturated aqueous NH4Cl
  2. extractionextracted twice with EtOAc
  3. extractionThe combined extract
  4. customwere evaporated under vacuo
  5. customto afford an orange solid
  6. extractionextracted 4 times with NaOH 0.1M
  7. filtrationThen the aqueous layer was filtered
  8. extractionextracted with EtOAc
  9. dry with materialThe combined organic layers were dried over magnesium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated

출처 및 근거

ORD 기록
ord-5e96189b418040f68b766b12f9391724
출처 데이터셋
uspto-grants-2012_06
특허 번호
US08202865B2

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