Toluene → 5-[3-(4-Bromo-phenyl)-benzo[d]isothiazol-6-yl]-pent-4-yn-1-ol

HRID 270321Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 270321
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:12]3[CH:13]=[CH:14][C:15](OS(C(F)(F)F)(=O)=O)=[CH:16][C:11]=3[S:10][N:9]=2)=[CH:4][CH:3]=1.C1(C)C=CC=CC=1.[CH2:32]([OH:37])[CH2:33][CH2:34][C:35]#[CH:36].C(N(CC)CC)C>C1COCC1.CCOC(C)=O.OS([O-])(=O)=O.[K+].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.[Cu]I.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:12]3[CH:13]=[CH:14][C:15]([C:36]#[C:35][CH2:34][CH2:33][CH2:32][OH:37])=[CH:16][C:11]=3[S:10][N:9]=2)=[CH:4][CH:3]=1

Komponenten

11

Edukt 4

HCID 1140TolueneHCID 8471TriethylamineHCID 793464-Pentyn-1-ol2×HCID 57428076Trifluoro-methanesulfonic acid 3-(4-bromo-phenyl)-benzo[d]isothiazol-6-yl ester

Produkt 1

HCID 223140325-[3-(4-Bromo-phenyl)-benzo[d]isothiazol-6-yl]-pent-4-yn-1-olAusbeute 72 %

Reagenzien, Katalysatoren, Lösungsmittel 6

HCID 11776TriphenylphosphineKatalysatorHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 8028TetrahydrofuranLösungsmittel4×HCID 8857Ethyl AcetateLösungsmittelHCID 516920Potassium bisulfateLösungsmittel

Versuchsvorschrift

3.0 g (6.846 mmol) Trifluoro-methanesulfonic acid 3-(4-bromo-phenyl)-benzo[d]isothiazol-6-yl ester were suspended three times with toluene prior to the reaction, then dissolved in 25 ml THF and added to 240 mg (0.34 mmol) PdCl2(PPh3)2. To this suspension 0.67 ml (7.19 mmol) 4-pentyn-1-ol in 1 ml THF were added, followed by 54 mg (0.205 mmol) triphenylphosphine in 1 ml THF and 2.9 ml (20.54 mmol) triethylamine. The solution was stirred for 20 min at RT prior to the addition of 13 mg (0.07 mmol) CuI. The solution was heated to 50° C. overnight. Further 132 μl (1.4 mmol) 4-pentyn-1-ol in 0.8 ml THF were added in two portions and stirring at 50° C. was continued for 5 h and at RT over night. The reaction mixture was diluted with EtOAc and 1M KHSO4. The inorganic phase was extracted with EtOAc and the combined organic phases were washed with water and brine and dried over Na2SO4. Column chromatography with a gradient hexane:EtOAc 2:1 to 1:1 gave 1.83 g (72%) 5-[3-(4-Bromo-phenyl)-benzo[d]isothiazol-6-yl]-pent-4-yn-1-ol as light yellow oil, MS: 371 (M, 1Br).

Aufarbeitung

  1. customto the reaction
  2. temperatureThe solution was heated to 50° C. overnight
  3. stirringstirring at 50° C.
  4. waitwas continued for 5 h and at RT over night
  5. extractionThe inorganic phase was extracted with EtOAc
  6. washthe combined organic phases were washed with water and brine
  7. dry with materialdried over Na2SO4

Quellen und Nachweise

ORD-Eintrag
ord-7a9d29709fcd44dca8ebf02b1cc498fe
Quelldatensatz
uspto-grants-2008_11
Patentnummer
US07449483B2

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