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

HRID 347092노트

반응식

HRID 347092 반응식
[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

참가 물질

11

반응물 4

HCID 1140TolueneHCID 8471TriethylamineHCID 793464-Pentyn-1-ol2회HCID 57428076Trifluoro-methanesulfonic acid 3-(4-bromo-phenyl)-benzo[d]isothiazol-6-yl ester

생성물 1

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

시약·촉매·용매 6

HCID 11776Triphenylphosphine촉매HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 178418476HCID 178418476, 화합물촉매HCID 8028Tetrahydrofuran용매4회HCID 8857Ethyl Acetate용매HCID 516920Potassium bisulfate용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-817e73b0c626474d95740d61639ba01a
출처 데이터셋
uspto-grants-2007_02
특허 번호
US07173043B2

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