Triethylamine → Phosphoric acid 3-[3-(4-bromo-phenyl)-benzo [d]isothiazol-6-yl]-1,1-dimethyl-prop-2-ynyl ester diethyl ester

HRID 966354Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 966354
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:12]3[CH:13]=[CH:14][C:15]([C:17]#[C:18][C:19]([CH3:22])([OH:21])[CH3:20])=[CH:16][C:11]=3[S:10][N:9]=2)=[CH:4][CH:3]=1.[Li+].CCC[CH2-].C(N(CC)CC)C.[CH2:35]([O:37][P:38](Cl)([O:40][CH2:41][CH3:42])=[O:39])[CH3:36]>C1COCC1.CCCCCC.O>[CH2:35]([O:37][P:38](=[O:39])([O:40][CH2:41][CH3:42])[O:21][C:19]([CH3:22])([CH3:20])[C:18]#[C:17][C:15]1[CH:14]=[CH:13][C:12]2[C:8]([C:5]3[CH:4]=[CH:3][C:2]([Br:1])=[CH:7][CH:6]=3)=[N:9][S:10][C:11]=2[CH:16]=1)[CH3:36]

Komponenten

8

Edukt 4

HCID 8471TriethylamineHCID 13139Diethyl chlorophosphateHCID 61028n-Butyl lithiumHCID 223138854-[3-(4-Bromo-phenyl)-benzo[d]isothiazol-6-yl]-2-methyl-but-3-yn-2-ol

Produkt 1

HCID 69289237Phosphoric acid 3-[3-(4-bromo-phenyl)-benzo [d]isothiazol-6-yl]-1,1-dimethyl-prop-2-ynyl ester diethyl esterAusbeute 33 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel3×HCID 8058HexaneLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

200 mg (0.54 mmol) 4-[3-(4-Bromo-phenyl)-benzo[d]isothiazol-6-yl]-2-methyl-but-3-yn-2-ol in 2 ml THF were treated with 36 μl (5.6 mmol) 1.6 M N-Butyllithium in hexane at −78° C. for 30 min. 112 μl (0.81 mmol, 1.5 eq) Triethylamine in 0.5 ml THF and 117 μl (0.8 mmol, 1.5 eq) Diethylchlorophosphate in 0.5 ml THF were added and the solution was stirred at −78° C. over night and at 0° C. for 4 h. Water was added, and the inorganic phase was extracted with EtOAc, the combined organic phases were washed with brine and dried over Na2SO4. Column chromatography on silica gel with hexane:EtOAc 3:1 gave 90 mg (33%) Phosphoric acid 3-[3-(4-bromo-phenyl)-benzo[d]isothiazol-6-yl]-1,1-dimethyl-prop-2-ynyl ester diethyl ester as yellow semisolid, MS: 508 (MH+, 1Br).

Aufarbeitung

  1. extractionthe inorganic phase was extracted with EtOAc
  2. washthe combined organic phases were washed with brine
  3. dry with materialdried over Na2SO4

Quellen und Nachweise

ORD-Eintrag
ord-9f5ff56b48884f87b3d6af591d23d7e2
Quelldatensatz
uspto-grants-2005_10
Patentnummer
US06951879B2

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