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CAS No. : | 111600-83-0 | MDL No. : | MFCD12026322 |
Formula : | C4H4BrNS | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | IIMLZWMRQNCPTM-UHFFFAOYSA-N |
M.W : | 178.05 | Pubchem ID : | 15020997 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P280-P301+P312-P302+P352-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H320-H335 | Packing Group: | |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With potassium carbonate; | Step 4 To a solution of tert-butyl N-tert-butoxycarbonyl-N-[[2-cyano-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]methyl]carbamate (2.2 g, 4.80 mmol, 1 eq), 5-bromo-4-methyl-thiazole (940 mg, 5.28 mmol, 1.1 eq) in dioxane (20 mL) and water (4 mL) was added potassium carbonate (1.66 g, 12.00 mmol, 2.5 eq) and <strong>[72287-26-4](1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride</strong> (351 mg, 0.48 mmol, 0.1 eq) under nitrogen. The reaction mixture was stirred at 100 C. for 12 hours. Water (100 mL) was added to the mixture, the resulting mixture was extracted with ethyl acetate (50 mL*3). The combined organic phase was washed with brine (50 mL), dried over sodium sulfate, filtered and concentrated in vacuum. The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=100:1 to 1:1). tert-Butyl N-tert-butoxycarbonyl-N-[[2-cyano-4-(4-methylthiazol-5-yl)phenyl]methyl]carbamate (1.7 g, 3.96 mmol, 82% yield) was obtained as a light yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium acetate; | Step 5 To a solution of 5-bromo-4-methyl-thiazole (800 mg, 4.49 mmol, 1 eq) and 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane (1.37 g, 5.39 mmol, 1.2 eq) in dioxane (10 mL) was added 1,1'-bis(diphenylphosphino)ferrocene-palladium(II)dichloride (164 mg, 0.22 mmol, 0.05 eq) and potassium acetate (882 mg, 8.99 mmol, 2 eq). The reaction mixture was stirred at 100 C. for 12 h. The reaction mixture was filtered and concentrated under reduced pressure to give 4-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiazole (1 g, crude) as a brown oil which was used without purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; sodium carbonate; In 1,4-dioxane; water; at 90℃; for 2h;Inert atmosphere; | To a solution of 5-bromo-4-methyl-1,3-thiazole (1.9 g, 10.7 mmol) in dioxane (19 mL) were added H2O (1.9 mL), <strong>[489446-42-6][4-([[(tert-butoxy)carbonyl]amino]methyl)phenyl]boronic acid</strong> (4.0 g, 16.0 mmol), Na2CO3 (2.3 g, 21.3 mmol) and Pd(dppf)Cl2·CH2Cl2 (871.4 mg, 1.1 mmol). The mixture was purged with N2 for 3 times and was stirred at 90 oC for 2 hours under N2 atmosphere. The resulting mixture was cooled to room temperature, diluted with water (50 mL) and extracted with ethyl acetate (3 x 50 mL). The combined organic layers was washed with brine (2 x 30 mL) and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography, eluted with petroleum ether in ethyl acetate (v/v = 1/1) to afford tert-butyl N-[[4-(4-methyl-1,3-thiazol- 5-yl)phenyl]methyl]carbamate (3 g, 91%) as a yellow solid. 1H NMR (400 MHz, DMSO-d6) d 8.98 (s, 1H), 7.53-7.42 (m, 3H), 7.33 (d, J = 8.0 Hz, 2H), 4.16 (d, J = 6.2 Hz, 2H), 2.45 (s, 3H), 1.40 (s, 9H). LC/MS (ESI, m/z): [(M + 1)]+ = 305.2 |
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