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CAS No. : | 154327-27-2 | MDL No. : | MFCD09749234 |
Formula : | C7H3ClFNS | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | IHMBREJYLPBYSM-UHFFFAOYSA-N |
M.W : | 187.62 | Pubchem ID : | 11240896 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-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 |
---|---|---|
51% | With sulfuryl dichloride; In dichloromethane; at 22℃; for 1.0h;Cooling with ice; | General procedure: GP3-2: 2-mercaptobenzothiazole in 10 volume of anhydrous DCM, was added by sulfuryl chloride (SO2Cl2, 1 volume) under ice-cooled condition. The mixture was stirred at rt for 1 hour, which was monitored by TLC. After consumption of starting material, the mixture was diluted by 30 volume of ether, following quenching carefully by adding water. Stirring was kept for 1 hour to make sure the SO2Cl2 was totally consumed and product was released. Organic layer was collected, neutralized by saturated NaHCO3, dried over Na2SO4 and purified by silica gel chromatograph to give the pure product, which was finally characterized by LC-MS and NMR.; 2-chloro-7-fluorobenzothiazole The title compound was prepared according to GP3-2, which was purified by flash column chromatography using PE/EA (20/1) as eluent to give the colorless oil. (420 mg, 22percent yield) 1H NMR (400 MHz, CDCl3) delta 7.76 (d, J=8.2 Hz, 1H), 7.45 (td, J=8.1, 5.9 Hz, 1H), 7.14 (t, J=8.7 Hz, 1H). 13C NMR (101 MHz, CDCl3) delta 156.11 (d, J=250.1 Hz), 154.27, 153.45 (d, J=2.8 Hz), 127.63 (d, J=7.3 Hz), 123.25 (d, J=17.6 Hz), 118.80 (d, J=3.7 Hz), 111.41 (d, J=18.3 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With hydrogenchloride; In 1,4-dioxane; butan-1-ol; at 90℃; for 18.0h; | 2-Chloro-5-fluoro-1,3-benzothiazole (29 mg, 0.16 mmol) and methyl trans-2-[(4'-amino-1,1'-biphenyl-4-yl)carbonyl]cyclopentanecarboxylate (50 mg, 0.16 mmol) were combined in 1-butanol. The solution was treated with 4 M HCl in dioxane (4 muL, 0.016 mmol) and heated at 90° C. for 18 h. The reaction mixture was concentrated under reduced pressure. The residue was suspended in methanol, and the resulting solid was collected by filtration and dried in vacuo. The title compound was obtained as a pale yellow solid (55 mg, 77percent); LC-MS m/z 475.3 (MH+), retention time 3.97 minutes. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With sulfuryl dichloride; at 20 - 60℃; for 100.0h; | Sulfuryl chloride (0.3 mL, 4.41 mmol) was added neat to 5-fluoro-benzothiazole-2-thiol (680 mg, 3.67 mmol). The mixture was stirred at RT for 1 hour, and then heated to 60°C for 40 mins. The resulting solution was cooled to room temperature, and poured onto ice, extracted with EtOAc (3x50 mL), washed with brine and dried over Na2S04. The dried organic layers were concentrated to give 2-chloro-5-fluorobenzo[d]thiazole (520 mg, 2.75 mmol, 75percent). ESI-MS (M+l): 187 calc. for C7H5CIFN4S 186. |
51% | With sulfuryl dichloride; In dichloromethane; at 20℃; for 1.0h;Cooling with ice; | General procedure: GP3-1: A solution of 2-halo substituted aniline (1.0 eq), potassium ethyl xanthate (1.2 eq or 2.2 eq,typically 2.2 eq) in 10 volume of anhydrous DMF was heated at 100 0Cor 120 0C for 4 hours under nitrogen. TLC monitored the progress ofreaction. After completion, the reaction mixture was cooled to room temperature,diluted with water (10 volume) and neutralized by 1 M HCl solution to pH 5. Theformed precipitate was collected by filtration, rinsed with water, firstlydried by rotavapor, and then dried by oil pump to afford 2-mercaptobenzothiazole.GP3-2: 2-mercaptobenzothiazole in 10 volume ofanhydrous DCM, was added by sulfuryl chloride (SO2Cl2, 1volume) under ice-cooled condition. The mixture was stirred at rt for 1 hour,which was monitored by TLC. After consumption of starting material, the mixturewas diluted by 30 volume of ether, following quenching carefully by addingwater. Stirring was kept for 1 hour to make sure the SO2Cl2was totally consumed and product was released. Organic layer was collected,neutralized by saturated NaHCO3, dried over Na2SO4and purified by silica gel chromatograph to give the pure product, which wasfinally characterized by LC-MS and NMR. |
Sulfuryl chloride (50 muL, 0.65 mmol) was added neat to <strong>[155559-81-2]5-fluoro-1,3-benzothiazole-2-thiol</strong> (100 mg, 0.54 mmol). The mixture was stirred at ambient temperature for 1 h, then heated at 60° C. for 30 minutes. The resulting solution was cooled to rt, and poured onto ice. The title compound was collected by filtration, washed with water, and dried under vacuum. The solid obtained was used without further purification; LC-MS m/z 188.1 (MH+), ret. time 3.27 min. |
With thionyl chloride; N,N-dimethyl-formamide; for 3.0h; | Step 2) Synthesis of 2-chloro-5-fluorobenzo [d] thiazole To a 50 mL of reaction flask were added 5-fluorobenzo [d] thiazole-2-thiol (1.00 g, 5.40 mmol) , thionyl chloride (5 mL) and N, N-dimethylformamide (0.10 mL) . The mixture was refluxed for 3 h and cooled to rt. The mixture was concentrated in vacuo to give a product, which was used directly in the next step. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; copper; sodium nitrite; In water; | STR159 A solution of 242 g (3.5 mol) of sodium nitrite in 440 ml of water is added dropwise with stirring to a mixture, cooled to -10° C., of 147 g (0.87 mol) of 2-amino-5-fluoro-benzothiazole, 1700 ml of conc. hydrochloric acid and 20 g of copper power and the reaction mixture is stirred at 0° C. for 60 minutes and at 50° C. for a further 60 minutes. It is then extracted with chloroform and the solvent is carefully removed by distillation from the organic phase in a water-jet vacuum. 80 g (49percent of theory) of 2-chloro-5-fluoro-benzothiazole are obtained as a crystalline residue of melting point 69° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | With caesium carbonate; In N,N-dimethyl-formamide; at 20℃; | Example 144; 5-[4-(6-Fluoro-benzothiazol-2-yloxy)-benzyl]-hexahydro-pyrrolo[3,4-c]pyrrole-2-carboxylic acid amideStep A: [4-(6-Fluoro-benzothiazol-2-yloxy)-phenyl]-methanol. A mixture of <strong>[154327-27-2]2-chloro-5-fluorobenzthiazole</strong> (2.2 g, 12.0 mmol), 4-hydroxylbenzyl alcohol (1.48 g, 12.0 mmol) and Cs2CO3 (8.6 g, 26.4 mmol) in DMF (30 mL) was stirred at rt overnight. The reaction was filtered and diluted with CH2Cl2 (200 mL) and concentrated. The crude mixture was purified via silica gel column chromatography (1% to 15% CH3OH/CH2Cl2) to afford the title compound (1.1 g, 34%). MS (ESI): Mass calcd for C14H10NO2SF, 275.0; m/z found, 276.1 [M+H]+ |
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