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Chemical Structure| 22876-20-6

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Product Details of [ 22876-20-6 ]

CAS No. :22876-20-6
Formula : C7H4ClNOS
M.W : 185.63
SMILES Code : S=C1OC2=CC(Cl)=CC=C2N1
MDL No. :MFCD00800495
Boiling Point : No data available
InChI Key :HAASPZUBSZGCKU-UHFFFAOYSA-N
Pubchem ID :2119214

Safety of [ 22876-20-6 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H332-H335
Precautionary Statements:P233-P260-P261-P264-P270-P271-P280-P301+P312-P302+P352-P304-P304+P340-P305+P351+P338-P312-P321-P330-P332+P313-P337+P313-P340-P362-P403-P403+P233-P405-P501

Application In Synthesis of [ 22876-20-6 ]

* 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.

  • Downstream synthetic route of [ 22876-20-6 ]

[ 22876-20-6 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 22876-20-6 ]
  • [ 3621-82-7 ]
YieldReaction ConditionsOperation in experiment
98.4% With bis(trichloromethyl) carbonate; In toluene; at 50 - 105℃; In a 500 ml four-necked reaction flask, 50 g (folds hundred) of 2-mercapto-6-chlorobenzoxazole and 300 ml of toluene and 40 g tris(trichloromethyl)carbonate were placed, The temperature was raised to 50 °C and the temperature was raised at a rate of 0.5 °C/min, Each heating temperature 10 °C, holding 10 minutes, when the temperature to 105 °C, reaction insulation for 1 hour, After the end of the incubation reaction, the solvent was distilled off under reduced pressure (the vacuum was maintained at -0.07 MPa when the distillation was started. when the temperature reaches 100 °C - 110 °C time, vacuum to -0.095 MPa, evaporating the solvent), solvent after evaporation to dryness, taken out when it is hot, the cooling crystallization 2,6-dichlorobenzoxazole, weight 50.82 g, content 98.1percent, molar yield 98.4percent.
96.1% With bis(trichloromethyl) carbonate; In N,N-dimethyl-formamide; at 110℃; for 2h; 2) :Using 6-chloro-2-mercaptobenzoxazole and bis(trichloromethyl) carbonate as raw materials,N,N-dimethylformamide was used as a catalyst to synthesize 2,6-dichlorobenzoxazole.The molar ratio of bis(trichloromethyl)carbonate to 6-chloro-2-mercaptobenzoxazole is 1.2:3.0,Reaction at 110 ° C for 2 hours,Product purity is 98.3percent,Yield 96.1percent,1H NMR,LC/MS,The IR spectrum confirmed that the product was 2,6-dichlorobenzoxazole;
78% With bis(trichloromethyl) carbonate; In toluene; at 50 - 105℃; for 1.33333h; Step 5,2mmol 2-mercapto-6-chlorobenzoxazole was placed in the flask,Add 10 ml of toluene as a solvent.4 mmol of solid triphosgene was added to the flask.Stir the temperature to 50 ° C, keep warm for 10 min,Slowly heat up again, each temperature is raised by 10 ° C10 min, when the temperature rose to 105 ° C, kept for 1 h; after extraction with sodium bicarbonate solution,Taking the organic phase and steaming it, after drying,The obtained 2,6-dichlorobenzoxazole was 0.293 g, and the yield was 78percent.
41% With phosphorus pentachloride; In toluene; at 120℃; for 16h; To a solution of 6-chlorobenzo[d]oxazole-2-thiol (5.Og, 27.lmmol) in toluene (l5OmL) was added PCI5 (28.2g, l36mmol) portion wise at rt. The reaction mixture was heated at 120°C for 16h. TLC showed the reaction to be complete. The reaction mixture was concentrated under reduced pressure to dryness. The residue was dissolved in Et20 (lOOmL). The insoluble solid was filtered and the filtrate was concentrated under reduced pressure. The crude residue was purified by column chromatography using silica gel (100-200 mesh), eluting with hexane to 3percent EtOAc in hexane to afford 2,6-dichlorobenzo[d]oxazole as an orange solid. Yield: 2.lg(41percent); 1H NMR (400 MHz, DMSO-d6): O 8.01 (d, J= 1.6Hz, 1H), 7.78 (d, J= 8.6Hz, 1H), 7.49 (dd, J= 1.6, 8.6Hz, 1H).
With phosphorus pentachloride; In toluene; for 2h;Reflux; General procedure: The substituted 2-aminophenol (1eq.) in water and 95percent ethanol was added potassium carbonate (1eq.) and CS2 (1eq.).The mixture was heated under reflux for 3 hours. After cooling, the solution was neutralized with 15 mL of acetic acid in 30 mL water. The precipitate was collected to give 2-thiolbenzoxazoles. Then, the substituted 2-thiolbenzoxazoles (1eq.) dissolved in toluene, PCl5 (1.5eq) was added dropwise. The mixture was heated to reflux for 2 hours. After the solvent was evaporated, the crude product was purified by silica gel column chromatography using PE-EA as an eluent.
With thionyl chloride; for 2h;Reflux; General procedure: Potassium hydroxide (46 mmol), ethanol (25 mL) and water (10 mL) were added to a dried round-bottomed flask sequentially, followed by the dropwise addition of CS2 (25 mmol), after 15 min, (un)substituted 2-aminophenol (23 mmol) was added, then the resulting solution was heated to reflux for 4 h. The reaction solution was acidified to pH~4 with dilute hydrochloric acid and then poured into water, extracted with ethyl acetate, the organic phase was washed with brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure and the residue was purified via silica gel column chromatography to obtain the intermediate the (un)substituted 2-mercaptobenzoxazole as a yellow solid. Then, the (un)substituted 2-mercaptobenzoxazole (5.5 mmol) was refluxed in SOCl2 (15 mL) for 2 h, excessive SOCl2 was removed under reduced pressure to give (un)substituted 2-chlorobenzoxazole as a yellow solid which was used in next reaction without further purification. Finally, 60 percent of NaH (1.0 mmol) was added into a solution of 3,3-dichloroallyloxyphe-noxy intermediates (1.0 mmol) in THF (5 mL), after 2 h, (un)substituted 2-chloro-benzoxazole (1.0 mmol) was added, the reaction mixture was stirred for another 5 h at room temperature. The reaction mixture was poured into water and extracted with ethyl acetate, the organic phase was washed with saturated sodium bicarbonate, brine, dried over anhydrous magnesium sulfate, concentrated and the residue was purified via silica gel column chromatography to afford the title compounds.

 

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