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CAS No. : | 56844-12-3 | MDL No. : | MFCD09264088 |
Formula : | C6H2BrClN2S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | CMIXHHOZGMSYKN-UHFFFAOYSA-N |
M.W : | 249.52 | Pubchem ID : | 12225261 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
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 |
---|---|---|
88% | With trichlorophosphate; at 120℃; for 3.0h; | Compound 3 (32.7 g, 142 mmol) was mixed with POCl3 (100 mL) and heated at 120 C for 3 h. Then the mixture was quenched into 5 M aq NaOH (1 L) and ice. The pH was adjusted to 7 using a saturated aq NaHCO3 solution. The formed precipitate was isolated by filtration and washed with water (3×200 mL). Drying gave 31.0 g (124 mmol, 88%) of 4 as a brown solid, mp. 112-118 C. A fraction of this material was further purified: the dry material was applied to the top of a packed silica gel plug and eluted with CH2Cl2, mp. 114-118 C; Rf (CH2Cl2/MeOH, 98/2)=0.67; 1H NMR (400 MHz, DMSO-d6) delta: 8.95 (s, 1H), 7.89 (s, 1H); 13C NMR (100 MHz, DMSO-d6) delta: 168.9, 153.2, 152.5, 130.2, 122.9, 118.5; IR (neat, cm-1): 3082, 1508, 1411, 959, 832, 816, 760; HRMS (EI, 70 eV, m/z): 247.8813 (calcd C6H2Br79Cl35N2S, 247.8811, M+). The 1H NMR spectrum corresponds with Ref. 41. 13C NMR spectroscopic data and a reference melting point have not been identified. |
72.7% | With trichlorophosphate; for 6.0h;Reflux; | [0121] 6-Bromothieno[2,3-d]pyrimidin-4(3H)-one (7.02 g, 30.4 mmol, 1.0 equiv) was taken up in 100 mL POCI3 and refluxed for 6 h. Upon completion, the reaction was concentrated in vacuo and the residue was taken up in 10 mL acetonitrile and heated to reflux for 10 min. The acetonitrile solution was then poured in a flask and cooled. The ppt was then filtered and washed with hexane to give 6-bromo-4-chlorothieno[2,3-d]pyrimidine (5.51 g, 72.7 % yield) as a tan solid. NMR (400 MHz, CHLOROFORM-d) delta ppm 8.80 (s, 1 H), 7.47 (s, 1 H). |
With trichlorophosphate; for 6.0h;Heating / reflux; | 6-Bromo-3No.-thieno[2,3-J]pyrirnidin-4-one (11.64g, 0.05mol) was added portion-wise to phosphoryl chloride (220ml) and the resulting mixture was heated under reflux for 6 hours. The excess phosphoryl chloride was then removed in vacua. The resulting residue was dissolved in dichloromethane (250ml) and washed with water (2xlOOml), followed by saturated sodium hydrogen carbonate solution (100ml). The organic layer was then dried (MgSCU) and the solvent was removed in vacuo to give 6-bromo-4-chlorothieno[2,3-d]pyrirnidine (9.06g) as a yellow solid, which was used without further purification. |
With trichlorophosphate; at 120℃; for 2.5h; | 6-Bromo-4-Chlorothieno[2,3-d]pyrimidine (4). Compound 3 (50.00 g, 216 mmol) was mixed with POCl3 (110 mL, 1180 mmol) and heated at 120 C for 2.5 h. Then the mixture was quenched into 5 M aq NaOH (900 mL) and ice. The formed precipitate was isolated by filtration and washed with water (3 x 200 mL). Drying gave 50.57 g (203 mmol, 94%) of 4 as a brown solid, mp. 113 - 114 C. A fraction of this material was further purified: the dry material was applied to the top of a packed silica gel plug and eluted with CH2C12, mp. 1 15 - 116 C; R/(CH2Cl2/MeOH, 98/2) = 0.67; 1H NMR (400 MHz, DMSO-d6) delta: 8.95 (s, 1H), 7.89 (s, 1H); 13C NMR (100 MHz, DMSC /6) delta: 168.9, 153.2, 152.5, 130.2, 122.9, 118.5; IR (neat, cm 1): 3082, 1508, 14011 , 959, 832, 816, 760; HRMS (EI, 70 eV, m z): 247.8813 (calcd C6H2Br79Cl35N2S, 247.881 1, M+). |
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