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CAS No. : | 146533-41-7 | MDL No. : | MFCD13151897 |
Formula : | C10H5BrCl2N2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | WEEFLZORZXLIJE-UHFFFAOYSA-N |
M.W : | 303.97 | Pubchem ID : | 19735262 |
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: |
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* 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 |
---|---|---|
86% | With trichlorophosphate; In water; N,N-dimethyl-aniline; toluene; at 30 - 100℃; for 5h; | 200 g of the intermediate 3 obtained in the third step was taken in a 3 L three-necked flask.Add 300g of toluene and 180g of N,N-dimethylaniline, mechanically stirred,230 g of phosphorus oxychloride was added dropwise at 30 C, and the temperature was raised to 55 C after the addition.After the solid is completely dissolved, the temperature is raised to 100 C, the reaction is carried out for 4 h, and then cooled to 25 C for use.450 g of water was mixed with 500 g of toluene, and cooled to 25 C with stirring.The above-mentioned alternate reaction solution was added, and the process control temperature was 30 C.Stir at 30 C for 1 h, then stand for stratification, and extract the aqueous phase with toluene several times.The toluene extract and the organic phase are combined, and the combined organic phases are decomposed under reduced pressure.Further, ethanol was added, and the mixture was stirred at 15 C for 1.5 hours, suction filtered, and dried.The product 5-(4-bromophenyl)-4,6-dichloropyrimidine 195.6 g, the yield was 86.0%,The liquid chromatographic test results of the obtained product are shown in Figure 2.HPLC purity is 99.93%,The test results came to the Waters 2489-1525 high performance liquid chromatograph produced by Waters. |
79% | With trichlorophosphate; at 90℃; | A stirred solution of 100 g 5-(4-bromophenyl)pyrimidine-4,6-diol (11, 0.374 mol) was added to 300 cm3 phosphorousoxy chloride. The reaction mass was heated to 90 Cand maintained until completion (monitored by HPLC).After completion of the reaction, the reaction mass wascooled to 10-15 C and quenched over water below 15 C.The obtained solid was filtered and washed with water until the pH of the filtrate became 6.5-7.0. The material was dried under reduced pressure at 65 C to obtain the crudesolid. The crude solid was further recrystallized in methanol and the obtained solid was filtered and dried toprovide 2. Yield: 90 g (79%); purity by HPLC: 99.7%;m.p.: 100-103 C. The spectral data of compound 2 werefound to agree with the reported data [8]. |
With N,N-dimethyl-aniline; trichlorophosphate; at 130℃; for 2h; | To a suspension of 5- (4-BROMOPHENYL)-PYRIMIDINE-4, 6-DIOL (9.90 G) in POCI3 (130 ml) was carefully added N, N-dimethylaniline (13.5 ML). The mixture was heated to 130C for 2 h. The dark brown solution was evaporated and the residue was poured into ice/water. The suspension was diluted with 2 N HCI and water and stirred for 20 min. The precipitate was collected and washed with water. The solid material was dissolved in EA, washed with 1 N aq. HCI and brine. The organic phase was dried over MGS04 and evaporated. The material was further purified by column chromatography on silica gel eluting with hexane: EA 95: 5 to 1: 1 followed by CRYSTALLISATION from hexane/EA AT-20C to give 4, 6-DICHLORO-5- (4- bromophenyl)-pyrimidine (8.3 g) as pale YELLOW CRYSTALS.'H-NMR (D6-DMSO) : 7.39-7. 44 (m, 2H), 7.72-7. 76 (m, 2H), 8.94 (s, 1 H). |
With N,N-dimethyl-aniline; trichlorophosphate; at 130℃; for 2h; | To a suspension of 5-(4-bromophenyl)-pyrimidine-4,6-diol (9.9O g) in POCl3 (13O mL) was carefully added JV,lambda/-dimethylaniline (13.5 mL). The mixture is heated to 1300C for 2 h. The dark brown solution is concentrated in vacuo and the residue was poured into ice/water. The suspension is diluted with 2 N HCl and water and stirred for 20 min. The precipitate that formed is collected and washed with water. The solid material is dissolved in EA, washed with 1 N aq. HCl and brine. The org. phase is dried over MgSO4 and evaporated. The material is further purified by column chromatography on silica gel eluting with Hex:EA 95:5 to 1 :1 followed by crystallisation from Hex/EA at -200C to give 4,6-dichloro-5-(4-bromophenyl)-pyrimidine as pale yellow crystals (8.3 g). 1H-NMR(D6-DMSO): delta 7.39-7.44 (m, 2H), 1.12-1.16 (m, 2H), 8.94 (s, IH). | |
With N,N-dimethyl-aniline; trichlorophosphate; at 130℃; for 2h; | d) To a suspension of 5-(4-bromophenyl)-pyrimidine-4,6-diol (9.90 g) in POCI3 (130 ml_) is carefully added N, N-dimethylaniline (13.5 ml_). The mixture is heated to 1300C for 2 h. The dark brown solution is evaporated and the residue is poured into ice/water. The suspension is diluted with 2 N HCI and water and stirred for 20 min. The precipitate is collected and washed with water. The solid material is dissolved in EA, washed with 1 N aq. HCI and brine. The organic phase is dried over MgSO4 and evaporated. The material is further purified by column chromatography on silica gel eluting with hexane:EA 95:5 to 1 :1 followed by crystallisation from hexane/EA at -200C to give 4,6-dichloro-5-(4-bromophenyl)- pyrimidine (8.3 g) as pale yellow crystals. 1H-NMR(D6-DMSO): 7.39-7.44(m, 2H)1 7.72-7.76(m, 2H), 8.94(s, 1 H). | |
To a suspension of 5-(4-bromophenyl)-pyrimidine-4,6-diol (9.90 g) in POCl3 (130 mL) was carefully added N,N-dimethylaniline (13.5 mL). The mixture is heated to 130 C. for 2 h. The dark brown solution is concentrated in vacuo and the residue was poured into ice/water. The suspension is diluted with 2 N HCl and water and stirred for 20 min. The precipitate that formed is collected and washed with water. The solid material is dissolved in EA, washed with 1 N aq. HCl and brine. The org. phase is dried over MgSO4 and evaporated. The material is further purified by column chromatography on silica gel eluting with Hex:EA 95:5 to 1:1 followed by crystallisation from Hex/EA at -20 C. to give 4,6-dichloro-5-(4-bromophenyl)-pyrimidine as pale yellow crystals (8.3 g).1H-NMR(D6-DMSO): delta 7.39-7.44 (m, 2H), 7.72-7.76 (m, 2H), 8.94 (s, 1H).LC-MS: tR=1.02 min. | ||
100 g | With triethylamine; trichlorophosphate; In acetonitrile; at 25 - 85℃; for 5h;Inert atmosphere; | Triethyl amine (130 mL) was added to a mixture of 5-(4-bromophenyl)-pyrimidine-4,6-diol (100 g), phosphoryl chloride (400 mL) and acetonitrile (600 mL) at 25-35C under nitrogen atmosphere for a period of 60 mins. The reaction mass was heated to 80-85C and stirred for 4 hrs. The reaction mass was distilled off under vacuum at below 75C followed by stripped off with acetonitrile. The reaction mass was cooled to 10-15C, water (500 mL) was added and stirred for 30 mins. Aqueous hydrochloric acid (2N, 500 ml) was added to the reaction mass at 10-15C and stirred for 30 mins. The solid obtained was filtered, washed with water and dried under vacuum at 40-45C for 6 hrs to get the title compound. Yield: 100 g; purity by HPLC: 99.0% |
With N,N-dimethyl-aniline; trichlorophosphate; at 70℃; for 4h; | Add 5-(4-bromophenyl)-4,6-dihydroxypyrimidine to a washed, dry round bottom flask.70 parts of phosphorus oxychloride (new steam),Then, 1 part of N,N-dimethylaniline was added dropwise thereto.Slowly turn on the magnetic stirrer and stir at room temperature for 15 minutes.Warmed to 70 C in 1 h,The reaction was carried out at this temperature for 3 h.After the reaction was terminated, it was naturally cooled to 55 C, and excess phosphorus oxychloride was distilled off under reduced pressure.Add the remaining mixture to the ice water, the temperature is controlled below 10 C, the natural yellow solid will be precipitated, and the pH of the solution will be adjusted.To be weakly acidic, it was washed twice with ice water and then with dichloroethane three times. After drying the wet product, a pale yellow product can be obtained (5-(4-Bromophenyl)-4,6-dichloropyrimidine). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In DMF (N,N-dimethyl-formamide); at 20℃; for 24h; | A solution of 4, 6-DICHLORO-5- (4-BROMOPHENYL)-PYRIMIDINE 1.79 mg) and 2- methoxyethanesulfamic acid amide potassium salt (4.54 g, Example 1) in DMF (25 ml) was stirred at rt for 24 h before bulk of the solvent was removed in vacuo. The residue was treated with 10% aq. citric acid. The suspension was filtered, and the mother liquor was extracted twice with EA. The organic phase was evaporated and combined with the solid material collected earlier. The crude product was purified by column chromatography on silica gel eluting with DCM containing 4% of methanol to give 2-METHOXYETHANESULFAMIC acid [6-CHLORO-5- (4-BROMOPHENYL)- pyrimidin-4-yl]-amide (640 mg) as a beige foam. LC-MS2 : TR = 4.46 min, [M+1] + = 422.93, [M-1]-= 420.82. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trichlorophosphate; | In analogy to Example 3, paragraph b), from 5-(p-bromophenyl)-4,6(1H,5H)-pyrimidinedione and POCl3, there was prepared 5-(p-bromophenyl)-4,6-dichloropyrimidine, melting point 99-100 C. (from hexane), and therefrom with p-chlorophenylsulfonamide, there was prepared N-[5-(p-bromophenyl)-6-chloro-4-pyrimidinyl]-p-chlorobenzenesulfonamide, melting point 266-268 C. (from CH3 CN). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dimethyl sulfoxide; at 20℃; for 18h; | f) A solution of <strong>[146533-41-7]4,6-dichloro-5-(4-bromophenyl)-pyrimidine</strong> (405 mg, 1.33 mmol) and 3-benzyloxypropylsulfamide potassium (752 mg, 2.66 mmol) in DMSO is stirred at rt under argon for 18 h. The clear solution is poured onto 10% aq. citric acid solution (50 mL) and extracted twice with EA (2x75 mL). The organic extracts are washed with water (50 mL) and the solvent is evaporated. The residue is purified by column chromatography on silica gel eluting with hexane/EA 3:2 to afford 1-benzyloxypropanesulfamic acid [6-chloro-5-(4-bromophenyl)-pyrimidin-4- yl]-amide (524 mg) as a colourless foam. LC-MS: tR = 1.05 min, [M+H]+ = 510.96; 1H NMR (CDCI3): delta 8.44 (s, 1H), 7.71-7.65 (m, 2H), 7.40-7.28 (m, 5H), 7.18-7.12 (m, 2H), 6.90 (s, 1H), 6.05 (t, J = 5.9 Hz, 1 H), 4.49 (s, 2H), 3.57 (t, J 0 5.9 Hz, 2H), 3.18 (q, J = 5.9 Hz, 2H), 1.88 (p, J = 5.9 Hz, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dimethyl sulfoxide; at 20℃; for 24h; | A solution of 5-(4-bromophenyl)-4,6-dichloro-pyrimidine (4.0O g, 13.2 mmol) and benzylsulfamide potassium salt (7.38 g, 32.9 mmol) in DMSO (30 mL) was stirred at rt for 24 h before being diluted with a 10% aq. citric acid solution (200 mL). The suspension that formed was filtered. The collected solid was washed well with water and dried under HV at 400C for 48 h to give the expected product as a white powder (6.15 g). 1H NMR (CDCl3): delta 4.23 (d, J = 5.9 Hz, 2H); 5.94 (t br., J = 6 Hz, IH); 7.05 (d, J = 8.2 Hz, 2H); 7.20-7.35 (m, 5H); 7.68 (d, J = 8.2 Hz, 2H); 8.61 (s, IH). LC-MS: tR = 1.02 min, [M+H]+ = 452.95. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A solution of 5-(4-bromophenyl)-4,6-dichloro-pyrimidine (4.00 g, 13.2 mmol) and benzylsulfamide potassium salt (7.38 g, 32.9 mmol) in DMSO (30 mL) was stirred at it for 24 h before being diluted with a 10% aq. citric acid solution (200 mL). The suspension that formed was filtered. The collected solid was washed well with water and dried under HV at 40 C. for 48 h to give the expected product as a white powder (6.15 g).1H NMR (CDCl3): delta 4.23 (d, J=5.9 Hz, 2H); 5.94 (t br., J=6 Hz, 1H); 7.05 (d, J=8.2 Hz, 2H); 7.20-7.35 (m, 5H); 7.68 (d, J=8.2 Hz, 2H); 8.61 (s, 1H).LC-MS: tR=1.02 min, [M+H]+=452.95. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
110 g | With sodium amide; In dimethyl sulfoxide; at 25 - 30℃; for 10h;Inert atmosphere; | To a solution of 5-(4-bromophenyl)-4,6-dichloro-pyrimidine (100 g) in dimethyl sulfoxide (700 ml), potassium(N-propylsulfamoyl)amide (145 g) was added at 25-30C under nitrogen atmosphere and stirred for 10 hrs. After reaction completion, pH of the reaction mass was adjusted to 2-3 using aqueous hydrochloric acid at 25-30C and stirred for 75 mins. The solid obtained was filtered, washed with water and suck dried under vacuum. Methanol (3500 ml) was added to the above compound and heated to reflux temperature then stirred for an hour at reflux. The reaction mass was distilled upto 450-550 mL remained in the flask. The reaction mass was cooled to 25-30C, stirred for 75 mins then further cooled to 0- 5C and stirred for 75 mins. The obtained solid was filtered, washed with methanol and dried under vacuum at 50-55C for 4 hrs to get the title compound. Yield: 110 g; Purity by HPLC: 99.10% |
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