* 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.
5-bromopyrimidine-4-carboxylic acid chloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With oxalyl dichloride;N,N-dimethyl-formamide; In dichloromethane; at 20℃;
S-bromopyrimidine^-carboxylic acid (prepared according to the procedure described in U.S patent 4,110,450) (1.0 eq, 6.14 g, 30.2 mmol) was suspended in CH2Cl2 (100 ml). Oxalylchloride (1.1 eq, 2.9 ml, 33.0 mmol) was added followed by 2 drops of DMF. The mixture was stirred at room temperature overnight and the volatiles were removed in vacuo. The residue was taken in MeOH (50 ml) and heated. After evaporation of MeOH in vacuo the compound was dissolved in CH2Cl2 and poured on a prepacked silica gel column. The material was eluted using 20% Ethyl acetate in hexanes. Evaporation of the solvent provided methyl-5- bromopyrimidine-4-carboxylate as a light orange crystalline solid (2.54 g, 39% yield). LCMS (ES): 95% pure, m/z 217 [M]+; 219 [M+2]+; 1H NMR (CDCl3, 400 MHz) delta 4.04 (s, 3H), 9.02 (s, IH), 9.21 (s, IH) ppm.
With thionyl chloride; In N,N-dimethyl-formamide; at 90℃; for 3.0h;
<strong>[64224-60-8]5-bromopyrimidine-4-carboxylic acid</strong> (0.6 g, 2.96 mmol) was dissolved in thionyl chloride (10 mL) N, N-dimethylformamide (0.05 mL) was added, The reaction was heated to 90 C for 3 hours. The reaction solution was concentrated to dryness, Toluene (10 mL) was added, Re-concentrated to dry, The crude product was used directly in the next step.
5-Bromopyrimidine-4-carboxylic acid can be prepared by heating a suspension of formamidine acetate (416 g) in ethanol (1800 cc) at 45 C, and adding simultaneously, on the one hand, a solution of sodium ethoxide obtained from sodium (138 g) and ethanol (3000 cc) and, on the other hand, a solution of mucobromic acid (516 g) in ethanol (800 cc). The addition is carried out over a period of 2 hours, the temperature being maintained between 45 C and 50 C. The reaction mixture is maintained at this temperature for 11/2 hours. The solution obtained is evaporated by dryness under reduced pressure (20 mm Hg). The residue is taken up in ice-water (1000 cc) and decolourizing charcoal (20 g) is added. After filtration the solution is washed with ethyl acetate (4000 cc). The aqueous phase is decanted and acidified with concentrated 12N hydrochloric acid (500 cc). The insoluble matter is filtered off and the filtrate is extracted with ethyl acetate (10000 cc). The organic layer is decanted and filtered over silica gel (1000 g). Elution is then carried out with ethanol (5000 cc). The resulting elude is evaporated to dryness under reduced pressure. After taking up the residue in diethyl ether (250 cc), 5-bromopyrimidine-4-carboxylic acid (74 g), melting at 200 C with decomposition, is obtained.
7
[ 144-55-8 ]
[ 64224-60-8 ]
[ 64224-61-9 ]
Yield
Reaction Conditions
Operation in experiment
With trifluoroborane diethyl ether; In ethanol; dichloromethane;
Ethyl 5-methylthiopyrimidine-4-carboxylate can be prepared by heating a solution of <strong>[64224-60-8]5-bromopyrimidine-4-carboxylic acid</strong> (3.4 g) in ethanol (34 cc) and boron trifluoride etherate (7.4 g) under reflux for 20 hours. After concentration to dryness under reduced pressure (20 mm Hg), methylene chloride (50 cc) is added to the residue and neutralisation is effected by the addition of an 8% (w/v) aqueous sodium bicarbonate solution. The aqueous phase is decanted and extracted with methylene chloride (50 cc). The combined organic phases are dried over sodium sulphate, filtered and evaporated under reduced pressure. Ethyl-5-methylthiopyrimidine-4-carboxylate (3.7 g), melting at 99-100 C, is thus obtained.
5-methylthiopyrimidine-4-carboxylic acid[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium methylate; In ethanol; water;
5-Methylthiopyrimidine-4-carboxylic acid can be prepared by heating <strong>[64224-60-8]5-bromopyrimidine-4-carboxylic acid</strong> (4.1 g), sodium methoxide (2.43 g) and methylmercaptan (2.16 g) under reflux for four and a half hours in ethanol (30 cc). After evaportion of the resulting solution to dryness under reduced pressure, the residue is dissolved in water (20 cc) and the solution acidified to pH 1 with 12N hydrochloric acid. The precipitate which forms is filtered off and washed with water (15 cc) to give 5-methylthiopyrimidine-4-carboxylic acid (2.8 g) melting at 270 C with decomposition.
With thionyl chloride; In N-methyl-acetamide; ethanol; dichloromethane; sodium hydrogencarbonate;
Ethyl 5-bromopyrimidine-4-carboxylate can be prepared by the addition of <strong>[64224-60-8]5-bromopyrimidine-4-carboxylic acid</strong> (45.6 g) to thionyl chloride (450 cc) and dimethylformamide (0.5 cc). The mixture is progressively heated to reflux, which is maintained until the evolution of gas ceases. Thereafter the solution is concentrated to dryness under reduced pressure. The residue is taken up in methylene chloride (100 cc) and then, after cooling in an ice-bath, in ethanol (315 cc). The solution is stirred for 11/2 hours at a temperature of about 20 C, and then heated under reflux for 30 minutes. The solution obtained is evaporated to dryness under reduced pressure. The residue is taken up in an 8% (w/v) aqueous sodium bicarbonate solution (200 cc) and diethyl ether (1500 cc). The organic phase is dried over sodium sulphate, filtered and evaporated to dryness under reduced pressure to give ethyl 5-bromopyrimidine-4-carboxylate (31 g), b.p. 87-90 C/0.15 mm Hg.
5-Bromo-4-pyrimidine carboxylic acid 1-84 (858 mg, 4.23 mmol) was dissolved in MeOH (15 mL) and thionyl chloride (77 mu, 1 .06 mmol) added dropwise at rt. The reaction mixture was heated to 70C and stirred at this temperature for 3 h. The reaction mixture was then cooled to rt and evaporated to dryness. The residue was re-dissolved in a mixture of water (25 mL) and saturated aq. NaHCOs (25 mL) before extracting with EtOAc (3 x 50 mL). The combined organic extracts were then washed with saturated aqueous NaHCOs (40 mL) and brine (40 mL) before drying over MgS04. Concentration in vacuo provided the title compound as a brown solid (502 mg, 2.31 mmol, 55%).
39%
Process 4 5-Bromopyrimidine-4-carboxylic acid (prepared according to the procedure described in U.S. Pat. No. 4,110,450) (1.0 eq, 6.14 g, 30.2 mmol) was suspended in CH2Cl2 (100 ml). Oxalylchloride (1.1 eq, 2.9 ml, 33.0 mmol) was added followed by 2 drops of DMF. The mixture was stirred at room temperature overnight and the volatiles were removed in vacuo. The residue was taken in MeOH (50 ml) and heated. After evaporation of MeOH in vacuo the compound was dissolved in CH2Cl2 and poured on a prepacked silica gel column. The material was eluted using 20% Ethyl acetate in hexanes. Evaporation of the solvent provided methyl-5-bromopyrimidine-4-carboxylate as a light orange crystalline solid (2.54 g, 39% yield). LCMS (ES): 95% pure, m/z 217 [M]+; 219 [M+2]+; 1H NMR (CDCl3, 400 MHz) delta 4.04 (s, 3H), 9.02 (s, 1H), 9.21 (s, 1H) ppm.
39%
<strong>[64224-60-8]5-bromopyrimidine-4-carboxylic acid</strong> (prepared according to the procedure described in U.S. Pat. No. 4,110,450) (1.0 eq, 6.14 g, 30.2 mmol) was suspended in CH2Cl2 (100 ml). Oxalylchloride (1.1 eq, 2.9 ml, 33.0 mmol) was added followed by 2 drops of DMF. The mixture was stirred at room temperature overnight and the volatiles were removed in vacuo. The residue was taken in MeOH (50 ml) and heated. After evaporation of MeOH in vacuo the compound was dissolved in CH2Cl2 and poured on a prepacked silica gel column. The material was eluted using 20% Ethyl acetate in hexanes. Evaporation of the solvent provided methyl-5-bromopyrimidine-4-carboxylate as a light orange crystalline solid (2.54 g, 39% yield). LCMS (ES): 95% pure, m/z 217 [M]+; 219 [M+2]+; 1H NMR (CDCl3, 400 MHz) delta 4.04 (s, 3H), 9.02 (s, 1H), 9.21 (s, 1H) ppm.
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
120K+ Compounds
Competitive Price
1-2 Day Shipping
