Structure of 937-18-8
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The BI-3802 was designed by Boehringer Ingelheim and could be obtained free of charge through the Boehringer Ingelheim open innovation portal opnMe.com, associated with its negative control.
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CAS No. : | 937-18-8 |
Formula : | C7H6N2O2 |
M.W : | 150.13 |
SMILES Code : | O=C(C1=CC(C#N)=CN1)OC |
MDL No. : | MFCD12924296 |
InChI Key : | KLLCRUMWQRYULP-UHFFFAOYSA-N |
Pubchem ID : | 10986409 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501 |
* 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 |
---|---|---|
45.4% | In acetonitrile; at -20 - 25℃; for 20.0833h; | 4-Cyano-lH-pyrrole-2-carboxylic acid methyl ester was prepared as described in Can. J. Chem., 59, 2673-76 (1981). lH-Pyrrole-2-carboxylic acid methyl ester (2.00 g, 16.00 mmol) was dissolved in acetonitrile (5 mL) and the solution was cooled to -20 0C. Chlorosulfonylisocyanate (3.40 g, 24.00 mmol) was dissolved in acetonitrile (5 mL) and added dropwise via syringe over a period of 5 min to the above solution. The solution was allowed to warm to 25 0C and was stirred for 20 h. The solution was cooled back to 0 0C, NN-dimethylformamide (2 mL) was added and the solution was heated to 50 0C for 15 min. The reaction mixture was poured into ice and was extracted with chloroform, washed with saturated aqueous sodium bicarbonate solution, dried over sodium sulfate, filtered and concentrated in vacuo. Purification by flash column chromatography (Merck silica gel 60, 40-63 μm, 40% ethyl acetate in hexanes) afforded the desired product, 4-cyano-lH-pyrrole-2- carboxylic acid methyl ester (1.09 g, 7.265 mmol, 45.4% yield) as an off-white solid. 1H NMR (400 MHz, CDCl3) δ: 3.91 (3H, s), 7.12 (IH, t, J= 2.0 Hz), 7.40 - 7.41 (IH, m), 9.60 (IH, bs). FT-IR (ATR) vmax (neat): 2228, 1691 cm"1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hypochlorite; ammonia; ammonium chloride; In diethyl ether; water; at -5℃; for 0.75h;Product distribution / selectivity; | Solid ammonium chloride (5.8 g, 109.4 mmol) was suspended in diethyl ether (300 mL) and the suspension was cooled to -5 0C. To this were added 29.56% aqueous ammonium hydroxide solution (16 mL) and 6.15% aqueous bleach solution ("Chlorox", 240 mL) over a period of 15 min. The mixture was stirred for 30 min at - 5 0C and then the layers were separated. The organic layer was washed with brine, filtered over sodium sulfate and stored over solid calcium chloride at -5 0C. 4-Cyano- lH-pyrrole-2-carboxylic acid methyl ester (Example 15a, 1.09 g, 7.265 mmol) was dissolved in N,N-dimethylformamide (30 mL) and a 60% dispersion of sodium <n="108"/>hydride in mineral oil (0.378 g, 9.445 mmol) was added. After stirring for 1 h at 25 0C, the above -0.36 M solution of monochloramine in ether (26 mL, 9.445 mmol) was added and stirred for 2 h at 25 0C. The reaction was quenched with saturated aqueous sodium thiosulfate solution followed by water. The layers were separated and the aqueous layer was extracted with diethyl ether. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to afford the crude desired product, l-amino-4-cyano-lH-pyrrole-2-carboxylic acid methyl ester, which was used in the next step without further purification. 1H NMR (400 MHz, CDCI3) δ: 3.88 (3H, s), 5.67 (2H, bs), 7.07 (IH, d, J= 1.7 Hz), 7.37 (IH, d, J= 1.7 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; bromine; In 1,4-dioxane; water; | EXAMPLE 3 Preparation of 2,4,5-Tribromopyrrole-3-carbonitrile STR10 Sodium hydroxide (50% in water, 0.4 mL) is added to a solution of the mixture obtained in Example 2 (0.85 g) in dioxane. The reaction mixture is heated at 80 C. for about 12 hours, cooled to about 10 C. and treated with additional sodium hydroxide (50% in water, 1.2 mL). Bromine (0.9 mL, 0.02 mol) is then added portionwise over 90 minutes to the reaction mixture while maintaining the temperature below 20 C. After the addition is complete, the cooling bath is removed and the reaction mixture is stirred for 90 minutes then poured into water. The aqueous mixture is acidified with hydrochloric acid and filtered. The filter cake is washed with water and dried to give the title product as a tan solid (0.72 g). |
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