Structure of 17601-94-4
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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. : | 17601-94-4 |
Formula : | C7H4BrN3O2 |
M.W : | 242.03 |
SMILES Code : | NC1=C(C=C(C=C1Br)[N+]([O-])=O)C#N |
MDL No. : | MFCD00054185 |
InChI Key : | MUHLVSZIVTURCZ-UHFFFAOYSA-N |
Pubchem ID : | 87173 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H312-H315-H319-H332-H335 |
Precautionary Statements: | P261-P280-P305+P351+P338 |
* 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 |
---|---|---|
With sodium tetrahydroborate; copper(II) ion; at 60 - 65℃; for 0.166667h;Green chemistry; | General procedure: The general procedure for the hydrogenation of nitro compounds is as follows: The three-neck round bottom flask equipped with a Teflon-coated condenser, thermopocket, and magnetic needle containing substrate (1 mmol) dissolved in methanol or water(1.2 mL) was stirred and heated at 60-65 C under atmospheric environment. To this clear-stirred solution, copper(II)salt (2 mol % of Cu(OAc)2 or CuCO3 or Cu(NO3)2 or 3 mol % of Cu(OH)2 or CuSO4 or 4 mol % of CuO or 6 mol% of CuCl2 catalyst, as per Table 3) was added. Sequentially portion-wise addition (each portion 0.25 equiv./min) of NaBH4 (2.0-2.5 molar ratio to the substrate, as per Table 2) was charged within10 min. With the instant addition of the first portion of NaBH4, black granular precipitate formation with concomitant (H2) gas evolution was observed. As per TLC confirmation, the starting material was consumed completely within 10 min. Upon reaction completion, the reaction mixture was then filtered to remove the parted black precipitates. Further to thus obtained filtered mixture, 10 mL water was added into the filtered solution. Now the product isolation method was reliant on the nature of the product obtained. Upon addition of water, if precipitation occurs in the case of the solid product, then the parted solid product was isolated upon simple filtration and dried, if not then the aqueous solution was extracted with EtOAc (5mL 2), the sequentially combined organic layer was washed with water (5mL 2) and dried over anhydrous sodium sulfate. After filtration, the solvent was removed under vacuo affording the desired amine. It was observed that the purity of the crude product was more than 99%by 1H NMR, henceforth, to obtain pure product no column or flash chromatographic separation technique was needed. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Examples of Amines Useful in the Present Invention 2-chloro-4,6-dinitroaniline 2-bromo-4,6-dinitroaniline 2-chloro-6-cyano-4-nitroaniline 2-bromo-6-cyano-4-nitroaniline 2,6-dicyano-4-nitroaniline 2-cyano-4,6-dinitroaniline |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With urea; | 4-Amino-8-bromo-6-nitro-quinazolin-2-ol 2-Amino-3-bromo-5-nitro-benzonitrile (1.9003 g, 7.85 mmol) was heated with urea (1.8862 g, 31.4 mmol) at 180-185 C. for 3 hrs. The cooled mixture was powered and treated with bicarbonate solution, filtered and washed with water. The solid was the collected and washed with ethanol, ether, and used for the next step reaction without further purification. 2.0 g product was obtained. Yield 89%; 1H NMR (500 MHz, DMSO-d6): δ 8.44455-8.45011 (d, J=2.78 Hz, 1H), 8.87071-8.87544 (d, J=2.365 Hz, 1H), 9.39866-9.40333 (d, J=2.335 Hz, 1H), 9.50740-9.51282 (d, J=2.71 Hz, 1H); ESI-MS: 285, 287 (M++1) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
EXAMPLE 45 Following the same procedure as in Example 44, but initially replacing the 26.2 parts of 2-bromo-4,6-dinitroaniline by an equimolecular quantity of 2-bromo-4-nitro-6-cyanoaniline, the dyestuff of the following formula is obtained. STR10 of which the elementary analysis is as follows: This dyestuff dyes polyester based fibers a reddish-yellow shade. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; at 20 - 80℃; for 10h; | To a stirred solution of <strong>[17601-94-4]2-amino-3-bromo-5-nitrobenzonitrile</strong> (2.4 g, 10 mmol) in dry Et3N (60 mL) was added CuI (380 mg, 5% mol) and Pd(PPh3)2Cl2 (470 mg, 5% mol) at room temperature. 3,3-dimethyl-but-1-yne (2.1 g, 25 mmol) was added dropwise to the mixture at room temperature. The reaction mixture was stirred at 80 C. for 10 h. The reaction mixture was filtered and the filtrate was poured into ice (60 g), extracted with ethyl acetate. The phases were separated and the organic phase was dried over Na2SO4. The solvent was removed under vacuum to obtain the crude product, which was purified by column chromatography (2-10% EtOAc in petroleum ether) to obtain 2-amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrile (1.7 g, 71%). 1H NMR (300 MHz, CDCl3) δ 8.28 (d, J=2.7 Hz, 1H), 8.27 (d, J=2.7 Hz, 1H), 5.56 (br s, 2H), 1.37 (s, 9H). |
71% | With CuI;Pd(PPh3)2Cl2; In ethyl acetate; triethylamine; Petroleum ether; | 2-Amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrile To a stirred solution of <strong>[17601-94-4]2-amino-3-bromo-5-nitrobenzonitrile</strong> (2.4 g, 10 mmol) in dry Et3N (60 mL) was added CuI (380 mg, 5% mol) and Pd(PPh3)2Cl2 (470 mg, 5% mol) at room temperature. 3,3-dimethyl-but-1-yne (2.1 g, 25 mmol) was added dropwise to the mixture at room temperature. The reaction mixture was stirred at 80 C. for 10 h. The reaction mixture was filtered and the filtrate was poured into ice (60 g), extracted with ethyl acetate. The phases were separated and the organic phase was dried over Na2SO4. The solvent was removed under vacuum to obtain the crude product, which was purified by column chromatography (2-10% EtOAc in petroleum ether) to obtain 2-amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrile (1.7 g, 71%). 1H NMR (300 MHz, CDCl3) δ 8.28 (d, J=2.7 Hz, 1H), 8.27 (d, J=2.7 Hz, 1H), 5.56 (br s, 2H), 1.37 (s, 9H). |
71% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; at 80℃; for 10h; | To a stirred solution of <strong>[17601-94-4]2-amino-3-bromo-5-nitrobenzonitrile</strong> (2.4 g, 10 mmol) in dry Et3N (60 mL) was added CuI (380 mg, 5% mol) and Pd(PPh3)2Cl2 (470 mg, 5% mol) at room temperature. 3,3-dimethyl-but-1-yne (2.1 g, 25 mmol) was added dropwise to the mixture at room temperature. The reaction mixture was stirred at 80 C. for 10 h. The reaction mixture was filtered and the filtrate was poured into ice (60 g), extracted with ethyl acetate. The phases were separated and the organic phase was dried over Na2SO4. The solvent was removed under vacuum to obtain the crude product, which was purified by column chromatography (2-10% EtOAc in petroleum ether) to obtain 2-amino-3-(3,3-dimethylbut-1-ynyl)-5-nitrobenzonitrile (1.7 g, 71%). 1H NMR (300 MHz, CDCl3) δ 8.28 (d, J=2.7 Hz, 1H), 8.27 (d, J=2.7 Hz, 1H), 5.56 (br s, 2H), 1.37 (s, 9H). |
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