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Structure of 106157-91-9
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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. : | 106157-91-9 |
Formula : | C6H6BrN3O |
M.W : | 216.04 |
SMILES Code : | BrCC(C1=NC(N)=NC=C1)=O |
MDL No. : | MFCD11656632 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H302-H314 |
Precautionary Statements: | P264-P270-P271-P280-P303+P361+P353-P304+P340-P305+P351+P338-P310-P330-P331-P363-P403+P233-P501 |
Class: | 8 |
UN#: | 1759 |
Packing Group: | Ⅱ |
* 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 |
---|---|---|
65% | With water; hydrogen bromide; bromine; In water; at 20℃; for 15h; | To a solution of <strong>[106157-82-8]1-(2-aminopyrimidin-4-yl)ethanone</strong> (412 mg, 3 mmol) in glacial acetic acid (1 mL) and 48% aq. HBr (0.3 mL), bromine (0.153 mL) in acetic acid (0.4 mL) was added and the resulting orange solution was stirred at room temperature for 15 hours. After diluting with ethyl acetate (15 mL), the precipitate was filtered and washed with ethyl acetate thus affording the title compound as a whitish solid (580 mg, 65%). 1H NMR (DMSO-d6/400 MHz) delta ppm: 4.9 (s, 2 H), 7.0 (d, 2 H), 8.5 (d, 2 H). |
65% | With hydrogen bromide; bromine; acetic acid; In water; at 20℃; for 15h; | Example 2 1- (2-AMINOPYRIMIDIN-4-YL)-2-BROMOETHANONE hydrobromide The title compound (a) was prepared by working as described in J. Het. Chem. 1985,22, 1723. A mixture of 3,3-dimethoxy-2-butanone (25 9, 189.16 MMOL) and N, N-DIMETHYLFORMAMIDE DIMETHYLACETAL (22.5 g, 189.16 MMOL) were stirred at 110C for 30 hours and then distilled (115C, 1 mmHg) thus obtaining 1-(DIMETHYLAMINO)-4, 4-DIMETHOXYPENT-1-EN-3-ONE, as a yellow solid (27.3 G, 146 mmol, 77%). Onto a solution of sodium (3.48 g, 151.67 MMOL) in anhydrous ethanol (400 mL), solid guanidine hydrochloride (14.5 G, 151.67 MMOL) was added at r. t. , to give a white suspension into which a solution of 1-(DIMETHYLAMINO)-4, 4-DIMETHOXYPENT-1-EN-3-ONE (28.4 g, 151.67 MMOL) in anhydrous ethanol (50 mL) was added. The mixture was refluxed for 19 hours. After cooling, the precipitate was filtered and washed with ethanol and with plenty of water, thus obtaining a white solid (8.56 G). The ethanolic solutions were concentrated to dryness, taken up with boiling ethyl acetate (1000 mL), filtered while hot and then cooled to yield a second crop. Total amount of 4- (1, 1-DIMETHOXYETHYL) PYRIMIDIN-2-AMINE : 17.66 G, 63. 5%. A solution of the said amine (17. 5 G, 95.5 MMOL) in formic acid was stirred at r. t. for 6 hours and concentrated to dryness and the residue was stirred in ethanol (50 mL) and then filtered thus obtaining 1- (2-aminopyrimidin-4-yl) ethanone (9.2 g, 70%). To a solution of 1- (2- aminopyrimidin-4-yl) ethanone (412 mg, 3 MMOL) in glacial acetic acid (1 mL) and 48% aq. HBr (0.3 mL), bromine (0.153 mL) in acetic acid (0.4 mL) was added and the resulting orange solution was stirred at r. t. for 15 hours. After diluting with ethyl acetate (15 mL) the precipitate was filtered and washed with ethyl acetate thus affording the title compound as a whitish solid (580 mg, 65%). |
65% | With hydrogen bromide; bromine; acetic acid; In water; at 20℃; for 15h; | To a solution of <strong>[106157-82-8]1-(2-aminopyrimidin-4-yl)ethanone</strong> (412 mg, 3 mmol) in glacial acetic acid (1 mL) and 48% aq. HBr (0.3 mL), bromine (0.153 mL) in acetic acid (0.4 mL) was added and the resulting orange solution was stirred at r.t. for 15 hours. After diluting with ethyl acetate (15 mL) the precipitate was filtered and washed with ethyl acetate thus affording the title compound as a whitish solid (580 mg, 65%). 1H NMR (DMSO-d6/400 MHz) delta ppm: 4.9 (s, 2 H), 7.0 (d, 2 H), 8.5 (d, 2 H). |
65% | With hydrogen bromide; bromine; acetic acid; In water; at 20℃; for 15h; | Example 3; 1 -(2-Aminopyrimidin-4-yl)-2-bromoethanone hydrobromi'de; A mixture of 3,3-dimethoxy-2-butanone (25 g, 189.2 mmol) and N1N- dimethylformamide dimethylacetal (22.5 g, 189.2 mmo.) were stirred at 1100C for 30 hours and then distilled (11511C, 1 mmHg) thus obtaining 1-(dimethyiamino)-4,4-dimethoxypent-1-en- 3-o?e, as a yellow solid (27.3 g, 146 mmol, 77%). Onto a solution of sodium (3.48 g, 151.7 mmol) in anhydrous ethanol (400 mL), solid guanidine hydrochloride (14.5 g, 151.7 mmol) was added at r.t. to give a white suspension into which a solution of 1-(dirnethylamino)-4,4- dimethoxypent-1-e?-3-one (28.4 g, 151.7 mmo.) in anhydrous ethanol (50 mL) was added. The mixture was refluxed for 19 hours. After cooling, the precipitate was filtered and washed with ethanol and with plenty of water, thus obtaining a white solid (8.5 g). The ethanolic solutions were concentrated to dryness, taken up with boiling ethyl acetate (1000 mL), filtered while hot, and then cooled to yield a second crop. The total amount of 4-(1 ,1- dimethoxyethyl)pyrimidin-2-arnine obtained was 17.7 g, 63.5%, A solution of the said amine (17.5 g, 95.5 mmol) in formic acid was stirred at room temperature for 6 hours and concentrated to dryness and the residue was stirred in efhanoi (50 mL) and then filtered thus obtaining 1-(2-aminopyrimidi?-4-yl)ethanone (9.2 g, 70%). To a solution of the 1-(2- <n="34"/>aminopyrimidin-4-yl)ethanone (412 mg, 3 mmoi) in glacial acetic acid (1 mL) and 48% aq. HBr (0.3 mL), bromine (0.153 mL) in acetic acid (0.4 mL) was added and the resulting orange solution was stirred at r.t. for 15 hours. After diluting with ethyl acetate (15 mL) the precipitate was filtered and washed with ethyl acetate thus affording the title compound as a whitish solid (580 rng, 65%).1H NMR (DMSO-d6 / 400 MHz) delta ppm: 4.9 (s, 2 H), 7,0 (d, 2 H), 8.5 (d, 2 H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
49% | In ethanol; at 70℃; for 3h; | EXAMPLE 59 2-(2-Amino-pyrimidin-4-yl)-1-cyclopropylmethyl-1,5,6,7-tetrahydro-pyrrolo[3,2-c]pyridin-4-one A mixture of 1-(2-aminopyrimidin-4-yl)-2-bromoethanone hydrobromide (0.9 g, 3 mmol), cyclopropylmethylamine (0.85 g, 12 mmol, 1.03 mL) and <strong>[50607-30-2]piperidin-2,4-dione</strong> (0.51 g, 4.5 mmol), dissolved in absolute ethanol (10 mL), was stirred under heating at 70° C. for 3 hours in a glass pressure tube. Ethanol was evaporated off and the crude reaction mixture was purified by flash chromatography on silica gel (eluant: DCM/MeOH 4:1) and then by crystallization from MeOH. The title compound was obtained as white solid (0.42 g, 49percent yield). 1H NMR (400 MHz, DMSO-D6) delta ppm 0.30-0.48 (m, 4 H) 1.12-1.26 (m, 1 H) 2.97 (t, J=6.77 Hz, 2 H) 3.45 (t, J=6.46 Hz, 2 H) 4.61 (d, J=7.07 Hz, 2 H) 7.34-7.44 (d, J=6.95Hz, 1 H and one s, 1H) 7.71 (s, 1 H) 8.15 (d, J=6.95 Hz, 1 H) 8.31 (s, 1 H). |