Structure of 1369959-12-5
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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. : | 1369959-12-5 |
Formula : | C3H2ClN3O2 |
M.W : | 147.52 |
SMILES Code : | O=[N+](C1=CC(Cl)=NN1)[O-] |
MDL No. : | MFCD29762425 |
InChI Key : | IAPLHVWLDQZZOU-UHFFFAOYSA-N |
Pubchem ID : | 135741948 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302 |
Precautionary Statements: | 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 |
---|---|---|
56% | With methoxybenzene; at 140℃; for 16.0h;Sealed tube; Inert atmosphere; | Compound 1-1 a (7.0 g, 47.4 mmol) was dissolved in anisole (150 ml) in a steal bomb. The vessel was sealed and the mixture heated at 140 C. The progress of the reaction was monitored by TLC and stopped after 16 h even though starting material was not completely consumed. The mixture was filtered and the filtrate was concentrated under vacuum. The residue was purified by column chromatography on silica gel (100-200 mesh) eluted with 20% EtOAc in p.ether which gave the title compound (4.0 g, 56 %) as a solid. LCMS (ES-) 145.99 [M-H]-. |
51% | at 140℃;Autoclave; | A solution of 3-chloro-l-nitro-pyrazole (4.0 g, 27 mmol) in anisole (20 mL) was heated to 140 C in an autoclave and stirred at 140C overnight. After cooling to 0C, the reaction mixture was diluted with hexane (200 mL), stirred for 30 min at 0C, and filtered. The solid was collected, washed with hexane (10 mL), and dried to give the title compound (2. l g, 51%) as a yellow solid. 1H NMR (400 MHz, DMSO-Mu): delta 14.96 (bs, 1H), 7.30 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With hydrogenchloride; tin(II) chloride dihdyrate; In methanol; at 20℃; for 6.0h; | Tin (II) chloride (12.8 g, 68 mmol) was added in portions to a solution of 3-chloro-5-nitro- lH-pyrazole (2.0 g, 13.6 mmol) in methanol (200 mL) and cone. HCl (10 mL) at 0 C. The reaction mixture was stirred at room temperature for 6 hours, and the organic solvent was removed under reduced pressure. The residue was diluted with water (20 mL), neutralized to pH 7 with Na2C03, then extracted with EtOAc (3 x 50 mL). The combined organic phases were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated to give the title compound (1.4 g, 87%), which was used without further purification. 1H NMR (400 MHz, DMSO-d6): delta 11.55 (bs, 1H), 5.26 (s, 2H), 5.21 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With di-tert-butyl-diazodicarboxylate; triphenylphosphine; In 2-methyltetrahydrofuran; at 20℃; | General procedure: To a solution of 3-methyl-5-nitro-lH-pyrazole (2.46 g, 19.40 mmol) and l -methyl-4- piperidinemethanol (5.00 g, 38.70 mmol) in dry Me-THF (190 mL). Di-tert-butyl azodicarboxylate (8.91 g, 38.70 mmol) and PPh3 (10.20 g, 38.70 mmol) were added. The solution was heated at 55 C over the weekend. The reaction mixture was diluted with EtOAc and water. The organic layer was separated and the aqueous layer was extracted thrice with EtOAc. The organic layers were combined, washed with brine, dried over MgS04, filtered and concentrated. The residue (yellow oil) was purified by column chromatography on silica gel (Irregular SiOH, 15-40 muiotaeta, 330 g, liquid loading in DCM, mobile phase: DCM/MeOH, gradient from 100:0 to 90: 10). The fractions containing the product were combined and evaporated to dryness to give 2.36 g of intermediate 195 (51% yield, yellow oil). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66%; 27% | With di-tert-butyl-diazodicarboxylate; triphenylphosphine; In 2-methyltetrahydrofuran; at 20℃; | General procedure: To a solution of 3-methyl-5-nitro-lH-pyrazole (2.46 g, 19.40 mmol) and l -methyl-4- piperidinemethanol (5.00 g, 38.70 mmol) in dry Me-THF (190 mL). Di-tert-butyl azodicarboxylate (8.91 g, 38.70 mmol) and PPh3 (10.20 g, 38.70 mmol) were added. The solution was heated at 55 C over the weekend. The reaction mixture was diluted with EtOAc and water. The organic layer was separated and the aqueous layer was extracted thrice with EtOAc. The organic layers were combined, washed with brine, dried over MgS04, filtered and concentrated. The residue (yellow oil) was purified by column chromatography on silica gel (Irregular SiOH, 15-40 muiotaeta, 330 g, liquid loading in DCM, mobile phase: DCM/MeOH, gradient from 100:0 to 90: 10). The fractions containing the product were combined and evaporated to dryness to give 2.36 g of intermediate 195 (51% yield, yellow oil). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With hydrogenchloride; tin(ll) chloride; In methanol; water; at 0 - 20℃; for 16.0h; | Aqueous HCI (16.8 mL, 544 mmol) was added over a period of 10 min to a solution of compound 1-1 b (4.0 g, 27.1 mmol) in MeOH (200 mL). The reaction mixture was cooled to 0 C and tin(ll) chloride (30.0 g, 158 mmol) was added portion wise and the resulting reaction mixture was stirred at rt. The progress of the reaction was monitored by TLC and after 16 h, when starting material was deemed consumed, the solvent was evaporated. The residue was diluted with EtOAc (100 mL) and 30% aqueous NaOH solution (120 mL) was added dropwise at 0 C until basic pH, then stirred at 0 C for 2h. Solid precipitates were filtered off through a pad of Celite and the cake was rinsed with EtOAc (50 mL) and water (50 mL). The organic phase was separated and the aqueous phase was extracted with EtOAc (50 mL). The combined organic layers were washed with brine (50 mL), dried (Na2S04), filtered and concentrated under vacuum which gave the title compound (3.5 g, 93 %). The compound was used in next step without further purification. MS (ES+) 1 18.04 [M+H]+. |
Tags: 1369959-12-5 synthesis path| 1369959-12-5 SDS| 1369959-12-5 COA| 1369959-12-5 purity| 1369959-12-5 application| 1369959-12-5 NMR| 1369959-12-5 COA| 1369959-12-5 structure
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