Structure of 940875-99-0
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CAS No. : | 940875-99-0 |
Formula : | C9H13ClN2O2 |
M.W : | 216.66 |
SMILES Code : | O=C(OCC)C1=CC=CC(NN)=C1.[H]Cl |
MDL No. : | MFCD06796173 |
InChI Key : | YMKGDNLSBACMSE-UHFFFAOYSA-N |
Pubchem ID : | 44607746 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302+H312+H332-H315-H319-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 |
---|---|---|
23% | In ethanol; for 18h;Reflux; | To a suspension of <strong>[940875-99-0]ethyl 3-hydrazinylbenzoate hydrochloride</strong> (500 mg, 2.31 mmol) in EtOH (20 mL) was added 4,4-dimethyl-3-oxopentanenitrile (318 mg, 2.54 mmol). The reaction mixture was heated to reflux for 18 hours, then cooled to ambient temperature and concentrated in vacuo. The crude product was purified by silica column chromatography, eluting with 0-5% MeOH/DCM to yield the product as a yellow oil (154 mg, 23% yield). MS (apci) m/z = 288.2 (M+H). |
23% | In ethanol; for 18h;Reflux; | Intermediate PI Ethyl 3 -(5 -amino-3 -tert-butyl- 1 H- yrazol- 1 - vPbenzoate [00364] To a suspension of <strong>[940875-99-0]ethyl 3-hydrazinylbenzoate hydrochloride</strong> (500 mg, 2.31 mmol) in EtOH (20 mL) was added 4,4-dimethyl-3-oxopentanenitrile (318 mg, 2.54 mmol). The reaction mixture was heated to reflux for 18 hours, then cooled to ambient temperature and concentrated in vacuo. The crude product was purified by silica column chromatography, eluting with 0-5% MeOH/DCM to yield the product as a yellow oil (154 mg, 23% yield). MS (apci) m/z = 288.2 (M+H). |
23% | In ethanol; for 18h;Reflux; | 1005481 To a suspension of <strong>[940875-99-0]ethyl 3-hydrazinylbenzoate hydrochloride</strong> (500 mg, 2.31 mmol) in EtOH (20 mL) was added 4,4-dimethyl-3-oxopentanenitrile (318 mg, 2.54 mmol). The reaction mixture was heated to reflux for 18 hours, then cooled to ambient temperature and concentrated in vacuo. The crude product was purified by silica column chromatography, eluting with 0-5% MeOH/DCM to yield the product as a yellow oil (154 mg, 23% yield). MS (apci) mlz = 288.2 (M+H). |
23% | In ethanol; for 18h;Reflux; | Intermediate PI Ethyl 3-(5-amino-3-tert-butyl-lH-pyrazol-l -vDbenzoate [00479] To a suspension of <strong>[940875-99-0]ethyl 3-hydrazinylbenzoate hydrochloride</strong> (500 mg, 2.31 mmol) in EtOH (20 mL) was added 4,4-dimethyl-3-oxopentanenitrile (318 mg, 2.54 mmol). The reaction mixture was heated to reflux for 18 hours, then cooled to ambient temperature and concentrated in vacuo. The crude product was purified by silica column chromatography, eluting with 0-5% MeOH/DCM to yield the product as a yellow oil (154 mg, 23% yield). MS (apci) m/z = 288.2 (M+H). |
23% | In ethanol; for 16h;Reflux; | To a suspension of <strong>[940875-99-0]ethyl 3-hydrazinylbenzoate hydrochloride</strong> (500 mg, 2.31 mmol) in EtOH (20 mL) was added 4,4-dimethyl-3-oxopentanenitrile (318 mg, 2.54 mmol). The reaction mixture was heated to reflux for 18 hours, then cooled to ambient temperature and concentrated in vacuo. The crude product was purified by silica column chromatography, eluting with 0-5% MeOH/DCM to yield the product as a yellow oil (154 mg, 23% yield). MS (apci) m/z = 288.2 (M+H). |
23% | In ethanol; for 18h;Reflux; | Intermediate P1 Ethyl 3 -(5 -amino-3 -tert-butyl- 1 H-pyrazol- 1 -yl)benzoate1006771 To a suspension of <strong>[940875-99-0]ethyl 3-hydrazinylbenzoate hydrochloride</strong> (500 mg, 2.31 mmol) in EtOH (20 mL) was added 4,4-dimethyl-3-oxopentanenitrile (318 mg, 2.54 mmol). The reaction mixture was heated to reflux for 18 hours, then cooled to ambient temperature and concentrated in vacuo. The crude product was purified by silica column chromatography, eluting with 0-5% MeOH/DCM to yield the product as a yellow oil (154 mg, 23% yield). MS (apci) mlz = 288.2 (M+H). |
23% | In ethanol; for 18h;Reflux; | To a suspension of <strong>[940875-99-0]ethyl 3-hydrazinylbenzoate hydrochloride</strong> (500 mg, 2.31 mmol) in EtOH (20 mL) was added 4,4-dimethyl-3-oxopentanenitrile (318 mg, 2.54 mmol). The reaction mixture was heated to reflux for 18 hours, then cooled to ambient temperature and concentrated in vacuo. The crude product was purified by silica column chromatography, eluting with 0-5% MeOH/DCM to yield the product as a yellow oil (154 mg, 23% yield). MS (apci) m/z = 288.2 (M+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In tetrahydrofuran; water; at -78 - -10℃; for 2.5h;Inert atmosphere; | To a solution of 2,4,6-trichloropyrimidine-5-carbaldehyde (3.9 g, 18.5 mmol) in tetrahydrofuran (100 mL) was added dropwise a solution of ethyl 3-hydrazinobenzoate hydrochloride (4.0 g, 18.5 mmol) in tetrahydrofuran/ water (50 mL, v: v = 9: 1) at -78 C under nitrogen atmosphere. Then triethylamine (7.7 mL, 55.4 mmol) was added dropwise and the mixture was stirred at -78 C for 30 minutes under nitrogen atmosphere. Then the mixture was warmed to -10 C and stirred for further 2 h. Upon completion of the reaction, the solvent was removed in vacuo. The residue was purified with silica gel column chromatography (ethyl acetate: petroleum ether = 1: 10) to give 1.01 g of the product (batch contained impurities) as a light yellow solid. MS (ESIpos): m/z = 337 (M+H)+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
17% | In water monomer; dimethyl sulfoxide; at 20℃; for 2h; | A solution of 3-hydrazinobenzoate hydrogen chloride (347 mg, 2.3 mmol) and 2-formylphenylboronic acid (500 mg, 2.3 mmol) in DMSO/H2O (10 mL, v/v = 1/4) was stirred at room temperature for 2 h. LCMS analysis showed no starting materials left. The reaction mixture was diluted by water (25 mL), extracted by EtOAc (2 x 25 mL), washed with brine (2 x 10 mL), dried over Na2SO4, filtered and concentrated in vacuo to give the crude product. Further purification by crystallization with MeOH/H2O (10 mL, v/v = 1/1) to afford the desired product ethyl m-(1-hydroxy-1,2-dihydro-2,3,1- benzodiazaborinin-2-yl)benzoate (117 mg, yield 17%) as a white solid. 1HNMR (400 MHz, DMSO-d6): δ 9.22 (s, 1H), 8.42 (d, J = 7.5 Hz, 1H), 8.25 (d, J = 3.5 Hz, 2H), 7.92 (dd, J = 8.1, 1.1 Hz, 1H), 7.87-7.76 (m, 3H), 7.69 (t, J = 7.3 Hz, 1H), 7.57 (t, J = 7.9 Hz, 1H), 4.35 (q, J = 7.1 Hz, 2H), 1.34 (t, J = 7.1 Hz, 3H) ppm. HPLC purity: 98.54% at 210 nm and 91.45% at 254 nm. MS: (M+H)+: m/z = 295.1 |
17% | In water monomer; dimethyl sulfoxide; at 20℃; for 2h; | A solution of 3-hydrazinobenzoate hydrogen chloride (347 mg, 2.3 mmol) and 2-formylphenylboronic acid (500 mg, 2.3 mmol) in DMSO/H2O (10 mL, v/v = 1/4) was stirred at room temperature for 2 h. LCMS analysis showed no starting materials left. The reaction mixture was diluted by water (25 mL), extracted by EtOAc (2 x 25 mL), washed with brine (2 x 10 mL), dried over Na2SO4, filtered and concentrated in vacuo to give the crude product. Further purification by crystallization with MeOH/H2O (10 mL, v/v = 1/1) to afford the desired product ethyl m-(1-hydroxy-1,2-dihydro-2,3,1- benzodiazaborinin-2-yl)benzoate (117 mg, yield 17%) as a white solid. 1HNMR (400 MHz, DMSO-d6): δ 9.22 (s, 1H), 8.42 (d, J = 7.5 Hz, 1H), 8.25 (d, J = 3.5 Hz, 2H), 7.92 (dd, J = 8.1, 1.1 Hz, 1H), 7.87-7.76 (m, 3H), 7.69 (t, J = 7.3 Hz, 1H), 7.57 (t, J = 7.9 Hz, 1H), 4.35 (q, J = 7.1 Hz, 2H), 1.34 (t, J = 7.1 Hz, 3H) ppm. HPLC purity: 98.54% at 210 nm and 91.45% at 254 nm. MS: (M+H)+: m/z = 295.1 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | To a solution of m-amino benzoic acid ethyl ester (1.65 g, 10.0 mmol) in concentrated HCl (10 mL) was added an aqueous solution (2.5 mL) of NaNO2 (690 mg, 1.0.0 mmol) at 0 C. the reaction mixture was stirred for 1 h. A solution of SnCl2.2H2O (4.52 g, 20 mmol) in concentrated HCl (1 mL) was then added at 0 C. The reaction solution was stirred for 2 h at room temperature. The precipitate was filtered and washed with ethanol and ether to yield ethyl 3-hydrazinobenzoate hydrogen chloride (2.1 g, yield 100%) as a white solid, which was used for the next reaction without further purification. 1H NMR (400 MHz, DMSO-d6): δ 9.09 (s, 1H), 7.68 (dd, J = 13.9, 8.2 Hz, 2H), 7.27 (d, J = 31.6 Hz, 2H), 4.97 (s, 3H), 3.92 (d, J = 5.5 Hz, 1H), 3.35 (s, 5H), 2.36 (s, 3H), 1.23 (s, 3H) ppm. MS: (M+H)+: m/z = 181.1. | |
100% | To a solution of m-amino benzoic acid ethyl ester (1.65 g, 10.0 mmol) in concentrated HCl (10 mL) was added an aqueous solution (2.5 mL) of NaNO2 (690 mg, 1.0.0 mmol) at 0 C. the reaction mixture was stirred for 1 h. A solution of SnCl2.2H2O (4.52 g, 20 mmol) in concentrated HCl (1 mL) was then added at 0 C. The reaction solution was stirred for 2 h at room temperature. The precipitate was filtered and washed with ethanol and ether to yield ethyl 3-hydrazinobenzoate hydrogen chloride (2.1 g, yield 100%) as a white solid, which was used for the next reaction without further purification. 1H NMR (400 MHz, DMSO-d6): δ 9.09 (s, 1H), 7.68 (dd, J = 13.9, 8.2 Hz, 2H), 7.27 (d, J = 31.6 Hz, 2H), 4.97 (s, 3H), 3.92 (d, J = 5.5 Hz, 1H), 3.35 (s, 5H), 2.36 (s, 3H), 1.23 (s, 3H) ppm. MS: (M+H)+: m/z = 181.1. |
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