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Chemical Structure| 6994-25-8 Chemical Structure| 6994-25-8
Chemical Structure| 6994-25-8

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Synonyms: 3-Amino-4-ethoxycarbonylpyrazole

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Product Details of Ethyl 3-amino-1H-pyrazole-4-carboxylate

CAS No. :6994-25-8
Formula : C6H9N3O2
M.W : 155.15
SMILES Code : O=C(C1=CNN=C1N)OCC
Synonyms :
3-Amino-4-ethoxycarbonylpyrazole
MDL No. :MFCD00005238
InChI Key :YPXGHKWOJXQLQU-UHFFFAOYSA-N
Pubchem ID :81472

Safety of Ethyl 3-amino-1H-pyrazole-4-carboxylate

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of Ethyl 3-amino-1H-pyrazole-4-carboxylate

* 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.

  • Upstream synthesis route of [ 6994-25-8 ]
  • Downstream synthetic route of [ 6994-25-8 ]

[ 6994-25-8 ] Synthesis Path-Upstream   1~1

  • 1
  • [ 6994-25-8 ]
  • [ 1353100-91-0 ]
YieldReaction ConditionsOperation in experiment
100% With copper(ll) bromide; isopentyl nitrite In acetonitrile at 50℃; To a 0° C. solution of ethyl 3-amino-1H-pyrazole-4-carboxylate (5.0 g, 32 mmol) and copper (II) bromide (7.2 g, 32 mmol) in acetonitrile (65 mL) was slowly added isoamyl nitrite (12 mL, 86 mmol). The reaction was heated to 50° C. and stirred overnight. The reaction was cooled to room temperature and quenched with 1 N aqueous hydrochloric acid (150 mL). The mixture was extracted with ethyl acetate (3.x.100 mL). The combined organics were washed with water, dried over sodium sulfate, filtered, and concentrated to give the title compound as a brown oil that partially solidified under vacuum overnight (7.1 g, 100percent). 1H NMR (400 MHz, CDCl3, δ): 9.78 (br. s., 1H), 8.10 (br. s., 1H), 4.33 (q, J=7.22 Hz, 2H), 1.36 (m, 3H).
81% With tert.-butylnitrite; copper(ll) bromide In acetonitrile at 20 - 70℃; for 3 h; Inert atmosphere To a solution of terf-BuONO (156 mmol, 16.5 g) in acetonitrile (300 mL) was added CuBr2 (156 mmol, 34.8 g). After the mixture was stirred at rt for 1 h under nitrogen, ethyl 3-amino-lH-pyrazole-4-carboxylate ( 129 mmol, 20.0 g) was added portionwise over 30 min. The reaction mixture was stirred at rt for 30 min and then was allowed to warm up to 70°C and was stirred for another 2 h. After cooling to rt, the solvent was removed under reduced pressure. The residue was diluted with EtOAc ( 1 L) and was washed with brine (200 mL x 3). The organic layer was dried over MgS04, filtered, and concentrated to afford ethyl 3-bromo-lH-pyrazole- 4-carboxylate (106 mmol, 23.2 g, 81 percent) and was used without any purification.LC-MS: m/z ES+= 219, 221.
References: [1] Patent: US2012/108619, 2012, A1, . Location in patent: Page/Page column 26.
[2] Patent: WO2012/9009, 2012, A2, . Location in patent: Page/Page column 56.
[3] Patent: WO2012/8999, 2012, A2, . Location in patent: Page/Page column 75.
[4] Journal of Organic Chemistry, 2012, vol. 77, # 22, p. 10050 - 10057.
[5] Patent: WO2014/188211, 2014, A1, . Location in patent: Page/Page column 78.
[6] Patent: WO2018/64119, 2018, A1, . Location in patent: Paragraph 0499; 0505; 0935.
 

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