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[ CAS No. 24922-02-9 ]

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Chemical Structure| 24922-02-9
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CAS No. :24922-02-9 MDL No. :MFCD00184570
Formula : C8H12O3 Boiling Point : 212.9°C at 760 mmHg
Linear Structure Formula :- InChI Key :N/A
M.W :156.18 g/mol Pubchem ID :262979
Synonyms :

Safety of [ 24922-02-9 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 24922-02-9 ]

  • Upstream synthesis route of [ 24922-02-9 ]
  • Downstream synthetic route of [ 24922-02-9 ]

[ 24922-02-9 ] Synthesis Path-Upstream   1~19

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YieldReaction ConditionsOperation in experiment
93%
Stage #1: With triethylamine; magnesium chloride In ethyl acetate at 0 - 40℃; for 20 h;
Stage #2: at 0 - 20℃; for 20 h;
To ethyl acetate (100 ml) suspension of potassium ethyl malonate (17.0 g, 0.10 mol) were added triethylamine (34.7 ml, 0.25 mol) and magnesium chloride (14.3 g, 0.15 mol) with cooling with ice, and then the resulting mixture was stirred at 40°C for 20 hours. To tetrahydrofuran (50 ml) solution of cyclopropanecarboxylicacid (4.30 g, 50.0 mmol) were added oxalyl chloride (4.36 ml, 50.0 mmol) and a catalytic amount of N,N-dimethylformamide with cooling with ice, and the resulting mixture was stirred as such for 1 hour and then at room temperature for 1 hour. The above-mentioned malonic acid solution was added to this acid chloride solution with cooling with ice, and the resulting mixture was stirred at room temperature for 20 hours. The reaction mixture was poured into 300 ml of aqueous 10 percent citric acid solution, and the mixture was extracted with ethyl acetate (300 ml .x. 3). The organic layer was successively washed with 500 ml of aqueous saturated sodium bicarbonate solution and 300 ml of brine, and dried over sodium sulfate. The solvent was evaporated, and7.26g (93percent) of the entitled compound was obtained as a colorless oil (this was directly used in the next reaction).1H-NMR(400MHz, CDCl3)δ: 0.94-0.99(2H, m), 1.10-1.15(2H, m), 1.28(3H, t, J=7.08Hz), 2.01-2.06(1H, m), 3.57 (2H, s), 4.21(2H, q, J=7.08Hz).
60%
Stage #1: With magnesium chloride In acetonitrile at 25℃; for 0.0833333 h;
Stage #2: With triethylamine In acetonitrile at 25℃; for 16 h;
To a solution of ethyl potassium malonate (6.5 g, 38.26 mmol) in acetonitrile was added MgCl2 (4.55 g, 47.8 mmol) and the mixture stirred for 5 min at 25° C. TEA (10.7 mL, 76.54 mmol) was then added, followed by dropwise addition of cyclopropanecarbonyl chloride (2 g, 19.13 mmol) and stirring was continued at 25° C. for 16 h, after which, the mixture was diluted with water, acidified to pH 3 with 6N HCl, extracted with diethylether (3*40 mL), dried over Na2SO4, and concentrated to give 3-Cyclopropyl-3-oxo-propionic acid ethyl ester (1.8 g, 60percent).
Reference: [1] Patent: EP1479681, 2004, A1, . Location in patent: Page 59
[2] Patent: US2011/71150, 2011, A1, . Location in patent: Page/Page column 31
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YieldReaction ConditionsOperation in experiment
55% With NaH In hydrogenchloride; diethyl ether; ethanol; hexane; ethyl acetate; mineral oil; Diethyl carbonate A.
3-Cyclopropyl-3-oxopropanoic acid, ethyl ester
To a slurry of NaH (60percent in mineral oil, 19.200 gm, 0.48 mol) in dry diethyl carbonate (80 ml) was added a solution of methyl cyclopropyl ketone (23.5 ml, 20.00 gm, 0.238 mol) in Et2 O (30 ml).
After the addition of approximately 10percent of the ketone solution, EtOH (0.25 ml) was added and addition of the ketone continued.
Soon after the addition was complete, the reaction became quite exothermic with vigorous H2 evolution.
Periodic cooling with an ice bath was required.
After one hour, H2 evolution had ceased and the mixture was diluted with Et2 O (200 ml) and hexane (185 ml).
The solution was cooled in an ice bath and carefully treated with 5percent HCl (10 ml), at which time a thick slurry developed.
The solid was collected by filtration and washed with hexane.
The solid was then partitioned between Et2 O and 5percent HCl until all of the solid had dissolved and the aqueous layer remained acidic.
The organic layer was separated and washed with H2 O, saturated NaHCO3, and brine, then dried (MgSO4), filtered and stripped.
The liquid residue was subjected to flash chromatography (Merck SiO2, 20percent EtOAc in hexane) to provide compound A (20.357 gm, 55percent) as a yellow liquid.
TLC Rf 0.24 (20percent EtOAc in hexane)
55% With NaH In hydrogenchloride; diethyl ether; ethanol; hexane; ethyl acetate; mineral oil; Diethyl carbonate A.
3-Cyclopropyl-3-oxopropanoic acid, ethyl ester
To a slurry of NaH (60percent in mineral oil, 19.200 g, 0.48 mol) in dry diethyl carbonate (80 ml) was added a solution of methyl cyclopropyl ketone (23.5 ml, 20.00 g, 0.238 mol) in Et2 O (30 ml).
After the addition of approximately 10percent of the ketone solution, EtOH (0.25 ml) was added and the addition of the ketone continued.
Soon after the addition was complete, the reaction became quite exothermic with vigorous H2 evolution.
Periodic cooling with an ice bath was required.
After one hour, H2 evolution had ceased and the mixture was diluted with Et2 O (200 ml) and hexane (185 ml).
The solution was cooled in an ice bath and carefully treated with 5percent HCl (10 ml), at which time a thick slurry developed.
The solid was collected by filtration and washed with hexane.
The solid was then partitioned between Et2 O and 5percent HCl until all of the solid had dissolved and the aqueous layer remained acidic.
The organic layer was separated and washed with H2 O, saturated NaHCO3, and brine, then dried (MgSO4), filtered and stripped.
The liquid residue was subjected to flash chromatography (Merck SiO2, 20percent EtOAc in hexane) to provide compound A (20.357 g, 55percent) as a yellow liquid.
TLC: Rf =0.24 (20percent EtOAc in hexane).
Reference: [1] Patent: US5506219, 1996, A,
[2] Patent: US5506219, 1996, A,
  • 3
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YieldReaction ConditionsOperation in experiment
60% With sodium t-butanolate In toluene at 15 - 75℃; 48g of sodium tert-butoxide was added to 500mL of toluene, cooled to 10°C and 225g of dimethyl carbonate was added dropwise. After stirring for 30 min, 75.7g cyclopropyl methyl ketone was added dropwise and the reaction temperature was controlled not higher than 15°C. Stirring was continued for 30 min, and the reaction temperature was raised to 75°C overnight. The reaction was cooled to room temperature, the solution was poured into 500mL of ice water, adjusted pH1-2 with hydrochloric acid. The organic phase was washed with water and saturated sodium chloride solution, dried and concentrated to give 83g og an orange oil (A-3-2), yield: 60percent, purity: 98.28percent.
Reference: [1] Patent: CN105218449, 2016, A, . Location in patent: Paragraph 0072; 0073
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YieldReaction ConditionsOperation in experiment
63% With n-butyllithium In tetrahydrofuran; hydrogenchloride; water a
Ethyl 3-cyclopropyl-3-oxopropanoate
To a cooled (-70° C.) solution of monoethyl malonate (33.97 g, 257.10 mmol) in THF (639 mL) was added n-BuLi (1.6M in hexanes, 319 mL, 514.19 mmol) and the mixture was stirred under an argon atmosphere for 15 min.
The resulting solution was cooled to -65° C. and cyclopropanecarbonyl chloride (15.55 g, 148.77 mmol) was added.
The reaction mixture was stirred for 1 h and then allowed to warm up to room temperature.
Some drops of water were added and THF was removed.
The residue was taken up in 1N HCl/Et2 O and extracted with Et2 O.
The organic phase was washed with saturated NaHCO3, dried and concentrated to a residue.
This was purified by chromatography on silica gel (hexane-EtOAc mixtures of increasing polarity) to afford the title compound as a yellow oil (14.7 g, 63percent).
1 H-NMR-(CDCl3) δ (TMS): 1.1 (m, 4H), 1.28 (t, J=7.2 Hz, 3H), 2.04 (m, 1H), 3.55 (s, 2H), 4.21 (q, J=7.2 Hz, 2H).
Reference: [1] Patent: US5827863, 1998, A,
[2] Journal of Medicinal Chemistry, 1997, vol. 40, # 4, p. 547 - 558
[3] Patent: US5157040, 1992, A,
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Reference: [1] Tetrahedron Letters, 1993, vol. 34, # 51, p. 8267 - 8270
[2] Bulletin de la Societe Chimique de France, 1973, p. 1711 - 1717
[3] Tetrahedron Letters, 1979, p. 2339 - 2342
[4] Patent: US2004/147561, 2004, A1, . Location in patent: Page 60
[5] Chemical Communications, 2017, vol. 53, # 58, p. 8136 - 8139
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Reference: [1] Patent: WO2016/102347, 2016, A1, . Location in patent: Paragraph 0355
[2] Patent: WO2017/211666, 2017, A1, . Location in patent: Paragraph 0269
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Reference: [1] Patent: US2005/96337, 2005, A1, . Location in patent: Page/Page column 45-46
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Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2001, vol. 11, # 6, p. 803 - 807
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Reference: [1] Synthesis, 2004, # 16, p. 2629 - 2632
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Reference: [1] MedChemComm, 2013, vol. 4, # 9, p. 1297 - 1304
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Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2001, vol. 11, # 6, p. 803 - 807
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Reference: [1] Synthesis, 1981, # 2, p. 130 - 133
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Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2012, vol. 22, # 20, p. 6338 - 6342
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Reference: [1] Journal of the American Chemical Society, 1947, vol. 69, p. 2073
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Reference: [1] Journal of the American Chemical Society, 1948, vol. 70, p. 497,499
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Reference: [1] Bioorganic and Medicinal Chemistry, 2001, vol. 9, # 10, p. 2727 - 2743
[2] Organic and Biomolecular Chemistry, 2006, vol. 4, # 1, p. 104 - 110
[3] Tetrahedron Letters, 1993, vol. 34, # 51, p. 8267 - 8270
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Reference: [1] Heterocycles, 1999, vol. 50, # 1, p. 479 - 483
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Reference: [1] Heterocycles, 1999, vol. 50, # 1, p. 479 - 483
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Reference: [1] Patent: WO2014/152738, 2014, A1, . Location in patent: Page/Page column 69
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