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CAS No. : | 2483-57-0 | MDL No. : | MFCD00075480 |
Formula : | C3H5NO4 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | ALBSWLMUHHZLLR-UHFFFAOYSA-N |
M.W : | 119.08 | Pubchem ID : | 17206 |
Synonyms : |
|
Num. heavy atoms : | 8 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.67 |
Num. rotatable bonds : | 3 |
Num. H-bond acceptors : | 4.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 25.93 |
TPSA : | 72.12 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.95 cm/s |
Log Po/w (iLOGP) : | 0.52 |
Log Po/w (XLOGP3) : | 0.11 |
Log Po/w (WLOGP) : | -0.56 |
Log Po/w (MLOGP) : | -1.35 |
Log Po/w (SILICOS-IT) : | -1.77 |
Consensus Log Po/w : | -0.61 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -0.45 |
Solubility : | 42.3 mg/ml ; 0.355 mol/l |
Class : | Very soluble |
Log S (Ali) : | -1.18 |
Solubility : | 7.87 mg/ml ; 0.0661 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | 0.31 |
Solubility : | 241.0 mg/ml ; 2.03 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 2.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.0 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319 | Packing Group: | N/A |
GHS Pictogram: |
* 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 |
---|---|---|
30% | With chloroamine-T In acetonitrile at 80℃; | 3.2. General Procedure for the Cycloaddition of Alkenes and a-Nitroketones General procedure: Chloramine-T (0.0625 mmol, 0.5 equiv) was added to a solution of 1 (0.125 mmol,1 equiv) and 2 (0.625 mmol, 5 equiv) (or 4 (0.625 mmol, 5 equiv) or 6 (0.625 mmol, 5 equiv))in CH3CN (0.2 mL). The mixture was then stirred at 80 C until the starting materialdisappeared, as monitored by TLC. Subsequently, the mixture was directly purified byflash chromatography (with ethyl acetate/petroleum ether as the eluent) to obtain thedesired product (3, 5 or 7). |
21% | With chloroformic acid ethyl ester; triethylamine In benzene for 6h; Heating; | |
15% | In xylene for 20h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | With hydroquinone In xylene for 20h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
22.7% | With triethylamine In ethanol for 48h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With piperidine In acetonitrile at 20℃; for 24h; other CH-acids; | |
90% | With piperidine In acetonitrile at 20℃; for 14h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With acetic anhydride In toluene for 12h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With ammonium acetate In N,N-dimethyl-formamide for 15h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; C25H30N2O2; copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66.82% | With ammonium acetate; magnesium sulfate; In dichloromethane; at 20℃; for 2h; | Example 1 :(E)-Methyl-2-nitro-3-(2,4,6-trimethoxyphenyl)acrylate; 2,4,6-trimethoxybenzaldehyde (20.75 g, 0.105 mol) was dissolved in dichloromethane (300 ml_) and to this solution magnesium sulphate (15 g, 0.124 mol), ammonium acetate (10 g, 0.129 mol) and <strong>[2483-57-0]methyl nitroacetate</strong> (12.60 g, 0.105 mol) were added and stirred at room temperature for 2 hours. At the end of two hours, water (300 ml_) was added to the reaction mass, the organic layer was separated and the aqueous layer extracted with dichloromethane (2 x 100 <n="19"/>ml_). The organic layers were combined and concentrated under reduced pressure to give a solid, which was crystallized from methanol (100 ml_). Yield: 22 g (66.82 %)1H NMR (CDCI3): delta 8.37 (s, 1 H), 6.08 (s, 2H), 3.86 (s, 3H), 3.84 (s, 3H), 3.82 (s, 6H).MS (ES+): 298 (M+1 ) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With 1,8-diazabicyclo[5.4.0]undeca-7-ene In tetrahydrofuran at 20℃; for 72h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
26.9% | With triethylamine; In toluene; at 20℃; for 3.5h;Heating / reflux; | To a solution of N-[1-(1H-indol-3-yl)ethyl]-N-isopropylpropan-2-amine (20.23 g) in toluene (200 mL) were added <strong>[2483-57-0]methyl nitroacetate</strong> (11.91 g) and triethylamine (13.94 mL) at room temperature, and the mixture was stirred for 30 min and heated under reflux for 3 hrs. After cooling, the reaction solution was washed successively with 1N hydrochloric acid (200 mL x 3) and then water (200 mL x 2). The mixture was dried over magnesium sulfate and concentrated under reduced pressure to give a Syn/Anti mixture. To the obtained residue was added ethanol (50 mL), and the mixture was stirred at room temperature to allow precipitation of crystals. To the precipitated crystals was added hexane (100 mL), and the crystals were collected by filtration (17.68 g, yield 33.7%). The mother liquor was purified by repeating silica gel column chromatography (developing solvent; ethyl acetate/hexane=1:4-1:2) and recrystallization to give the title compound (14.09 g, yield 26.9%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With diethyl amine hydrochloride; In toluene;Heating / reflux; | [0359] 5-Fluoro-2-hydroxybenzaldehyde (7.14 g, 50.96 mmol), diethyl amine hydrochloride (6.7Og, 61.15 mmol) and <strong>[2483-57-0]methyl nitroacetate</strong> (5.62 mL, 61.15 mmol) were added together in toluene (90 mL) and stirred together at reflux under a N2 atmosphere. A Dean-Stark apparatus was fitted to the system to remove the H2O generated by the reaction. The reaction was allowed to reflux overnight, after which the mixture was cooled and diluted with H2O. The organic layer was separated, washed with brine, dried over anhydrous Na2SO4 and concentrated. Purification by flash chromatography on silica gel afforded the product as an orange solid (5.90 g, 55%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With potassium carbonate; In neat (no solvent); at 90℃; for 17h; | General procedure: The nitroalkane,nitroethane (10mmol), was mixed with the Michael acceptor,methyl acrylate (10mmol). Afer through mixing, thepotassium carbonate catalyst (30mol%) was added to themixture. Heating or cooling was applied only when required, according to staring materials (Table 4). The reaction wasleft standing for the appropriate time. The catalyst was thenfiltered using a small column fitted with cotton and Florisil.The filtrate was then evaporated in vacuo and the crudeproduct was purified via column chromatography using amixture of cyclohexane and ethyl acetate afording the pure6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: orthoformic acid triethyl ester; aniline With water; acetic acid In ethanol for 0.5h; Heating / reflux; Stage #2: methyl 2-nitroacetate In ethanol; acetic acid for 3.5h; Heating / reflux; Stage #3: With hydrogenchloride; water; hydrogen; sodium hydrogencarbonate more than 3 stages; | 20.A EXAMPLE 20; (αR,γS,2S)-N-((3S,4S)-3,4-dihydro-3-hydroxy-2H-1-benzopyran-4-yl)-γ-hydroxy-4-[(1-phenyl-1H-imidazol-4-yl)methyl]-α-(phenylmethyl)-2-[[(2,2,2-trifluoroethyl)amino]carbonyl]-1-piperazinepentanamide; To a solution of aniline (3.16 mL, 34.7 mmol) in ethanol (66 mL) was added acetic acid (3.5 mL), followed by triethylorthoformate (5.77 mL, 34.7 mmol). The mixture was heated to reflux for 30 min, the cooled to ambient temperature. Methyl nitroacetate (6.38 mL, 69.4 mmol) was added, and the reaction was again heated to reflux for 3.5 hours. The mixture was then cooled to 0° C., and the precipitate that formed was collected by filtration and dried in vacuo, affording 5.16 g of the nitro enamine as a white solid. This material was dissolved in triethylorthoformate (60 mL). To the solution was added 10% Pd/C (1.70 g), and the reaction was placed under 2.5 atm of H2 at 70° C. for 2 hours. The reaction was filtered through celite and concentrated in vacuo. The residue was dissolved in THF (300 mL) and cooled to 0° C., followed by addition of 1 N aqueous HCl until the solution was pH 1. After 30 min at 0° C. the solution was adjusted to pH 8 with saturated aqueous NaHCO3 and extracted with ethyl acetate (300 mL). The organic layer was washed with brine (300 mL), dried (MgSO4), and concentrated in vacuo. Purification by flash chromatography (65% ethyl acetate in hexane) afforded the title compound as a yellow solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With [1,2-bis-(phenylsulfinyl)ethane]palladium(II) acetate; 2,6-dimethyl-1,4-benzoquinone; acetic acid In 1,4-dioxane; dimethyl sulfoxide at 45℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With [bis(acetoxy)iodo]benzene;rhodium(II) pivalate; at 20℃; for 48h;Neat (no solvent); | Example 12. Synthesis of 4'-{(lR,2S)-2-[(2-butoxy-5-chlorobenzoyl)amino]- cyclopropyl}biphenyl-4-carboxylic acid (Compound 108); neat 12.45 38% 95% 12.46Ref Org Lett 2003, 5, 2327; To a mixture of 4-bromostyrene (5.75 g, 31.4 mmol) and rhodium (II) trimethylacetate dimer (47 mg, 0.077 mmol) is added <strong>[2483-57-0]methyl nitroacetate</strong> (934 mg, 7.85 mmol) followed by iodobenzene diacetate (3.43 g, 10.65 mmol). After stirring at room temperature for 48 h, the crude mixture is applied directly to a silica gel column and flash chromatographed (hexanes to 93:7 hexanes/ethyl acetate) to afford 12.45 (2.24 g, 95%) as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With piperidine In benzene Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With 1,4-diisocyanatobenzene; triethylamine; In tetrahydrofuran; at 25℃; for 192h;Inert atmosphere; | A. Preparation of methyl 5-{(tert-butyldimethylsilyloxy)methyl].Soxazole-3-carboxylate (C50). A solution of O-terf«butytdimethylsily1propy?-3~ol (16 g, 94 mmol) and <strong>[2483-57-0]methyl nitroacetate</strong> (11.20 g, 94 mmol) in tetrahydrofuran (400 mL) was treated with 1 ,4-phenylene diisocyanate (38 g) followed by addition of ten drops of triethylamine. The reaction mixture was then stirred for eight days at about 25betaC. A few drops of water were then added and the crude mixture was stirred for about 3 hours and filtered through a plug of Celite. The filtrate was concentrated, and the resultant residue was purified by silica gel chromatography (gradient; 10:90 ethyl acetate: heptane to 40:60 ethyl acetateiheptane) to provide C50 as a white solid, Yield: 11.5beta g, 45%, 1H NMR (400 MHz, CDCI3) * 0.10 (6H, S), 0.90 (9H1 S), 3.96 (3H, s), 4.80 (2H, s), 6.59 (1H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | A slurry of4-bromo-2-nitroaniotaine (30.4 g; 0.14 mol.) in 2M aq. nitric acid (350 ml_) was cooled to 50C then treated dropwise with a solution of sodium nitrite (9.7 g; 0.14 mol.) in water (75.0 ml_). The solution was stirred at 5 0C for 15 min., quickly filtered then added dropwise to a suspension of <strong>[2483-57-0]methyl nitroacetate</strong> (6.3 g; 0.053 mol.) and sodium acetate (90.0 g) in water 200 ml_) and ethanol (200 ml_). The mixture was stirred at room temperature for 10 min. then filtered and the solid washed with water to afford the title compound (16.3 g; 89%) as a yellow solid. 1 H NMR (400 MHz, DMSO-alphaf6) D ppm 3.98 (s, 3 H) 7.83 (d, J=9.09 Hz, 1 H) 8.06 (dd, J=9.09, 2.02 Hz, 1 H) 8.41 (d, J=2.02 Hz, 1 H) 13.24 (s, 1 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With silica gel-supported polyphosphoric acid; In 1,2-dichloro-benzene; for 2h;Reflux; | Typical procedure: A mixture of alpha-nitroketones (0.5 mmol), alkynes (0.5 mmol) and PPA/SiO2 (20 wt. %, 0.25 g) was stirred in toluene (5.0 mL) under reflux for 4 h. After the reaction, the used supported reagents were removed by filtration. The filtrate was evaporated to leave crude product, which was purified by column (ethyl acetate/n-Hexane = 1:5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With 1,4-diisocyanatobenzene; triethylamine; In tetrahydrofuran; at 25℃; for 192h;Inert atmosphere; | A solution of O-tert-butyldimethylsilylpropyn-3-ol (16 g, 94 mmol) and <strong>[2483-57-0]methyl nitroacetate</strong> (11.20 g, 94 mmol) in tetrahydrofuran (400 mL) was treated with 1,4-phenylene diisocyanate (38 g) followed by addition of ten drops of triethylamine. The reaction mixture was then stirred for eight days at about 25C. A few drops of water were then added and the crude mixture was stirred for about 3 hours and filtered through a plug of Celite. The filtrate was concentrated, and the resultant residue was purified by silica gel chromatography (gradient; 10:90 ethyl acetate:heptane to 40:60 ethyl acetate:heptane) to provide C50 as a white solid. Yield: 11.56 g, 45%. 1H NMR (400 MHz, CDCl3) d 0.10 (6H, s), 0.90 (9H, s), 3.96 (3H, s), 4.80 (2H, s), 6.59 (1H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; C25H30N2O2; copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; C25H30N2O2; copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; (S,S)-2,2'-isopropylidenebis(4-phenyl-2-oxazoline); copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; C25H30N2O2; copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; C25H30N2O2; copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; (S,S)-2,2'-isopropylidenebis(4-phenyl-2-oxazoline); copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; C25H30N2O2; copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; (S,S)-2,2'-isopropylidenebis(4-phenyl-2-oxazoline); copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; C25H30N2O2; copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; (S,S)-2,2'-isopropylidenebis(4-phenyl-2-oxazoline); copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; C25H30N2O2; copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; C25H30N2O2; copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; (S,S)-2,2'-isopropylidenebis(4-phenyl-2-oxazoline); copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; C25H30N2O2; copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With silver hexafluoroantimonate; iodosylbenzene; sodium carbonate; (S,S)-2,2'-isopropylidenebis(4-phenyl-2-oxazoline); copper(l) chloride; In benzene; at 20℃; for 3h;Inert atmosphere; Molecular sieve; | General procedure: CuCl (1.0 mg, 0.01 mmol, 2 mol %), AgSbF6 (4.1 mg, 0.012 mmol, 2.4 mol %), and bis(oxazoline) 2 (0.012 mmol, 2.4 mol %) were weighed in the glove box and charged together in a flask. After removal from glove box, the vial was capped and benzene (5 mL) was added. The solution was stirred for 1 h at room temperature, after which styrene (2.5 mmol, 5.0 equiv) was added to the catalyst solution. In a separate vial, PhIO (121 mg, 0.55 mmol, 1.10 equiv), Na2CO3 (122 mg, 1.15 mmol, 2.30 equiv), and molecular sieves (approx. 100 mg) were charged in a vial and purged under argon for 10 min. The solids were then quickly transferred to the catalyst solution, followed by <strong>[2483-57-0]methyl nitroacetate</strong> (1) (59.5 mg, 0.50 mmol). The solution was stirred at room temperature for 3 h. The reaction was quenched with water (5 mL) and organic layer was extracted with ethyl acetate (2×10 mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude oil residue was purified by flash column chromatography to give the pure 1-nitrocyclopropyl carboxylate 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With 4-methyl-morpholine; titanium tetrachloride; In tetrahydrofuran; tetrachloromethane; at 0 - 20℃; for 17.8333h;Inert atmosphere; | Building Block B5.1: 4-Bromomethyl-5-(3-methoxy-phenyl)-2-(2-trimethylsilanyl-ethoxymethyl)-2H-[1,2,3]triazole a) (E/Z)-3-(3-Methoxy-phenyl)-2-nitro-acrylic acid methyl ester A solution of titan tetrachloride (27.6 g, 142 mmol) in CCl4 (39 ml) was dropped within 20 min to THF (260 ml) at 0 C. under an atmosphere of argon. Then, m-anisaldehyde (10.0 g, 71.2 mmol) and <strong>[2483-57-0]methyl 2-nitroacetate</strong> (8.75 g, 71.2 mmol) were added to the yellow suspension. A solution of N-methylmorpholine (29.4 g, 285 mmol) in THF (47 ml) was added slowly within 110 min at 0 C. to the reaction mixture. The reaction mixture was allowed to warm to rt and stirring was continued for 16 h. The reaction mixture was poured onto water and extracted with TBME. The organic layer was washed with brine, dried over sodium sulfate, filtered, and the solvents were evaporated under reduced pressure. The crude product was purified by chromatography on silica (Biotage Isolera Four, heptane/EtOAc 98/2 for 5 min, then to heptane/EtOAc 80/20 in 50 min, then heptane/EtOAc 80/20 for 10 min) to give the product as mixture of E/Z isomers (10.04 g, 58%). [1H NMR (400 MHz, DMSO-d6) delta ppm 7.86/8.38 (s, 1H), 7.02-7.47 (m, 4H), 3.88/3.92 (s, 3H), 3.75/3.77 (s, 3H); LCMS RtD=1.07/1.08 min; [M+H]+=not found] |
With 4-methyl-morpholine; titanium tetrachloride; In tetrahydrofuran; tetrachloromethane; at 0 - 20℃; for 16.92h;Inert atmosphere; | A solution of titan tetrachloride (27.6 g, 142 mmol) in CCI4 (39 ml) was dropped within 20 min to THF (260 ml) at 0 C under an atmosphere of argon. Then, m-anisaldehyde (10.0 g, 71.2 mmol) and <strong>[2483-57-0]methyl 2-nitroacetate</strong> (8.75 g, 71 .2 mmol) were added to the yellow suspension. A solution of N-methylmorpholine (29.4 g, 285 mmol) in THF (47 ml) was added slowly within 1 10 min at 0C to the reaction mixture. The reaction mixture was allowed to warm to rt and stirring was continued for 16 h. The reaction mixture was poured onto water and extracted with TBME. The organic layer was washed with brine, dried over sodium sulfate, filtered, and the solvents were evaporated under reduced pressure. The crude product was purified by chromatography on silica (Biotage Isolera Four, heptane/EtOAc 98/2 for 5 min, then to heptane/EtOAc 80/20 in 50 min, then heptane/EtOAc 80/20 for 10 min) to give the product as mixture of E/Z isomers (10.04 g, 58%). [1H NMR (400 MHz, DMSO-d6) delta ppm 7.86/8.38 (s, 1 H), 7.02 - 7.47 (m, 4H), 3.88/3.92 (s, 3H), 3.75/3.77 (s, 3H); LCMS RtD = 1.07/1.08 min; [M+H]+ = not found] |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With 1-(3,5-bis(trifluoromethyl)phenyl)-3-((1S,2S)-2-(pyrrolidin-1-yl)cyclohexyl)thiourea; In 1,2-dichloro-ethane; at -20℃; for 24h; | General procedure: Prepared according to the general procedure Section 4.2 as a colorless oil (55.7 mg, 90% yield), a mixture of two inseparable diastereoisomers. 1H NMR (400 MHz, CDCl3) delta 7.37-7.28 (m, 8H), 7.26 (d, J=1.6 Hz, 2H), 5.49 (d, J=9.9 Hz, 1H), 5.43 (d, J=8.6 Hz, 1H), 4.33 (ddd, J=12.5, 9.6, 6.1 Hz, 2H), 3.84 (s, 3H), 3.84 (s, 3H), 3.83 (s, 3H), 3.71-3.60 (m, 4H), 3.49-3.42 (m, 2H), 3.35 (dd, J=18.7, 4.2 Hz, 1H); 13C NMR (100 MHz, CDCl3) delta 190.2, 190.2, 163.9, 163.3, 160.6, 160.5, 137.0, 136.1, 129.1, 129.1, 128.4, 128.4, 128.3, 128.0, 91.0, 90.9, 53.8, 53.5, 53.2, 53.1, 41.6, 41.2, 41.0, 41.0; IR (thin film) nu/cm-1: 2957, 2924, 2853, 1757, 1732, 1595, 1553, 1172, 1052, 940, 861, 549, 521; HRMS (ESI) calcd for C14H15NO7 (M-H)-: 308.0776, found: 308.0779; [alpha]D20+35.6 (c 1.0, CH2Cl2). The enantiomeric excess was determined by HPLC with a Chiralpak AD-H column (hexane/i-PrOH=90:10, lambda=208 nm, 0.8 mL/min), tmajor=21.0 min, tminor=23.0 min, 84% ee; tmajor=26.7 min, tminor=29.0 min, 79% ee. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | In methanol; at 20℃; for 48h; | General procedure: Aromatic aldehyde (1.0 mmol) and alkyl nitroacetate (2.2 mmol) were dissolved in dry alcohol (methanol, ethanol or isopropanol depending on alkyl nitroacetate taken) (1 mL) at 0 C. After complete dissolution amine (2.2 mmole) was added and the mixture was stirred at room temperature for 24-78 hours until formation of precipitate completes. The precipitate was filtered and washed by small amount of alcohol and diethyl ether. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | In methanol; at 20℃; for 72h; | General procedure: Aromatic aldehyde (1.0 mmol) and alkyl nitroacetate (2.2 mmol) were dissolved in dry alcohol (methanol, ethanol or isopropanol depending on alkyl nitroacetate taken) (1 mL) at 0 C. After complete dissolution amine (2.2 mmole) was added and the mixture was stirred at room temperature for 24-78 hours until formation of precipitate completes. The precipitate was filtered and washed by small amount of alcohol and diethyl ether. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | In methanol; at 20℃; for 48h; | General procedure: Aromatic aldehyde (1.0 mmol) and alkyl nitroacetate (2.2 mmol) were dissolved in dry alcohol (methanol, ethanol or isopropanol depending on alkyl nitroacetate taken) (1 mL) at 0 C. After complete dissolution amine (2.2 mmole) was added and the mixture was stirred at room temperature for 24-78 hours until formation of precipitate completes. The precipitate was filtered and washed by small amount of alcohol and diethyl ether. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | In methanol; at 20℃; for 72h; | General procedure: Aromatic aldehyde (1.0 mmol) and alkyl nitroacetate (2.2 mmol) were dissolved in dry alcohol (methanol, ethanol or isopropanol depending on alkyl nitroacetate taken) (1 mL) at 0 C. After complete dissolution amine (2.2 mmole) was added and the mixture was stirred at room temperature for 24-78 hours until formation of precipitate completes. The precipitate was filtered and washed by small amount of alcohol and diethyl ether. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
22% | With diethylamine; In methanol; at 20℃; for 72h; | General procedure: 4-nirobenzaldehyde (150 mg, 1.0 mmol) and alkyl nitroacetate (2.2 mmol) were dissolved in dry alcohol (methanol or isopropanol depending on alkyl nitroacetate taken) (1 mL) at 0 C. After complete dissolution diethylamine (160 mg, 2.2 mmol) was added and the mixture was stirred at room temperature for 72 hours. The solution was evaporated and mixture dissolved in 20 ml of chloroform. Hydrochloric acid (10%, 5 ml) was added and the mixture was stirred for 10 min. Organic layer was separated and dried over Na2SO4, the solvent was evaporated and the product was purified by column chromatography (CHCl3:EtOH - 20:1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | In toluene; at 0 - 20℃; for 4h;Inert atmosphere; | To a solution of methyl alpha-nitroacetate (0.9 mL, 10.0 mmol) in PhMe (50.0 mL) at 0 C was added Ti(OiPr)4 (8.3 mL, 28.0 mmol) under argon. The mixture was allowed warm to room temperature, then stirred for additional 4 h. HCl (1.0 M, 20.0 mL) was added, the solid was filtered off. The liquid was extracted with Et2O (3 x 20 mL) and concentrated in vacuo. Purification by flash chromotography on silica gel (EtOAc/n-hexane = 1:10) to give the pure isopropyl alpha-nitroacetate as a colorless oil (1353.1 mg, 9.2 mmol, 92%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With piperidine; In methanol; for 5h;Reflux; | General procedure: A solution of 7-dithylamino, 3-formyl coumarine 1 (0.02 moles, 4.902 g) and active methylene compounds b-f(0.02 moles, Supplemental File), equipped with a magnetic stirrer, was prepared in 15 mL of methanol. After dissolution,a catalytic amount of piperidine was added and the reaction mixture was refluxed for appropriate time (Table 1). After complete reaction, the compounds 1b-1f obtained were separated, washed with methanol and recrystallized in ethanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With 3-amino propanoic acid; In methanol; at 5℃; for 24h; | To a stirred solution of 0.2 g (0.8 mmol) of aldehyde 22 and 0.29 g (2.4 mmol) of <strong>[2483-57-0]methyl 2-nitroacetate</strong> in dry methanol (15 mL) at +5C was added 0.36 g (4.0 mmol) of beta-alanine. The mixture was stirred for 1 d at the same temperature (monitored by TLC) and evaporated under reduced pressure. Purification of the product by column chromatography (petroleum ether/ethyl acetate, 20:1) afforded of title compound (0.23 g, 85%) as a transparent viscous oil. [Found: C, 52.31; N, 3.84; H, 7.02. C15H25NO6Si requires C, 52.42; N, 4.08; H, 7.28%]; Rf (petroleum ether/ethyl acetate, 20:1) 0.35; -71.1 (c 1.1, CH2Cl2); numax (liquid film) 2954, 2926, 1738, 1539, 1438, 1379, 1250, 1151, 1110, 1044, 840 cm-1; deltaH (500 MHz, d-chloroform/chloroform): 6.95 (1H, d, J 10.8 Hz, HC=C), 5.76 (1H, dt, J 5.2, 2.3 Hz, H-4), 5.57 (1H, dt, J 5.6, 1.9 Hz, H-3), 4.57 (2H, dd, J 8.7, 6.7 Hz, OCH2O), 3.84 (3H, s, CH3OC=O), 3.51 (2H, dd, J 9.9, 6.1 Hz, CH2-OMOM), 3.34 (3H, s, CH3O), 3.19 (1H, dd, J 8.0, 2.5 Hz, H-2), 3.13-3.17 (1H, m, H-1), 1.87 (1H, quint, J 2.5 Hz, H-5), 0.02 (9H, s, (CH3)3Si); deltaC (125.77 MHz, d-chloroform/chloroform): 159.36 (C=O), 142.02 (NO2C=CH), 141.88 (HC=CNO2), 132.23 (C3), 127.31 (C4), 96.76 (OCH2O), 67.64 (CH2OMOM), 55.32 (CH3O), 53.21 (CH3OCO), 50.26 (C2), 42.28 (C1), 40.98 (C5), -2.92 ((CH3)3Si); deltaN (50.68 MHz, d-chloroform/chloroform): 370.46 (NO2); m/z (APCI): 343 (100%, MH+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.9% | With ammonium bicarbonate; In ethanol; for 2h;Reflux; | Anhydrous ethanol (800 mL), biphenyl mono formaldehyde (100 g, 0.55 mol), <strong>[2483-57-0]methyl nitroacetate</strong> (81.2 g,0.61mol) and ammonium bicarbonate (43.4g, 0.55mol) were added in turn to a 2000mL three-necked bottle and reacted for 2 hours under reflux.200 mL of water was cooled, crystallized, filtered, and dried to obtain 153.7 g of compound (III) in a yield of 98.9% and purity (HPLC) of 99.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With 1,4-diaza-bicyclo[2.2.2]octane; In ethanol; at 80℃; | Methyl nitroacetate (5) (500 mg, 4.47 mmol) and 1-nonyne (4)(434 mg, 3.50 mmol) were dissolved in absolute EtOH (6.8 mL). DABCO(26.4 mg, 0.24 mmol) was added and the mixture was heated to 80 C.After 72 h at 80 C, the mixture was concentrated under vacuum. Thecrude product was purified by silica gel column chromatography(hexane-EtOAc 9:1). White solid (575 mg, 73%). m.p: 48-49 C. 1HNMR (400 MHz, Chloroform-d) delta 6.41 (s, 1H), 3.96 (s, 3H), 2.80 (t,J=7.6 Hz, 2H), 1.71 (p, J=7.5 Hz, 2H), 1.57-1.20 (m, 8H), 0.88 (t,J=6.9 Hz, 3H). 13C NMR (101 MHz, CDCl3) delta 175.9, 160.7, 156.0,101.4, 52.8, 31.6, 28.9, 28.8, 27.4, 26.7, 22.6, 14.0. Rf=0.46; (EtOAchexane3:7), HRMS (ESI): calculated C12H19NO3Na: 248.1257, found:248.1257. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.7% | With DBN; In N,N-dimethyl-formamide; at 60 - 65℃; for 4h; | Stirring, thermometer,In a 500 ml four-necked flask with a reflux condenser,200 g of N,N-dimethylformamide,60.0 g (0.5 mol) of 2-<strong>[2483-57-0]nitroacetic acid methyl ester</strong>,60.0 g (0.5 mol) of 2-chloromethyl acrylate,1.5 g DBN, stirring reaction at 60-65 C for 4 hours,Cool to 20-25 C, pass 30 grams of ammonia,The reaction was stirred at 40-45 C for 4 hours, and then stirred at 140-145 C for 5 hours.At the same time, the low boiler is distilled off, cooled to 20-25 C, and the solvent is distilled off under reduced pressure.Add 40 g of methyl tert-butyl ether, filter, and dry72.3 g of a white solid 2,6-dihydroxy-3-nitropyridine, liquid phase purity 99.3%, product yield 92.7%. |
Tags: 2483-57-0 synthesis path| 2483-57-0 SDS| 2483-57-0 COA| 2483-57-0 purity| 2483-57-0 application| 2483-57-0 NMR| 2483-57-0 COA| 2483-57-0 structure
[ 5616-81-9 ]
tert-Butyl 2-(methylamino)acetate
Similarity: 0.50
[ 5616-81-9 ]
tert-Butyl 2-(methylamino)acetate
Similarity: 0.50
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P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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