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Search for reports by entering the product batch number.
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CAS No. : | 762-42-5 |
Formula : | C6H6O4 |
M.W : | 142.11 |
SMILES Code : | O=C(OC)C#CC(OC)=O |
MDL No. : | MFCD00008456 |
InChI Key : | VHILMKFSCRWWIJ-UHFFFAOYSA-N |
Pubchem ID : | 12980 |
GHS Pictogram: | ![]() ![]() |
Signal Word: | Danger |
Hazard Statements: | H227-H302-H314 |
Precautionary Statements: | P210-P264-P270-P280-P301+P312+P330-P301+P330+P331-P303+P361+P353-P304+P340+P310-P305+P351+P338+P310-P363-P370+P378-P403+P235-P405-P501 |
Class: | 8 |
UN#: | 3265 |
Packing Group: | Ⅱ |
* 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 |
---|---|---|
58% | Stage #1: at 20℃; for 2 h; Stage #2: With xylene In methanol at 90 - 120℃; for 16 h; Inert atmosphere | Benzyl 2-amino-2-(hydroxyimino)-1,1-dimethylethylcarbamate (2.0 g, 8.0 mmol) was dissolved in 30 mL MeOH, dimethyl acetylenedicarboxylate (DMAD, 1.1 mL, 9.0 mmol) was added slowly. The mixture was stirred for 2 h at room temperature, and then concentrated under reduced pressure to give a white oil. The mixture of the oil and 80 mL xylene was stirred at 90 °C for 2 h and 120 °C for 2 h, then refluxed for 12 h under nitrogen, concentrated to yield the crude product. The crude product was recrystallized with 2 mL MeOH and 10 mL tert-butyl methyl ether to afford 5 as a yellow solid (1.7 g, 58 percent): 1H-NMR (DMSO-d6) δ: 7.35 (m, 5H), 5.00 (s, 2H), 3.83 (s, 3H), 1.48 (s, 6H); ESI-MS m/z 360 (M)-, 384 (M+Na) +. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
23% | In methanol; water; at 70℃; | To a solution of dimethyl acetylenedicarboxylate (5 g, 35.18 mmol) in methanol (25 mL)-water (2.5mL) was added dropwise methylhydrazine (1.945 g, 42.22 mmol) at room temperature. The reaction mixture was stirred at 70C overnight, cooled to room temperature, concentrated under reduced pressure, diluted with water, and extracted with ethyl acetate. The organic layer was washed with saturated brine, and dried over anhydrous sodium sulfate. The obtained residue was purified by silica gel column chromatography [eluent: hexane-ethyl acetate (90:10-3:4)] to give the title compound (1.26 g) as a colorless oil (yield 23%). MS (ESI+): [M+H]+157. 1H NMR (300 MHz, DMSO-d6) delta 3.79 (3H, s), 3.88 (3H, s), 6.00 (1H, s), 10.06 (1H, s). |
5 g | In methanol; water; at 0 - 70℃; for 10h; | The compound methyl hydrazine (10g) was dissolved in methanol (20mL) and water (10mL), cooled to 0 degree, stirred for 15min, then compound 21 (12g) was added dropwise to the reaction system, heated to 70 degrees for 10h, then the system temperature was returned to room temperature, the reaction 12h, filtered off with suction, the filter cake was washed with water (5mL), dried to give 22 as a pale yellow solid 5g |
5 g | In methanol; water; at 0 - 70℃; for 10.25h; | The compound methyl hydrazine (10 g) was dissolved in methanol (20 mL) and water (10 mL).The temperature was lowered to 0 , stirred for 15 min, and then Compound 21 (12 g) was added dropwise to the reaction system.Heat to 70 for 10 h, then return the system temperature to room temperature.After 12 h of reaction, suction filtration, and the filter cake was washed with water (5 mL).Get 22 pale yellow solids 5g |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
16% | Alternatively, to a solution of 4-chloro-3-methyl aniline (20.0 g, 0.141 mol) in MEOH (400 mL) was added drop-wise dimethyl acetylenedicarboxylate (21.07 g, 0.148 mol). The reaction mixture was stirred at ambient temperature for 30 minutes. The solvent was removed by evaporation and the residue was added to stirred diphenyl ether (300 mL), which has been preheated to 250°C. After 30 minutes, the mixture was cooled to ambient temperature and the resulting precipitate was collected and washed with 1 L of hot petroleum ether to give a mixture (29.0 g) of 2-methoxycarbonyl-6-chloro-7-methyl-4-oxoquinoline and 2- methoxycarbonyl-6-chloro-5-methyl-4-oxoquinoline as a gray solid.The mixture was dissolved in boiling methanol (1 L) and filtered hot. The collected solids were boiled in 1.2 L of methanol and filtered hot to afford (6. 45 g, 16percent) of 2-METHOXYCARBONYL-6-CHLORO-7-METHYL-4-OXOQUINOLINE |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; at 20℃; | Example 11; Part A; A reaction mixture of 3-phenyl-1 H-1 ,2,4-tpiazol-5-amiotane (160 mg, 1 mmol) and dimethyl but-2-ynediotaoate (123 mul_, 1 mmol) in methanol (2 ml_) was stirred at room temperature for overnight Purification using reverse phase HPLC gave compound 11-1 as a solid after lyophilization HPLC-MS RT= 3 08 mm, mass calculated for formula Ci3H10N4O3270 08, observed LCMS m/z 271 28 (M+H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | In methanol; at 4 - 20℃; | 4. Synthesis of 2-(5-methoxyquinolin-8-ylamino)-but-2-enedioic acid dimethyl ester (46); To a solution of 5-methoxyquinolin-8-ylannine 45 (2.7 g, 15.3 mmol) in methanol (20 ml_) at 40C, dimethylacetylenedicarboxylate (2.1 ml_, 16.8 mmol) was added. The reaction mixture was stirred and allowed to warm to room temperature for 3 hours. The solvent was evaporated and the residue was washed with MeOH and hexane, yielding an orange solid that was dried under vacuum (3.8 g, 79%).1H-NMR (400 MHz, CDCI3, ppm): 10.63 (NH, s, 1 H), 8.90 (H-2, dd, 1 H, J=1.7 and 4.2 Hz), 8.53 (H-4, dd, 1 H, J=1.7 and 8.4 Hz), 7.41 (H-3, dd, 1 H, J=4.2 and 8.4 Hz), 6.95 (H-7, d, 1 H, J=8.3 Hz), 6.73 (H-6, d, 1 H, J=8.3Hz), 5.44 (s, 1 H, CH=), 3.96 (OCH3, s, 3H), 3.77 (CO2CH3, s, 3H), 3.69 (CO2CH3, s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | Step l:Methyl 3-hydroxy-l-methyl-lH-pyrazole-5-carboxylate (3_41_2) [00351] Triethylamine (66 mL, 474.4 mmol) was added to a solution of methylhydrazine sulfuric acid salt (30.4 g, 211 mmol) in water (150 mL) and methanol (300 mL) at room temperature. The mixture was stirred for 0.5 hour at room temperature, but-2-ynedioic acid dimethyl ester (30 g, 211 mmol) was added and the mixture was stirred for 18 hours at 70C. The reaction mixture was kept at room temperature for two days and the solid was collected by filtration and dried to give 12 g of the desired compound. The filtrate was concentrated, treated with ice and the solid was collected by filtration, and dried to give an additional 5 g of the desired compound 3_41_2 (17 g, 52 % yield) as a yellow solid. [00352] NMR (400 MHz, DMSO-c: delta = 3.79 (s, 3H), 3.88 (s, 3H), 6.01 (s, 1H), 10.05 (s, 1H). | |
16.6% | TEA (44.2 mL, 316.7 mmol) was added to a solution of methylhydrazine sulfate (20.3 g, 140.7 mmol) in H2O (100 mL) and MeOH (200 mL) at room temperature, and the mixture was stirred for 0.5 h at rt. Dimethyl but-2-ynedioate (20 g, 140.7 mmol) was added to the mixture, the mixture was stirred for 18 h at 70 C., followed by stirring at rt for 36 h. The reaction mixture was filtered, and the filtrate concentrated under reduced pressure to give the product as a white solid (3.65 g, 16.6% yield). | |
TEA (21 .95 ml_, 158.33 mmol) was added to a solution of compound a (10.99 g, 70.37 mmol) in H2O (50 ml_) and MeOH (100 ml_) at room temperature. The mixture was stirred for 0.5 h at room temperature, Compound 13-1 (10 g, 70.37 mmol) was added and the mixture was stirred for 18 h at 70C. The solution was kept at room temperature for 2 h, and the solid was collected by filtration and dried to give the desired compound 13-2 (4.7 g, 47%) as a crude product which was used directly in next step. LCMS m/z 157 [M+1 ]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.42 g | A solution of hydroxylamine hydrochloride (38.6 ml, 38.6 mmol) in MeOH was added to a solution of potassium hydroxide (38.6 ml, 38.6 mmol, Eq: 4) in MeOH at 0 C. The resulting mixture was filtered and the filtrate was added to a 150 mL round-bottomed flask containing <strong>[2286-54-6]3,3-<strong>[2286-54-6]diphenylpropanenitrile</strong></strong> (2 g, 9.65 mmol). The mixture was heated at reflux for 16 h, cooled and evaporated to dryness. The residue was dissolved in EtOAc, washed with brine, dried (MgSO4) and evaporated to dryness. The crude product was dissolved in CHCl3 (50 ml), treated with dimethyl but-2-ynedioate (1.65 g, 11.6 mmol, Eq: 1.2) and heated at reflux for 1 h and then evaporated to dryness. The residue was dissolved in xylene (10 ml), heated at 120 C. in a microwave oven for 4 h and evaporated to dryness. Chromatography (80 g SiO2; 20 to 100% EtOAc in hexanes) gave the title product as an off-white solid (0.42; 12%). LCMS: m/z=348.9 (MH+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With methylhydrazine sulfuric acid; triethylamine; In methanol; for 15h;Reflux; | The lOOmmol methyl hydrazine sulfate was added to a three-necked round-bottomed flask, dissolved with 200mL of methanol, followed by addition of 200mmol triethylamine free, finally adding lOOmmol dimethyl butynoate, heated to 60 C, magnetic stirring, refluxed 15h ;After the reaction is complete, stop heating, cooled to 5 C, allowed to stand for 2 days, until the white crystals precipitated, filtered, washed with ethanol, and dried to obtain methyl 3-hydroxy-1-methylpyrazole-5-carboxylate Rate of 60%, purity 95% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32% | With 4,4'-bipyridine; In tetrahydrofuran; at 60℃; for 14h;Inert atmosphere; Sealed tube; | Reaction of 7a: In a glove box, a glass tube having PTFE stopcock (J. Young),equipped with a magnetic stirring bar, was charged with 9e (1.5 mg, 0.010 mmol), 11 (58 mg,0.22 mmol), THF (0.4 mL), and 7a (29 mg, 0.20 mmol). The tube was sealed by the stopcockand was taken out from the glove box. The mixture was heated at 60 °C with stirring for 14 h.After cooling to room temperature, the volatiles were removed from the reaction mixture underreduced pressure. The residue was purified by column chromatography on silica gel(CHROMATOREX DIOL, eluent: hexane:CHCl3 = 7:1) to afford (E)-12a (27 mg, 32percent) as awhite solid. Geometry of the carbon?carbon double bond was assigned on the analogy of that of (E)-8a. Dimethyl 2,3-bis(4,4,6-trimethyl-1,3,2-dioxaborinan-2-yl)fumarate [(E)-12a] 1H NMR (400 MHz, CDCl3) delta 4.20-4.34 (m, 2H), 3.75 (s, 6H), 1.65-1.80 (m, 4H), 1.34 (s, 6H),1.27 (s, 6H), 1.23 (d, J = 6.0 Hz, 6H). 13C NMR (101 MHz, CDCl3) delta 169.4, 71.4, 65.4, 52.3,45.7, 31.2, 27.61 (either meso or racemate), 27.59 (either meso or racamate), 23.1. The boron-bound carbon was not detected due to quadrupolar relaxation. 11B NMR (128 MHz,CDCl3) delta 25.1. HRMS (APCI, positive) m/z calcd for C18H31B2O8+ [M + H]+: 397.2200, found:397.2190. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With triethylamine; In ethanol;Reflux; | General procedure: A suspension of 1,6-disubstituted quinoline-2,4-(1H,3H)-diones 1a-d (1 mmol) and dialkyl acetylenedicarboxylates2a,b (2 mmol) in 25 mL absolute ethanol and 0.5 mL oftriethylamine, was gently refluxed for 12-18 h (the reactionwas monitored by TLC). The resulting precipitateswere filtered off, dried and recrystallized from statessolvents. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | Et3N (17.3 mL, 0.12 mol) was added to a solution of dimethyl but-2-ynedioate (8 g, 0.05mmol) in MeOH (80 mL), H20 (40 mL) and stirred at RT for 30 min. Methyl hydrazinesulfate (8.92 g, 61.9 mol) was added and the reaction mixture was stirred at 70 C for 22 h.The solution was allowed to stand at R T overnight and the solid formed was filtered, driedunder high vacuum to afford methyl5-hydroxy-2-methyl-pyrazole-3-carboxylate (3.5 g,40%) as a pale brown solid.LCMS: m/z: 157.3 [M+Ht. |
Tags: Dimethyl acetylenedicarboxylate | Urease | Others | Alkynyls | Esters | Aliphatic Chain Hydrocarbons | Biological Buffers | Fluorescence Labeling Reagents | Organic Building Blocks | Steroids | Fluorescent Dyes | Other Inhibitors/Agonists | Small Molecule Positive Drugs | Structure | 762-42-5
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