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CAS No. : | 96-31-1 | MDL No. : | MFCD00008286 |
Formula : | C3H8N2O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MGJKQDOBUOMPEZ-UHFFFAOYSA-N |
M.W : | 88.11 | Pubchem ID : | 7293 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P501-P260-P314 | UN#: | N/A |
Hazard Statements: | H373 | 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 |
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80% | for 4 h; Reflux | To warmed ethanolic sodium ethoxide solution (prepared by dissolving (10 mmol) of sodium metal in 40 ml absolute ethanol), was added each of 1,3-dimethylurea and 2-cyanoacetic acid (10 mmol), the refluxing was continued for 2- 4 h with control by (TLC) and then cooled to room temperature, poured into cold water (100 ml). The solid product precipitated was filtered off, washed with water and dried, to produce compound 2 in high yields as yellow crystals (80 percent) from methanol. |
Yield | Reaction Conditions | Operation in experiment |
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With acetic anhydride; acetic acid |
Yield | Reaction Conditions | Operation in experiment |
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75% | With acetic anhydride; trifluoroacetic acid In chloroform; acetic acid at 80℃; for 4h; | |
60% | With acetic anhydride; acetic acid; trifluoroacetic acid In chloroform at 50℃; | 2 PREPARATIVE EXAMPLE 2 (PE 2): Synthesis of 2-nitrobenzyl-blocked 5-phenyl-1,3- dimethylbarbituric acid (b-PhDMBA) To a solution of 1,3-dimethylurea (2.66 grams, 30.0 mmol) and phenylmalonic acid (5.40 grams, 30.0 mmol) in CHCl·, (70 mL) was added AcOH (5.5 mL, 96.0 mmol). The resultant reaction mixture was heated at 50 °C. Acetic anhydride (11.3 mL, 120.0 mmol) and trifluoracetic acid (0.5 mL, 6.6 mmol) were added, and the reaction mixture was then heated at reflux while stirring overnight. The following morning, the volatile components were removed under reduced pressure, and the residue was added to water (100 mL). After stirring for 2 hours, the solid that formed was collected via filtration, washing with additional water. The solid was then dissolved in CH2CI2 and washed with saturated aqueous (sat. aq.) NaCl. The organic layer was dried over MgS04, filtered, and concentrated to afford 1,3 -dimethyl-5 -phenylbarbituric acid (4.20 grams, 60% yield) as a white solid. |
50% | With sulfuric acid; acetic anhydride; acetic acid; trifluoroacetic acid In chloroform at 70 - 80℃; for 4h; Inert atmosphere; |
50% | With acetic anhydride; acetic acid; trifluoroacetic acid In chloroform at 80℃; for 4h; Inert atmosphere; | |
With acetic anhydride; acetic acid | ||
With acetic anhydride; acetic acid; trifluoroacetic acid In chloroform at 70 - 80℃; for 4h; | 1.1.c c. Add 1,3-dimethylurea (1.0 mmol), α-arylmalonic acid (1.0 mmol) and CHCl 3 (2.5 mL) to the reaction flask in turn, then add AcOH (3.2 mmol) and react The mixture was heated to 70 °C.After addition of Ac2O (4.0 mmol) and CF3CO2H (0.22 mmol), the temperature was raised to 80 ° C and stirred for 4 h.The solvent was evaporated on a rotary evaporator and the obtained oil was stirred in water for 2The resulting solid was washed well with ice water, dried and evaporatedEtOAc. The solution was washed with brine (5 mL) dry Recrystallization from ethanol (10-20 mL) gave the desired product or obtained by column separation (petrole ether: ethyl acetate = 3:1).(11a-11g) |
Yield | Reaction Conditions | Operation in experiment |
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With hydrogenchloride at 225℃; for 0.25h; |
Yield | Reaction Conditions | Operation in experiment |
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With potassium hydroxide; tetrabutylammomium bromide 1.) THF, 0 deg C, 2 h, 2.) THF, 60 deg C, 4 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
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With pyridine; at 0 - 26℃; | Step 1 l,3,6-Trimethylpyrimidine-2,4(lH,3H)-dione: To a stirred solution of N, N- dimethyl urea (80.0 g, 907.955 mmol) and 4-dimethylaminopyridine (110.92 g, 907.955 mmol) in dry pyridine (1.4 lit.), acetic anhydride (905.86 g, 2996.254 mmol) was added dropwise at 00C. The reaction mixture was stirred at room temperature for overnight. The excess of solvent was evaporated under reduced pressure and quenched into 2 Nu HCl (1.0 lit.) and extracted with chloroform (3 x 300 ml). The organic layer was washed with 2 Nu HCl (1.0 lit.) and saturated aqueous sodium hydrogen carbonate solution (1.0 lit.), dried over anhydrous sodium suphate. The solvent was evaporated under reduced pressure to give 95.15 g of the product as a white solid; 1H-NMR (300 MHz, CDCl3) delta 2.24 (s, 3H), 3.33 (s, 3H), 3.41 (s, 3H), 5.62 (s, IH). | |
With pyridine; dmap; at 0 - 20℃; | Step 1 : l ,3,6-Trimethylpyrimidine-2,4(lH,3H)-dione: To a stirred solution of N,N- dimethyl urea (80.0 g, 907.955 mmol) and 4-dimethylaminopyridine (1 10.92 g, 907.955 mmol) in dry pyridine (1.4 L) was added acetic anhydride (905.86 g, 2996.254 mmol) dropwise at 0 C. The reaction mixture was stirred at room temperature for overnight. The excess of solvent was distilled under reduced pressure, quenched with 2 N HC1 (1000 ml) and extracted with chloroform (3 x 300 ml). The organic layer was washed with 2 N HCI ( 1000 ml) followed by saturated solution of sodium bicarbonate ( 1000 ml) and dried Na2SC> ). The solvent was evaporated under reduced pressure to give 95.15 g of the product as a white solid;-NMR (300 MHz, CDCI3) delta 2.24 (s, 3H), 3.33 (s, 3H), 3.41 (s, 3H), 5.62 (s, 1 H). | |
With pyridine; dmap; at 20℃; for 3h;Inert atmosphere; | To a stirred suspension of N,N?-dimethylurea (commercial) (72.1 g, 819 mmol) and DMAP (100 g, 819 mmol) in pyridine (300 mL) under N2 was added dropwise with stirring acetic anhydride (255 mL, 2701 mmol). On complete addition the reaction mixture was allowed to stir at RT for 3 hours. After this time, the volatiles were removed under reduced pressure to afford a viscous orange pyridine solution, which was seeded with product. The mixture was stored at 0-4 C. for 7 days. The resulting crystalline solid was then filtered under reduced pressure, washed with diethyl ether and dried to afford the title compound as colourless crystals. The mother liquors were further purified by chromatography on silica eluting with 30-50% EtOAc in iso-hexane. The resulting solid was diluted with diethyl ether (500 mL) and was stored at 0-4 C. overnight. The resulting crystals were filtered off and washed with iso-hexane, then dried to afford the title compound as colourless crystals and combined. The title product was obtained as white crystals. [1755] 1H NMR (400 MHz, CDCl3) delta 5.58 (1H, s), 3.38 (3H, s), 3.30 (3H, s), 2.22 (3H, s); [1756] LC-MS Rt=0.55 min [M+H]+ 155.4 (Method: 2minLC_v003). |
With pyridine; dmap; In pyridine; at 20℃; for 3h;Inert atmosphere; | To a stirred suspension of N,N'-dimethylurea (commercial) (72.1 g, 819 mmol) and DMAP (commercial) (100 g, 819 mmol) in pyridine (300 mL) under N2 was added dropwise with stirring acetic anhydride (255 mL, 2701 mmol). On complete addition the reaction mixture was allowed to stir at RT for 3 hours. After this time, the volatiles were removed under reduced pressure to afford a viscous orange pyridine solution, which was seeded with product. The mixture was stored at 0-4 C. for 7 days. The resulting crystalline solid was filtered under reduced pressure, washed with diethyl ether and dried to afford the title compound as colourless crystals. The mother liquors were further purified by chromatography on silica eluting with 30-50% EtOAc in iso-hexane. The resulting solid was diluted with diethyl ether (500 mL) and was stored at 0-4 C. overnight. The resulting crystals were filtered off and washed with iso-hexane, then dried to afford the title compound as colourless crystals and combined. The title product was obtained as white crystals. 1H NMR (400 MHz, CDCl3) delta 5.58 (1H, s), 3.38 (3H, s), 3.30 (3H, s), 2.22 (3H, 5); LC-MS Rt=0.55 min [M+H]+ 155.4 (method: 2minLC_v003). |
Yield | Reaction Conditions | Operation in experiment |
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In chloroform; water at 225℃; for 4h; other chlorinated compounds; other temp.; var. times; |
Yield | Reaction Conditions | Operation in experiment |
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73% | With sulfuric acid; lithium bromide In 1-methyl-pyrrolidin-2-one at 100℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
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70% | With sulfuric acid; lithium bromide In 1-methyl-pyrrolidin-2-one at 100℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
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85% | With sulfuric acid; lithium bromide In 1-methyl-pyrrolidin-2-one at 100℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
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79% | With sulfuric acid; lithium bromide In 1-methyl-pyrrolidin-2-one at 100℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With sulfuric acid; lithium bromide In 1-methyl-pyrrolidin-2-one at 120℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
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80% | With sulfuric acid; lithium bromide In 1-methyl-pyrrolidin-2-one at 80℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
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at 225℃; |
Yield | Reaction Conditions | Operation in experiment |
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80% | With 5percent K-silica gel at 150℃; for 8h; | |
at 150℃; for 8h; | 36 The procedure in example-1 was exactly repeated except that for the charge 3.16 xlO"mol N, N'dimethyl urea, 15.56 x10"3 mol dibutyl carbonate and 200 mg 5% K-silica gel catalyst were added. After cooling to room temperature the LC analysis of reaction crude showed 87 % diphenyl urea conversion and selectivity to N-methyl butyl carbamate to be 98%. | |
at 150℃; for 8h; | 36 The procedure in example-1 was exactly repeated except that for the charge 3.16×10 mol N,N'dimethyl urea, 15.56×103 mol dibutyl carbonate and 200 mg 5% K-silica gel catalyst were added. After cooling to room temperature the LC analysis of reaction crude showed 87% diphenyl urea conversion and selectivity to N-methyl butyl carbamate to be 98%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
W.R. Grace silica gel; at 150℃; under 26618.1 Torr; for 12h;Conversion of starting material; | The procedure in example-38 was exactly repeated except that for the charge 6.32 x10"3 mol N, N'dimethyl urea, 15 ml dimethyl carbonate and 400 mg W. R. Grace silica gel catalyst were added. After cooling to room temperature the reaction mixture was filtered to separate the catalyst. Analysis of reaction crude by LC showed conversion of N, N' diphenyl urea to be 91 % and selectivity to N-methyl methyl carbamate to be 98 %. | |
silica gel; at 150℃; under 26618.1 Torr; for 12h; | The procedure in example-38 was exactly repeated except that for the charge 6.32×103 mol N,N'dimethyl urea, 15 ml dimethyl carbonate and 400 mg W. R. Grace silica gel catalyst were added. After cooling to room temperature the reaction mixture was filtered to separate the catalyst. Analysis of reaction crude by LC showed conversion of N,N' diphenyl urea to be 91% and selectivity to N-methyl methyl carbamate to be 98%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | In water at 100℃; for 17h; | |
82% | at 100℃; for 16h; Inert atmosphere; | 7 Preparation of 5-Benzyl-l,3-dimethyl-[l,3,5]triazinan-2-one Benzylamine (5 mL, 45.8 mmol), formaldehyde (37% w/w solution, 7.5 mL, 91.6 mmol), and N,N'-dimethylurea (4.03 g, 45.8 mmol) were combined in a reaction flask equipped with a reflux condenser and heated to 100 °C under an nitrogen atmosphere for 16 h. After it was cooled to room temperature, the reaction mixture was quenched with water (50 mL) and extracted with CH2CI2 (50 mL x 2). The combined organic layers were washed with brine, dried over anhydrous Na2S04, filtered, and concentrated. The residue was purified by flash chromatography (silica gel, EtOH as eluent) to give 5- benzyl-l,3-dimethyl-[l,3,5]triazinan-2-one (8.28 g, 82% yield), isolated as a colorless solid. FontWeight="Bold" FontSize="10" H NMR (400 MHz, CDCb) δ 7.40-7.27 (m, 5 H), 4.12 (s, 4 H), 3.93 (s, 2 H), 2.86 (s, 6 H). |
77% | In water at 100℃; for 14h; Inert atmosphere; | 5-Benzyl-1 ,3-dimethyl-1 ,3,5-triazinan-2-one (21 ) Benzylamine (9.81 g, 91.7 mmol) was dissolved in formaldehyde (14.7 g, 183 mmol, 40% aq. solution) and heated to 100 °C under argon atmosphere. N,N’~ dimethylurea (8.07 g, 91.7 mmol) was added and the mixture was stirred for 14 h. The mixture was washed with water and extracted with dichloromethane (2x200 mL). The combined organic layers were washed with brine solution and dried over sodium sulfate. The solvent was removed in vacuo and the crude product was pu rified by column chromatography (1 :1 petroleum ether: ethyl acetate) to give the title compound 21 as yellow crystals (15.5 g, 70.9 mmol, 77% yield). 1H NMR (0091) (CDCL, 400 MHz) d = 2.85 (s, 6 H), 3.90 (s, 2 H), 4.16 (s, 4 H), 7.28 (m, 5 H) ppm. 13C NMR (CDCL, 101 MHz) d = 32.47, 55.36, 67.72, 127.70, 128.60, 129.11 , 137.49, 156.04 ppm. ESI-MS (m/z): 220.10 [M+H]+. |
74% | In water at 100℃; for 16h; | |
72% | at 100℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | In ethanol; | EXAMPLE 71 Ethyl S-(acetylamino)-1,2,3,4-tetrahydro-2-methyl-7-nitro-8-isoquinolinepropanoate A 3 L 3-neck flask was charged with 3-nitro-phthalic acid (502 g, 2.38 mol) and 1,3-dimethyl urea (230 g, 2.62 mol). This was heated slowly to 170 C. then allowed to cool. One liter ethanol was added to the reaction product before it solidified. The product which crystallized was filtered, washed with ethanol and ether, and air dried to a yellow powder, 420.7 g. A second crop was 50.4 g for a yield of 96%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
After 6.3 hours, GC analysis showed 100% conversion of N,N'-dimethyl urea and the yield of methyl methyl carbamate was 95.5 mmol. | ||
Example 11 Methyl methyl carbamate was produced by charging the following components to a 300 ml stirred autoclave: The reaction was carried out in accordance with the procedure described in Example 1 except that N,N'-dimethyl urea replaced methyl amine and the liquid phase was analyzed by gas chromatography (GC) at the end of the reaction. After 6.3 hours, GC analysis showed 100% conversion of N,N'-dimethyl urea and the yield of methyl methyl carbamate was 95.5 mmol. |
Yield | Reaction Conditions | Operation in experiment |
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With Isopropylbenzene; methanesulfonic acid; In water; toluene; | EXAMPLE 10 1-Naphthalenyl methylcarbamate To a 500 ml, 3-necked flask, equipped with an agitator and a condenser were added 36.0 g (0.25 mol) of 1-naphthol, 35.2 g (0.40 mol) of 1,3-dimethylurea, 150 ml of cumene, and 38.4 g (0.40 mol of acid) of a 98% by weight methanesulfonic acid solution (Aldrich, reagent grade). The resulting solution was heated to reflux (about 154 C.) and stirred at that temperature for about 6 hours. After 6 hours the solution was cooled to 90 C. and diluted with 100 ml of deionized water. The resulting two-phase mixture was stirred for 15 minutes at about 80 C., and then the organic layer separated from the aqueous layer. The organic layer was mixed with 50 ml of deionized water and cooled to 0 C. After stirring the mixture for 30 minutes at a temperature of about 0 C. the resulting slurry was filtered and the recovered crystals washed with 25 ml of deionized water, followed by 20 ml of cold (5 C.) cumene. The crystals were dried in a vacuum oven at 60 C. to provide 11.3 g of title product. The above product was purified by dissolving it in 50 ml of hot (90 C.) toluene. Once all product had dissolved, the solution was cooled to 0 C. and stirred for 30 minutes at that temperature. The resulting slurry was filtered and the recovered crystals washed with 30 ml of toluene. This material, dried in a vacuum oven at 60 C., provided 10.1 g of 1-naphthalenyl methylcarbamate. m.p.=139-140 C. The product was identified as 1-naphthalenyl methylcarbamate by comparing n.m.r. spectra with a 1-naphthalenyl methylcarbamate reference standard. The n.m.r. analyses were conducted on a 60 mHz instrument in CDCl3: delta=2.75 (doublet, 3H); 5.45 (singlet, 1H); 7.25-8.20 (broad multiplet, 7H). | |
With Isopropylbenzene; methanesulfonic acid; In water; toluene; | Example 10 1-Naphthalenyl methylcarbamate To a 500 ml, 3-necked flask, equipped with an agitator and a condenser were added 36.0 g (0.25 mol) of 1-naphthol, 35.2 g (0.40 mol) of 1,3-dimethylurea, 150 ml of cumene, and 38.4 g (0.40 mol of acid) of a 98% by weight methanesulfonic acid solution (Aldrich, reagent grade). The resulting solution was heated to reflux (about 154C) and stirred at that temperature for about 6 hours. After 6 hours the solution was cooled to 90C and diluted with 100 ml of deionized water. The resulting two-phase mixture was stirred for 15 minutes at about 80C, and then the organic layer separated from the aqueous layer. The organic layer was mixed with 50 ml of deionized water and cooled to 0C. After stirring the mixture for 30 minutes at a temperature of about 0C the resulting slurry was filtered and the recovered crystals washed with 25 ml of deionized water, followed by 20 ml of cold (5C) cumene. The crystals were dried in a vacuum oven at 60C to provide 11.3 g of title product. The above product was purified by dissolving it in 50 ml of hot (90C) toluene. Once all product had dissolved, the solution was cooled to 0C and stirred for 30 minutes at that temperature. The resulting slurry was filtered and the recovered crystals washed with 30 ml of toluene. This material, dried in a vacuum oven at 60C, provided 10.1 g of 1-naphthalenyl methylcarbamate. m.p. = 139-140C. The product was identified as 1-naphthalenyl methylcarbamate by comparing n.m.r. spectra with a 1-naphthalenyl methylcarbamate reference standard. The n.m.r. analyses were conducted on a 60 mHz instrument in CDCl3: delta = 2.75 (doublet, 3H); 5.45 (singlet, 1H); 7.25-8.20 (broad multiplet, 7H). |
Yield | Reaction Conditions | Operation in experiment |
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52.5% | With hydrogenchloride; sodium hydroxide; Isopropylbenzene In water | 15 2,3-Dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate EXAMPLE 15 2,3-Dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate To a 250 ml, 3-neck flask, equipped with an agitator, a condenser, and a sub-surface gas addition system were added 11.0 g (0.125 mol) of 1,3-dimethylurea, 16.2 g (0.125 mol) of dibutylamine, and 100 ml of cumene. The solution was heated until the solvent began to reflux (about 151° C.). Heating was continued for about 6 hours while the solvent was refluxed and the monomethylamine generated during the reaction was allowed to escape. When monomethylamine evolution appeared to cease, the solution was cooled to about 80° C. and 16.4 g (0.10 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-ol were added. Anhydrous hydrochloric acid gas (4.6 g, 0.125 mol) was added sub-surface to the liquid at a rate such that the temperature of the contents of the flask remained about 80° C. The resulting solution was heated to about 115° C. and stirred at that temperature for 16 hours. After 16 hours the solution was heated to reflux (about 154° C.) and stirred at that temperature for one hour. The solution was then cooled to about 80° C. and 50 ml of deionized water were added. The pH of the resulting two-phase mixture was increased to about 4.0 using a few drops of a 50% sodium hydroxide solution. The two-phase mixture was then stirred for 30 minutes at about 80° C. and the organic layer was separated from the aqueous layer. The organic layer was mixed with 25 ml of deionized water and cooled to about 0° C. After stirring the two-phase mixture for 30 minutes at a temperature of about 0° C. the resulting slurry was filtered and the recovered crystals washed with 20 ml of deionized water. These crystals, dried in a vacuum oven at 60° C., provided 11.6 g (52.5% yield) of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate. mp=151.0°-152.0° C. |
52.5% | With hydrogenchloride; sodium hydroxide; Isopropylbenzene In water | 15 2,3-Dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate Example 15 2,3-Dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate To a 250 ml, 3-neck flask, equipped with an agitator, a condenser, and a sub-surface gas addition system were added 11.0 g (0.125 mol) of 1,3-dimethylurea, 16.2 g (0.125 mol) of dibutylamine, and 100 ml of cumene. The solution was heated until the solvent began to reflux (about 151°C). Heating was continued for about 6 hours while the solvent was refluxed and the monomethylamine generated during the reaction was allowed to escape. When monomethylamine evolution appeared to cease, the solution was cooled to about 80°C and 16.4 g (0.10 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-ol were added. Anhydrous hydrochloric acid gas (4.6 g, 0.125 mol) was added sub-surface to the liquid at a rate such that the temperature of the contents of the flask remained about 80°C. The resulting solution was heated to about 115°C and stirred at that temperature for 16 hours. After 16 hours the solution was heated to reflux (about 154°C) and stirred at that temperature for one hour. The solution was then cooled to about 80°C and 50 ml of deionized water were added. The pH of the resulting two-phase mixture was increased to about 4.0 using a few drops of a 50% sodium hydroxide solution. The two-phase mixture was then stirred for 30 minutes at about 80°C and the organic layer was separated from the aqueous layer. The organic layer was mixed with 25 ml of deionized water and cooled to about 0°C. After stirring the two-phase mixture for 30 minutes at a temperature of about 0°C the resulting slurry was filtered and the recovered crystals washed with 20 ml of deionized water. These crystals, dried in a vacuum oven at 60°C, provided 11.6 g (52.5% yield) of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate. mp = 151.0°-152.0°C. |
Yield | Reaction Conditions | Operation in experiment |
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With hydrogenchloride; In ethanol; water; ethyl acetate; | EXAMPLE 2 To a mixture of ethyl veratroylacetate (10 g) and N,N'-dimethylurea (3.84 g) were added conc. hydrochloric acid (1 drop) and ethanol (1 ml). The mixture was heated at 120 C. for 3.5 hours under reduced pressure. To the residue was added another conc. hydrochloric acid (2 drops) and the mixture was heated again at 120 C. for 4 hours under reduced pressure. To the reaction mixture was added water and extracted with ethyl acetate. The extract was dried over magnesium sulfate and evaporated under reduced pressure. The residue was triturated with a mixture of isopropyl ether and ethyl acetate to give 6-(3,4-dimethoxyphenyl)-1,3-dimethyl-2,4(1H,3H)pyrimidinedione (7.60 g). mp 118-120 C. IR (Nujol): 1700, 1660 cm-1 NMR (DMSO-d6, delta): 7.24 (1H, s), 7.20 (2H, s), 5.72 (1H, s), 3.90 (3H, s), 3.88 (3H, s), 3.28 (3H, s), 3.20 (3H, s). |
Yield | Reaction Conditions | Operation in experiment |
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EXAMPLE 4 6-(3,4-Dichlorophenyl)-1,3-dimethyl-2,4(1H,3H)pyrimidinedione (5.27 g) was obtained according to substantially the same manner as that of Example 2 from <strong>[53090-43-0]ethyl 2-(3,4-dichlorobenzoyl)acetate</strong> (10.0 g) and N,N'-dimethylurea (3.71 g). mp: 172-175 C. IR (Nujol): 1695, 1660, 1620 cm-1 NMR (DMSO-d6, delta): 7.83 (1H, d, J=2 Hz), 7.80 (1H, d, J=8 Hz), 7.50 (1H, dd, J=2 Hz, 8 Hz), 5.68 (1H, s), 3.23 (3H, s), 3.10 (3H, s). |
Yield | Reaction Conditions | Operation in experiment |
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With hydrogenchloride; sodium hydrogencarbonate; In ethanol; | EXAMPLE 12 To a mixture of ethyl nicotinoylacetate (2.30 g) and N,N'-dimethylurea (1.05 g) were added conc. hydrochloric acid (a few drops) and ethanol (1 ml) and the mixture was stirred at 110-115 C. for 4 hours under reduced pressure (30 mmHg). After being cooled to ambient temperature, the solution was adjusted to pH 7.0 with an aqueous solution of sodium bicarbonate and extracted with ethyl acetate. The extract was washed with brine, dried over magnesium sulfate and evaporated to give 6-(3-pyridyl)-1,3-dimethyl-2,4(1H,3H)-pyrimidinedione (0.91 g). mp: 120-122 C. IR (Nujol): 1705, 1660 cm-1 NMR (DMSO-d6, delta): 8.68 (2H, m), 7.95 (1H, m), 7.53 (1H, dd, J=4.5 Hz), 5.70 (1H, s), 3.23 (3H, s), 3.10 (3H, s). |
Yield | Reaction Conditions | Operation in experiment |
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72% | In water; | EXAMPLE 2 1-N-methylamino-3,5-dimethyl-adamantane hydrochloride 2.43 grams of <strong>[941-37-7]1-bromo-3,5-dimethyl-adamantane</strong> was heated with 1.36 grams of N,N'-dimethylurea for 35 minutes at 160 C. The warming was performed in a closed container in an oil bath with a thermostat. The cooled reaction product was treated with water, and the 1-N-methylamino-3,5-dimethyl-adamantane hydrochloride isolated as described in Example 1. Yield: 1.41 grams (72% of theoretical yield) Melting point: 257 C. |
Yield | Reaction Conditions | Operation in experiment |
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With hydrogenchloride; Isopropylbenzene In water | 12 2,3-Dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate Example 12 2,3-Dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate To a 500 ml, 3-neck flask, equipped with an agitator, a condenser, and a sub-surface gas addition system were added 41.1 g (0.25 mol) of 2,3-dihydro-2,2-dimethylbenzofuran-7-ol, 35.2 g (0.40 mol) of 1,3-dimethylurea, and 180 ml of cumene. The solution was heated to reflux (about 156°C) and a total of 30 ml of cumene were removed by distillation in order to remove a small amount of water present in the reaction flask. Anhydrous hydrochloric acid gas (14.6 g, 0.40 mol) was added sub-surface to the liquid over a three hour period while refluxing the solution. After hydrochloric acid addition, the resulting solution was stirred at the reflux temperature for 8 hours, then cooled to about 80°C. Deionized water (50 ml) was added. The resulting two-phase mixture was stirred for 15 minutes at about 80°C and then the organic layer was separated from the aqueous layer. The organic layer was mixed with 50 ml of deionized water and the resulting two-phase mixture heated to about 80°C. The mixture was stirred for about 15 minutes at 80°C and then the organic layer was again separated from the aqueous layer. The organic layer was mixed, once more, with 25 ml of deionized water and the resulting mixture cooled to about 0°C. After stirring for one hour at a temperature of about 0°C the resulting slurry was filtered and the recovered crystals washed with 25 ml of deionized water, followed by 10 ml of chilled (0°C) cumene. These crystals, dried in a vacuum oven at 50°C, provided 15.5 g of 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate. m.p. = 148.0°-150.0°C. Further product was isolated from the filtrate as follows. The organic layer of the filtrate was separated from the aqueous layer and the organic solvent removed by vacuum distillation to provide an oily residue. Hexane (100 ml) was added to the residue. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With triethylamine In water at 25 - 200℃; | C1 Example C1Synthesis of imidazolidin-2,4-dione Compound; In a 1000 ml glass vessel equipped with a stirrer, thermometer, a dropping funnel and a distillation unit was charged 290 g (2.0 mol) of 40 wt % aqueous glyoxal solution. And then, triethylamine is added thereto to prepare a basic mixed solution (At this time, the solution had a pH of 9). To the mixed solution was gradually added dropwise a solution comprising 176 g (2.0 mol) of 1,3-dimethylurea and 176 ml of water while maintaining a liquid temperature to 25 to 35° C. After stirring the solution at room temperature for 3 hours, the mixture was reacted by elevating the temperature to 200° C. over 2 hours while removing triethylamine and water under normal pressure by distillation. After completion of the reaction, the obtained reaction mixture was distilled under reduced pressure (105 to 107° C./0.67 to 1.33 kPa) to obtain 217 g (Isolation yield; 85%) of 1,3-dimethylimidazolidin-2,4-dione as a pale yellowish liquid.Physical properties of the obtained 1,3-dimethylimidazolidin-2,4-dione were as follows.1H-NMR (300 MHZ, DMSO-D6, δ (ppm)); 2.83 (3H, s), 2.85 (3H, s), 3.93 (2H, s)CI-MS (m/e); 129 (M+1) |
63% | Stage #1: N,N'-Dimethylurea With triethylamine In water at 0℃; for 0.333333h; Inert atmosphere; Stage #2: Glyoxal In water at 20℃; for 3h; Inert atmosphere; Stage #3: With sulfuric acid In water for 12h; Reflux; Inert atmosphere; | |
40% | With 1-hydroxyethylene-(1,1-diphosphonic acid) In water at 90℃; for 2h; Green chemistry; |
Stage #1: Glyoxal; N,N'-Dimethylurea With triethylamine In water at 35℃; for 3h; Stage #2: With sulfuric acid In water at 100℃; for 6h; | 9.1 Synthesis of N,N-dimethylhydantoin: In a 50 mL round-bottomed flask, add 1.21 g (20.0 mmol) of glyoxal liquid and adjust its pH to about 9 with triethylamine; take another 1.80 g (20.0 mmol) of 1,3-dimethylurea and dissolve in 5 mL of distilled water Then, the above glyoxal system was added dropwise, and the oil was heated and stirred at 35 ° C. After 3h of reaction,0.4 mL of concentrated sulfuric acid was slowly added dropwise to the reaction system, the reaction temperature was raised to 100 ° C, and the reaction was refluxed for 6 h.After the reaction was completed, the temperature was lowered to room temperature, and the solution was concentrated under reduced pressure. The obtained product was dissolved by adding 20 mL of water, the pH of the solution was adjusted to about 7 with solid sodium carbonate, and extracted with ethyl acetate (30 mL x 3). The extracts were combined and sampled for TLC detection. Isolation and purification: normal phase column chromatography, eluting with petroleum ether: ethyl acetate 3: 1, TLC monitoring, elution until the fraction does not contain the target product.The target product was obtained as a pale yellow oil. Weigh, calculate the yield, and store it in a sealed container. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With 1H-imidazole; N,N-dimethyl-formamide In neat (no solvent) at 150℃; for 3h; | |
50% | With zirconyl chloride octahydrate for 0.15h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
11.6% | With chloro-trimethyl-silane; In N,N-dimethyl-formamide; at 20℃;Inert atmosphere; | 00186] A mixture of 1,2-diphenylethanone (300 mg, 1.53 mmol), 3-ethoxy-4- hydroxy-5-nitrobenzaldehyde (324 mg, 1.53 mmol), and 1,3-dimethylurea (174 mg, 1.98 mmol) in DMF (5 mL) was added TMSC1 (1.0 g, 9.12 mmol), and the reaction mixture was stirred at room temperature overnight under nitrogen. LCMS showed that about 30% of starting materials were consumed. H20 (10 mL) was added to quench the reaction, and the aqueous layer was extracted with EtOAc (30 mLx3). The combined organic layer was washed with brine (20 mL), dried over Na2S04, filtered, and concentrated. The residue was purified by column chromatography (PE: EtOAc=l :2) and preparative HPLC to afford Compound 41 as a yellow solid (82 mg, yield: 11.6%). 1H NMR (DMSO- 6 400 MHz): |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With MCM-41 mesoporous silica In ethanol; water at 80 - 90℃; for 14h; Green chemistry; | General synthetic procedure for preparation of thioamide (4): General procedure: In a typical reaction a solution of amide (1 mmol), rhodanine (1.2 mmol) and Morpholine (1.2 mmol) in EtOH/water (2 + 2 ml) were refluxed at 80-90 °C till completion using 40 mg of MCM-41 catalyst. The completion of the reaction was indicated by the disappearance of the starting material in thin layer chromatography. After completion of the reaction the solvent was evaporated in a rotary evaporator and the crude product was taken in dichloromethane and filtered to separate the products as filtrate from the catalyst (residue). Then the crude product was purified by silica gel column chromatography where the compound (5) came out from the column with 25%EtOAc/75% petroleum ether, but thioamide (4) came out with 65%EtOAc/35% petroleum ether making their separation easy. The thioamides (4) were characterized by IR, 1H NMR, 13C NMR, CHN and X-ray single crystal analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With dinitrogen pentoxide In carbon dioxide at 0 - 5℃; for 0.5h; liquid CO2; | General procedure: General nitration procedure.12-14 A steel autoclave (25 cm3) equippedwith sapphire windows containing urethane 1c or amide 3 or 5 (10.0 mmol)was filled with liquid CO2 to 60 bar pressure and cooled to 0 °C. ThenN2O5 (2.4 g, 22.0 mmol) solution in liquid CO2 (~ 4 g) cooled to 0-5 °Cwas gradually pressed out from an auxiliary high-pressure cell by a freshCO2 flow (2 g min-1) to the reaction autoclave. During the addition, thepressure in the latter raised up to 80 bar. The reaction mixture was stirredat 0-5 °C for the time specified in Table 1. Then, CO2 was removed bydecompression and the residue was poured onto ice water (50 ml). Theresulted suspension was extracted with EtOAc (4 × 20 ml), the combinedorganic extracts were washed successively with saturated aqueous NaHCO3(2 × 20 ml) and water (25 ml) and dried over anhydrous Na2SO4. Thesolvent was removed under reduced pressure to afford corresponding nitrocompounds 2, 4 (see Table 1). Compounds 2a,b and 7 were synthesizedby similar procedures using 1.2 g (11.0 mmol) or 6.0 g (55 mmol) ofN2O5, respectively. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With toluene-4-sulfonic acid In acetonitrile at 80℃; for 2h; regioselective reaction; | 3-(5-Aryl-1,3-dimethyl-2-oxo-2,3-dihydro-1H-imidazol-4-yl]-5-methylindolin-2-ones 3a-r and 3-(2,5-Diaryl-3-oxo-1,2,3,6-tetrahydropyrrolo[2,3-c]pyrazol-4-yl)indolin-2-ones 5a-m General procedure: A mixture of substituted 3-(2-aryl-2-oxoethylidene)indolin-2-one 1 (1 mmol), 1,3-dimethylurea (2, 1.2 mmol) or 5-amino-2-phenyl-2,4-dihydro-3H-pyrazol-3-one (4, 1 mmol), PTSA·H2O (0.3 mmol), and MeCN (5 mL) was added to a 25 mL flask and reacted at 80 °C (monitored by TLC) for 2 h. After completion, the mixture was cooled to r.t. and the precipitate obtained was isolated by filtration and drying. Compounds 3 or 5 were purified by recrystallization (DMF or EtOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With toluene-4-sulfonic acid; In acetonitrile; at 80℃; for 5h; | General procedure: The mixture of substituted isatins 1 (1 mmol), phthalic anhydride or succinic anhydride 2 (1 mmol), 1,3-dimethylurea (1,3-diethylurea) 3 (1.5 mmol), p-TSA?H2O (0.2 mmol), and CH3CN (3 mL) was put in a 25 mL flask and reacted under 80 C (monitored by TLC) about 5 h. After completion, the reaction the mixture was cooled to room temperature and the precipitate was obtained by filtration. Compound 4 was purified by recrystallization from EtOH. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With toluene-4-sulfonic acid; In acetonitrile; at 80℃; for 5h; | General procedure: The mixture of substituted isatins 1 (1 mmol), phthalic anhydride or succinic anhydride 2 (1 mmol), 1,3-dimethylurea (1,3-diethylurea) 3 (1.5 mmol), p-TSA?H2O (0.2 mmol), and CH3CN (3 mL) was put in a 25 mL flask and reacted under 80 C (monitored by TLC) about 5 h. After completion, the reaction the mixture was cooled to room temperature and the precipitate was obtained by filtration. Compound 4 was purified by recrystallization from EtOH. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86.9% | With sulfuric acid; nitric acid In dichloromethane at -5 - 0℃; | 1 100 g of N,N'-dimethylurea was dissolved in 200 mL of dichloromethane to prepare a solution, and slowly added to a mixed acid of 278 g of 98% concentrated nitric acid and 233 g of 98% concentrated sulfuric acid for nitration. The reaction temperature was -5 ° C to 0 ° C. After the addition was completed, the reaction mixture was poured into 400 g of ice water and diluted.The temperature of the diluted solution was raised to 20 ° C to carry out a hydrolysis reaction, and the hydrolysis time was 60 min. After the reaction was terminated, the liquid phase was separated by hydrolysis, and the dichloromethane phase was dried over anhydrous magnesium sulfate, and then concentrated to obtain 150 g of methyl(nitroso)amine, yield 86.9%, purity. ≥99.3%. |
82.2% | With sulfuric acid; nitric acid In dichloromethane at -5 - 0℃; | 1 Example 1 Preparation of methyl(nitroso)amine 100g of N,N'-dimethylurea was dissolved in 200 mL of dichloromethane to prepare a solution, and slowly added to 278 g of concentratedNitrification reaction is carried out in a mixed acid composed of 98% concentrated nitric acid and 233 g concentrated sulfuric acid having a mass concentration of 98%. The reaction temperature isDegree -5 ° C ~ 0 ° C, after the addition is completed, the reaction mixture is poured into ice water, the dichloromethane layer is separated, the aqueous phase is extracted with dichloromethaneThe methylene chloride layer and the extract are combined and washed successively with a sodium carbonate aqueous solution having a mass concentration of 5% and distilled water to obtainA solution of N,N'-dimethyl-N,N'-dinitrourea in dichloromethane.200 g of a 20% by mass aqueous solution of sulfuric acid was added to the reaction flask, heated to boiling, and N,N'- was added dropwise.The hydrolysis reaction of dimethyl-N,N'-dinitrourea in dichloromethane is carried out, and after the completion of the dropwise addition, the mixture is kept for 30 minutes, and the heating is stopped.The hydrolyzate was extracted with dichloromethane, and the extract was dried over anhydrous magnesium sulfate and concentrated to yield 142 g of methyl(nitroso)amine.The purity is ≥99.0%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
10% | With hafnium tetrakis(trifluoromethanesulfonate); at 80℃; for 24h; | To the mixture of ethyl acetoacetate (130 mg, 1 mmol) and urea (72 mg,1.2 mmol) was added Hf(OTf)4 (8 mg, 0.01 mmol). The reaction was stirred at 80 C for 24 h.Flash column chromatography afforded (DCM/EA = 5:2) 21 (15 mg, 10%) as a white solid; mp115-116 C. 1H-NMR(400 MHz, CDCl3): d 5.16 (s, 1H), 3.39 (s, 3H), 3.32 (s, 3H), 2.22 (s, 3H) ppm;13C-NMR (100 MHz, CDCl3): d 162.4, 152.6, 151.4, 101.2, 31.7, 27.9, 20.2 ppm; LRMS (ESI+): m/z calcdfor C7H10N2O2 [M + H]+ 155.1; found 155.1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With tetrabutylammonium tetrafluoroborate In acetonitrile at 20℃; for 4h; Electrochemical reaction; Inert atmosphere; Green chemistry; |
Tags: 96-31-1 synthesis path| 96-31-1 SDS| 96-31-1 COA| 96-31-1 purity| 96-31-1 application| 96-31-1 NMR| 96-31-1 COA| 96-31-1 structure
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P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
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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