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CAS No. : | 115-22-0 | MDL No. : | MFCD00004460 |
Formula : | C5H10O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | - |
M.W : | 102.13 | Pubchem ID : | - |
Synonyms : |
|
Num. heavy atoms : | 7 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.8 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 1.0 |
Molar Refractivity : | 27.55 |
TPSA : | 37.3 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) : | -7.01 cm/s |
Log Po/w (iLOGP) : | 1.2 |
Log Po/w (XLOGP3) : | -0.12 |
Log Po/w (WLOGP) : | 0.35 |
Log Po/w (MLOGP) : | 0.08 |
Log Po/w (SILICOS-IT) : | 0.2 |
Consensus Log Po/w : | 0.34 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -0.33 |
Solubility : | 47.6 mg/ml ; 0.466 mol/l |
Class : | Very soluble |
Log S (Ali) : | -0.21 |
Solubility : | 63.0 mg/ml ; 0.617 mol/l |
Class : | Very soluble |
Log S (SILICOS-IT) : | -0.39 |
Solubility : | 41.8 mg/ml ; 0.409 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.0 |
Signal Word: | Danger | Class: | 3 |
Precautionary Statements: | P210-P403+P235 | UN#: | 1224 |
Hazard Statements: | H225 | Packing Group: | Ⅲ |
GHS Pictogram: |
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* 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 |
---|---|---|
With water; nickel at 70℃; Hydrogenation; | ||
With ethanol; platinum at 70℃; Hydrogenation; | ||
With lithium aluminium tetrahydride; diethyl ether |
With ethanol; sodium | ||
With sodium tetrahydroborate | ||
With lithium aluminium tetrahydride In diethyl ether for 2h; Heating; | ||
With hydrogen In ethanol at 20℃; for 4h; | XXVI.1 XXVI .1 2-Methyl-butane-2,3-diol3-Hydroxy-3-methyl-2-butanon (5 ml) was dissolved in ethanol (20 ml). PtO2 (100 mg) was added and the mixture was hydrogenated at room temperature for 4h and 3 bar.The mixture was concentrated in vacuo.Yield: 3.87 g | |
With hydrogen In ethanol at 20℃; for 4h; | XXVI.1 XXVI.1 2-Methyl-butane-2,3-diol 3-Hydroxy-3-methyl-2-butanon (5 ml) was dissolved in ethanol (20 ml). PtO2 (100 mg) was added and the mixture was hydrogenated at room temperature for 4 h and 3 bar. The mixture was concentrated in vacuo. Yield: 3.87 g | |
With sodium tetrahydroborate In water; acetonitrile at 5 - 23℃; for 3h; | 1 25 parts of the compound represented by the formula (I-1-a) and 125 parts of acetonitrile were added and stirred at 23 ° C. for 30 minutes.The obtained mixed solution was cooled to 5 ° C.,A mixed aqueous solution of 3.24 parts of sodium borohydride and 48.62 parts of ion exchanged water was added dropwise over 1 hour,The mixture was stirred at 5 ° C. for 2 hours and concentrated.420 parts of ethyl acetate and 170 parts of ion-exchanged water were charged in the obtained concentrated residue,The mixture was stirred at 23 ° C. for 30 minutes, allowed to stand and separated, and the organic layer was washed with water.170 parts of ion-exchanged water was charged in the recovered organic layer,The mixture was stirred at 23 ° C. for 30 minutes, allowed to stand and separated, and the organic layer was washed with water.This washing operation was repeated 5 times.By concentrating the recovered organic layer,To obtain 20.04 parts of a compound represented by the formula (I-1-b) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With ethanol; hydroxylamine | ||
With hydroxylamine |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.7% | With sodium sulfate for 12h; Heating; | |
With potassium hydroxide | ||
With potassium carbonate |
With methanol; potassium formate at 130℃; | ||
Multi-step reaction with 2 steps 1: diethyl ether 2: diluted HCl | ||
Multi-step reaction with 2 steps 1: sodium methylate 2: diluted HCl |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With oxalic acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With sodium ethanolate In ethanol at 0℃; | |
89.1% | With sodium ethanolate In ethanol at 0℃; for 22h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With N-benzyl-N,N,N-triethylammonium chloride; cesium fluoride In toluene for 24h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With pyridine; acetic acid; | Example 33 Preparation of 3-cyano-2-dicyanomethylen-4,5,5-trimethyl-2,5-dihydrofuran 21 A mixture of 92% 3-hydroxy-3-methylbutan-2-one 20 (9.5 g, 85.6 mmol), malononitrile (12.3 g, 186 mol), two drops of acetic acid and pyridine (50 ml) was stirred at room temperature for 24 hours. The reaction temperature was controlled without exceeding the room temperature by the use of an ice bath at the beginning of the reaction. The reaction mixture was then poured into 800 ml ice water with vigorous stirring. The precipitate was collected by vacuum filtration and recrystallized from ethanol to give 13.6 g (80% yield) of white crystals: mp 203 C. (lit. 199 C., Melikian, G.; Rouessac, F. P.; Alexandre, C. Synth. Commun. 1995, 25,19, 3045). 1H NMR (300 MHz, CDCl3) delta 1.61 (s, 6 H), 2.35 (s, 3 H); 13C NMR (75 MHz, CDCl3) delta 14.26, 24.47, 58.65, 99.87, 104.98, 109.07, 110.51, 111.11, 175.30, 182 63 ppm. |
67.8% | With lithium ethoxide; In ethanol; at 75℃; for 10h;Inert atmosphere; | (3) Dissolve 3-hydroxy-3-methyl-2-butanone (1.0 g, 10 mmol), malononitrile (1.33 g, 20 mmol) and lithium ethoxylate (0.001 g, 0.02 mmol) in 25 In mL EtOH, the mixture was heated at 75C for 10 hours under a dull nitrogen atmosphere, then cooled and filtered, washed three times with deionized water, and the product was green (1.35 g, 67.8%). Product 3 (TCF) is obtained |
59% | With sodium methylate; sodium; In ethanol; at 20℃; for 3h;Reflux; | Sodium metal (6.5 mmol) was dissolved in 15 mL of absoluteethyl alcohol in a water bath at room temperature to introducesodium ethoxide solution, followed by adding 3-hydroxy-3-methylbutan-2-one (45 mmol) and malononitrile (90 mmol) withstirring. After stirring for 1 h at room temperature, an additional 20 mL of absolute ethyl alcohol was added. The mixture was refluxed for another 2 h. After cooling in a refrigerator, the resultant precipitate was filtered under vacuum, subjected to washing with aminimal quantity of cold ethyl alcohol, and air-dried to give an off white crystalline product. The filtrate was then concentrated,cooled and filtered off to give a second crop (total yield 59%). mp202Ce204 C. 1H NMR (400 MHz, CDCl3): ppm 2.36 (s, 3H), 1.64 (s,6H). |
50% | With sodium ethanolate; In ethanol; for 2h;Reflux; | NaOEt (0.9 g, 13 mmol) was added to EtOH (10 mL) solution which include 3-hydroxy-3-methyl-2-butanone (9 g, 88 mmol) and malonitrile (12 g, 181 mmol) and then stirred for 1 h. After that,30 mL EtOH was added and the mixture was then refluxed for 1 h,which was then cooled in refrigerator. The solid precipitate was filtered and washed with minimal amount of cold EtOH, affording the compound 1 as off-white crystalline solid (8.8 g, 44 mmol, 50.0%). 1H NMR(400 MHz, DMSO-d6) delta (ppm): 2.37 (s, 3H), 1.60 (s, 6H). MS (ESI-TOF): calculated for C11H8N3O-, [M-H]-, m/z, 198.07, found: 198.42. |
48.4% | With sodium ethanolate; In ethanol; at 20℃; for 12h;Inert atmosphere; | Following literature reported procedure synthesis of fluorophore 1 and 2 was carried out in two steps starting from readily available compounds A and B.2 Briefly, 3-hydroxy-3-methyl-2-butanone (A, 9.0 g, 88 mmol) and malononitrile (B, 12.0 g, 181 mmol) were added to a stirred solution of sodium ethoxide in ethyl alcohol under nitrogen atmosphere. The resulting solution was stirred for 12 h at room temperature. Solvent was removed under high vacuum and the residue was purified by recrystallization from ethyl alcohol to give an off-white crystalline solid 2-(3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene)malononitrile (C). Yield (8.5 g, 48.4%). |
44% | With sodium ethanolate; In ethanol;Inert atmosphere; Reflux; | Probe 1 was synthesized in two steps starting from readily available compound (4-formylphenyl)boronic acid.2 To a stirred solution of sodium ethoxide (0.9 g, 13 mmol) in dry ethanol 3-hydroxy-3-methyl-2-butanone (A, 9.0 g, 88 mmol) and malononitrile (B, 12.0 g, 181 mmol) were added under nitrogen atmosphere. The mixture was refluxed overnight under N2 atmosphere. Completion of the reaction was monitored by TLC. After completion of the reaction, excess solvent was removed under rotary evaporator. The residue was purified by recrystallization from ethanol to give an off-white crystalline solid 2-(3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene)malononitrile (C). Yield (7.5 g, 44%). The product was dried under high vacuum and used in the next step. |
38% | With sodium ethanolate; In ethanol; for 2h;Inert atmosphere; Reflux; | Probe 1 was synthesized in two steps starting from readily available compound 3-(4-hydroxy-3,5-dimethoxyphenyl)acrylaldehyde.3,4 First, 3-hydroxy-3-methyl-2-butanone (A, 9.0 g, 88 mmol) and malononitrile (B, 12.0 g, 181 mmol) were added to a stirred solution of sodium ethoxide (0.9 g, 13 mmol) in ethanol under nitrogen atmosphere. The mixture was refluxed for 2 h under inert atmosphere. Excess solvent was removed under rotary evaporator. The residue was purified by recrystallization from ethyl alcohol to give an off-white crystalline solid 2-(3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene)malononitrile (C). Yield (6.5 g, 38%). In the second step, 3-(4-hydroxy-3,5-dimethoxyphenyl)acrylaldehyde (D, 0.5 g, 2.42 mmol), 2-(3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene)malononitrile (C, 0.531 g, 2.66 mmol) and ammonium acetate (0.205 g, 2.66 mmol) were dissolved in 20 mL dry THF/Ethanol (4:1; v/v) mixture under N2 atmosphere. The resulting solution was allowed to stir for 30 minutes at room temperature. After this time, 10 mL more solvent mixture was added and the solution was refluxed for 2 hours in dark condition under inert atmosphere. The mixture was allowed to cool at room temperature, and the excess solvent was evaporated under reduced pressure. The crude product was purified by silica gel column chromatography (40% hexane/ethyl acetate) to give the desired product (0.185 g, yield 20%). IR (cm-1, 3325, 2924, 2847, 2216, 2182, 1594, 1562, 1524, 1501, 1455, 1429, 1308, 1108). 1H NMR (400 MHz, DMSO-d6) delta 9.67 (s, 1H), 7.83 (d, 1H, J = 16 Hz), 7.33-7.22 (broad, 2H), 7.06-6.94 (t, 2H; J = 16 Hz), 6.68-6.64 (d, 1H, J = 15.2 Hz), 3.82 (s, 6H), 1.76 (s, 6H). 13C NMR (100.6 MHz, DMSO-d6) delta 177.9, 176.2, 149.7, 148.8, 142.0, 125.5, 113.5, 112.8, 112.7, 111.7, 108.5, 106.7, 99.5, 96.9, 56.8, 53.6, 25.9. Anal. calcd. for C22H19N3O4: C, 67.86; H, 4.92; N, 10.79. Found: C, 64.22; H, 5.35; N, 10.8. |
35% | With sodium ethanolate; at 25℃; for 20h; | A mixture of 1.50 g (0.065 mol)The metal sodium was dissolved in 190 mL of absolute ethanol,6.7 mL (0.064 mol) of compound 6 obtained in step 6) and 8.50 g (0.13 mol) of malononitrile were added;Stirred at room temperature for 20 hours,Steamed to remove ethanol,The residue was added with about 50 mL of water,With 6M hydrochloric acid to adjust the pH value of 4-5,Precipitate a large amount of tan oil;After sufficient washing with water,And then recrystallized twice with ethanol,After drying, 4.50 g of a pale yellow solid was obtained as compound 7,Yield: 35%. |
35% | With sodium; In ethanol; at 20℃; for 20h; | Dissolve 1.5 g (0.065 mol) of sodium metal in 190 ml of absolute ethanol,6.7 ml (0.064 mol) of compound 6 obtained in step S50 and 8.5 g (0.13 mol) of malononitrile were added,Then stirred at room temperature for 20 h,Ethanol was removed by rotary evaporation, the crude product obtained after the rotary evaporation was added with 50 ml of water,Then 6 mol / 1 hydrochloric acid solution to adjust the pH value of 4 ~ 5,A large amount of tan oil was precipitated; the oil was washed thoroughly with water and then recrystallized twice from ethanol,This gave 4.5 g of a pale yellow solid as compound 7 in 35% yield. |
35% | With ethanol; sodium; at 20℃; for 20h; | Dissolve 1.5 g (0.065 mol) sodium metal in 190 ml absolute ethanol and add 6.7 ml (0.064 mol) step 6) Obtained compound 6 and 8.5 g (0.13 mol) of malononitrile; stir at room temperature for 20 hours, rotovap to remove ethanol, add about 50 mL of water to the residue, adjust the pH to 4 to 5 with 6 M hydrochloric acid, and precipitate a large amount of tan oil. After washing well with water, it was recrystallized twice with ethanol and dried to give 4.5 g of pale yellow solid as compound 7 in a yield of 35%. |
35% | With sodium; In ethanol; at 25℃; for 20h; | 1.5 g, 0.065 mol of sodium metal, was dissolved in 190 ml of absolute ethanol.6.7 ml, ie 0.064 mol, of compound 6 obtained in step 7) and 8.5 g, ie 0.13 mol of malononitrile, are added.Then stirred at room temperature for 20 h,The ethanol was removed by rotary evaporation, and 50 ml of water was added to the crude product obtained by rotary evaporation.Then, using a 6 mol/l hydrochloric acid solution to adjust the pH to 4 to 5, a large amount of brownish oil was precipitated;After thoroughly washing the oil with water, it was recrystallized twice with ethanol and then dried.4.5 g of a pale yellow solid was obtained as compound 8 in a yield of 35%. |
31.8% | With magnesium ethylate; In ethanol; at 60℃; for 10h; | A mixture of 3-hydroxy-3-methyl-2-butonone (5) (1.5 g, 14.7 mmol), malonontrile(6) (2.91 g, 44 mmol), magnesiumethoxide (2.02 g, 17.6 mmol) and absolute ethanol (20 mL) was stirred at 60 oCfor 10 h. Then the solvent was evaporated, and the residue was collected andwashed with 20 mL water. Then, the residue was recrystallized from ethanol togive product 7 as a yellow solid.Yield: 930 mg (31.8%). 1H NMR (CDCl3, 500 MHz): delta 2.37(s, 3H), 1.64 (s, 6H). |
With ethanol; sodium;Reflux; | Acceptor 2-(3-cyano-4,5,5-trimethylfuran-2(5H)-ylidene)malononitrile (TCF) was synthesized according to a method published in the literature [13] with slight modification. In a 100 mL round-bottomed flask, a solution of sodium ethoxide was prepared by adding sodium (0.09g, 3.91mmol) to ethanol (60mL). To this solution 3- hydroxy-3-methyl-2-butanone (3.32mL, 30 mmol) and malononitrile (4.00g, 60 mmol) were added. The resulting mixture refluxed overnight. After concentration in vacuo, the residue was washed with diluted aqueous HCl. The crude precipitate was filtered and recrystallized from ethanol and gave the desired product, yield: 314g (95%, yellow solid). 2.37g (78%). C11H9N3O (199.209): calcd. C 66.32, H 4.55, N 21.09; found C 65.96, H 4.54, N 20.95.1H NMR (CDCl3, 400.1MHz, 20C): ||=1.63 (s, 6H), 2.36 (s, 3H), ppm. 13C NMR (CDCl3, 100.62MHz, 20C): ||=14.30, 24.49, 58.65, 99.84, 104.94, 109.06, 110.48, 111.12, 175.28, 182.61ppm. | |
With pyridine; acetic acid; at 25℃; for 24h; | Take 306 mg of 3-0H-3-CH3-2 butanone represented by Formula 7 in pyridine,Add 2-3 drops of acetic acid,Then 396 mg of malononitrile represented by Formula 8 was added,The molar ratio of 1: 2, in a 25 C oil bath for 24h,Then suction filtration,Get pure product 4 | |
With sodium ethanolate; In ethanol; for 2h;Inert atmosphere; Reflux; | (1) Using 10 ml of ethanol as the reaction solvent, carefully add 504 mg of sodium ethoxide to ethanol. Then, add 15 g of compound and 6.72 g of malononitrile in turn, with the molar ratio between 1:2 and 1:4, protected by nitrogen. Stirred 1h has reached a uniform purpose. Then, 30 ml of ethanol was added and the mixture was heated under reflux for 1 hour. After the reaction was completed, the reaction mixture was cooled. The pH of the reaction system was adjusted to 4-5 with 6M concentrated hydrochloric acid, and a large amount of solid was formed under cooling. The compound 2 was obtained by suction filtration and washing. The structure of compound 2 was characterized by NMR and ordinary mass spectrometry. | |
With pyridine; acetic acid; at 25℃; for 24h; | 3-OH-3-CH3-2 butanone represented by formula 6 306 mg dissolved in pyridine, plus 2-3 drops of acetic acidFurther, 396 mg of malononitrile represented by Formula 7 was added, and the molar ratio of the two was 1:2, and the reaction was carried out in an oil bath at 25 C for 24 hours.Then suction filtration to obtain pure product 8 | |
Add 5mmol, 1.00g 3-hydroxy-3-methylbutan-2-one to absolute ethanol, add 5mmol, 0.33g malononitrile, stir for 20 minutes under ice bath, add 5mmol, 0.34 g sodium ethoxide, moved to room temperature and stirred for 2 hours. After the reaction was completed, the solid was filtered and washed with anhydrous ethanol to obtain a gray-green solid; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With toluene-4-sulfonic acid In o-xylene for 5h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 44% 2: 20% | With methyl(triphenylphosphine)gold(I); sulfuric acid In methanol; water at 70℃; for 2h; | |
1: 44% 2: 20% | With water In methanol at 70℃; for 2h; | 44 Example 44 Example 44 To a solution in which 0.01 g of methyl(triphenylphosphine)gold (0.02 mmol) was dissolved in 2 ml of methanol, 0.18 g of 2-methyl-3-butin-2-ol (2 mmol) and an aqueous solution in which 0.05 g of concentrated sulfuric acid (0.5 mmol) was dissolved in 0.5 nil of water were added. After stirring at 70° C. for 2 hours, 3-hydroxy-3-methyl-2-butanone was obtained in 44% yield, and 3-methyl-2-butenal was obtained in 20% yield (catalyst turnover number: 64). |
1: 53 %Chromat. 2: 15 %Chromat. | With 2-dicyclohexyl(2′,6′-dimethoxybiphenyl)phosphine gold(I)bis(trifluoromethanesulfonyl)imide; water In methanol at 20℃; for 24h; Inert atmosphere; |
With (1,3-bis(2,6-diisopropyl-4-(4-((trimethylammonio)methyl)-1H-1,2,3-triazol-1-yl)phenyl)imidazolidin-2-ylidene)chlorogold(I) dichloride; water In water-d2 at 80℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: water; Raney nickel; ammonia / 70 - 100 °C / 51485.6 Torr / Hydrogenation 2: water; formic acid / 100 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: (i) Na, liq. NH3, (ii) /BRN= 1616385/ 2: H2 / Pd / ethanol 3: H2SO4 / Heating 4: H2 / Pd / ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
~ 100% | With sodium ethanolate; In ethanol; for 0.133333h;Microwave irradiation; | A mixture of 3- hydroxy-3-methylbutan-2-one (3 mmol, 306 mg), 2-pyridylacetonitrile (3 mmol, 355 mg) and sodium ethoxide (0.3 mmol), prepared from sodium (0.3 mmol, 6.9 mg), in ethanol (0.3 mL) was irradiated under focused microwave at 20 W for 8 minutes. Solvent was removed by rotary evaporation and the residue was purified via a flash chromatography on silica gel with a gradient eluent of dichloromethane to 1 % ethanol in dichloromethane to afford 606 mg of product as a brown oil at almost quantitative YIELD. 1H NMR (CDCL3) 6 8.63-8. 67 (m, 1H), 7.71-7. 75 (m, 2H), 7.18-7. 26 (m, 1H), 2.14 (s, 3H), 1.47 (S, 6H). |
With sodium ethanolate; sodium; In ethanol; dichloromethane; | 2-Imino-3-(2'-pyridyl)-4,5,5-trimethyl-2,5-dihydrofuran. A mixture of 3-hydroxy-3-methylbutan-2-one (3 mmol, 306 mg), 2-pyridylacetonitrile (3 mmol, 355 mg) and sodium ethoxide (0.3 mmol), prepared from sodium (0.3 mmol, 6.9 mg), in ethanol (0.3 mL) was irradiated under focused microwave at 20 W for 8 minutes. Solvent was removed by rotary evaporation and the residue was purified via a flash chromatography on silica gel with a gradient eluent of dichloromethane to 1% ethanol in dichloromethane to afford 606 mg of product as a brown oil at almost quantitative yield. 1H NMR (CDCl3) delta 8.63-8.67 (m, 1H), 7.71-7.75 (m, 2H), 7.18-7.26 (m, 1H), 2.14 (s, 3H), 1.47 (s, 6H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃; | 81.1 A solution of O-protected L-serine product of Example 29, Step 1 (37.8 g, 85.2mmol), 3-hydroxy-3-methyl-2-butanone (9.05 ml_, 86 mmol), DCC (17.8 g, 86 mmol)and DMAP (10.5 g, 86 mmol) in DCM (200 ml_) was stirred at RT overnight. Thereaction mixture was then diluted with water, extracted with DCM, dried andconcentrated. The residue was filtered with a fritted disk and purified by flash-chromatography over silica gel (eluted with Hexanes/EtOAc 95:5 to 80:20) to give29.95 g (67%) of ketone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
12.04 g (73%) | With phosphorus tribromide In diethyl ether; water | 6 Preparation of Compounds of Formula (b) PREPARATION 6 Preparation of Compounds of Formula (b) Preparation of Formula (b) where R1 and R2 are methyl, and R5 and R6 are hydrogen To 10.5 ml (10.2 g, 0.1 mol) of 3-hydroxy-3-methyl-2-butanone at -5° C. was added dropwise phosphorus tribromide (3.75 ml, 0.04 mol). After one hour of stirring at room temperature, the mixture was cooled and treated with water and diethyl ether. The organics were separated, washed with water, then dried and evaporated to obtain 12.04 g (73%) of crude 3-bromo-3-methyl-2-butanone as an oil, 1 H NMR (CDCl3): δ1.9 (s,3H), 2.45 (s,3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | General procedure: A mixture of 3-hydroxy-3-methylbutan-2-one 1 (10 mmol) and the substituted cyanoacetamides 2a-d (10 mmol) with a solution of sodium ethoxide (0.5 mmol) in ethanol (10 mL) was stirred at room temperature. After evaporation of the solvent, the residue was acidified with 6 M aqueous HCl. The mixture was neutralised with a solution of potassium carbonate (10%), then extracted with CH2Cl2 (3×25 mL). The combined organic layers were dried on MgSO4, filtered and concentrated in vacuum. The recovered solid was recrystallised in ethanol to provide compounds 3a-d. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | Stage #1: 1-cyanoacetylpiperidine; 3-Hydroxy-3-methyl-2-butanone With sodium ethanolate In ethanol at 20℃; for 24h; Stage #2: With hydrogenchloride; water Stage #3: With potassium carbonate In water | 4.3. General procedure 2: synthesis of N-alkyl-2,5-dihydro-2-imino-4,5,5-trialkylfuran-3-carboxamide 3a-d General procedure: A mixture of 3-hydroxy-3-methylbutan-2-one 1 (10 mmol) and the substituted cyanoacetamides 2a-d (10 mmol) with a solution of sodium ethoxide (0.5 mmol) in ethanol (10 mL) was stirred at room temperature. After evaporation of the solvent, the residue was acidified with 6 M aqueous HCl. The mixture was neutralised with a solution of potassium carbonate (10%), then extracted with CH2Cl2 (3×25 mL). The combined organic layers were dried on MgSO4, filtered and concentrated in vacuum. The recovered solid was recrystallised in ethanol to provide compounds 3a-d. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With lithium hydroxide In methanol; water at 80℃; for 18h; | |
51% | With lithium hydroxide monohydrate In methanol; water at 80℃; for 18h; | 3 Example 3: Preparation of (1E)-4-hydroxy-1-mesityl-4-methylpent-1-en-3-one Example 3: Preparation of (IE) -4-Hydroxy-l-mesityl-4- methylpent-1-en-3-oneMesityl aldehyde (4.5 ml, 30.0 mmol), 3-hydroxy-3-methyl- 2-butanone (3.5 ml, 30.0 mmol) and LiOH»H20 (0.84 g, 20.0 mmol) were dissolved in a mixture of methanol (60 ml) and water (20 ml) and the reaction mixture was heated to 80 °C for 18 hours. Methanol was removed under reduced pressure and the remaining aqueous phase was extracted with dichloromethane (3 * 50 ml) . The combined organic layers were dried (sodium sulfate), filtered, and concentrated in vacuo. The crude product was purified by column chromatography (silica gel, 20% ethyl acetate in hexane) and finally recrystallized from hexane to give the ' -hydroxyenone (3.54 g, 51%) as a colourless solid.Rf = 0.6 (30% ethyl acetate in hexane);13C NMR (100 MHz, CDC13) : δ [ppm] = 202.4, 143.8, 138.9, 137.2, 130.9, 129.3, 123.7, 75.3, 26.3, 21.1;XH NMR (400 MHz, CDC13) : δ [ppm] = 8.02 (d, J = 16.0 Hz, 1 H), 6.91 (s, 2 H), 6.67 (d, J = 16.0 Hz, 1 H) , 4.07 (s, 1 H), 2.35 (s, 6 H), 2.29 (s, 3 H), 1.44 (s, 6 H) ;HRMS (ESI): calculated for [Ci5H20O2+H+] : m/z = 233.1536, found: m/z = 233.1539;IR (v/cnf1, neat): 3489, 2971, 2945, 2370, 2350, 1673, 1600, 1464, 1441, 1154; mp : 75-77 °C (hexane);Elementary analysis: calculated for Ci5H2o02 : [C] 77.55%, [H] 8.68%, [0] 13.77%; found: [C] 77.51%, [H] 8.65%, [O] 13.67%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With sodium methylate In methanol at 35 - 40℃; for 5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | General procedure: In a round-bottomed flask equipped with a condenser, a mixture of alpha-hydroxyketone 3 (3 mmol), diethyl malonate (480 mg, 3 mmol) and a solution of sodium ethoxide (6 mmol) in ethanol (3.9 mL) was stirred at 20 C for 30 min; then 1,3,5-<strong>[290-87-9]triazine</strong> (240 mg, 3 mmol) was added and stirred for 3 h. After addition of alkyl halide (3 mmol), the reaction was then allowed to proceed under stirring under different conditions proper to every compound. The mixture was then concentrated in vacuum and the residue was extracted by dichloromethane (2×15 mL). The combined organic layers were dried on MgSO4, filtered and evaporated and the residue was crystallised from ethanol-chloroform to afford the corresponding N-alkylCerpegin 1,6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | General procedure: In a round-bottomed flask equipped with a condenser, a mixture of alpha-hydroxyketone 3 (3 mmol), diethyl malonate (480 mg, 3 mmol) and a solution of sodium ethoxide (6 mmol) in ethanol (3.9 mL) was stirred at 20 C for 30 min; then 1,3,5-<strong>[290-87-9]triazine</strong> (240 mg, 3 mmol) was added and stirred for 3 h. After addition of alkyl halide (3 mmol), the reaction was then allowed to proceed under stirring under different conditions proper to every compound. The mixture was then concentrated in vacuum and the residue was extracted by dichloromethane (2×15 mL). The combined organic layers were dried on MgSO4, filtered and evaporated and the residue was crystallised from ethanol-chloroform to afford the corresponding N-alkylCerpegin 1,6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | General procedure: In a round-bottomed flask equipped with a condenser, a mixture of alpha-hydroxyketone 3 (3 mmol), diethyl malonate (480 mg, 3 mmol) and a solution of sodium ethoxide (6 mmol) in ethanol (3.9 mL) was stirred at 20 C for 30 min; then 1,3,5-<strong>[290-87-9]triazine</strong> (240 mg, 3 mmol) was added and stirred for 3 h. After addition of alkyl halide (3 mmol), the reaction was then allowed to proceed under stirring under different conditions proper to every compound. The mixture was then concentrated in vacuum and the residue was extracted by dichloromethane (2×15 mL). The combined organic layers were dried on MgSO4, filtered and evaporated and the residue was crystallised from ethanol-chloroform to afford the corresponding N-alkylCerpegin 1,6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | General procedure: In a round-bottomed flask equipped with a condenser, a mixture of alpha-hydroxyketone 3 (3 mmol), diethyl malonate (480 mg, 3 mmol) and a solution of sodium ethoxide (6 mmol) in ethanol (3.9 mL) was stirred at 20 C for 30 min; then 1,3,5-<strong>[290-87-9]triazine</strong> (240 mg, 3 mmol) was added and stirred for 3 h. After addition of alkyl halide (3 mmol), the reaction was then allowed to proceed under stirring under different conditions proper to every compound. The mixture was then concentrated in vacuum and the residue was extracted by dichloromethane (2×15 mL). The combined organic layers were dried on MgSO4, filtered and evaporated and the residue was crystallised from ethanol-chloroform to afford the corresponding N-alkylCerpegin 1,6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | General procedure: In a round-bottomed flask equipped with a condenser, a mixture of alpha-hydroxyketone 3 (3 mmol), diethyl malonate (480 mg, 3 mmol) and a solution of sodium ethoxide (6 mmol) in ethanol (3.9 mL) was stirred at 20 C for 30 min; then 1,3,5-<strong>[290-87-9]triazine</strong> (240 mg, 3 mmol) was added and stirred for 3 h. After addition of alkyl halide (3 mmol), the reaction was then allowed to proceed under stirring under different conditions proper to every compound. The mixture was then concentrated in vacuum and the residue was extracted by dichloromethane (2×15 mL). The combined organic layers were dried on MgSO4, filtered and evaporated and the residue was crystallised from ethanol-chloroform to afford the corresponding N-alkylCerpegin 1,6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | General procedure: In a round-bottomed flask equipped with a condenser, a mixture of alpha-hydroxyketone 3 (3 mmol), diethyl malonate (480 mg, 3 mmol) and a solution of sodium ethoxide (6 mmol) in ethanol (3.9 mL) was stirred at 20 C for 30 min; then 1,3,5-<strong>[290-87-9]triazine</strong> (240 mg, 3 mmol) was added and stirred for 3 h. The mixture was then concentrated in vacuum and neutralized with HCl solution (18%). The mixture was extracted by chloroform (3×10 mL). The combined organic layers were dried on MgSO4, filtered and evaporated and the residue was purified on a silica column (EtOH/CH2Cl2: 5/95) to afford the corresponding NH-Cerpegin 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | General procedure: In a round-bottomed flask equipped with a condenser, a mixture of alpha-hydroxyketone 3 (3 mmol), diethyl malonate (480 mg, 3 mmol) and a solution of sodium ethoxide (6 mmol) in ethanol (3.9 mL) was stirred at 20 C for 30 min; then 1,3,5-<strong>[290-87-9]triazine</strong> (240 mg, 3 mmol) was added and stirred for 3 h. After addition of alkyl halide (3 mmol), the reaction was then allowed to proceed under stirring under different conditions proper to every compound. The mixture was then concentrated in vacuum and the residue was extracted by dichloromethane (2×15 mL). The combined organic layers were dried on MgSO4, filtered and evaporated and the residue was crystallised from ethanol-chloroform to afford the corresponding N-alkylCerpegin 1,6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With sodium acetate; In ethanol; at 20℃; for 4h;Inert atmosphere; | O-tert-Butylhydroxylamine hydrochloride (16.0 g, 0.13 mol), sodium acetate (19.3 g, 0.23 mol) and 3-hydroxy-3-methyl-2-butanone (12.0 g, 0.12 mol) were added to 100 mL of ethanol at room temperature. After stirring for 4 h, the reaction mixture was concentrated and extracted with ethyl acetate. The organic layer was washed with water and dried over magnesium sulfate. The solvent was evaporated to give the crude product which was purified by distillation (86 C/30 Torr) to afford L2H as a colorless liquid. Yield 16.0 g (77%). FT-IR (numax, cm-1): 3428 (s), 2978 (s), 2932 (s), 1639 (w), 1457 (m), 1364 (s), 1241 (m), 1195 (s), 1174 (s), 1145 (s), 1013 (s), 988 (m), 952 (s), 858 (s), 788 (w), 721 (w), 591 (w), 565 (w), 541 (w), 476 (w), 441 (w). 1H NMR (CDCl3, 300 MHz): deltaH 1.26 (s, 9H, CNOC(CH3)3), 1.26 (s, 6H, (CH3)2COH), 1.66 (s, 1H, -OH), 1.72 (s, 3H, CH3CNO). 13C NMR (C6D6, 75 MHz): deltaC 10.2 (CH3CNO), 27.6 (CH3CNOC(CH3)3), 28.2 ((CH3)2COH), 72.6 ((CH3)2COH), 78.2 (CH3CNOC(CH3)3), 159.9 (CH3CNOC(CH3)3). Anal. Calc. for C9H19NO2: C, 62.3; H, 11.1; N, 8.1. Found: C, 61.4; H, 11.1; N, 7.6%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40.7% | With tris-(dibenzylideneacetone)dipalladium(0); 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; sodium t-butanolate In tetrahydrofuran at 65℃; for 3.5h; | 8.1 Step 1: 3-hydroxy-1-(4-methoxy-3-(3-methoxypropoxy)phenyl)-3-methylbutan-2-one [8.1a] Step 1: 3-hydroxy-1-(4-methoxy-3-(3-methoxypropoxy)phenyl)-3-methylbutan-2-one [8.1a] A 200 mL round-bottomed flask was charged with 4-bromo-1-methoxy-2-(3-methoxypropoxy)benzene (13.0 g, 47.2 mmol), NaOt-Bu (13.62 g, 142 mmol), xantphos (0.820 g, 1.417 mmol), Pd2dba3 (0.649 g, 0.709 mmol) and THF (Volume: 140 mL). To the mixture was added 3-hydroxy-3-methylbutan-2-one (9.65 g, 94 mmol). The flask was fitted with a reflux condenser and the mixture was heated to 65° C. in an aluminum chip bath for 3.5 h. After cooling, the mixture was filtered through diatomaceous earth with EtOAc and water washes. The pH of the aqueous layer was adjusted to 2, the layers were separated, and the aqueous layer extracted twice with EtOAc. The combined organic layers were dried over Na2SO4, filtered, and concentrated onto 6 g diatomaceous earth. The material was purified by silica gel column chromatography, EtOAc/heptane 0 to 70% to give product (5.7 g, 19.23 mmol, 40.7% yield). LC-MS (m/z): 297.3 [M+H]+. |
28 g | With tris-(dibenzylideneacetone)dipalladium(0); 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; sodium t-butanolate In tetrahydrofuran at 60℃; for 8h; Inert atmosphere; | 20.2 Step 2: Preparation of 3-hydroxy-l-[4-methoxy-3-(3-methoxypropoxy)phenyl]-3- methyl-biitan-2-one To a solution of 4-bromo- l-methoxy-2-(3-methoxypropoxy)benzene (27.9 g, 0. 1 mol) in THF ( 300 ml. ) was added 3-hydroxy-3-methyl-butan-2-one ( 20 g, 0.2 mol), Pd2(dba)3 (1 .37 g, 1 .5 mmol ), Xantphos ( 1.74 g, 3.0 mmol ) and sodium /tvv-butoxidc (28 g, 0.3 mol ). The resulting mixture was stirred for 8 h at 60 °C under argon atmosphere. After being cooled to rt, the resulting suspension was filtered with suction. The filter cake was poured into water. The resulting mixture was acidified to pH=3 with 2 M hydrochloride acid, and then extracted with ethyl acetate (400 ml. ) 2 times. The combined organic layers were washed with water (200 111L) and brine, dried over anhydrous Na2S04 and concentrated to give 3 -hydroxy- l-[4-methoxy-3 - (3-methoxypropoxy) phenyl ]-3-methyl-butan-2-one (28 g) as a yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 84 %Spectr. 2: 84 %Spectr. | With silver carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In chloroform at 60℃; for 18h; | |
1: 85 %Spectr. 2: 82 %Spectr. | With silver(l) oxide; N,N,N',N'-tetramethylguanidine In acetonitrile at 80℃; for 12h; Autoclave; | |
1: 98 %Spectr. 2: 97 %Spectr. | With silver nitrate; 1-ethyl-3-methylimidazolium acetate at 60℃; for 18h; Schlenk technique; | 2.3. General procedures for the synthesis of 2-oxazolidinones and ahydroxylketones General procedure: The synthesis of 2-oxazolidinones and a-hydroxyl ketones wasperformed in a 15 mL Schlenk tube. AgNO3 (0.0125 mmol,0.25 mol%), [C2C1im][OAc] (6 mmol), 2-aminoethanols (5 mmol)and propargyl alcohols (7.5 mmol) were first added. Then the systemwas purged with CO2 three times and the mixture was stirredat 60 °C under 0.1 MPa of CO2 for 12 h. Afterwards, the mixture wasextracted with diethyl ether (5 x 10 mL) and the upper layers werecollected and concentrated under vacuum to give the raw products,which were further purified by column chromatography on silicagel using petroleum ether/ethyl acetate (v/v, 5:1-1:1) as the eluent.When the recyclability of the catalytic system was investigated, thelower layer was recycled and reused directly for the next roundafter drying under vacuum at 60 °C for 4 h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98%; 91%Chromat. | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride; In acetonitrile; at 80℃; under 15001.5 Torr; for 24h;Autoclave; Sealed tube; | General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 4a (76.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 C) and the autoclave was heated at this temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. The mixture was diluted with EtOAc, and the yield of cyclic carbonate 5a and alpha-hydroxy ketone 6a was determined by gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m * 0.25 mum) using a flame ionization detector using biphenyl (40 mg) as the internal standard. Then, the residue was obtained by removing the solvent under vacuum and further purified by column chromatography (petroleum ether/EtOAc 100:1-5:1) to obtain 5a and 6a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 95% 2: 67 %Chromat. | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride In acetonitrile at 80℃; for 24h; Autoclave; Sealed tube; chemoselective reaction; | 4-Methyl-1,3-dioxolan-2-one (5a); Typical Procedure (Table 2) General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 4a (76.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 °C) and the autoclave was heated at this temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. The mixture was diluted with EtOAc, and the yield of cyclic carbonate 5a and α-hydroxy ketone 6a was determined by gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m * 0.25 µm) using a flame ionization detector using biphenyl (40 mg) as the internal standard. Then, the residue was obtained by removing the solvent under vacuum and further purified by column chromatography (petroleum ether/EtOAc 100:1-5:1) to obtain 5a and 6a. 4-Methyl-1,3-dioxolan-2-one (5a) Colorless liquid; yield: 98 mg (95%). 1H NMR (400 MHz, CDCl3): δ = 4.84-4.92 (m, 1 H), 4.58 (t, J = 8.4 Hz, 1 H), 4.04 (t, J = 8.4 Hz, 1 H), 1.49 (d, J = 6.0 Hz, 3 H). 13C{1H} NMR (100.6 MHz, CDCl3): δ = 155.1, 73.7, 70.7, 19.4. |
1: 94 %Spectr. 2: 98 %Spectr. | With silver(l) oxide; N,N,N',N'-tetramethylguanidine In acetonitrile at 80℃; for 12h; Autoclave; | |
1: 98 %Spectr. 2: 92 %Spectr. | Stage #1: carbon dioxide; 2-methyl-but-3-yn-2-ol With C15H18N2O2 In acetonitrile at 25℃; for 24h; Inert atmosphere; Schlenk technique; Stage #2: propylene glycol With 1-methyl-2,3,4,6,7,8-hexahydro-1H-pyrimido[1,2-a]pyrimidine In acetonitrile at 80℃; for 24h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With sodium methylate; In methanol; at 50℃; for 18h; | Sodium (70 mg, 3.04 mmol) was slowly added at 0 C to dry methanol(5 mL). After complete dissolution, 3-hydroxy-3-methyl-butan-2-one 4 (1.05 mL, 10 mmol) and ethyl phenylsulfonylacetate (2.51 g,11 mmol) were added at 0 C. The mixture was then heated at 50 Covernight. After cooling to room temperature, the solvent was removedunder reduced atmosphere to give an oily residue. Et2O was added toprecipitate the product. The solid was filtered, washed with Et2O anddried. Recrystallization in a mixture Et2O/EtOAc (40 mL/4 mL) gavecompound J as white solid (1.5 g, 56%); m. p. 172 C; 1H NMR (CDCl3,300 MHz, delta/ppm) 8.08 (d, J=7.5 Hz, 2H), 7.66 (t, J=7.3 Hz, 1H),7.56 (t, J=7.2 Hz, 2H), 2.51 (s, 3H), 1.47 (s, 6H). 13C NMR (CDCl3,101 MHz, delta/ppm) 179.1, 164.7, 139.4, 134.4, 129.3, 128.8, 126.9,86.7, 24.3, 12.6. IR (nu/cm-1) 1746, 1320, 1311, 1266, 1149, 1084,1029, 719, 685. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 97% 2: 65 %Chromat. | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride In acetonitrile at 80℃; for 24h; Autoclave; Sealed tube; chemoselective reaction; | 4-Methyl-1,3-dioxolan-2-one (5a); Typical Procedure (Table 2) General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 4a (76.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 °C) and the autoclave was heated at this temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. The mixture was diluted with EtOAc, and the yield of cyclic carbonate 5a and α-hydroxy ketone 6a was determined by gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m * 0.25 µm) using a flame ionization detector using biphenyl (40 mg) as the internal standard. Then, the residue was obtained by removing the solvent under vacuum and further purified by column chromatography (petroleum ether/EtOAc 100:1-5:1) to obtain 5a and 6a. |
89 %Spectr. | Stage #1: carbon dioxide; 2-methyl-but-3-yn-2-ol With C15H18N2O2 In acetonitrile at 25℃; for 24h; Inert atmosphere; Schlenk technique; Stage #2: 1,2-dihydroxybutane With 1-methyl-2,3,4,6,7,8-hexahydro-1H-pyrimido[1,2-a]pyrimidine In acetonitrile at 25℃; for 24h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67%Chromat.; 98% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride; In acetonitrile; at 80℃; under 7500.75 Torr; for 24h;Autoclave; Sealed tube; | General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 4a (76.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 C) and the autoclave was heated at this temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. The mixture was diluted with EtOAc, and the yield of cyclic carbonate 5a and alpha-hydroxy ketone 6a was determined by gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m * 0.25 mum) using a flame ionization detector using biphenyl (40 mg) as the internal standard. Then, the residue was obtained by removing the solvent under vacuum and further purified by column chromatography (petroleum ether/EtOAc 100:1-5:1) to obtain 5a and 6a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69%Chromat.; 98% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride; In acetonitrile; at 80℃; under 7500.75 Torr; for 24h;Autoclave; Sealed tube; | General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 4a (76.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 C) and the autoclave was heated at this temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. The mixture was diluted with EtOAc, and the yield of cyclic carbonate 5a and alpha-hydroxy ketone 6a was determined by gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m * 0.25 mum) using a flame ionization detector using biphenyl (40 mg) as the internal standard. Then, the residue was obtained by removing the solvent under vacuum and further purified by column chromatography (petroleum ether/EtOAc 100:1-5:1) to obtain 5a and 6a. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 94% 2: 67 %Chromat. | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride In acetonitrile at 80℃; for 24h; Autoclave; Sealed tube; chemoselective reaction; | 4-Methyl-1,3-dioxolan-2-one (5a); Typical Procedure (Table 2) General procedure: A 50-mL stainless steel autoclave equipped with a magnetic stir bar was charged with ZnCl2 (27.2 mg, 20 mol%), DBU (76 mg, 50 mol%), 4a (76.1 mg, 1 mmol), 2a (126.1 mg, 1.5 mmol), and CH3CN (2.0 mL) successively and sealed at r.t. The pressure was adjusted to 1 MPa with CO2 at the preset temperature (80 °C) and the autoclave was heated at this temperature for 24 h. After the reaction was complete, the reactor was cooled in ice-water bath, and then excess CO2 was carefully vented. The mixture was diluted with EtOAc, and the yield of cyclic carbonate 5a and α-hydroxy ketone 6a was determined by gas chromatograph (Agilent 6890) equipped with a capillary column (HP-5 30 m * 0.25 µm) using a flame ionization detector using biphenyl (40 mg) as the internal standard. Then, the residue was obtained by removing the solvent under vacuum and further purified by column chromatography (petroleum ether/EtOAc 100:1-5:1) to obtain 5a and 6a. |
89 %Spectr. | Stage #1: carbon dioxide; 2-methyl-but-3-yn-2-ol With C15H18N2O2 In acetonitrile at 25℃; for 24h; Inert atmosphere; Schlenk technique; Stage #2: 1,2-Cyclohexanediol With 1-methyl-2,3,4,6,7,8-hexahydro-1H-pyrimido[1,2-a]pyrimidine In acetonitrile at 25℃; for 24h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 69 %Chromat. 2: 71 %Chromat. | With 1,8-diazabicyclo[5.4.0]undec-7-ene; zinc(II) chloride In acetonitrile at 80℃; for 24h; Autoclave; Sealed tube; | |
1: 76 %Chromat. 2: 80 %Chromat. | With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 120℃; for 10h; Autoclave; | General procedure for the reaction of vicinal diols, propargylic alcohols and CO2 General procedure: The reactions were performed in a 50 ml autoclave with a Teflon vessel inside equipped with magnetic stirring under 3.0 MPa CO2. After introducing DBU (60.8 mg, 0.4 mmol), propylene glycol (76.1 mg, 1 mmol), 2-methyl-3-butyn-2-ol (126.2 mg, 1.5 mmol), DMF (2 ml), the autoclave was sealed and filled with CO2 to keep thepressure of CO2 under 3.0 MPa. Then, the reaction mixture was stirred at 120 °C for 10 h. When the reaction completed, the autoclave was cooled to ambient temperature and residual CO2 was carefully released. Subsequently, the mixture was flushed with DMF and analyzed by GC using biphenyl as an internal standard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: sodium hydride / diethyl ether; mineral oil / 1 h / 20 °C / Cooling with ice; Inert atmosphere 1.2: 4 h / 20 °C 2.1: copper(II) sulfate; magnesium sulfate; hydrogenchloride / water; diethyl ether / 48 h / 20 °C 3.1: palladium 10% on activated carbon; hydrogen / acetic acid methyl ester / 6 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium ethanolate; sodium In ethanol at 55℃; for 0.5h; Microwave irradiation; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 3-Hydroxy-3-methyl-2-butanone; 2,2,3,3-tetrafluorobutane-1,4-diol In chloroform at 23℃; for 0.5h; Stage #2: With sulfuric acid In chloroform at 60℃; for 6h; Molecular sieve; Stage #3: With potassium carbonate In chloroform at 23℃; for 0.5h; Molecular sieve; | 2 Example 2: Synthesis of salt represented by formula (I-6) 6.39 parts of compound represented by formula (I-6-a), compound represented by formula (I-1-b) 15. After charging 22 parts and 100 parts of chloroform and stirring at 23 ° C. for 30 minutes, 0.61 part of sulfuric acid was charged, refluxed at 60 ° C. for 6 hours in the presence of molecular sieve, and then cooled to 23 ° C. To the obtained reaction product, 65 parts of a 10% aqueous potassium carbonate solution was added, and the mixture was stirred at 23 ° C. for 30 minutes. Then, it was allowed to stand and the liquid was separated. 60 parts of ion-exchanged water was added to the recovered organic layer, and the mixture was stirred at 23 ° C. for 30 minutes and separated to recover the organic layer. This washing operation was performed four times. The obtained organic layer is concentrated, and the concentrated mass is separated by a column (silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Inc., developing solvent: n-heptane / ethyl acetate = 10/1). As a result, 12.21 parts of the compound represented by the formula (I-6-c) was obtained. |
Tags: 115-22-0 synthesis path| 115-22-0 SDS| 115-22-0 COA| 115-22-0 purity| 115-22-0 application| 115-22-0 NMR| 115-22-0 COA| 115-22-0 structure
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Precautionary Statements-General | |
Code | Phrase |
P101 | If medical advice is needed,have product container or label at hand. |
P102 | Keep out of reach of children. |
P103 | Read label before use |
Prevention | |
Code | Phrase |
P201 | Obtain special instructions before use. |
P202 | Do not handle until all safety precautions have been read and understood. |
P210 | Keep away from heat/sparks/open flames/hot surfaces. - No smoking. |
P211 | Do not spray on an open flame or other ignition source. |
P220 | Keep/Store away from clothing/combustible materials. |
P221 | Take any precaution to avoid mixing with combustibles |
P222 | Do not allow contact with air. |
P223 | Keep away from any possible contact with water, because of violent reaction and possible flash fire. |
P230 | Keep wetted |
P231 | Handle under inert gas. |
P232 | Protect from moisture. |
P233 | Keep container tightly closed. |
P234 | Keep only in original container. |
P235 | Keep cool |
P240 | Ground/bond container and receiving equipment. |
P241 | Use explosion-proof electrical/ventilating/lighting/equipment. |
P242 | Use only non-sparking tools. |
P243 | Take precautionary measures against static discharge. |
P244 | Keep reduction valves free from grease and oil. |
P250 | Do not subject to grinding/shock/friction. |
P251 | Pressurized container: Do not pierce or burn, even after use. |
P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
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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