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CAS No. : | 1180-71-8 | MDL No. : | MFCD00075922 |
Formula : | C26H30O8 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | KBDSLGBFQAGHBE-MSGMIQHVSA-N |
M.W : | 470.51 | Pubchem ID : | 179651 |
Synonyms : |
Limonoic acid 3,19:16,17 dilactone;di-δ-lactone Limonoic Acid;Obaculactone.;NSC 36508;Limonine;Evodin;Dictamnolactone;Citro
|
Chemical Name : | (4aS,6aR,8aR,8bR,9aS,12S,12aS,14aR,14bR)-12-(Furan-3-yl)-6,6,8a,12a-tetramethyldecahydrooxireno[2,3-d]pyrano[4',3':3,3a]isobenzofuro[5,4-f]isochromene-3,8,10(1H,6H,8aH)-trione |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: at 60℃; for 3 h; Stage #2: With sodium tetrahydroborate In tetrahydrofuran; methanol at 0℃; for 1 h; |
0 ° C to acetic anhydride (100 mL) Slowly adding chromium trioxide (11 g, 110 mmol), To be stirred until orange, The addition of the raw material Obacunone (45 g, 99.1 mmol) And the temperature was raised to 60 ° C. The reaction was continued for 3 hours. TLC (PE: EA = 2: 1) was used to monitor the reaction end. After completion of the reaction, the reaction solution was concentrated and the concentrate was separated by ethyl acetate (200 mL) and water (200 mL) The organic phase was dried over magnesium sulfate and concentrated. Intermediate 2 (46.0 g, 98.2 mmol) was dissolved in tetrahydrofuran (200 mL) and methanol (20 mL). Sodium borohydride (6.0 g, 150 mmol) was slowly added at 0 ° C, TLC (PE: EA = 1: 1) showed the end of the reaction, the reaction was concentrated and the concentrate was extracted with ethyl acetate (200 mL), and the reaction was concentrated at 0 ° C for 1 hour. ), Washed successively with saturated sodium bicarbonate (100 mL), water (100 mL), and saturated brine (100 mL). The organic phase was concentrated by drying over magnesium sulfate and the remaining crude product was purified by flash silica gel to give intermediate 3 (33.0 g, 70.2 mmol) was dissolved in tetrahydrofuran (100 mL), and the eluent was petroleum ether (PE): ethyl acetate (EA) = 1: 1; And methanol (100 mL) were added lithium hydroxide (2.4 g, 100 mmol). The reaction was stirred at room temperature for 3 hours. TLC (PE: EA = 1: 1) showed that the reaction material disappeared and the reaction product was adjusted to pH = 5 to 6, ethyl acetate (2 x 100 mL). The combined organic phases were dried over magnesium sulfate, filtered and concentrated to give crude intermediate 4 (24.0 g, 71percent yield). Intermediate 4 (24.0 g, 49.2 (DE) (10.5 g, 60.0 mmol) was added dropwise to a solution of anhydrous tetrahydrofuran (300 mL) under nitrogen,15.7 g, 60.0 mmol) was added and the reaction was stirred at room temperature under nitrogen for 16 hours. TLC (PE: EA = 1: 1) was monitored and the reaction was complete. After completion of the reaction, the mixture was washed with saturated brine (3 x 50 mL) The organic phase was concentrated by suction over magnesium sulfate and the resulting residue was purified by flash silica gel column to give intermediate 5 (18.0 g, yield 78percent). The eluent was petroleum ether (PE): ethyl acetate (EA) 2: 1; Intermediate 5 (18.0 g, 38.3 mmol) was dissolved in anhydrous tetrahydrofuran (200 mL) and a solution of borane tetrahydrofuran (50 mL, 1 M in THF, 50 mmol) was slowly added dropwise. After stirring for 16 hours, H2O2 (50 mL) and saturated sodium bicarbonate solution (50 mL) were added to the reaction solution. The reaction was continued at room temperature for 2 hours. The reaction solution was separated and the aqueous phase was passed through ethyl acetate (3 x 50 mL), the combined organic phases were dried over magnesium sulfate and concentrated by filtration. The resulting residue was purified by flash silica gel column to give product intermediate 6 (11.0 g, yield 58percent) eluting with petroleum ether (PE): ethyl acetate (EA) = 4: 1; (DE) (5.9 g, 33.8 mmol), triphenylphosphine (8.9 g, 33 mmol) were added in anhydrous tetrahydrofuran (300 mL) under nitrogen under reduced pressure (11.0 g, 22.5 mmol) 33.8 mmol). The reaction was stirred at room temperature under nitrogen for 16 hours. TLC (PE: EA = 1: 1) was monitored. The reaction was complete and washed with saturated brine (3 x 50 mL). The organic phase was dried over magnesium sulfate The resulting residue was recrystallized from ethanol to give the final product limonin (8.0 g, yield 76percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With pyridine; hydroxylamine hydrochloride; In ethanol; for 2.5h;Reflux; | 1.0 g (0.002 mol) of <strong>[1180-71-8]limonin</strong> (III) was added to a 100 ml eggplant flask,Hydrochloric acid hydroxylamine 1.1 g (0.016 mol)Anhydrous ethanol 45ml,Pyridine 15ml,Heated to reflux for 2.5 h.Thin layer chromatography (TLC)After the reaction was complete, the reaction solution was cooled to room temperature,Pour it into the pre-configured 5% dilute hydrochloric acid 125ml,Adjust its pH for the acid, ice water cooling.The aqueous layer was extracted three times with 50 ml of dichloromethane and the combined extracts were washed three times with saturated brine and dried over anhydrous sodium sulfate.Filtration and evaporation of the solvent under reduced pressure.The crude product was chromatographed on dichloromethane: methanol (125: 1)0.98 g of a white solid, 95% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Microwave irradiation; Sealed tube; | To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
75% | In tetrahydrofuran; for 24h;Reflux; | <strong>[1180-71-8]Limonin</strong> (1 g, 2.13 mmol) was added to a 100 mL three-neck flask. Benzylamine (1.37 g, 12.78 mmol) and tetrahydrofuran (30 mL) were refluxed for 24 hours. The reaction was complete by TLC and a portion of the solvent was evaporated under reduced pressure. Add 100mL of water to the residue, The pH was adjusted to acidic with 5% dilute hydrochloric acid, the aqueous layer was extracted three times with dichloromethane (80 mL×3), and the organic layers were combined. The saturated saline solution was washed three times (100 mL x 3) and dried over anhydrous sodium sulfate. Filter and remove the solvent under reduced pressure. The crude product was purified by column chromatography (dichloromethane:methanol = 100:1) to give 0.92 g of a white solid (I-4) in a 75% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With montmorillonite K-10; In dichloromethane; for 10h;Sonication; | General procedure: To a round-bottom flask was added montmorilloniteK-10 (0.3 g mmol-1), and 1 (2.0 mmol) in CH2Cl2 wasdispersed on K-10. Then the appropriate amine (3.6 mmol)was added dropwise and the mixture was sonicatedin an ultrasonic bath; the progress of the reaction wasmonitored by TLC and after completion of the reaction(10-12 h), the products were extracted by washing theK-10 with CH2Cl2. The organic phase was dried withNa2SO4, filtered and the solvent was removed in vacuo toyield the crude products. The crude products were purifiedby column chromatography over silica gel using 2-5%EtOH-CH2Cl2 as eluent to give analytically pure products3a-o. The products were characterized by correspondingspectroscopic data (1H and 13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With montmorillonite K-10; In ethanol; at 80℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH (8.0 mL)in a glass tube was added dropwise the appropriate amine(3.6 mmol) and K-10 (0.3 g mmol-1); the quartz tubewas sealed with reaction mixture and introduced intoa microwave oven. The flask was irradiated for 30 min(150 W) the temperature of 80 C. After completion of thereaction the mixture was filtered, the organic phase wasdried with Na2SO4, filtered and the solvent was evaporatedunder reduced pressure to give the crude products. All thecompounds were purified by column chromatographyon silica gel using 2-5% EtOH-CH2Cl2 as eluent to giveanalytically pure products 3a-m. The products werecharacterized by corresponding spectroscopic data (1H and13C NMR, and HRMS). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With montmorillonite K-10; In ethanol; for 12h;Reflux; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH(8.0 mL) in round-bottom flask (equipped with a refluxcondenser and recirculating chiller) was added dropwisethe appropriate amine (3.6 mmol) and K-10 (0.3 g mmol-1)and stirred. The reaction mixture was then heated at refluxand the progress of the reaction was monitored by TLC.After completion of the reaction (12-36 h), the mixturewas filtered, the organic phase was dried with Na2SO4,filtered and the solvent was evaporated under reducedpressure to give the crude products. All compounds werepurified by column chromatography on silica gel using2-5% EtOH-CH2Cl2 as eluent to give analytically pureproducts 3a-o. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With montmorillonite K-10; In ethanol; for 24h;Reflux; | General procedure: To a solution of 1 (2.0 mmol) in absolute EtOH(8.0 mL) in round-bottom flask (equipped with a refluxcondenser and recirculating chiller) was added dropwisethe appropriate amine (3.6 mmol) and K-10 (0.3 g mmol-1)and stirred. The reaction mixture was then heated at refluxand the progress of the reaction was monitored by TLC.After completion of the reaction (12-36 h), the mixturewas filtered, the organic phase was dried with Na2SO4,filtered and the solvent was evaporated under reducedpressure to give the crude products. All compounds werepurified by column chromatography on silica gel using2-5% EtOH-CH2Cl2 as eluent to give analytically pureproducts 3a-o. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | 0 ° C to acetic anhydride (100 mL) Slowly adding chromium trioxide (11 g, 110 mmol), To be stirred until orange, The addition of the raw material Obacunone (45 g, 99.1 mmol) And the temperature was raised to 60 ° C. The reaction was continued for 3 hours. TLC (PE: EA = 2: 1) was used to monitor the reaction end. After completion of the reaction, the reaction solution was concentrated and the concentrate was separated by ethyl acetate (200 mL) and water (200 mL) The organic phase was dried over magnesium sulfate and concentrated. Intermediate 2 (46.0 g, 98.2 mmol) was dissolved in tetrahydrofuran (200 mL) and methanol (20 mL). Sodium borohydride (6.0 g, 150 mmol) was slowly added at 0 ° C, TLC (PE: EA = 1: 1) showed the end of the reaction, the reaction was concentrated and the concentrate was extracted with ethyl acetate (200 mL), and the reaction was concentrated at 0 ° C for 1 hour. ), Washed successively with saturated sodium bicarbonate (100 mL), water (100 mL), and saturated brine (100 mL). The organic phase was concentrated by drying over magnesium sulfate and the remaining crude product was purified by flash silica gel to give intermediate 3 (33.0 g, 70.2 mmol) was dissolved in tetrahydrofuran (100 mL), and the eluent was petroleum ether (PE): ethyl acetate (EA) = 1: 1; And methanol (100 mL) were added lithium hydroxide (2.4 g, 100 mmol). The reaction was stirred at room temperature for 3 hours. TLC (PE: EA = 1: 1) showed that the reaction material disappeared and the reaction product was adjusted to pH = 5 to 6, ethyl acetate (2 x 100 mL). The combined organic phases were dried over magnesium sulfate, filtered and concentrated to give crude intermediate 4 (24.0 g, 71percent yield). Intermediate 4 (24.0 g, 49.2 (DE) (10.5 g, 60.0 mmol) was added dropwise to a solution of anhydrous tetrahydrofuran (300 mL) under nitrogen,15.7 g, 60.0 mmol) was added and the reaction was stirred at room temperature under nitrogen for 16 hours. TLC (PE: EA = 1: 1) was monitored and the reaction was complete. After completion of the reaction, the mixture was washed with saturated brine (3 x 50 mL) The organic phase was concentrated by suction over magnesium sulfate and the resulting residue was purified by flash silica gel column to give intermediate 5 (18.0 g, yield 78percent). The eluent was petroleum ether (PE): ethyl acetate (EA) 2: 1; Intermediate 5 (18.0 g, 38.3 mmol) was dissolved in anhydrous tetrahydrofuran (200 mL) and a solution of borane tetrahydrofuran (50 mL, 1 M in THF, 50 mmol) was slowly added dropwise. After stirring for 16 hours, H2O2 (50 mL) and saturated sodium bicarbonate solution (50 mL) were added to the reaction solution. The reaction was continued at room temperature for 2 hours. The reaction solution was separated and the aqueous phase was passed through ethyl acetate (3 x 50 mL), the combined organic phases were dried over magnesium sulfate and concentrated by filtration. The resulting residue was purified by flash silica gel column to give product intermediate 6 (11.0 g, yield 58percent) eluting with petroleum ether (PE): ethyl acetate (EA) = 4: 1; (DE) (5.9 g, 33.8 mmol), triphenylphosphine (8.9 g, 33 mmol) were added in anhydrous tetrahydrofuran (300 mL) under nitrogen under reduced pressure (11.0 g, 22.5 mmol) 33.8 mmol). The reaction was stirred at room temperature under nitrogen for 16 hours. TLC (PE: EA = 1: 1) was monitored. The reaction was complete and washed with saturated brine (3 x 50 mL). The organic phase was dried over magnesium sulfate The resulting residue was recrystallized from ethanol to give the final product limonin (8.0 g, yield 76percent). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In 1,2-dichloro-ethane; at 85℃; for 16h;Sealed tube; | General procedure: An oven-dried culture tube containing the tetrayne precursor in organic solvent (initial concentration of 0.02-0.03 M) and the indicated number of equivalents of trapping component(s) was closed with a Teflon-lined cap and the solution was heated at 85-90 C for 16 h. The half-life for conversion of each of the polyynes used here to the corresponding benzyne was approx. 3-4 h. The product(s) was separated and purified by chromatography on silica gel. Full experimental details and characterization data for all new compounds (polyyne HDDA substrates andproducts) and a description of the computational methods and results are providedin the Supplementary Information. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | A 1000 ml three-necked flask was charged with <strong>[1180-71-8]limonin</strong> (40.0 g, 85.01 mmol) andDichloromethane (500 mL),Cooled to 0 C with stirring,Aluminum trichloride (51.0 g, 382.5 mmol) was added in portions,After addition, keep stirring 20min,Add 4-chlorobutyryl chloride (14.4 g, 102.0 mmol) dropwiseA mixed solution of dichloromethane (15 mL)Dropwise, maintaining 0 ~ -5 1 hour,The reaction was further stirred at room temperature for 2 hours,Stop the reaction, the reaction solution was slowly poured into 500mL ice water,The methylene chloride layer was separated, the aqueous layer was extracted twice with dichloromethane (300 mL × 2)The combined organic layers were washed three times (300 mL x 3) with 1 mol / L aqueous sodium hydroxide solution,Washed with saturated brine twice (300 mL × 2), dried over anhydrous sodium sulfate, filtered,The solvent was evaporated under reduced pressure.The crude product was purified by column chromatography (methylene chloride: methanol = 160: 1) to give 20.5 g of pale green solid (IV-2) in a yield of 42% | |
42% | General procedure: To a solution of <strong>[1180-71-8]limonin</strong> (1) or deoxy<strong>[1180-71-8]limonin</strong> (6) (17.0 mmol) in CH2Cl2 (125 mL) at 0C was added anhydrous AlCl3 slowly (10.2 g, 76.5 mmol). After stirring the reaction mixture at 0C for 20 min, the acyl chlorides (2.2 g, 19.5 mmol) dissolved in CH2Cl2 (5.0 mL) was added slowly and stirred for another 1 h. The reaction mixture was then warmed to room temperature and stirred for 3 h. After that, the mixture was poured into ice water (100 mL), and extracted with CH2Cl2 (100 mL × 3). The combined organic extracts were then washed with 1N NaOH aqueous solution (100 mL × 3), brine (100 mL × 2), dried over anhydrous Na2SO4 and concentrated under vacuum. The resulting residue was then purified through flash chromatography on silica gel (CH2Cl2/MeOH = 0-1%) to give desired products in 31-53% yields. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
31% | General procedure: To a solution of <strong>[1180-71-8]limonin</strong> (1) or deoxy<strong>[1180-71-8]limonin</strong> (6) (17.0 mmol) in CH2Cl2 (125 mL) at 0C was added anhydrous AlCl3 slowly (10.2 g, 76.5 mmol). After stirring the reaction mixture at 0C for 20 min, the acyl chlorides (2.2 g, 19.5 mmol) dissolved in CH2Cl2 (5.0 mL) was added slowly and stirred for another 1 h. The reaction mixture was then warmed to room temperature and stirred for 3 h. After that, the mixture was poured into ice water (100 mL), and extracted with CH2Cl2 (100 mL × 3). The combined organic extracts were then washed with 1N NaOH aqueous solution (100 mL × 3), brine (100 mL × 2), dried over anhydrous Na2SO4 and concentrated under vacuum. The resulting residue was then purified through flash chromatography on silica gel (CH2Cl2/MeOH = 0-1%) to give desired products in 31-53% yields. 2.2.1.1. 23-Chloroacetyl <strong>[1180-71-8]limonin</strong> (2a) Yield 31%. Light green solid. m.p. > 200oC. 1H NMR (300 MHz, CDCl3) delta 7.62 (s, 1H), 7.24 (s, 1H), 5.50 (s, 1H), 4.77 (d, J = 13.1 Hz, 1H), 4.55 (s, 2H), 4.46 (d, J = 13.0 Hz, 1H), 4.03 (s, 2H), 2.99 (dd, J = 17.0, 3.7 Hz, 1H), 2.93 - 2.79 (m, 1H), 2.68 (d, J = 15.7 Hz, 1H), 2.58 - 2.40 (m, 2H), 2.22 (d, J = 13.0 Hz, 1H), 1.98 - 1.75 (m, 3H), 1.59 - 1.51 (m, 1H), 1.29 (s, 3H), 1.18 (s, 3H), 1.14 (s, 3H), 1.08 (s, 3H). ESI-MS (m/z): 569.2 [M+Na]+. | |
30.2% | A 250 mL three-necked flask was charged with <strong>[1180-71-8]limonin</strong> (8 g, 17 mmol) andDichloromethane (125 mL),Cooled to 0 C with stirring,Aluminum trichloride (10.2 g, 76.5 mmol) was added in portions,Insulation stir for 20 minutes,Chloroacetyl chloride (2.2 g, 19.5 mmol) was added dropwiseDichloromethane (5 mL) was added dropwise,Keep 0 ~ -5 reaction for 1 hour,Stirring was continued at room temperature for 3 hours, the reaction was stopped,The reaction solution was slowly poured into 100mL of ice water, the methylene chloride layer was separated, the aqueous layer was extracted twice with dichloromethane (100mL × 2)The combined organic layers were washed three times with 100 mL × 3 aqueous solution of 1 mol / L sodium hydroxide,Washed with saturated saline twice (100 mL × 2),Dried over anhydrous sodium sulfate, suction filtered and the solvent evaporated under reduced pressure.The crude product was purified by column chromatography (methylene chloride: methanol = 180: 1)2.8 g of light green solid (IV-1) was obtained in a yield of 30.2% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
43% | With ammonium hydroxide; In tetrahydrofuran; at 20℃; for 4h;Cooling with ice; | In a 100 mL three-neck flask, <strong>[1180-71-8]limonin</strong> (1 g, 2,13 mmol) and tetrahydrofuran (30 mL) were added. Aqueous ammonia (20 mL) was added dropwise under ice-cooling conditions. After completion of the dropwise addition, the ice bath was removed and the reaction was completed at room temperature for 4 hours. A part of the solvent was distilled off under reduced pressure. The residue was added with 100 mL of water and the pH was adjusted to acidic with 5% dilute hydrochloric acid. The aqueous layer was extracted three times with dichloromethane (80 mL × 3). The organic layers were combined and washed three times with saturated brine (100 mL × 3) and dried over anhydrous sodium sulfate. Filter and remove the solvent under reduced pressure. The crude product was purified by column chromatography (dichloromethane:methanol = 100:1) to give 0.45 g of a white solid (I-1). The yield was 43%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | In tetrahydrofuran; water; at 20℃; for 4h;Cooling with ice; | In a 100 mL three-neck flask, <strong>[1180-71-8]limonin</strong> (1 g, 2,13 mmol) and tetrahydrofuran (30 mL) were added. Aqueous ammonia (20 mL) was added dropwise under ice-cooling conditions. After completion of the dropwise addition, the ice bath was removed and the reaction was completed at room temperature for 4 hours. A part of the solvent was distilled off under reduced pressure. The residue was added with 100 mL of water and the pH was adjusted to acidic with 5% dilute hydrochloric acid. The aqueous layer was extracted three times with dichloromethane (80 mL × 3). The organic layers were combined and washed three times with saturated brine (100 mL × 3) and dried over anhydrous sodium sulfate. Filter and remove the solvent under reduced pressure. The crude product was purified by column chromatography (dichloromethane:methanol = 100:1) to give 0.45 g of a white solid (I-1). The yield was 43%. Using <strong>[1180-71-8]Limonin</strong> (1) and aqueous methylamine as raw materials, operate the same method as in I-1. The crude product was purified by column chromatography (dichloromethane:methanol = 100:1) to give 0.74 g of a white solid (I-2). The yield was 69%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | In tetrahydrofuran; for 4h;Reflux; | In a 100 mL three-necked flask, limonoid (1 g, 2.13 mmol), N,N-dimethylethylenediamine (1.69 g, 19.19 mmol) and tetrahydrofuran (30 mL) were added and refluxed for 4 hours. The reaction was complete by TLC and a portion of the solvent was evaporated under reduced pressure. The residue was added with 100 mL of water and the pH was adjusted to acidic with 5% dilute hydrochloric acid. The aqueous layer was extracted three times with dichloromethane (80 mL × 3), and the combined organic layer was washed three times with saturated brine (100 mL × 3) and dried over anhydrous sodium sulfate. Filter and remove the solvent under reduced pressure. The crude product was purified by column chromatography (dichloromethane:methanol = 100:1) to give 0.68 g of a white solid (I-11). The yield was 68%. |
Tags: 1180-71-8 synthesis path| 1180-71-8 SDS| 1180-71-8 COA| 1180-71-8 purity| 1180-71-8 application| 1180-71-8 NMR| 1180-71-8 COA| 1180-71-8 structure
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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