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CAS No. : | 120-21-8 | MDL No. : | |
Formula : | C11H15NO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MNFZZNNFORDXSV-UHFFFAOYSA-N |
M.W : | 177.24 | Pubchem ID : | 67114 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H312-H315-H319-H335 | 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 |
---|---|---|
92% | With Aliquat 336; potassium carbonate In dimethyl sulfoxide at 95℃; for 72 h; | 4-fluorobenzaldehyde (2.5 g, 0.02 mol), diethyl amine(5.12 g, 0.07 mol), K2CO3 (4.15 g), DMSO (25.0 mL) and Aliquat-336 (0.05 mL) were added into a one-necked flask (100 mL) fitted with a stirrer and a condenser. The mixture was stirred for 72 h at 95C, and then cooled to room temperature. The yellow precipitation was obtained after ice water wasintroduced into the flask. The crude product was washed with cool water for 2-3 times, and thenrecrystallized from ethanol. Yellow solid (4-diethylaminobenzaldehyde) was obtained. Yield: 92percent.Anal. Calcd. for C11H15NO: C, 74.54; H, 8.53; N, 7.90; Found: C, 74.67; H, 8.58; N, 7.85; 1H NMR(500 MHz, CDCl3, ppm) δ 9.71(s, 1H), 7.72(q, 2H), 6.69 (d, J = 8.8 Hz, 2H), 1.24 (t, 6H), 3.46 (q,4H). The second step: The potassium (0.78 g, 0.02 mol) was introduced into tert-butanol (11.3 mL,0.12 mol) in a 50 mL one-necked flask fitted with a condenser. After fully reaction, 4-picoline (0.975mL, 10 mmol) and 4-diethylaminobenzaldehyde (1.77 g, 10 mmol) were added. The mixture washeated for 2 hours at 80°C under stirring; tert-butanol was evaporated, then added to 200 mLdichloromethane and washed once with 200 mL ice water, stirred. The water phase was extracted withdichloromethane for 3 times. The organic phase was dried on sodium sulfate, solvent was evaporated,and the crude solid was recrystallized in toluene. Yield: 86percent. 1H NMR (500 MHz, DMSO, ppm) δ8.43 (d, J = 5.2 Hz, 2H), 7.42 (t, J = 8.8 Hz, 2H), 7.23 (d, J = 5.4 Hz, 2H), 7.04 (d, J = 8.7 Hz, 2H),6.27-6.66 (m, 2H), 3.39 (m, 4H), 1.13 (t, 6H). 13C NMR (500 MHz, CDCl3, ppm) δ 148.56-146.96 (m,py), 134.57 (s, py), 128.86 (s, benzene) 120.51-119.95 (d, benzene), 111.56 (s, CH=CH), 44.47 (s,CH2), 12.62 (s, CH3). Anal. Calcd. for C17H20N2 (EI-MS: 253.3): C, 80.91; H, 7.99; N, 11.10. Found: C,80.76; H, 7.91; N, 11.01. IR data (KBr, cm−1): 3026 w, 2974 m, 1581 s, 1520 vs, 1408 m, 1355 m,1329 w, 1272 m, 1185 m, 1158 m, 1074 w, 972 w, 818 m, 795 m, 518 w. m.p. 258 °C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | Stage #1: With tin(IV) chloride In dichloromethane at 20℃; for 2 h; Inert atmosphere Stage #2: With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In water; dimethyl sulfoxide at 20℃; for 2 h; |
General procedure: In a round-bottomed flask equipped with a stirring bar and rubber septum was placed a 1 M solution of SnCl4 in anhydrous CH2Cl2 (1 mL, 1 mmol). To this solution was added PhSCF2H (1; 240.2 mg, 1.5 mmol) in anhydrous CH2Cl2 (1.5 mL), followed by a solution of an aromatic compound (0.5 mmol) in anhydrous CH2Cl2 (1 mL). The reaction was allowed to proceed for 2 h before it was quenched with a solution of IBX (140 mg, 0.5 mmol) in DMSO/H2O (4 mL; 3:1 v:v). After 2 h of stirring at rt, the reaction mixture was quenched by addition of a saturated aqueous solution of sodium thiosulfate (10 mL), then basified with a saturated aqueous solution of sodium hydrogen carbonate (10 mL), followed by stirring and extraction with CH2Cl2 (3 × 10 mL). The combined organic layers were washed with water (3 × 10 mL) and brine (10 mL), dried (anhydrous MgSO4), filtered and concentrated (aspirator). The residue was purified by PTLC, radial chromatography or column chromatography to furnish analytically pure product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With piperidine; ethanol | ||
With piperidine In methanesulfonic acid for 4h; Reflux; Inert atmosphere; | 2-[(E)-4-(Diethyl amino) styryl]-1-methyl-pyridinium iodide (B) The title material (B) was prepared by previously reported method [15] . The equimolar ratio of A (7.052 g, 30 mmol) and 4-(N, N-diethyl amino)-benzaldehyde (5.317 g, 30 mmol) in a dried methanol (50 ml) was placed in round bottom flask. After the addition of the above mixture, the piperidine was added as a catalyst and the mixture solution refluxed for 4 h under nitrogen atmosphere. The resulting red precipitate suspension was cooled and then precipitate was filtered off and finally washed with diethyl ether to remove the starting material. The final product was then successively recrystallized using mixture solvent methanol-acetonitrile (1:1). | |
With piperidine In methanol for 6h; Reflux; Inert atmosphere; | 2-[(E)-4-(diethyl amino) styryl]-1-methyl-pyridinium iodide 2 The title material (2) was synthesized according to the previously reported method [16]. To a solution of 1 (2.35 g 10 mmol) in hot methanol (30 ml), 4-diethylamino benzaldehyde (1.8 g 10 mmol), and piperidine (0.98 ml, 10 mmol) were added. Then the mixture solution was refluxed for 6 h under a dry nitrogen atmosphere. Once the reaction was complete, the purple precipitate was filtered off and washed with ether for removal of unreacted starting materials. The title compound 2 was purified by successive recrystallized from methanol (m.p. 256 °C). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With potassium hydroxide; sodium hydroxide In neat (no solvent) Heating; | Synthesis of the p-Aminobenzoic Acids. General Procedure General procedure: Potassium hydroxide (3.6 g, 64 mmol) and sodium hydroxide (2.4 g, 60 mmol) weremixed and quickly crushed in a porcelain dish. Then the corresponding aldehyde(15 mmol) was added and the mixture was heated on a hot-plate under stirring until thealdehyde melted and additionally 5 minutes. When liquid aldehydes were used, heatingwas continued until temperature reached 140C. After cooling, the crude solid productmixture was added to water (100 mL) and ice (30 g) and acidified with hydrochloric acidto pH 4. The precipitate was collected, dried and recrystallized from ethanol. |
With potassium hydroxide; sodium hydroxide | ||
With cross-linked porous conjugated polymer In acetonitrile for 10h; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With piperidine In ethanol for 72h; Reflux; | 1 4.4 Synthesis of 1-alkyl-2-[4-(diethylamino)styryl]pyridinium halides 15-20 General procedure: To an ethanol solution (80 mL) of 1-alkyl-2-methylpyridinium halides 8-13 (8 mmol) were added 4-(diethylamino)benzaldehyde 14 (14.2 g, 8 mmol) and piperidine (a few drops). The mixture was refluxed for 3 days. After the reaction was completed, the reaction mixture was concentrated. The product was purified by column chromatography (SiO2, MeOH-CHCl3) to afford orange to red solid. |
With piperidine In methanol Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 211 3-(4-Diethylamino-benzylamino)-4-methoxy-N-phenyl-benzamide The title compound has been made using the procedure of Example 50, but using 3-amino-4-methoxy-N-phenyl benzamide and 4-diethylaminobenzaldehyde as starting materials, which are commercially available from Aldrich; m.p. 180-181 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34%; 28% | In methanol; for 16h;Heating / reflux; | EXAMPLE 14Synthesis of 4,4'-((4-(diethylamino)phenyl)methylene)jb/s(5-methyl-1 /-/-pyrazol-3(2H)- one) and 4-(4-(diethylamino)benzylidene)-3-methyl-1 A7-pyrazol-5(4H)-one; To a solution of <strong>[132712-71-1]3-methyl-1H-pyrazol-5-ol</strong> (0.50 g, 5.10 mmol) in anhydrous methanol (30 mL) was added 4-(diethylamino)benzaldehyde (0.90 g, 5.10 mmol) and the reaction mixture was heated at reflux for 16 h. The reaction mixture was cooled to ambient temperature, during which time a bright orange precipitate was deposited. The solid was collected by suction filtration, washed with methanol (10 mL), air-dried and dried under high vacuum to afford 4,4'-((4-(diethylamino)phenyl)methylene)b/s(5- methyl-1H-pyrazol-3(2H)-one) in 28% yield (0.26 g): mp 223-224 0C (methanol); 1H NMR (300 MHz,) delta 11.45 (br s, 4H), 6.90 (d, J = 8.8 Hz, 2H), 6.51 (d, J = 8.8 Hz, 2H), 4.66 (s, 1 H), 3.25 (q, J = 7.0 Hz, 4H), 2.07 (s, 6H), 1.02 (t, J = 7.0 Hz, 6H); 13C NMR (75 MHz, DMSO-Gf6) 5 161.4, 145.4, 139.7, 129.9, 128.2, 111.3, 104.9, 43.7, 31.8, 12.5, 10.4; MS (ES-) m/z 354.1 (M - 1 ). The mother liquors were concentrated in vacuo and the residue was purified by column chromatography eluted with 1% 7 M methanolic ammonia in ethyl acetate, to afford 4-(4-(diethylamino)benzylidene)-3- <n="92"/>methyl-1H-pyrazol-5(4H)-one as an orange solid in 34% yield (0.45 g): mp 207-208 0C (ethyl acetate/methanol); 1H NMR (300 MHz, CDCI3) delta 8.57 (br s, 1 H), 8.53 (d, J = 9.1 Hz, 2H), 7.19 (s, 1 H), 6.70 (d, J = 9.1 Hz1 2H), 3.47 (q, J = 7.0 Hz, 4H), 2.21 (s, 3H), 1.23 (t, J = 7.0 Hz, 6H); 13C NMR (75 MHz, CDCI3) delta 166.6, 151.8, 151.7, 147.1 , 137.5, 121.7, 119.1 , 111.2, 45.0, 13.7, 12.8; MS (ES+) m/z 258.3 (M + 1 ) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With diethylamine; potassium hydroxide In ethanol; water at 80℃; for 12h; | 1.1 (1) Select two flasks (500 mL),4-Aminoacetophenone (5.40 g, 40 mmol) and N,N-diethyl-4-aminobenzaldehyde (7.08 g, 40 mmol) were dissolved in ethanol (40 mL) and diethylamine (2 mL, 20 mmol) , stir for 5 minutes,Potassium hydroxide (8.97 g, 160 mmol) was dissolved in water (40 mL), and a potassium hydroxide aqueous solution was slowly added dropwise to a two-necked flask.After heating and refluxing at 80 ° C for 12 hours, it was cooled to room temperature, washed with water, extracted with dichloromethane, and the organic phase was removed to give a crude product.Purified by silica gel column(dichloromethane: petroleum ether: ethyl acetate = 1:1: 0.1) gave a dark yellow solid. Name product 3 (10.36 g, yield 88%), |
62% | With preheated fly-ash Microwave irradiation; Sealed tube; | General procedure for synthesis of chalcones General procedure: Appropriate mixture of aryl methyl ketone (2 mmol) substituted benzaldehydes (2 mmol) and preheated fly-ash (0.5g) taken in 50ml corning glass tube and tightly capped. The reaction mixture was subjected to microwave irradiation for 8-10 minutes at 460W, 2450Hz, in a microwave oven (Scheme1) (LG Grill, Intellowave, Microwave Oven, 160-800W) and then cooled toroom temperature. Added 10 ml of dichloromethane, the organic layer has been separated which on evaporation yields the solid product. The solid, on recrystallization with benzene-hexane mixture gives glittering pale yellow solid. |
34% | With sodium hydroxide In ethanol; water at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With sodium hydroxide In methanol; water at 20℃; Cooling with ice; | |
78% | Stage #1: 3,5-dibromo-2-hydroxyacetophenone; 4-Diethylaminobenzaldehyde With sodium hydroxide In methanol; water at 20℃; Cooling with ice; Stage #2: With hydrogenchloride In methanol; water at 0℃; | 4.2. General procedure for the synthesis of chalcones 1-2 General procedure: An aqueous solution of NaOH (60%, 25 mL/mmol acetophenone) was added dropwise to an ice-cooled solution of dihalogenated 2'-hydroxyacetophenone (1.0 equiv) and 4-diethylaminobenzaldehyde (1.3 equiv) in MeOH (25 mL/mmol acetophenone). The reaction was allowed to reach room temperature and was stirred over night. The reaction mixture was cooled to 0 °C and acidified with concd HCl (37%). The crude precipitate was filtered off, washed with water and recrystallized from EtOH. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluoroacetic acid; In dichloromethane; at 20℃; for 24h;Inert atmosphere; | Methyl 3-(1H-pyrrol-2-yl)propanoate 2b (250 mg, 1.6 mmol) and 4-diethylamino-benzaldehyde 3b (145 mg, 0.8 mmol) were dissolved in 150 mL dry CH2Cl2 (argon was bubbled through CH2Cl2 for 30 min) under argon atmosphere. One drop of TFA was added and the reaction mixture was stirred at room temperature for 24 h under argon. p-Chloranil (202 mg, 0.8 mmol) was added and stirring was continued for 30 min under argon. Then, triethylamine (2.0 mL) and BF3*OEt2 (2.0 mL) were added, and the reaction mixture was stirred at room temperature overnight under argon. The reaction mixture was washed with H2O (40 mL), brine (40 mL), dried over Na2SO4, filtered, and evaporated. The crude mixture was purified by column chromatography on SiO2 (Hexane: EtOAc = 6:1 ~ 3:1) to afford 4d (222 mg, 0.43 mmol, 53% yield) as a red solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | In toluene Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With piperidine at 100 - 130℃; for 8h; | 2.5.1.1. 4-(4-N,N-Dimethyl-cinnamenyl)-nitro-benzene General procedure: In a threeneckedflask equipped with a magnetic stirrer, 4-N,N-dimethylbenzaldehyde,4-nitrophenyl acetic acid and piperidine were addedwith molar ratio of 1:3:3. The mixture was heated to 100 C for 3 hunder stirring, then the reaction was kept at 130 °C for 5 h. Theproduct was extracted with CH2Cl2 for three times. The combinedorganic layer was dried by anhydrous MgSO4. The solvent wasremoved under reduced pressure to give the crude product, whichwas further purified by column chromatography (C6H12:CH2Cl22:1,v/v) to afford the desired target as the paint yellow solid (yield, 75%, m.p., 246.0-248.0 °C). |
With piperidine Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92.9% | With <i>L</i>-proline In ethanol at 80℃; for 0.5h; | Synthesis of the targeted molecules 4-diethylaminobenzaldehyde(0.886g, 5 mmol) and Cyanoacetamide (0.504 g, 5 mmol) were dissolved in ethanol(30 ml),and then L-proline (0.086g, 0.25 mmol) was added as catalyst. The mixtures were heated to 80 °C and stirred for 0.5 h. After the reaction was finished, the mixture was cooled to the room temperature, and yellow-green solid was precipitated. After filtration, the residue was washed with the mixture of ethanol and water (1:1 by volume) to get the pure compound (1.130g, yield: 92.9%). The CDPA-E was characterized only by 1HNMR as it was synthesized by others before. The 1H NMR data were asfollow: 1H NMR (500 MHz, CDCl3) δ 8.15 (s, 1H), 7.89 (d, J = 9.0 Hz, 2H), 6.70 (d, J = 9.0 Hz, 2H), 6.21 (s, 1H), 5.78 (s,1H), 3.46 (q, J = 7.0Hz, 4H), 1.24 (t, J =7.0 Hz, 6H);13C NMR (126 MHz,CDCl3) δ 164.25, 153.25, 151.37, 134.04, 119.17, 118.89, 111.18,93.55, 44.73, 12.51. MS (m/z): 243.1411 [M] + (Calcd: 243.1413); |
66% | With potassium hydroxide In ethanol; water at 20 - 50℃; for 7h; | General procedure: To a solution of appropriate p-aminobenzaldehyde 1a-n (20 mmol) and cyanoacetamide (20 mmol) in ethanol (20 ml) a few drops of potassium hydroxide solution (10% in water) at 50° C was added. The solution was set aside for seven hours at room temperature. The precipitatewas filtered off and recrystallized from ethanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: o-hydroxyacetophenone; 4-Diethylaminobenzaldehyde With sodium hydroxide In methanol at 72℃; for 12h; Stage #2: With dihydrogen peroxide; sodium hydroxide In water at 25℃; for 5h; | 1.1.B1 Step B1, Flps compound synthesis: General procedure: Take a 100mL eggplant-shaped bottle, and add 1.1 equivalents (500mg) of o-hydroxyacetophenone, 1 equivalent of p-diethylaminobenzaldehyde,Dissolve with 25mL of methanol to obtain a solution. Under the condition of stirring, 10 equivalents of NaOH are slowly added to the solution and mixed uniformly, and then refluxed at 72 ° C for 12h.After the reaction was completed and cooled to room temperature, 10 equivalents of NaOH were formulated into a 0.5 mol / L aqueous solution, and the mixture was slowly added to the above mixture under stirring to mix well.Continue to add 5 equivalents of H2O2, and continuously stir at room temperature (25 ° C) for 5h. After the reaction, add 100g of ice-water mixture to quench the reaction, and adjust the pH of the reaction system to neutral with 6mol / L hydrochloric acid. A large amount of solid was precipitated. The solid was suction-filtered and washed twice with purified water at 0 ° C. The solid was pump-dried with an oil pump to obtain the pure product of Flp-1, which was separated by column chromatography to obtain the pure product of Flp-2 and Flp-3. product;In step B1, the precursor A is any one of p-diethylaminobenzaldehyde Flp-2b or Flp-3b,The corresponding synthesized Flps compounds were named Flp-1, Flp-2, and Flp-3, respectively, and analyzed Flp-1, Flp-2, and Flp-3: |
85% | Stage #1: o-hydroxyacetophenone; 4-Diethylaminobenzaldehyde With sodium hydroxide In ethanol; water at 20℃; for 24h; Stage #2: With dihydrogen peroxide; sodium hydroxide In ethanol; water at 20 - 50℃; for 20h; | 1 Example 1: Synthesis of probe EPC A mixture consisting of 2'-hydroxyacetophenone (1 mL, 8.3 mmol) and 4-diethylaminobenzaldehyde (8.3 mmol) was added to the flask, and ethanol (15 mL) was used as the solvent. Then NaOH (66.4 mmol) dissolved in 2 mL of water was added to the flask and stirred at room temperature for 24 hours. Then NaOH (16.6 mmol), 2 mL of water and 3 mL of 30% H2O2 were added to the mixture again, stirred at room temperature for 15 minutes, and then heated to 50 °C for reaction for 5 hours. After cooling to room temperature, the reaction system was neutralized to neutrality, and then extracted with dichloromethane and washed with water three times. The residue is recrystallized to obtain a yellow powder product, which is 2-(4-(diethylamino)phenyl)-3-hydroxy-4H-chromen-4-one, referred to as EPC. The yield was 85%. |
56% | Stage #1: o-hydroxyacetophenone; 4-Diethylaminobenzaldehyde With potassium hydroxide In 1,4-dioxane; ethanol at 0 - 20℃; Stage #2: With dihydrogen peroxide; sodium hydroxide In 1,4-dioxane; ethanol at 0 - 20℃; | 4.1.1. General procedure for the synthesis of NRA 1-1720,21 General procedure: A mixture of 2-hydroxyacetophenone (1 equiv) and the corresponding aldehyde (1 equiv) in ethanol (40 mL) and 1,4-dioxane (20 mL) was cooled to 0-10 C, 40% w/v KOH (5 equiv) solution was added dropwise. Then the reaction mixture was stirred at room temperature and monitored by TLC until the reaction completion. HCl (10%) was added to neutralize the reaction mixture. Ethyl acetate (50 mL) was then added, organic layer was separated and washed with H2O (50 mL) and brine (50 mL), dried over anhydrous sodium sulfate and concentrated in vacuum. The residue was dissolved in 1,4-dioxane (50 mL) and ethanol (30 mL), cooled in an ice-water bath, NaOH (5.4% w/v) solution (5 equiv), 35% H2O2(8 equiv) was added dropwise. The reaction mixture was stirred in an ice bath for 2 h and subsequently at room temperature overnight, resulting in a yellow suspension. After acidification with 2 M HCl to neutrality, ethyl acetate (3*50 mL) was used to extract the product, and the organic layer was washed with H2O (50 mL) and brine (50 mL), then dried over anhydrous sodium sulfate and concentrated in vacuum. The product was purified by column chromatography.The total yields for the two steps were varied from 40%to 65%. |
50% | Stage #1: o-hydroxyacetophenone; 4-Diethylaminobenzaldehyde With sodium hydroxide In ethanol; water at 20℃; for 24h; Stage #2: With dihydrogen peroxide In ethanol; water at 55℃; for 1h; | |
50% | Stage #1: o-hydroxyacetophenone With sodium hydroxide In ethanol for 0.0833333h; Stage #2: 4-Diethylaminobenzaldehyde In ethanol at 20℃; for 18h; Stage #3: With dihydrogen peroxide; sodium hydroxide In ethanol at 20℃; for 3h; Cooling with ice; | |
Stage #1: o-hydroxyacetophenone; 4-Diethylaminobenzaldehyde Stage #2: With dihydrogen peroxide In ethanol | ||
Stage #1: o-hydroxyacetophenone; 4-Diethylaminobenzaldehyde With sodium hydroxide In methanol Stage #2: With dihydrogen peroxide In water Stage #3: With hydrogenchloride In water | ||
Multi-step reaction with 2 steps 1: sodium hydroxide / ethanol; water / 24 h / 20 °C 2: sodium hydroxide; dihydrogen peroxide / ethanol; water / 5.25 h / 20 - 50 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51.5% | Stage #1: 2,3,3-trimethylindoleniune With hydrogenchloride In water at 20℃; for 0.5h; Stage #2: 4-Diethylaminobenzaldehyde In ethanol for 4h; Reflux; Inert atmosphere; | 5.2.2. Synthesis of simplified vinca alkaloids (5a-k) General procedure: General procedure: Concentrated hydrochloric acid (1.5 mL) was added dropwise into 2,3,3-trimethylindolenine (159.2 mg, 1.0 mmol). The mixture was stirred at room temperature for 30 min. Then excess reagent was removed by rotary evaporation under reduced pressure to give 2,3,3-trimethylindolenine hydrochloride (2) 195.7 mg (1.0 mmol). The HCl saltwas then dissolved in anhydrous ethanol (10 mL) followed the addition of substituted indole-3-carbaldehyde 4a-k (1.1 mmol). The mixture was allowed to reflux for 4 h in an atmosphere of pure nitrogen. The reaction was monitored by TLC until the disappearance of starting materials. Then the reaction mixture was cooled to room temperature and extracted with dichloromethane (3 x 50 mL). The combined organic layer was washed with water and brine, and dried over anhydrous MgSO4. Removal of excess solvent was carried on by rotary evaporation under reduced pressure to get the crude product. The residue was further purified by flash column chromatography using ethyl acetate/petroleum ether (3:2, v/v) as the eluent to give pure products (5a-k). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
15 mg | Example 5. Synthesis of N-benzyl derivatives of Amphotericin B.;200 mg (0.22 mmol) of Amphotericin B is dissolved in 3 ml of dimethyl formamide (DMF) in25 ml round-bottomed flask equipped with a magnetic stirrer. Next, 0.3 mmol of aromatic aldehyde is added and stirred at room temperature for 1 hour. After 1 hour 3 ml of anhydrousmethanol, 0.3 mmol of sodium cyanoborohydride (NaBH3CN) and catalytic amount (0.015ml) of acetic acid are added. The reaction progress is monitored by thin layer chromatography(TLC) on Silica Gel (60 F254, Merck) in chloroform: methanol: water (20:6:1 v/v) solventsystem. The reaction mixture is cooled to -5 C, and then 0.015 ml of methylamine intetrahydrofurane is added. The reaction mixture is left for 10 minutes and then addeddropwise to 150 ml of diethyl ether. The resulting pale yellow precipitate is filtered underreduced pressure on a Millipore funnel. The crude product is twice washed with diethyl ether(2x50 ml) and then dried in a vacuum dessicator. The residue is purified by columnchromatography on normal phase, where the solid phase is Silica Gel and solvent system ischloroform: methanol: water (20:6: 1 v/v). The fractions with pure product were collected andcombined, then evaporated under reduced pressure at temperatures not exceeding 35 o C. Thefollowing derivatives of Amphotericin B are obtained:a) In the reaction with z 4-(N,N-diethylamino)benzaldehyde is obtained 15 mg of N-(4-N,N-diethylaminobenzyl)amphotericin B (A19) TLC Rr= 0.75; UV-vis: Amax (MeOH) 406; 382; 363 nm; E.f:n (MeOH, A= 406nm) = 1150(theoretically for C58H88N20 17 is 1363); MS-ESI found m/z: 1083.3 [M-HL calculated forCssHssN2017 [Mt" 1084.6 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | Stage #1: 4,5-diiodo-1-methyl-1H-imidazole With ethylmagnesium bromide In tetrahydrofuran at 25℃; for 0.5h; Inert atmosphere; Stage #2: 4-Diethylaminobenzaldehyde In tetrahydrofuran at 25℃; for 24h; Inert atmosphere; | 4.1.2 (4-Iodo-1-methyl-1H-imidazol-5-yl)(3,4-dimethoxyphenyl)methanol (3b) General procedure: EtMgBr (2.0M solution in THF, 55ml, 110mmol) was added to a solution of 4,5-diiodo-1-methyl-1H-imidazole (35.1g, 105mmol) in anhydrous THF (500ml) at 25°C under N2 atmosphere. The resulting mixture was stirred for 30min and 3,4-dimethoxybenzaldehyde (17.4g, 105mmol) was added to this solution. After stirred at 25°C for 24h, sat. NH4Cl (50ml) was added to quench the reaction and the THF was removed under reduced pressure. Then the resulting suspension was filtered, washed by H2O (300ml) and Et2O (50ml), and dried in vacuo to give 3b (35.3g, 90%) as a white solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With dodecatungstosilic acid; phosphorus pentoxide In neat (no solvent, solid phase) at 20℃; for 0.05h; Green chemistry; | General method for the synthesis of Schiff bases 1-25 General procedure: A mixture of 1-aminoanthraquinone (1 mmol), a substituted aromatic aldehyde or ketone (1 mmol) and dodecatungstosilicic acid/P2O5 (0.2 g, 1 mol % of 1-aminoanthraquinone/P2O5) as a catalyst was ground in a mortar with a pestle under solvent-free conditions at room temperature for 1-3 min, Scheme 1. The reaction mixture turned to a pasty material that indicated the completion of the reaction. Crushed ice was added to afford precipitates of the Schiff bases. In order to remove the catalyst, the product was washed several times with ice-cold water. The solid products were obtained in excellent yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium hydroxide; In ethanol; water; at 20℃; for 2h; | General procedure: To a solution of 2-12 in ethanol (100 mg, 0.62 mmol, 13 ml/mmol) was added the suitably functionalized benzaldehydes (0.62 mmol), followed by a solution of KOH 20% in water (0.8 ml/mmol). The solution is stirred at room temperature for 2 h. The reaction mixture was concentrated in vacuo and diluted with distilled water. The aqueous layer was extracted with ethyl acetate and dried (Na2SO3). The organic phase was evaporated in vacuo to yield crude products which were subjected to column chromatography by using amino silica gel as adsorbent and solvent system of hexane: ethyl acetate (7:3) followed by silica gel column chromatography by using chloroform: methanol (9.5:0.5) to yield Series 2 derivatives except for 2-6 and 2-9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With piperazine; In ethanol; for 4h;Reflux; | General procedure: To the solution of 2-(1H-benzimidazol-2-yl)acetonitrile (80 mg, 0.51 mmol), 4-methylbenzaldehyde (60 mg, 0.50 mmol) in ethanol (1.5 mL) was added 1,4-diazacyclohexane (45 mg, 0.52 mmol). The mixture was refluxed for 4 h in room temperature. The crude product was filtered off and purified by silica gel chromatography using cyclohexane-acetone-ethyl acetate (10:1:1) as eluant to afford compound 6 (120 mg, 93%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With piperazine In ethanol for 4h; Reflux; | 4.3 2-(1H-benzimidazol-2-yl)-3-(4-methylphenyl)acrylonitrile (6) General procedure: To the solution of 2-(1H-benzimidazol-2-yl)acetonitrile (80 mg, 0.51 mmol), 4-methylbenzaldehyde (60 mg, 0.50 mmol) in ethanol (1.5 mL) was added 1,4-diazacyclohexane (45 mg, 0.52 mmol). The mixture was refluxed for 4 h in room temperature. The crude product was filtered off and purified by silica gel chromatography using cyclohexane-acetone-ethyl acetate (10:1:1) as eluant to afford compound 6 (120 mg, 93%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | at 100 - 140℃; for 4h; | 2.2.1. 3,11-Diamino-7-(4-(diethylamino)phenyl)dibenzo[c,h]xanthen-14-ium trifluoro-methanesulfonate (1a) A solution of 4-diethylaminobenzaldehyde (0.3 mmol, 53.2 mg) and 6-aminonaphthalen-1-ol (0.6 mmol, 95.5 mg) in trifluoromethanesulfonic acid (2 mL) was stirred at 100 °C for 2 h, after that, the mixture was allowed to react for another 2 h at 140 °C, cooled to room temperature and poured into 40 mL brine, filtered, the residuewas subjected to flash column chromatography (silica gel, CH2Cl2:MeOH 10:1 (v:v)) to give a black powder (65.0 mg), yield 36%, mp 199.0-203.0 °C. IR ν (KBr, cm1): 3348, 3227, 2925, 1594, 1454, 1385, 1345, 1263, 1185, 1158, 1028, 639. 1H NMR (400 MHz, DMSO-d6) δ 8.87 (d, J 9.1 Hz, 2H, 2 Ar-H), 7.67 (d, J 9.3 Hz, 2H, 2 Ar-H), 7.56 (d, J 9.2 Hz, 2H, 2 Ar-H), 7.48 (d, J 8.5 Hz, 2H, 2 Ar-H), 7.27 (d, J 9.1 Hz, 2H, 2 AreH), 7.12 (br, 4H, 2 NH2), 7.01 (d, 2H, 2 AreH), 6.99 (s, 2H, 2 AreH), 3.53 (q, J 6.5 Hz, 4H, 2 CH2), 1.22 (t, J 6.9 Hz, 6H, 2 CH3). 13C NMR (101 MHz, DMSO-d6) δ 160.4, 155.0, 154.9, 149.9, 140.3, 133.6, 127.4, 127.1, 124.4, 119.3, 118.1, 117.5, 113.0, 111.5, 107.9, 44.4, 13.0. HRMSESI : m/z 458.2232 (calcd for [MeCF3SO3], 458.2232). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With [1-methylpyrrolidin-2-one-SO3H]Cl; In neat (no solvent); at 20℃; for 1h; | General procedure: The corresponding aldehyde (1.0 mmol), 2-aminobenzothiazole(1.0 mmol), diethyl phosphite (1.0 mmol), and AIL (10 mol%)were mixed together and stirred at room temperature for appropriate time (Table 2). After the completion of the reactionas monitored by TLC, the mixture was washed with CH2Cl2(3 ×3 mL). The combined extracts were filtered and thesolvent was removed under reduced pressure to afford thecrude product, which was purified by recrystallization fromethylacetate/n-hexane. The catalyst, which does not dissolve inCH2Cl2,remainedintheresidue. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78.4% | With sodium hydroxide In ethanol; water for 2h; Reflux; | 3.1 2.3.1 3-(4-(diethylamino)phenyl)-2-(thiophen-2-yl)acrylonitrile (1a) 4-diethylaminobenzaldehyde (2 g, 11.3 mmol) and thiophene-2-acetonitrile (1.44 mL, 13.6 mmol) were taken in a two neck round bottom flask containing 30 mL freshly distilled ethanol. 6 M NaOH (0.1 mL) was added to this reaction mixture at room temperature after that the resulting mixture was refluxed for 2 h. After cooling to room temperature, the mixture was poured into water and extracted with chloroform. The collected organic extracts were dried by Na2SO4. The solvent was removed under vacuum and the residue was further purified by column chromatography on silica gel by using a hexane as an eluent to give orange yellow color solid with yield 78.40% (2.5 g). 1H NMR (CDCl3, ppm): δ 1.24 (t, 6H), 3.43-3.47 (q, 4H), 6.69-7.82 (ArH, 7H). 13C NMR (CDCl3, ppm): δ 12.62, 44.53, 111.18, 118.43, 120.45, 124.29, 127.89, 131.45, 140.50, 140.76, 149.37. IR (KBr pellet, cm-1): 3096, 2970, 2897, 2207, 1605, 1575, 1406, 1341, 1272, 1196, 1153, 1076, 1015, 848, 808, 712. Anal. Calcd. for C17H18N2S: C, 72.30; H, 6.42; N, 9.92. Found: C, 72.18; H, 6.62; N, 9.87. HRMS (ESI): Anal. Calcd. for C17H18N2S: 282.1263. Found: 283.1259 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With pyrrolidine; oxygen In ethanol; water at 20℃; for 24h; | 4 Embodiment 4 This example describes a synthesis test carried out in a reaction system of a benzaldehyde raw material B containing an amine group. Since the intermediate of the raw material of the raw material is unfavorable for conversion to the target product in water or a pure organic solvent, resulting in a low yield of the target product, the reaction is carried out using a mixed solvent.The reaction system includes: raw material A (1.0 mmol),Starting material B (1.1 mmol), pyrrolidine (10.0 mmol); reaction medium: ethanol (16.0 mL) + water (4.0 mL);The reaction system is open to the atmosphere or to the oxygen.In terms of molar ratio, starting material A: starting material B: pyrrolidine = 1: 1.1: 10.The structural formula of the raw materials A and B is shown in Fig. 1, and the structural formula of the final product C produced is shown in Fig. 2. The reaction process is as follows: in the reaction medium, the raw material A is slowly added in the presence of pyrrolidine, and the raw material B is slowly added after being stirred and dissolved, and the reaction is carried out at room temperature (the reaction may also be heated, for the convenience of operation, the uniform temperature reaction in this embodiment), The reaction system was passed through the atmosphere and kept stirring for 24 h. After the reaction, the reaction solution was adjusted to pH=7.0 with a 6.0 mol/L aqueous hydrochloric acid solution.The insoluble solid was filtered to give a crude product.The crude product is reconstituted in a hot saturated solution of ethanol-water (ethanol: water = 100:1)After crystallization, the yellow solid obtained by filtration is the corresponding final product of 3-hydroxyflavone and its derivatives. |
46.3% | With pyrrolidine In ethanol at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | Stage #1: 5-Bromo-2-hydroxyacetophenone; 4-Diethylaminobenzaldehyde With morpholine In 1,2-dichloro-ethane at 100℃; for 0.416667h; Microwave irradiation; Stage #2: With sodium hydroxide In ethanol; dihydrogen peroxide at 20℃; for 48h; Cooling with ice; | 6-Bromo-2-(4-diethylamino)phenyl-3-hydroxy-4H-chromen-4-one (1): 1-(5-Bromo-2-hydroxyphenyl)ethanone (1.7 g, 7.75 mmol, 1 eq.) and 4-(diethylamino)benzaldehyde (1.56 g, 8.52mmol, 1.1 eq.) were solubilized in 1,2-dichloroethane (10 mL) and morpholine (10 mL).The reaction solution was irradiated by microwave (25 min, 100 C, 200 W). The volatileswere removed in vacuo to give a reddish brown solid, which was solubilized in ethanol(15 mL). To the stirred mixture cooled in an ice bath, were added sequentially an aq. 5 MNaOH solution (20 mL, 13 eq.) and H2O2 (30% w/w in H2O, 7.65 mL, 10 eq.). After stirringovernight, the mixture was neutralized by an aq. 1 N HCl solution, and the resultingprecipitate was filtered and washed with water and cyclohexane sequentially. Compound1 was obtained as an orange solid. (2.24 g, 77%). Rf = 0.38 (Toluene/Acetone 4:1) or 0.58(DCM/MeOH, 99.5:0.5). 1H-NMR (CDCl3, 200 MHz): d 1.15 (t, 3J = 7.0 Hz, 6H, NCH2-CH3),3.41 (q, 3J = 7.0 Hz, 4H, NCH2-CH3), 6.67 (d, 3J = 9.0 Hz, 2H, Hmeta), 7.35 (d, 3J = 8.8 Hz,1H, H8), 7.62 (dd, 3J = 8.8 Hz, 4J = 2.4 Hz, 1H, H7), 8.05 (d, 3J = 9.0 Hz, 2H, Hortho), 8.26(d, 4J = 2.4 Hz, 1H, H5), 9.37 (s, 1H, OH). 13C-NMR (CDCl3, 50 MHz): d 12.7 (N-CH2-CH3),44.5 (N-CH2-CH3), 110.9 (Cm), 116.7 (Cp), 119.8 (Ci), 122.3 (C8), 127.6 (C6), 129.5 (C7),135.5 (Co), 136.9 (C5), 147.3 (C10), 149.1 (C2), 153.7 (C9), 171.0 (C4). HRMS (ESI+): m/z calcdfor C19H18NO3BrH+: 388.0543, 390.0522 [M + H]+; found: 388.0550, 390.0529 [M + H]+. |
41.4% | With pyrrolidine In ethanol at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With potassium hydroxide In methanol at 20℃; for 48h; | 4.1.1.4. 5-Methoxy, 6-methoxy or 5,6-dimethoxy-2-(4-substituedbenzilidene)-2,3-dihydro-1H-inden-1-one derivatives(15-38). General procedure: A mixture of appropriate indan-1-one derivative(2 mmol), benzaldehyde derivative (2 mmol) and potassium hydroxide(2 mmol, 0.112 g) in methanol (10 mL) was stirred at roomtemperature for 48 h. The resulting colored solid was filtered, driedand crystallized from EtOH [63]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With potassium hydroxide In methanol at 20℃; for 48h; | 4.1.1.4. 5-Methoxy, 6-methoxy or 5,6-dimethoxy-2-(4-substituedbenzilidene)-2,3-dihydro-1H-inden-1-one derivatives(15-38). General procedure: A mixture of appropriate indan-1-one derivative(2 mmol), benzaldehyde derivative (2 mmol) and potassium hydroxide(2 mmol, 0.112 g) in methanol (10 mL) was stirred at roomtemperature for 48 h. The resulting colored solid was filtered, driedand crystallized from EtOH [63]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With potassium tert-butylate; In ethanol; for 3h;Reflux; | Potassium tert-butoxide (11.2 mg, 0.1 mmol) was added to an absolute ethyl alcohol solution containing <strong>[622-75-3]1,4-phenylenediacetonitrile</strong> (6) (0.156 g, 1 mmol) and 4 (0.39 g, 2.2 mmol), then stirred and refluxed for 3 h. After cooling to the room temperature, the solvent was removed on a rotary evaporator, and the crude product was recrystallized from a petroleum ether/trichloromethane mixture to give aurantius power, yield 0.30 g (63%). 1H NMR (400 MHz, CDCl3) delta 7.86 (d, J = 8.9 Hz, 4H), 7.66 (s, 4H), 7.42 (s, 2H), 6.70 (d, J = 8.2 Hz, 4H), 3.44 (q, J = 7.1 Hz, 8H), 1.22 (t, J = 7.1 Hz, 12H). 13C NMR (100 MHz, CDCl3): delta 149.4, 142.3, 135.1, 131.8, 125.8, 119.5, 111.3, 103.0, 44.6, 12.7. HRMS (ESI): m/z Calcd. For [M+H]+: 475.2783, Found: 475.2858. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: 0.005 mol of appropriate rhodanine-3-alkanoicacid, 5 g molecular sieves 4 A, 25 cm3 isopropyl alcohol,0.0055 mol appropriate aldehyde and 2.53 g (0.025 mol)triethylamine were placed in a flask. The mixture washeated under a reflux condenser for 5 h in nitrogen. Afterheating, the solution was filtered hot. The permeate wascooled and 50 cm3 of 2M hydrochloric acid solution wasadded. The resulting sediment was filtered using Buechnerfunnel and crystallised from isopropyl alcohol or glacialacetic acid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
33% | With water; sodium hydroxide In ethanol at 78℃; | 4.2. General procedure for the preparation of compounds A1-D7 General procedure: For the reactions, 4-piperidinone or corresponding ketones (1 mmol) and 2-bromobenzaldehyde or corresponding aldehydes(2.5 mmol) were dissolved in ethanol (10 mL). The mixture wasrefluxed at 78 °C and added with 0.5 mL 40% NaOH or AcOH/HCl.Reactions were monitored by TLC, when the reactions were accomplished, cooled on ice. The products could precipitate or be purified by crystallization and column chromatography using PE/EA as the eluent. Among these compounds, A4, A6, C5, D1, D2, D3 and D4 were unreported. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With potassium tert-butylate; In N,N-dimethyl-formamide;Reflux; Inert atmosphere; | 4-Methyl-2-phenylpyridine (500?mg, 2.96?mmol), 4-N,N-diethylaminobenzaldehyde (620?mg, 3.5?mmol) and t-BuOK (700?mg, 6.2?mmol) were dissolved in DMF (20?mL). The reaction mixture was heated at reflux overnight, then CH2Cl2 (150?mL) was added. The organic phase was washed first with water and then with an aqueous solution of 1?M KOH, dried with MgSO4 and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (silica, CH2Cl2:petroleum ether?=?7:3) to obtain 2 as a yellow powder (546?mg). Yield: 56percent. 1H NMR (400?MHz, CDCl3) delta (ppm): 8.61 (1H, d, J?=?5.2?Hz), 8.06 (2H, d, J?=?7.2?Hz), 7.75 (1H, s) 7.51 (2H, t, J?=?7.4?Hz), 7.45 (3H, d, J?=?8.5?Hz), 7.30 (1H, d, J?=?16.3?Hz), 7.26 (1H, m), 6.86 (1H, d, J?=?16.2?Hz), 6.68 (2H, d, J?=?8.8?Hz), 3.40 (4H, q, J?=?7.1?Hz), 1.20 (6H, t, J?=?7.0?Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | Stage #1: 4,4'-dimethyl-2,2'-bipyridines With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78 - 20℃; for 2h; Schlenk technique; Inert atmosphere; Stage #2: 4-Diethylaminobenzaldehyde In tetrahydrofuran; hexane at 20℃; for 1h; Schlenk technique; Inert atmosphere; Stage #3: With pyridinium p-toluenesulfonate In tetrahydrofuran; hexane; toluene at 110℃; for 4h; Schlenk technique; Inert atmosphere; | 4 2.1.1.4 4,4'-p-[(N,N-diethyl)aminostyryl]-2,2'-bipyridine (4) Diisopropylamine (607.1 mg, 6 mmol) was dissolved in THF (2.5 mL) in a Schlenk tube and the mixture was cooled to 0 °C. A n-BuLi solution (1.6 M in hexane, 3.75 mL, 6 mmol) was added slowly. After stirring one hour, the solution was cooled to -78 °C and 4,4'-dimethyl-2,2'-bipyridine (501.1 mg, 2.72 mmol) in THF (13 mL) was added dropwise and the mixture stirred at low temperature for 2 h. p-(N,N-diethyl)aminobenzaldehyde (957.1 mg, 5.4 mmol) was dissolved in 6 mL of THF (6 mL) and added slowly. The resulting mixture was stirred for one hour at low temperature and overnight at room temperature. After hydrolyzing with distilled water (12 mL), the phases were separated, the organic phase was dried over MgSO4, filtered and the solvent was removed under reduced pressure. The dialcohol was dissolved in toluene (40 mL) in a round-bottomed flask and pyridinium p-toluenesulfonate (PPTS, 67.6 mg, 0.27 mmol) was added. The mixture was heated at reflux for 4 h. After cooling to room temperature, the solvent was removed under reduced pressure and dichloromethane (16 mL) was added. The mixture was washed with a saturated solution of NaHCO3. The precipitated bipyridine was filtered, abundantly washed first with H2O and then with Et2O to obtain 4 as an orange powder (970 mg). Yield: 71%. 1H NMR (400 MHz, CDCl3) δ (ppm): 8.63 (2H, d, J = 5.1 Hz), 8.48 (2H, s), 7.47 (4H, d, J = 8.9 Hz), 7.42 (2H, d, J = 16.2 Hz), 7.36 (2H, dd, J = 5.3, 1.8 Hz), 6.92 (2H, d, J = 16.2 Hz), 6.71 (4H, d, J = 8.9 Hz), 3.43 (8H, q, J = 7.1 Hz), 1.22 (12H, t, J = 7.1 Hz). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With sodium ethanolate In ethanol at 70℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With potassium tert-butylate; In tetrahydrofuran; at 60℃; | General procedure: Add (0.5 g, 2.8 mmol) aldehyde in a stirred mixture of potassium tertiary-butoxide (0.60 g, 4.23 mmol) and 3, 3,-diethoxypropionitrile(0.63 g, 5.64 mmol) in 5 ml THF. Reflux the reaction mixture for overnight at 60 C, add 20 ml water to the solution and the mixture after cooling. It was extracted with diethyl ether. The organic phase was washed with water, sodium bicarbonate and then brine solution androtary evaporated under vacuum to get reddish oil. Then 20 ml of hydrochloric acid solution (1 M) was added and the solution was refluxedffior 1 h, neutralized and extracted with diethyl ether. The combined organic phase was washed with saturated NaOH solution. The product obtained was puriffied by using hexane/ethyl acetate system by column chromatography.3.2. Synthesis of (E)-3-(4-(diethylamino) phenyl)-2-formylacrylonitrile Red crystalline solid. Yield-68%.Melting point-96-98 C1HNMR (500 MHz, CDCl3): delta = 9.47 (s, 1 H), 7.95 (d, J=8.5 Hz,2 H), 7.65 (s, 1 H), 6.71 (d, J=8.5 Hz, 2 H), 3.49 (q, J=7.0 Hz, 4 H),1.26 (t, J=7.0 Hz, 6 H).13CNMR (126 MHz, CDCl3): delta =187.70, 157.64, 152.43, 135.04,118.91, 116.51, 111.47, 103.65, 44.97, 12.53.CHN analysis: Expected: C, 73.66; H, 7.06; N, 12.27; Results: C,73.62, H, 7.05 N, 12.29. Molecular formula: C14H16N2OFT-IR: 1668(C=O stretch), 2218 (C?N stretch), 1474(Ar-C=Cstretch), 1607(C=C stretch)Mass: Calculated 228.1263 for C14H16N2O found 229.1327 (M+1) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With sodium hydroxide In ethanol at 20℃; for 24h; | 3.1. Synthesis of (E)-3-(4-(diethylamino)phenyl)-2-(thiophen-2-yl)acrylonitrile The aromatic aldehyd 4-(diethylamino)benzaldehyde, NaOH,EtOH, 2-(thiophen-2-yl)acetonitrile were obtained from (SigmaAldrich, India). The (E)-3-(4-(diethylamino)phenyl)-2-(thiophen-2-yl)acrylonitrile was synthesized by Knoevenagel condensation reaction[5e8].Fig. 1 and Table 1 show the reaction scheme of synthesisof our title compound (DPTA) single crystal.The 2-(thiophen-2-yl) acetonitrile (2 g, 0.0162mmole), 4-(diethylamino) benzaldehyde (2.8 g, 0.0162mmole), 2.5 g of 40%NaOH was dissolved in ethanol (30 ml) and stirred at room temperaturefor 24 h. The reactor was monitored by TLC analysis. Afterthe completion of the reaction, the crude mass was allowed to bepurified by various fractions in column chromatography techniquesusing the mixture of 20% of Hexane: EtOAc as the mobile phasesolvent. The complete reaction and total synthesized derivatives ofcompounds are shown in Fig. 2 (a) and (b). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With piperidine In acetonitrile for 24h; Reflux; | General procedure for the synthesis of compounds 3a-e. General procedure: To a solutionof 4-methyl-2-oxo-2H-chromene-3-carbonitrile 1 (185 mg, 1 mmol)and aldehyde 2a-e (1 mmol) in acetonitrile (5 ml) one drop of piperidinewas added. The reaction mixture was stirred under reflux for appropriatetime (see Scheme 1). The precipitate formed was filtered off, washed withethanol and dried in air. If no solid precipitate formed, the solvent wasdistilled off in vacuo. The residue was purified by crystallization or bycolumn chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With hydrazine hydrate In ethanol at 78℃; for 7h; Green chemistry; | General procedure for synthesis of (E)-N′-benzylidene-2-(hydroxymethyl)benzohydrazide derivates General procedure: Hydrazine hydrate (85%, 2 mmol) was added dropwise to a solution of phthalide (0.1340 g, 1 mmol, 1 equiv) in 8 mL ethanol, and the mixture was stirred for 5 min. An aldehyde (1 equiv) was added to the mixture, followed by stirring at 78 °C (oil bath) for 7-8 h until the completion of the reaction (as determined by TLC). The reaction mixture was cooled to room temperature, and the solid product was separated by filtration and washed with 95% ethanol. Finally, the desired pure product 4 was obtained after drying. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | In methanol at 80℃; for 0.5h; | General procedure for the synthesis of compounds (12-43). General procedure: First, 0.5 g of 2-hydrazinoadenosine (11) and different aralkyl or alkylaldehyde compounds (1.1 equivalent) were combined in methanol(30 ml) and heated by microwave at 80 °C for 30 min. The crudeproducts (12-13, 17, 19, 21-32, and 35-39) were precipitated frommethanol, and the other products (14-16, 18, 20, 33-34, and 40-43) were purified from the reaction mixture using silica gel column chromatography. All the crude products were further purified by MPLC on reverse phase C18 material to yield the products(12-43). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | In dimethyl sulfoxide; at 110℃; for 0.583333h;Sonication; | Accurately weigh 36mg (0.05mmol) C60,35 mg (0.20 mmol) of 4-N,N-diethylaminobenzaldehyde and59 mg (0.30 mmol) of N-(4-methoxy-benzyl)-glycine was added toIn a 250 mL round bottom flask,Then take 80 mL of dimethyl sulfoxide and add it.Ultrasonic oscillation for 15 min,Dissolve C60 and aldehyde completely and mix glycine evenly.The oil bath is heated to 110 C and magnetically stirred for 20 min at a constant temperature.Heating was then stopped and the reactor was cooled to room temperature.The solvent was removed by distillation under reduced pressure, and the residual solid was sufficiently dissolved with a small amount of carbon disulfide, and then separated by column chromatography, and washed with a mixed solvent of n-hexane: carbon disulfide = 1:1, and the brown product strip was washed. Rotating the solution by rotary evaporation gave a brownish black solid as a product.After drying under vacuum for 10 h, the yield was 45%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With acetic acid;Reflux; | General procedure: A mixture of 1 mmol of pyrimidine 1a-1c, 1 mmol of aldehyde 2a-2f, and 1 mmol of 5,5-dimethylcyclohexane-1,3-dione(3) in 10 mL of glacial acetic acid was refluxed for 8-10 h. The mixture was cooled to room temperature, and the precipitate was filtered off, washed with ethanol, and (if necessary) recrystallized from ethanol or DMF. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96.1% | at 120℃; for 5h; Molecular sieve; Green chemistry; | 1-5 Example 5 Example 5 differs from Example 1 in that a supported molecular sieve catalyst with yttrium oxide as the active component is added.Preparation of supported molecular sieve catalyst: roast mesoporous molecular sieve MCM-48 at 550°C for 3h to obtain activated molecular sieve carrier; add 20g of activated molecular sieve carrier to the autoclave, add 3g of hydrogenated castor oil and heat to Pressurized to 5MPa at 90 for 30min, calcined at 550 for 3h to obtain a modified molecular sieve carrier; 2g of yttrium nitrate was dissolved in 30g of water to make a yttrium nitrate solution; the modified molecular sieve carrier was immersed in a yttrium nitrate solution for 8h, Suction filtration, drying at 100°C for 5h, and calcination at 550°C for 4h to obtain a supported molecular sieve catalyst with a loading of 8.0%.Synthesis of 2-(4-(diethylamino)phenyl)-3-hydroxy-6-nitro-4-one: 4-(diethylamino)benzaldehyde (3.54g, 0.02mol) and 2-hydroxyl -5-Nitroacetophenone (3.80g, 0.021mol) as the reaction raw material, adding the supported molecular sieve catalyst prepared above (calculated as yttrium, 0.09g, 0.001mol), heating to 120 for 5h, and reacting after the reaction The solution was cooled naturally to 60°C, added 10g of absolute ethanol to beat for 15min, filtered with suction, and the filter residue was washed with 5g of absolute ethanol and dried at 60°C for 12h to obtain 6.84g of 2-(4-(diethylamino)phenyl)- 3-Hydroxy-6-nitro-4-one, yield 96.1%, purity 99.3%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69.8% | With piperidine; acetic acid In butan-1-ol at 130℃; for 24h; Molecular sieve; | 4.2.12 7-(Diethylamino)-3-nitro-2H-chromen-2-one (12) To a solution of 4-(Diethylamino) salicylaldehyde (4.26g, 21.90mmol) in n-Butanol (50mL), Ethyl nitroacetate (2.46mL, 21.90mmol), Piperidine (0.3mL), AcOH (0.6mL) and molecular sieve added. The mixture was refluxed at 130°C for 24h. The mixture was cooled to room temperature, and the precipitate was filtered out, then dissolved in 40mL of DMF at 80°C. The filtered filtrate was added dropwise to 500mL ice water, the precipitated precipitate was filtered out, and a yellow solid was obtained after drying (4.06g, 69.8% yield). 1H NMR (400MHz, DMSO-d6) δ 9.04 (s, 1H), 7.74 (d, J=9.1Hz, 1H), 6.92 (dd, J=9.1, 1.9Hz, 1H), 6.65 (s, 1H), 3.54 (q, J=7.0Hz, 4H), 1.16 (t, J=7.0Hz, 6H). ESI-MS: m/z [M+ H]+ calcd for C13H15N2O4+ 263.10, found 263.22. Mp 195.2-198.4°C. |
69.8% | With piperidine; acetic acid In butan-1-ol at 130℃; for 24h; Molecular sieve; | 4.2.12 7-(Diethylamino)-3-nitro-2H-chromen-2-one (12) To a solution of 4-(Diethylamino) salicylaldehyde (4.26g, 21.90mmol) in n-Butanol (50mL), Ethyl nitroacetate (2.46mL, 21.90mmol), Piperidine (0.3mL), AcOH (0.6mL) and molecular sieve added. The mixture was refluxed at 130°C for 24h. The mixture was cooled to room temperature, and the precipitate was filtered out, then dissolved in 40mL of DMF at 80°C. The filtered filtrate was added dropwise to 500mL ice water, the precipitated precipitate was filtered out, and a yellow solid was obtained after drying (4.06g, 69.8% yield). 1H NMR (400MHz, DMSO-d6) δ 9.04 (s, 1H), 7.74 (d, J=9.1Hz, 1H), 6.92 (dd, J=9.1, 1.9Hz, 1H), 6.65 (s, 1H), 3.54 (q, J=7.0Hz, 4H), 1.16 (t, J=7.0Hz, 6H). ESI-MS: m/z [M+ H]+ calcd for C13H15N2O4+ 263.10, found 263.22. Mp 195.2-198.4°C. |
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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