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CAS No. : | 3471-32-7 | MDL No. : | MFCD02656457 |
Formula : | C7H10N2O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | - |
M.W : | 138.17 | Pubchem ID : | - |
Synonyms : |
|
Signal Word: | Danger | Class: | 8,6.1 |
Precautionary Statements: | P261-P280-P301+P310-P305+P351+P338 | UN#: | 2923 |
Hazard Statements: | H301-H315-H318-H335 | Packing Group: | Ⅲ |
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 |
---|---|---|
60% | In ethanol for 4h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With Amberlite IR 120; In ethanol; at 80℃; for 10h; | General procedure: A mixture of the carbonyl compound (5, 1.0 mmol), arylhydrazine (6, 1.2 mmol), and the solid acid (7, Amberlite, 1.5 g, obtained from Aldrich Chemical Co.) was refluxed in absolute ethanol (10 ml) for 8 h. The reaction was monitored by thin-layer chromatography(TLC), and upon completion the mixture was cooled to room temperature, the catalyst filtered off, and the product was washed thoroughly with ethylacetate (30 ml). The combined organics were washed with water, dried (Na2SO4), and concentrated in vacuo. The resulting residue was chromatographed on a silicagel column eluting with ethylacetate-hexane mixtures to obtain the purified indole (8). This was fully characterized by infrared, 400-MHz 1H NMR, high-resolution mass spectrometry, and melting point (solids). |
82% | With 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide; In ethyl acetate; at 110℃; for 0.166667h;Microwave irradiation; Sealed vessel; | General procedure: T3P (50% in EtOAc) (0.55-0.68 mmol) was added to a mixture of hydrazine (59 mg, 0.55 mmol) and ketone/aldehyde (0.55 mmol) in a microwave vial. The reaction volume was then made up to 0.5 mL with EtOAc and the vessel was sealed under air. The mixture was heated under microwave irradiation (Biotage Initiator) at 100-150 C for 5-15 min. The solvent was evaporated under reduced pressure and the oily residue was purified by filtration through a plug of silica gel (eluent: isohexane/EtOAc, 8:2) to yield the desired indole or tetrahydrocarbazole. When the reaction was conducted on a 5 mmol scale the product (3a) was purified by precipitation from acetone/water. |
71% | With acetic acid; for 4.5h;Reflux; | To a solution of cyclohexanone (0.30 mL, 2.86 mmol) in glacial acetic acid (1 mL), methyl 4-methoxyphenyl hydrazine (0.501 g, 2.87 mmol) was added over 1 h. The mixture was refluxed for 3.5 h and left stirring until reaching room temperature. It was then cooled in ice for 20 min and then 75 % (v/v) aqueous MeOH (4 mL) was added. The solid formed was filtered and washed with 12 mL of the same aqueous methanol to give a beige solid. Yield: 0.409 g (2.03 mmol, 71 %). mp 93-95 C. 1H NMR (300 MHz, CDCl3): delta 7.56 (sbr, 1H, NH), 7.18 (d, 1H, J = 9.0 Hz, H-1), 6.93 (d, 1H, J = 2.4 Hz, H-4), 6.77 (dd, 1H, J = 8.7 and 2.4 Hz, H-2), 3.86 (s, 3H, OCH3), 2.72-2.68 (m, 4H, H-6 and H-7), 1.90-1.89 (m, 4H, H-5 and H-8) ppm. 13C NMR (75.4 MHz, CDCl3): delta 153.84 (C-3), 153.06 (C-8a), 130.68 (C-9a), 128.17 (C-4a), 110.90 (C-1), 110.50 (C-2), 110.02 (C-4b), 100.23 (C-4), 55.95 (OCH3), 23.33 (C-6 or C-7), 23.18 (C-5 and C-8), 20.94 (C-6 or C-7) ppm. Anal. calcd for C13H15NO: C, 77.91; H, 7.223; N, 6.983 %; found: C, 77.58; H, 7.51; N, 6.96 %. |
With hydrogenchloride; In water; at 50 - 60℃; for 5h; | General procedure: Substituted phenyl hydrazine (14 mmol) was solved in the mixture of concentrated hydrochloric acid and water (50 mL, 1:20) and then ketone (16.8 mmol) was added dropwise at rt. After that, the mixture was stirred for more than 5 h at 50-60 . When the reaction cooled to rt, some rice shape solids appeared in the system. The mixture was filtered and the solid was washed with enough water until neutral.T he crude product was recrystallized in hexane to afford 1k-1q in 72-95% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | In ethanol | |
In ethanol Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | In acetic acid; trifluoroacetic acid for 12h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With hydrogenchloride for 0.25h; Heating; | |
73% | With hydrogenchloride In water for 0.416667h; Heating; | General procedure for the synthesis of 1-aryl-3-methyl-5-aminopyrazoles (3a-e). General procedure: To a solution of the corresponding arylhydrazine (1a-e) (10 mmol) in concentrated hydrochloric acid (5 mL), 820 mg of 3-aminocrotonitrile (2) (10 mmol) was added with magnetic stirring. The mixture was left to react for 10 minutes and then more HCl was added (5 mL) while heating for 15 additional minutes. After completion of the reaction, a yellow solution was obtained which was then cooled by addition of crushed ice and neutralized with concentrated ammonium hydroxide. Finally, the formed precipitate corresponding to aminopyrazoles 3a-e, was vacuum filtered and washed with cold water. |
With hydrogenchloride In water for 16h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With hydrogenchloride; In ethanol; water;Heating / reflux; | A mixture of commercially available (4-methoxyphenyl)-hydrazine (17.4 g, 0.1 mol) and commercially available pivaloylacetonitrile (13.8 g, 0.11 mol) in EtOH (500 mL) and cone. HCl (50 mL) was heated at reflux overnight. After removal of the solvent, the residue was purified by column chromatography to afford 3-t-butyl-1-(4- methoxyphenyl)-lH-pyrazol-5-amine (20 g, 82% yield). |
82% | With acetic acid; In ethanol; for 3h;Reflux; | 4,4-Dimethyl-3-oxo-pentanenitrile (14.28 g, 1 14 mmol) and 4- methoxyphenyl hydrazine (19.89 g, 1 14 mmol) were dissolved in a mixture of absolute ethanol (170 mL) and glacial acetic acid (5.0 mL) then heated to reflux for 3 h, before allowing to standing overnight at RT. The resulting red/brown solid was filtered off and the filtrate was then diluted with water (500 mL), and basified with 880 ammonia solution until the pH = 5. This aqueous solution was extracted into diethyl ether (3 x). The combined organics were dried (MgSO4) and evaporated in vacuo to a brown oil. Trituration (pentane) gave the title compound as a light purple/brown solid (23.07 g, 94.1 mmol, 82%). LCMS (method 1): Rt 2.87 min, m/z 246/247 [MH+]. |
82% | With acetic acid; In ethanol; for 3h;Reflux; | a. 5-tert-Butyl-2-(4-methoxy-phenyl)-2H-pyrazol-3-ylamine (Intermediate 13a) 4,4-Dimethyl-3-oxo-pentanenitrile (14.28 g, 114 mmol) and 4-methoxyphenyl hydrazine (19.89 g, 114 mmol) were dissolved in a mixture of absolute ethanol (170 mL) and glacial acetic acid (5.0 mL) then heated to reflux for 3 h, before allowing to standing overnight at RT. The resulting red/brown solid was filtered off, and the filtrate was then diluted with water (500 mL), and basified with 880 ammonia solution until the pH=5. This aqueous solution was extracted into diethyl ether (3*). The combined organics were dried (MgSO4) and evaporated in vacuo to a brown oil. Trituration (pentane) gave the title compound as a light purple/brown solid (23.07 g, 94.1 mmol, 82%). LCMS (method 1): Rt 2.87 min, m/z 246/247 [MH+]. |
With acetic acid; In ethanol; for 3h;Heating / reflux; | A. General Methods for Synthesis of Heterocyclic Amines; A1 General Procedure for the Preparation of N1-Aryl-5-aminopyrazoles; [Show Image] N1-(4-Methoxyphenyl)-5-amino-3-tert-butylpyrazole: A mixture of 4-methoxyphenylhydrazine hydrochloride (3.5 g), 4,4-dimethyl-3-oxopentanenitrile (2.5 g), EtOH (30 mL), and AcOH (1 mL) was heated at the reflux temperature for 3 h, cooled to room temp., and poured into a mixture of Et2O (100 mL) and a 10% Na2CO3 solution (100 mL). The organic layer was washed with a saturated NaCl solution, dried (MgSO4) and concentrated under reduced pressure. The solid residue was washed with pentane to afford the desired pyrazole as a pale brown solid. (4.25g): 1H-NMR (DMSO-d6) δ 1.18 (s, 9H); 3.78 (s, 3H); 5.02 (br s, 2H); 5.34 (s, 1H); 6.99 (d, J=8 Hz, 2H); 7.42 (d, J=8 Hz, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With triethylamine In ethanol Heating / reflux; | N.a Intermediates Example N; [4-HYDRAZINO-1-(4-METHOXYPHENYL)-1 H-PYRAZOLO [314-ALPYRIMIDINE]; a. [5-AMINO-1- (4-METHOXYPHENYL)-1 H-PYRAZOLE-4-CARBONITRILE.] A mixture of 4-methoxyphenylhydrazine hydrochloride (5.00 g, 28.6 [MMOL),] [ETHOXYMETHYLENEMALONONITRILE] (3.49 g, 28. 6 [MMOL)] and triethylamine (4.8 mL, 34.3 [MMOL)] in 75 mL of absolute ethanol was heated at reflux overnight. The solvent was removed under vacuum and the residue was extracted between ethyl acetate and saturated aqueous sodium bicarbonate. The organic phase was dried over sodium sulfate and the solvent evaporated. The residue was purified by flash chromatography with [HEXANE/ETHYL] acetate to give 4.88 g [(80%)] of product as an off-white crystalline solid. 'H NMR (DMSO) [8] 7.70 (s, 1 H), 7.35 (d, 2H), 7.05 (d, [2H),] 6.50 (br s, 2H), 3.80 (s, 3H) ppm |
72% | In ethanol at 100℃; Microwave irradiation; | |
64% | In ethanol at 105℃; for 0.333333h; microwave irradiation; |
44% | In ethanol at 20℃; for 24h; | |
In ethanol for 4h; Heating; | ||
In methanol at 100 - 120℃; microwave irradiation; | ||
In ethanol at 100℃; | ||
With triethylamine In ethanol at 20℃; | ||
In ethanol | ||
With triethylamine In ethanol for 1h; Reflux; | ||
In ethanol for 6h; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: ethanol / Heating 2: isoamyl nitrite / tetrahydrofuran 3: 1 N aq. NaOH / ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With acetic acid; In ethanol; at 20℃; for 3h;Heating / reflux; | EXAMPLE 9; 6-Methoxy-2,3,4,9-tetrahydro-l.ff-carbazol-3-ol [Compound No. 91; 4-Methoxyphenylhydrazine (0.644 g, 3.688 mmol) was suspended in acetic acid (20 mL) and ethanol (10 mL). 4-Hydroxycyclohexanone (0.420 mg, 3.688 mmol) was dissolved in acetic acid (10 mL) and then added to the reaction mixture at room temperature, with stirring. The reaction mixture was heated under reflux for 3 hours. The solvents were partially removed under reduced pressure and then the reaction mixture was diluted with water (25 mL) and extracted with ethyl acetate (2x50 mL). The organic layers were collected and dried (MgSO4), and the solvents were removed under reduced pressure to give a brown oil. The crude product was purified by column chromatography using silica gel and (ethyl acetate/n-hexane Vz). Fractions containing the required material were collected and the solvent removed under reduced pressure to give the product as a fine crystalline material (661 mg, 83%), mpl00-103C [CW. Bird, A.G.H. Wee, J.Heterocycl.Chem., 1985, 22, 191-192, mpl03-106C], RF=0.17 (ethyl acetate/n-hexane 1/1). IR (KBr): 3392, 2916, 2841, 1622, 1590, 1483, 1436, 1214, 1176, 1050, 1020, 830, 798 cm."1 1H NMR (CDCl3): 7.6O(1H. br), 7.19(1H, d, J=8.7Hz), 6.92(1H, d, J=2.4Hz), 6.81(1H, dd, J=2.4 & 8.71Hz), 4.29(1H, m), 3.86(3H, s), 3.09-2.67(4H, m), 2.11-2.02(2H, m), 1.75(1H5 br). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In toluene; at 20℃; for 12h;Heating / reflux; | The title compound is prepared according to a published literature procedure (see J. Med.Chem. 2002, 45, 2994-3008): 3.9 g (31.5 mMol) of pivaloylacetonenitrile are added to a solution of 5.5 g (31.5 mMol) 4-methoxyphenylhydrazine in 50 ml of toluene at rt, and the resulting yellow solution is heated to and kept under reflux for 12 h. After completion the reaction mixture is concentrated and dried to give the title compound as a yellow solid: MS:[M+1]+ = 246. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In ethanol; at 120 - 150℃; for 0.5h; | 2-(4-methoxy-phenyl)-1 ,2-dihydro-pyrazolo[4,3-c]quinolin-3-one: To 1 ml of EtOH, 4-chloro- quinoline-3-carboxylic acid ethyl ester (1 .00 mmol), (4-methoxyphenyl)-hydrazine (1.05 mmol) and 350 mul of triethylamine are added. The mixture is stirred in a sealed flask in a microwave reactor for 10 min at 1509C and then for 10 min at 1209C. Then, further (4- methoxyphenyl)-hydrazine (0.5 mmol) is added. The mixture is stirred under the same conditions for 10 min at 150C and then slowly cooled to rt. The precipitated solid is filtered off, washed with EtOH and diethyl ether and dried under vacuum to yield the title compound in the form of a yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With NiCl2·6H2O In lithium hydroxide monohydrate at 20℃; for 3h; Green chemistry; | General procedure for the synthesis of Phthalazin-1(2H)-ones: General procedure: In a round bottom flask a mixture of 2-carboxybenzaldehyde (1 mmol), hydrazine derivative (1.2 mmol), NiCl2.6H2O (10 mol%) and 4 ml water was added and then allowed to stir at room temperature for the given time period as mentioned in Table 4. The progress of the reaction was monitored by TLC. After completion of the reaction, it was extracted with ethyl acetate (3x20 mL), washed with deionized water and brine solution, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography (20-25% EtOAc/hexane) to get the desired product. |
83 %Chromat. | With montmorillonote K-10 at 100℃; for 0.0166667h; Microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With triethylamine In acetic acid at 120℃; for 30h; | 4.a; 5.a; 2 To a suspension of ethyl 3-oxohexanoate (0.58 mL, 3.62 mmol) and (4- methoxyphenyl)hydrazine (0.50 g, 3.62 mmol) in AcOH (3.5mL) was added Et3N (0.58 mL, 4.16mmol). The mixture was stirred at 120°C for 30 h. The solvent was removed by evaporation, and the residue was dissolved in DCM/EtOAc which was washed with saturated aqueous NaHC03, followed by water and dried using phase separator. Concentration in vacuo, and purification using silica chromatography (CH2Cl2:Et20 3: 1) gave l-(4-methoxyphenyl)-3 -propyl- lH-pyrazol-5(4H)-one (495 mg, 59%). |
59% | With acetic acid; triethylamine at 120℃; for 30h; | 4.a; 5.a Example 4 and 5 5-(3,5-dimethylisoxazol-4-yl)-1-(4-hydroxyphenyl)-3-propyl-1H-pyrazole-4-c- arbaldehyde oxime (E4) 5-(3,5-dimethylisoxazol-4-yl)-N'-hydroxy-1-(4-hydroxyphenyl)-3-propyl-1H-p- yrazole-4-carboximidamide (E5) Step (a): To a suspension of ethyl 3-oxohexanoate (0.58 mL, 3.62 mmol) and (4-methoxyphenyl)hydrazine (0.50 g, 3.62 mmol) in AcOH (3.5 mL) was added Et3N (0.58 mL, 4.16 mmol). The mixture was stirred at 120° C. for 30 h. The solvent was removed by evaporation, and the residue was dissolved in DCM/EtOAc which was washed with saturated aqueous NaHCO3, followed by water and dried using phase separator. Concentration in vacuo, and purification using silica chromatography (CH2Cl2:Et2O 3:1) gave 1-(4-methoxyphenyl)-3-propyl-1H-pyrazol-5(4H)-one (495 mg, 59%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
48% | With zinc(II) chloride In 1,2-dimethoxyethane at 110℃; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With 2,2,2-trifluoroethanol for 0.5h; Reflux; regioselective reaction; | 4.2. General procedure for preparation of the arylpyrazole derivatives Arylhydrazine (1.2 mmol) in TFE (0.5 ml) was slowly added to a solution of β-dicarbonyl (1.2 mmol) and N,N-dimethylformamide dimethyl acetal (1.2 mmol) in TFE (0.5 ml) at room temperature. The progress of reactions was monitored by TLC. After completion of the reaction solvent was evaporated under reduced pressure, and water (10 ml) was added to the residue and extracted with ethylacetate (2× 10 ml). The organic layer was successively washed with sodium hydrogen carbonate solution and water, and then dried with magnesium sulfate. Evaporation of the solvent afforded 4-carboxylate pyrazole. If necessary the products were further purified by column chromatography on silica gel.CommentReactions with 1,3-cyclohexanedione were carried out at reflux temperature (refPreviewPlaceHolderTable 2, entries 10-12). In the case of open-chain β-diketones, under optimal reaction conditions two equivalents of DMFDMA were used (refPreviewPlaceHolderTable 2, entries 13-18). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With 2,2,2-trifluoroethanol at 20℃; for 0.5h; regioselective reaction; | 4.2. General procedure for preparation of the arylpyrazole derivatives Arylhydrazine (1.2 mmol) in TFE (0.5 ml) was slowly added to a solution of β-dicarbonyl (1.2 mmol) and N,N-dimethylformamide dimethyl acetal (1.2 mmol) in TFE (0.5 ml) at room temperature. The progress of reactions was monitored by TLC. After completion of the reaction solvent was evaporated under reduced pressure, and water (10 ml) was added to the residue and extracted with ethylacetate (2× 10 ml). The organic layer was successively washed with sodium hydrogen carbonate solution and water, and then dried with magnesium sulfate. Evaporation of the solvent afforded 4-carboxylate pyrazole. If necessary the products were further purified by column chromatography on silica gel.CommentReactions with 1,3-cyclohexanedione were carried out at reflux temperature (refPreviewPlaceHolderTable 2, entries 10-12). In the case of open-chain β-diketones, under optimal reaction conditions two equivalents of DMFDMA were used (refPreviewPlaceHolderTable 2, entries 13-18). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With Bathocuproine; palladium diacetate; acetic acid In methanol; chlorobenzene at 40℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | In ethanol for 0.333333h; Reflux; | 2.2 2.2 Preparation of the ethyl 5-amino-1-(4-methoxyphenyl)-1H-pyrazole-4-carboxylate (L) The ligand was prepared following the procedure described in the literature [16]. To a mixture of 4-methoxyphenylhydrazine (9 mmol, 1.24 g) dissolved in 10 mL of boiling ethanol was added slowly a solution of ethyl (ethoxymethylene)cyanoacetate (9 mmol, 1.52 g) dissolved in 10 mL of ethanol. The reaction medium was refluxed for 20 min. Then, the mixture was poured into 50 mL of ice-cold water. The precipitate was collected by filtration and washed with water. Yield: 1.58 g (83%). Mp: 151-153 °C. IR (KBr. cm-1): 3400-3140; 2995; 2912; 1677; 1621; 1552; 1528; 1280; 781-697. H NMR (300 MHz, CDCl3, δ ppm): 7.72 (s, 1H), 7.36 (d, J = 8.9 Hz, 2H), 6.95 (d, J = 8.6 Hz, 2H), 5.13 (br, 2H), 4.23 (q, J = 7.1 Hz, 2H), 1.29 (t, J = 7.1 Hz, 3H). |
70% | In ethanol at 20 - 85℃; for 10h; | To a solution of 4-methoxyphenyl hydrazine 1 (500 mg, 3.59 mmol) in ethanol (3 mL) was added ethyl 2-cyano-3-ethoxyacrylate 2 (600 mg, 3.53 mmol) at room temperature. The reac- tion temperature was increased to 85 °C and the mixture was stirred at this temperature for 10 h. The reaction mixture was cooled to room temperature and then poured into ice-cold 2N NaOH solution (10 mL). This mixture was filtered and the remanens dried in vacuo to give the crude ethyl ester (0.65 g, 70%). 1 H NMR (DMSO-d6, 400 MHz) δ 7.65 (1 H, s), 7.43-7.40 (2H, d), 7.08-7.06 (2H, d), 6.17 (2H, s), 4.23-4.18 (2H, m), 3.81 (3H, s ), 1 .28-1 .24 (3H, t). |
70% | In ethanol for 6h; Heating; | General procedure for synthesis ofsubstituted ethyl 5-amino-1H-pyrazole-4-carboxylate (2) General procedure: Ethyl 5-amino-1-phenyl-1H-pyrazole-4-carboxylate (2a)Phenylhydrazine (1 equivalent) in ethanol was added drop wise to ethanolic solution of ethylehoxymethylene cyanoacetate (1 equivalent). The reaction was refluxed at 70 C for 6-7 hours. The reaction mixture was poured in ice cold water and stirred for 15-20 min when a precipitate separates out. The precipitate formed was filtered off and dried. Yield: 90%; Melting point: 92°C; LC-ESI-MS (m/z): 232.2 (M+1). |
Stage #1: 4-Methoxyphenylhydrazine; ethyl (ethoxymethylene)cyanoacetate In ethanol at 85℃; for 10h; Stage #2: With sodium hydroxide In ethanol Cooling with ice; | IM21.1 IM21: 2-(4-Methoxy-phenyl)-2H-pyrazol-3-ylamineStep 1:To a solution of 4-methoxyphenyl hydrazine 1 (500 mg, 3.59 mmol) in ethanol (3 mL) was added ethyl 2-cyano-3-ethoxyacrylate 2 (600 mg, 3.53 mmol) at room temperature. The reaction temperature was increased to 85° C. and the mixture was stirred at this temperature for 10 h. The reaction mixture was cooled to room temperature and then poured into ice-cold 2N NaOH solution (10 mL). This mixture was filtered and the remanens dried in vacuo to give the crude ethyl ester (0.65 g, 70%). 1H NMR (DMSO-d6, 400 MHz) δ 7.65 (1H, s), 7.43-7.40 (2H, d), 7.08-7.06 (2H, d), 6.17 (2H, s), 4.23-4.18 (2H, m), 3.81 (3H, s), 1.28-1.24 (3H, t). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | Stage #1: 1-(benzo[b]furan-2-yl)ethanone; phenylacetylene With potassium <i>tert</i>-butylate In dimethyl sulfoxide at 100℃; for 0.5h; Stage #2: 4-Methoxyphenylhydrazine In dimethyl sulfoxide at 100℃; | 3.13 General procedure for the synthesis of 5-benzyl-4,5-dihydropyrazoles General procedure: To a 15-mL flask, ketones 1 (1.2mmol), arylacetylenes 2 (1.0mmol), DMSO (4.0mL), and KOtBu (1.5mmol) were successively added. The reaction mixture was heated (100°C) and stirred at 100°C for 30min, followed by the addition of hydrazines 3 (1.2mmol). The reaction mixture was kept at the same temperature (100°C) for an additional 3-6h until completion (monitored by TLC). Upon cooling to room temperature, the reaction mixture was diluted with H2O (10mL), neutralized with NH4Cl. When precipitated, the residue was filtered off, washed with water, and recrystallized. If the residue did not precipitate, the reaction mixture was extracted with ethyl acetate (3×10mL). The organic extract was washed with H2O (3×5mL)and dried over magnesium sulfate. After filtration, the solvent was evaporated to dryness under reduced pressure and the residue was purified by flash column chromatography (petroleum ether/ethyl acetate 20:1) to afford 5-benzyl-4,5-dihydropyrazoles 4. 4.3.13 3-(Benzofuran-2-yl)-5-benzyl-1-(4-methoxyphenyl)-4,5-dihydro-1H-pyrazole (4mab) Yellow crystals; mp 145-146 °C; 1H NMR (500 MHz, CDCl3): δ 7.58-7.56 (m, 2H), 7.40-7.23 (m, 9H), 7.00-6.95 (m, 2H), 6.82 (s, 1H), 4.71-4.65 (m, 1H), 3.86 (s, 3H), 3.34-3.21 (m, 2H), 3.08 (dd, J=16.6, 4.9 Hz, 1H), 2.67 (dd, J=13.8, 10.1 Hz, 1H) ppm; 13C NMR (125 MHz, CDCl3): δ 155.2, 154.0, 150.3, 138.7, 137.8, 137.3, 129.4, 128.8, 128.5, 126.8, 125.0, 123.2, 120.9, 116.2, 114.8, 111.5, 105.2, 62.2, 55.7, 37.2, 37.1 ppm; HRMS (m/z) (ESI): calcd for C25H23N2O2 383.1760 [M+H+]; found 383.1750. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With sodium acetate; palladium diacetate In butanone at 50℃; for 3h; | 1 Example 1 0.5 mmol of p-methoxyphenylhydrazine, 0.5 mmol sodium acetate, 0.01mmol palladium acetate was added to the reaction tube with 2ml butanone, Heated to 50 degrees Celsius Magnetic stirring for 3 hours. The reaction is completed, After reduced to room temperature filter paper filter, Spin the solvent, Recrystallization obtained products, The yield is 97%. |
94% | With oxygen; palladium diacetate; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetone; toluene at 50℃; for 3h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With bis-triphenylphosphine-palladium(II) chloride; sodium dodecyl-sulfate; potassium carbonate; p-toluenesulfonyl chloride In water at 60℃; | Typical procedure for Pd-catalyzed Suzuki cross-coupling of arylhydrazines with aryl boronic acids General procedure: A mixture of arylhydrazine 1 (0.24mmol, 1.2equiv.), aryl boronic acid 2 (0.2 mmol), K2CO3(0.6 mmol, 3.0 equiv.), p-toluenesulfonylchloride (0.24 mmol, 1.2 equiv.), sodium dodecyl sulfate (0.02 mmol, 10 mol %), and PdCl2(PPh3)2(0.01 mmol, 5 mol %) was stirred at 60 °C in water (2.0 mL) for 4-8 h under air.After completion of the reaction (indicated by TLC), the mixture was quenched with saturatedNaCl solution, extracted by EtOAc,and dried with Na2SO4. The crude product was purified by flash columnchromatography to provide the corresponding product 3. |
79% | With [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride; potassium carbonate In methanol at 50℃; for 3h; | General procedure for Suzuki-Miyaura reaction General procedure: To a round bottle with a magnetic stir bar, catalyst, arylhydrazine (0.5 mmol), (hetero)arylboronic acid (0.75 mmol), Base (1.0 mmol) and 3 ml of solvent were added. The reaction mixture was conducted at 50 °C for the required time, and then the solvent was removed under reduced pressure. The residual was diluted with Et2O (5 mL), followed by extraction twice (2×5 mL) with Et2O. The organic layer was dried with anhydrous MgSO4, filtered and evaporated under vacuum. The conversions rates were analyzed by gas chromatography, based on the peak area normalization method. The corrected factor was determined by samples against a standard of n-heptane. The crude products were purified by silica-gel column chromatography using petroleum ether as an eluent, and the isolated yield was then calculated based on the feeding of the aryl halide. The isolated corresponding products were characterized by 1H NMR and 13C NMR. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With bis-triphenylphosphine-palladium(II) chloride; sodium dodecyl-sulfate; potassium carbonate; p-toluenesulfonyl chloride; In water; at 60℃; | General procedure: A mixture of arylhydrazine 1 (0.24mmol, 1.2equiv.), aryl boronic acid 2 (0.2 mmol), K2CO3(0.6 mmol, 3.0 equiv.), p-toluenesulfonylchloride (0.24 mmol, 1.2 equiv.), sodium dodecyl sulfate (0.02 mmol, 10 mol %), and PdCl2(PPh3)2(0.01 mmol, 5 mol %) was stirred at 60 C in water (2.0 mL) for 4-8 h under air.After completion of the reaction (indicated by TLC), the mixture was quenched with saturatedNaCl solution, extracted by EtOAc,and dried with Na2SO4. The crude product was purified by flash columnchromatography to provide the corresponding product 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With hydrogenchloride In water for 16h; Reflux; | |
With sulfuric acid In 1,4-dioxane at 80℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | In ethanol; water at 20℃; for 15h; | General procedure for preparation of 4-oxo-3-substituted phenyl-3,4-dihydrophthalazine-1-carboxylic acid (23a-h) General procedure: To a solution of 22 (13 g, 0.067 mol) in water (100 mL), an appropriate phenyl hydrazine (0.067 mol) in ethanol (200 mL) was added. After stirring at room temperature for 15 h, the resultant precipitate was filtered, washed with dichloromethane and dried under vacuum to afford the title compounds 23a-h. |
36.2% | In ethanol; water at 20℃; for 12h; | 5.1.13 General procedure for the preparation of 3-substituted phenyl-4-oxo-3,4-dihydrophthalazine- 1-carboxylic acid (13a-e) General procedure: A mixture of compounds 11 (15.7g, 81mmol) and 12a-e (88mmol) in ethanol (25.5mL) and water (62.7mL) was stirred at room temperature for 12h. The precipitate was collected by filtration, and then dissolved in 5% potassium hydroxide solution, stirred for 1h. The reaction mixture was filtrated, washed with dichloromethane, and then acidified to pH 3-4 by concentrated hydrochloric acid. The target compounds 13a-e was collected by filtration. |
In ethanol; water at 20℃; for 15h; | 4.3.2 Preparation of intermediates 9a-s and 10a-s General procedure: Prepare a mixed solution of 30mL of ethanol and water (1:2), dissolve the corresponding aromatic hydrazine hydrate (10.30mmol) in 20mL of the mixed solution and drop into the 10mL mixed solution of compound 8. The mixture was stirred at room temperature for 15h. Precipitation was filtered and washed with dichloromethane twice, then vacuum dried to give intermediates 9a-s. To the corresponding intermediate 9a-s (10.0mmol), thionyl chloride (15mL) was added and the mixture was heated to reflux for 5-7h. Extra liquid was evaporated under reduced pressure to give compound 10a-s |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | at 160℃; for 0.166667h; Microwave irradiation; Sealed tube; | General procedure: To a dried microwave tube was added phenylhydrazine (108mg, 1 mmol) and formamide (0.82 mL, 20 mmol). The tube was sealed with a plastic microwave septum and then placed into the microwave cavity and irradiated at 160 °C, 250 psi, and 230W for 10 min. After completion of reaction (TLC), the mixture was cooled to r.t.; distilled H2O (10 mL) was added, and the mixture extracted with EtOAc (3 × 10 mL). The combined organic extracts were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography using a mixture of n-hexane and EtOAc as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With Amberlite IR 120 In ethanol at 80℃; for 10h; | EXPERIMENTAL General procedure: A mixture of the carbonyl compound (5, 1.0 mmol), arylhydrazine (6, 1.2 mmol), and the solid acid (7, Amberlite, 1.5 g, obtained from Aldrich Chemical Co.) was refluxed in absolute ethanol (10 ml) for 8 h. The reaction was monitored by thin-layer chromatography(TLC), and upon completion the mixture was cooled to room temperature, the catalyst filtered off, and the product was washed thoroughly with ethylacetate (30 ml). The combined organics were washed with water, dried (Na2SO4), and concentrated in vacuo. The resulting residue was chromatographed on a silicagel column eluting with ethylacetate-hexane mixtures to obtain the purified indole (8). This was fully characterized by infrared, 400-MHz 1H NMR, high-resolution mass spectrometry, and melting point (solids). |
In ethanol; water for 24h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With Amberlite IR 120 In ethanol at 80℃; for 8h; | EXPERIMENTAL General procedure: A mixture of the carbonyl compound (5, 1.0 mmol), arylhydrazine (6, 1.2 mmol), and the solid acid (7, Amberlite, 1.5 g, obtained from Aldrich Chemical Co.) was refluxed in absolute ethanol (10 ml) for 8 h. The reaction was monitored by thin-layer chromatography(TLC), and upon completion the mixture was cooled to room temperature, the catalyst filtered off, and the product was washed thoroughly with ethylacetate (30 ml). The combined organics were washed with water, dried (Na2SO4), and concentrated in vacuo. The resulting residue was chromatographed on a silicagel column eluting with ethylacetate-hexane mixtures to obtain the purified indole (8). This was fully characterized by infrared, 400-MHz 1H NMR, high-resolution mass spectrometry, and melting point (solids). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With oxygen; potassium carbonate In dimethyl sulfoxide at 20℃; for 18h; Further stages; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With acetic acid In ethanol for 2h; Reflux; | 5.1.1. General procedure for the preparation of 1-substituted 1,5,6,7-tetrahydro-4H-indazol-4-ones(8a-h) General procedure: To a solution of compound 7 (3 g, 18 mmol) in a mixture ofethanol and acetic acid (2:1) (48 mL) or, for the synthesis of compounds8 e-g, only glacial acetic acid (30 mL) the suitable hydrazine(18 mmol) was added and the reaction mixture was heated underreflux for 2 h. Then, the reaction mixture was poured onto crushedice and the solid was filtered off, dried and purified by chromatography(DCM/AcOEt 9:1) as eluent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With bis(benzonitrile)palladium(II) dichloride; camphor-10-sulfonic acid; tetrabutyl ammonium fluoride In tetrahydrofuran at 50℃; for 3h; | Typical procedure forthe product General procedure: A mixture of arylhydrazine (1 mmol), triethoxy(phenyl)silane (1.2 mmol), Pd(PhCN)2Cl2 (5 mol%) and CSA (camphorsulfonic acid, 1 mmol) was stirred in thesolvent of TBAF (1 M in THF, 1.0 ml) at 50oC for 3 hours under air. After cooling down to room temperature, the insoluble was firstremoved by filtration and then the solvent was removed undera reduced pressure. The cross-coupling products were purified by silica gelchromatography with a mixture of petroleum ether and ethyl acetate. Thecross-coupling products were confirmed by melting point and spectroscopic (1HNMR, 13C NMR and HRMS-EI) analysis, which wereall consistent with the literature results. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68.067 % de | In dichloromethane at 20℃; for 3h; Molecular sieve; Inert atmosphere; Overall yield = 57 %; Overall yield = 180 mg; | 4.2 General experimental procedure 1: preparation of aryl hydrazones General procedure: A ketone (1.0equiv, 1.0 mmol) was added to a room temperature solution of aryl hydrazine (1.2equiv, 1.2mmol) in CH2Cl2 (8mL) containing 4 molecular sieves under a nitrogen atmosphere. After stirring at room temperature for three hours, the solution was filtered and the filtrate was concentrated. The residue was dissolved in hexane (12mL), was passed through a plug of basic alumina and was concentrated in vacuo to provide a diastereomeric mixture of the hydrazone as a yellow oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With cobalt(II) phthalocyanine; copper diacetate In dichloromethane at 20℃; | 27 Synthesis of 4-methoxydiphenylamine Aniline reaction flask was added 0.093 g (1 mmol), 4- hydrazino anisole 0.179 g(1.3 mmol), CoPc 0.057 Ke (0.1 mmol), Cu (OAc) 2 0.02 g (0.1 mmol) and 10 ml of methylenechloride, 20 °C reaction; TLC until the reaction was followed completely finished; thecrude product after the reaction was subjected to column chromatography (petroleumether: ethyl acetate = 100: 1) to give the target product (92% yield). |
85% | With tetrabenzoporphyrinatocobalt(II); copper diacetate In acetonitrile at 0℃; for 13h; chemoselective reaction; | 3.23 4.2.1. General procedure for N-arylation of amines (2) with arylhydrazines (1). General procedure: Into a 25 mL round-bottom flask, amine (2) (1 mmol), Cu(OAc)2 (0.02 g, 0.1 mmol) and acetonitrile (4 mL) were added, the mixture was stirred and cooled to 0 °C. Then, CoPc (0.057 g, 0.1 mmol) was added, the solution of arylhydrazine (1) (2 mmol) in acetonitrile (2 mL) was added successively at a rate of 0.2 mmol per hour while stirring for 13 h in air. After completion of the reaction monitored by TLC analysis (developing solvent: ethyl acetate/petroleum ether (1:8)), the mixture was filtered, concentrated, and the residue was further purified by column chromatography using ethyl acetate/petroleum ether (1:100) as eluent to afford N-aryl amine 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With acetic acid; for 4h;Reflux; | General procedure: Compound 1 (10 mmol) was dissolved in acetic acid (30 mL), andlevulinic acid (15 mmol) was added to the stirred solution which wasthen refluxed for 4 h. After cooling to room temperature, the mixturewas poured into water (200 mL) and then the solution was treated with30% sodium hydroxide to slight acidity (pH = 5-6). The precipitatedsolid was filtered off, recrystallised from ethanol and dried in vacuo togive compound 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With potassium permanganate In acetonitrile at 80℃; for 3h; Schlenk technique; regioselective reaction; | 4.2 General experimental procedure for thesynthesis of 3-arylcoumarins (3) and3-arylquinolinone derivatives (5) General procedure: In a 50 mL Schlenk tube, a solution of coumarins 1 (orquinolinone derivatives 4) (0.5 mmol), arylhydrazines 2(1.0 mmol), and KMnO4 (1.5 mmol, 237 mg) in CH3CN (10mL) was stirred at 80°C for 3.0 h. After the reaction wasfinished, the mixture was diluted with saturated NaClsolution (50 mL). Then the aqueous layer was extractedwith EtOAc (3 × 15 mL). The organic phase was dried overanhydrous Na2SO4 and concentrated under vacuum. Thecrude product was purified by silica gel column chromatographyusing ethyl acetate/petroleum ether (1:5 to 2:1) aseluant to obtain the desired product 3 (or 5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69.5% | In methanol; at 20℃; for 2h; | General procedure: The equimolar aldehyde 3a?3d (1 mmol) and substituted phenylhydrazine 5a?5s (1 mmol) weremixed in CH3OH (10 mL) and stirred at room temperature [18]. After about 2 h, the reaction wascompleted (monitored by TLC). The residual crude was purified via silica gel column chromatogramusing a gradient mixture of petroleum ether and ethyl acetate to obtain the pure target compounds6a?6ai (in 45?80percent yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium permanganate In acetonitrile at 90℃; for 1h; Schlenk technique; regioselective reaction; | 4.2. General experimental procedure for the synthesis of 2-arylquinoline N-oxides (3) General procedure: Quinoline N-oxides 1 (0.3 mmol), arylhydrazines 2 (0.45 mmol), and KMnO4 (0.6 mmol, 94.8 mg) in acetonitrile (3.0 mL) were added to a 25 mL Schlenk tube. The mixture was heated at 90 °C for 60 min (monitored by TLC). After completion of the reaction, the solvent was distilled under vacuum. 10 mL ethylacetate was added to the residuum, and 30 mL saturated sodium chloride solution washed three times. The organic phase was dried over anhydrous NaSO4 and concentrated under vacuum. The crude product was purified by silica gel column chromatography to give the desired products 3 using ethyl acetate/petroleum ether (1:10 to 1:3) as eluant. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With [2,2]bipyridinyl; water; oxygen; palladium diacetate; trifluoroacetic acid In 1,4-dioxane at 90℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46.86% | With triethylamine; In ethanol; at 80.0℃; for 6.0h; | To the reactor was added 200 mg (1 mmol) of <strong>[87080-27-1]licorice chalcone A</strong> and 106.16 mg (1.3 mmol) of p-methoxyphenylhydrazine, Add 50ml of anhydrous ethanol as the reaction solvent, add 0.5mL of triethylamine as a catalyst, placed on a magnetic stirrer, with electric The mixture was heated to 80 C and refluxed for 6 hours. The solid solution was mixed with the above reaction system after the reaction was completed The residue was purified by column chromatography and dried to obtain brown crystalline powder (127 mg) in a total yield of 46.86%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | Stage #1: trans-1-(3,5-Dimethoxyphenyl)-2-nitroethylene With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In acetonitrile at 20℃; for 0.166667h; Stage #2: 4-Methoxyphenylhydrazine In acetonitrile at 20℃; for 4.75h; diastereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
38% | In ethanol at 90℃; | General procedure (GP4) for the preparation of pyrazoles 30a-39a, 41a-46a, 34b, 35b, 37b-40b, 42b-44b General procedure: Hydrazine derivatives (2mmol, 2.0 equal) was added to a solution of flavones (1mmol, 1.0 equal) or isoflavones (1 mmol, 1.0 equal) in EtOH (10 mL). The mixture was stirred for 8-12h at 90°C and the solvent was then evaporated in vacuum. The residue was purified by silica gel column chromatography, eluting with a solution of 10%-30% MeOH in dichloromethane (Scheme S3), to yield yellow solid 30a-39a, 41a-46a, 34b, 35b, 37b-40b, 42b-44b. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With palladium diacetate; potassium carbonate In 1-methyl-pyrrolidin-2-one at 60℃; for 3h; | |
91% | With tris(2-thienyl)phosphine; palladium diacetate; potassium carbonate In 1-methyl-pyrrolidin-2-one at 60℃; for 3h; | 4 Example 4 General procedure: In the reaction flask, aryl hydrazine (1 mmol), brominated aromatic hydrocarbon (1.1 mmol), Pd(OAc) 2 (0.02 mmol), ligand TFP (0.03 mmol), K2CO3 (2.0 mmol) and 2 mL of NMP were added and stirred. Then, the reaction was carried out by heating to 60 ° C. After reacting for 3 hours, the reaction was completely monitored by TLC, and the mixture was cooled to room temperature. The solid was filtered off, and then, after adding 1 mL of water, the mixture was extracted three times with 2 mL of diethyl ether, and the combined extracts were evaporated to dryness. The product is obtained by column separation using an ester mixed solvent as an eluent. The reaction conditions and reaction results are shown in Table 4, and the reaction formula is as follows: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 6 steps 1: hydrogenchloride / water / Heating 2: sulfuric acid / 230 °C / 19502 Torr 3: sulfuric acid; copper / 210 °C 4: copper dichloride; sodium hydroxide / water / 0.5 h / 350 °C 5: sulfuric acid; potassium dichromate / water / 170 °C 6: hydrogen iodide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | With potassium <i>tert</i>-butylate; ammonium acetate; tetra-(n-butyl)ammonium iodide at 20℃; for 6h; Electrolysis; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; acetic acid In methanol at 60℃; Inert atmosphere; | 2 6.2 Synthesis of 6-methyl-1-(4-phenylbutylamino)-1H-2,3,4,9-tetrahydrocarbazole (5) General procedure: To a solution of 1,2-cyclohexanedione (2243 mg, 20 mmol) and concentrated hydrochloric acid (13 mL) in acetic acid (40 mL), p-tolylhydrazine hydrochloride (1586 mg, 10 mmol) in methanol (25 mL) was added dropwise slowly over 10 min. After the addition, the resulting mixture was heated to 60 °C, and stirred overnight. The solvent was evaporated, and the residue was pH adjusted to weak alkaline with saturated NaHCO3. The mixture was extracted with AcOEt (3 * 20 mL). The combined organic extract was washed with brine, dried over anhydrous Na2SO4, and concentrated. The residue was purified by silica gel chromatography (petroleum ether/AcOEt, 12/1 v/v) to give intermediate 7 (1235 mg, 62%) as a brown powder. The mixture of intermediate 7 (102 mg, 0.5 mmol), 4-phenylbutylamine (0.12 mL, 0.8 mmol) and catalytic p-TsOH in toluene (10 mL) was refluxed at 140 °C for 16 h with a Dean-Stark trap in place. The solvent was evaporated and the residue was dissolved in methanol. NaBH4 (177 mg) was then added at 0 °C. The solution was heated to 80 °C until TLC indicated the reaction was complete. The reaction was quenched with water and concentrated. Subsequently, the mixture was extracted with AcOEt twice and the combined organic layers were dried over anhydrous Na2SO4. After evaporation of the solvent, the resulting residue was purified by column chromatography on silica gel (petroleum ether/AcOEt, 4/1 v/v) to give compound 5 (123 mg, Yield: 72%). | |
Stage #1: cyclohexane-1,2-dione; 4-Methoxyphenylhydrazine In water at 23℃; for 16h; Stage #2: With hydrogenchloride In water at 120℃; for 12h; | General procedure to prepare ketones iii General procedure: A mixture of a substituted phenylhydrazine i (3.0 mmol), 1,2-cyclohexanedione ii (6.0 mmol), and water (50 mL) was stirred at room temperature (23 °C) in a 250 mL round bottom flask. After 16 h,10 mL of aqueous 1 M HCl was added and the reaction was heated to reflux. After 12 h, the reaction was refrigerated to induce crystallization. The resulting solid was filtered and air dried to provide the crude product. The desired product was purified by flash column chromatography (SiO2) using 20-30% ethyl acetate in hexanes as the eluent. NMR of products were compared to literature values to confirm structure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With silver(I) acetate; lithium carbonate In 1,2-dichloro-ethane at 110℃; for 12h; Schlenk technique; Green chemistry; | 1 This example is 4-methoxybenzophenone(3aa) specific preparation method and structural analysis. To 15mL Schlenk in an atmospheric oxygen or air atmosphereTo the reaction tube, p-methoxybenzoquinone compound 1a (27.6 mg, 0.20 mmol) was added in that order.Carbonyl formate 2a (30 mg, 0.20 mmol), silver acetate (3.5 mg, 0.02 mmol),Lithium carbonate (15 mg, 0.20 mmol), 1,2-dichloroethane (DCE, 1 mL) was reacted at 110 ° C for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, suction filtered over Celite, and evaporated.The crude product was separated by chromatography on a prepared silica gel plate.The selected developer or eluent is a volume ratio of petroleum ether to ethyl acetate of 100:1,The product 4-methoxybenzophenone 3aa was obtained in a yield of 82% (34.8 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In ethanol for 16h; Reflux; | 3-Methyl-1-(4-(trifluoromethyl)phenyl)-1H-pyrazol-5-amine (SI-1). General procedure: (E)-3-aminobut-2-enenitrile (2.3 g, 28 mmol) and (4-(trifluoromethyl)phenyl)hydrazine (5.0 g, 28 mmol) were taken EtOH (30 mL) heated to reflux for 16 hr. The mixture was cooled and poured into water (100 mL) and extracted with EtOAc (2x 100 mL). The organic phase was washed with brine, dried over MgSO4, filtered and then concentrated to yield 6.7 g (99% crude yield) of SI-1 as a dark red oil, which was used in the next step without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With iodine In dimethyl sulfoxide at 80℃; for 9h; | 3 Synthesis of compound 3c: In the air atmosphere,Add 0.5 mmol of cyclohexanone to a solution containing 0.1 mmol of elemental iodine in DMSO.Add 0.5 mmol of 4-methoxyphenylhydrazine and stir at 80 °C for 9 hours.During the reaction, it was monitored by TLC to complete reaction. After the reaction is completed, water is added to quench it.It is then extracted with ethyl acetate and dried over anhydrous Na 2 SO 4 .The pure product azobenzene (3c) was isolated by flash column chromatography under reduced pressure.Isolated yield: 72%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid; In 1,4-dioxane; at 110℃; for 3h;Cooling with ice; | To a solution of (4-methoxyphenyl)hydrazine (1 g, 5.6 mmol) and tert-butyl 4-oxopiperidine-1- carboxylate (1 .13 g, 5.6 mmol) in 1 ,4-dioxane (10 ml_) was added cone. H2S04 (1 ml_) at ice bath temperature. Then the reaction mixture was heated at 1 10 C for 3 h. The reaction mixture was cooled to room temperature, the precipitate was filtered off. The solid was dissolved in water basified with NaOH solution and extracted with dichloromethane. The organic phase was separated and dried over Na2S04, filtered and the solvent was removed to give the title compound as a pale yellow gummy liquid (0.60 g, 53 %). The crude product as such was taken for the next step. (0322) MS: 203 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With tetrafluoroboric acid; water In acetonitrile at 20℃; for 3h; | General experimental procedure for synthesis of pyrazoles using HBF4 as catalyst room temperature General procedure: In a round bottom flask a mixture of hydrazine derivative (1 mmol) and 1,3-diketone (1.2 mmol) was taken and Fluoroboric acid (20 mol%) was added to it and then allowed to stir at room temperature for the given time period as mentioned in Table 3. The progress of the reaction was monitored by TLC. After completion of the reaction it was extracted with ethyl acetate (3×10 mL), washed with distilled water and brine solution, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified through silica gel column chromatography to get the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.074 g | With oxygen; acetic acid In acetonitrile at 80℃; for 10h; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With potassium phosphate; 1,3-dicyano-5-fluoro-2,4,6-tris(diphenylamino)benzene In acetonitrile at 20℃; for 24h; Inert atmosphere; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With potassium phosphate; 1,3-dicyano-5-fluoro-2,4,6-tris(diphenylamino)benzene In acetonitrile at 20℃; for 24h; Inert atmosphere; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With potassium phosphate; 1,3-dicyano-5-fluoro-2,4,6-tris(diphenylamino)benzene In acetonitrile at 20℃; for 24h; Inert atmosphere; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With potassium phosphate; 1,3-dicyano-5-fluoro-2,4,6-tris(diphenylamino)benzene In acetonitrile at 20℃; for 24h; Inert atmosphere; Irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 6-chloro-9-(1-methylethyl)-9H-purine; 4-Methoxyphenylhydrazine With N-ethyl-N,N-diisopropylamine In butan-1-ol at 150℃; Microwave irradiation; Stage #2: With oxygen In butan-1-ol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrahydrofuran at 20℃; for 15h; | General procedure for the synthesis of compounds 1, 2, 6-16and 18-39. General procedure: 1-10- Carbonyl diimidazole 43 (0.97 mmol; 1.5 eq) wasadded to a solution of 2-amino- 6-fluoro benzoic acid (0.65 mmol;1.0 eq) in tetrahydrofuran (7 ml) in a round-bottom flask equippedwith a stirring bar in dry conditions. The obtained mixture wasstirred for 24 h at room temperature and then the appropriatehydroxylamine 45a,b, amine 46a-k or hydrazine 47a-t was added(1.30 mmol; 2.0 eq) and the reaction mixture was stirred at roomtemperature for 16 h. At the end the mixture was quenched withsaturated aqueous sodium bicarbonate and the organic solutionwas extracted with ethyl acetate, washed with brine and dried overNa2SO4.After filtration and concentration, the crude material was purifiedby column chromatography on silica gel with a mixture ofdichloromethane/ethyl acetate in the opportune volumes to givethe expected products 1, 2, 6e16 and 18e37.Hydrochloride salts 38 and 39 were prepared by reacting a solutionof the hydrazides 20 or 21 (0.08 mmol, 1 eq) in ethanol(0.5 ml) with aqueous HCl 37% added dropwise. The mixture wasstirred for 30 min at room temperature and then the white precipitatewasseparated by filtration andwashed with cold ethanol toobtain the desired products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: glacial acetic acid / 8 h / Reflux 2: orthoperiodic acid / methanol / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With triruthenium dodecacarbonyl; C32H34N3P2(1+)*Cl(1-); anhydrous Sodium acetate In o-dimethylbenzene at 130℃; for 24h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride In ethanol; lithium hydroxide monohydrate for 18h; Reflux; |
Tags: 3471-32-7 synthesis path| 3471-32-7 SDS| 3471-32-7 COA| 3471-32-7 purity| 3471-32-7 application| 3471-32-7 NMR| 3471-32-7 COA| 3471-32-7 structure
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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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