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CAS No. : | 4360-47-8 | MDL No. : | MFCD00001930 |
Formula : | C9H7N | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | ZWKNLRXFUTWSOY-QPJJXVBHSA-N |
M.W : | 129.16 | Pubchem ID : | 1550846 |
Synonyms : |
|
Num. heavy atoms : | 10 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 1.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 41.09 |
TPSA : | 23.79 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.7 cm/s |
Log Po/w (iLOGP) : | 1.82 |
Log Po/w (XLOGP3) : | 1.96 |
Log Po/w (WLOGP) : | 2.11 |
Log Po/w (MLOGP) : | 2.01 |
Log Po/w (SILICOS-IT) : | 2.3 |
Consensus Log Po/w : | 2.04 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.25 |
Solubility : | 0.72 mg/ml ; 0.00558 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.08 |
Solubility : | 1.06 mg/ml ; 0.00823 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -2.53 |
Solubility : | 0.378 mg/ml ; 0.00292 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.99 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H317-H319 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; diethyl ether; zinc(II) chloride Erwaermen des Reaktionsprodukts mit Wasser; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With hydrogen; In methanol; at 20℃; for 9h; | General procedure: The mixture of the substrate (0.250 mmol), 0.5% Pd/MS3A or 0.5% Pd/MS5A (10 wt % of the substrate) and MeOH (1 mL) was stirred under H2 atmosphere (balloon) at room temperature. After a given period, the reaction mixture was filtered through a membrane filter (Millipore, Millex-LH, 0.45 mm), and the filtrate was concentrated in vacuo to produce the corresponding reduced product. |
84% | With water; palladium diacetate; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane; In dichloromethane; water; at 25℃; for 12h;Schlenk technique; Inert atmosphere; | Replace the gas environment in the Shrek tube with a nitrogen environment, add <strong>[4360-47-8]cinnamonitrile</strong> 0.25 mmol, palladium acetate 0.00125 mmol, methylene chloride 0.5 mL, water 0.275 mmol, add pinacol borane 0.275 mmol with stirring, and react at room temperature for 12 h After the completion of the reaction, the reaction liquid obtained was subjected to column chromatography, and the target product obtained in 84% yield was a colorless liquid. |
80% | With triethylsilane; 5%-palladium/activated carbon; hydrogen; In methanol; at 20℃; under 2068.65 Torr; for 0.333333h;Flow reactor; | General procedure: Nitro compound or olefin(5 mmol) and hydrogen source (25 mmol) were dissolved inMeOH (10 mL, 0.5 M). After flushing the column with MeOH,the substrate/reagent solution was pumped through the columnat the specified temperature with a flow rate of 0.108 mL/minby using Vapourtec E-series equipment (with a peristalticpump). Alternatively, a syringe pump can be used. The firstcolumn volume was discarded, the second was collected. Thesolvent was evaporated, the residue added to distilled water (20 mL), and extracted with diethyl ether or dichloromethane(3 × 15 mL). The combined organic phases were dried overMgSO4, filtered, and the solvent was removed in vacuo. |
42% | With sodium tetrahydroborate; ruthenium(III) trichloride hydrate; In 1-methyl-pyrrolidin-2-one; water; at 0℃; for 1h; | General procedure: To a 15-mL 1-neck reaction flask fitted with a glass stopper [Note: A larger-scale reaction may require the use of a pressure vessel and/or addition of NaBH4 in small portions.] were added a small spin bar, 0.18-0.20 mmol of substrate, 0.60 mL of 5:1 (v/v) [10:1 (v/v) in Table 1, entry 3] liquid amide(s)/H2O, and 7.0 mg (0.034 mmol) of ruthenium(III) chloride hydrate (Sigma-Aldrich Catalog No. 206229). After cooling the latter mixture to 0 C (external ice-H2O bath), 9.0 mg (0.24 mmol) of NaBH4 powder was added in one portion; and the mixture was subsequently stirred at 0 C for 60 min. The reaction was then quenched by addition of 2.0 mL of 2 M aqueous HCl to the reaction flask, followed by 1.0 mL of pentane and subsequent stirring of the mixture at 0 C for 15 min. The product was then isolated by dilution of the reaction mixture with 10 mL of 4:1 (v/v) pentane/dichloromethane; and solid material was removed by filtration through a small pad of Hyflo Super-Cel filtering aid. After dilution of the filtrate with 10 mL of pentane, removal of the liquid amide(s) was accomplished by washing the filtrate with 10% (w/v) aqueous NaCl (4 15 mL portions). The organic layer was subsequently dried over anhydrous MgSO4, filtered, and the volatile organic solvents were removed by evaporation at reduced pressure. |
100%Chromat. | With sodium tetrahydroborate; 2,5% palladium on carbon; acetic acid; In toluene; at 20℃; for 1h;Inert atmosphere; | General procedure: A 25 mL round-bottomed flask with stir bar is flushed with inert gas and charged with Pd/C catalyst (2.5 mol %), the substrate (1 mmol), tert-butylbenzene (internal standard, 1 mmol), and 5 mL of toluene. The flask is clamped over a magnetic stirrer, and the contents are stirred. Acetic acid (2 mmol) is added in a single portion via pipette. Powdered NaBH4 (4 mmol) is added in a single portion directly to the stirring heterogeneous solution (Note: Addition of the NaBH4 causes the rapid evolution of small hydrogen gas bubbles. Avoid open flames). The contents of the reaction flask are left to stir in the open air at room temperature for 1 h. Workup is conducted by quenching the reaction mixture with several mLs of 0.1 M HCl until no further hydrogen evolution is observed. The solution is then made basic using NaHCO3 and the organic portion is extracted after the addition of diethyl ether. The organic layer is then dried with MgSO4 and then filtered through glass wool or celite. Reactions are analyzed by GC/MS. |
87%Chromat. | With lithium borohydride; C30H21F6N2NiO2P; In tetrahydrofuran; at 70℃; for 3h;Schlenk technique; Inert atmosphere; | General procedure: A Schlenk flask was charged with an appropriate amount of complex 4c (0.025mmol, 2.5mol%), LiBH4 (2.0mmol) and the corresponding organic cyanide (1.0mmol). The flask was cycled with nitrogen and vacuum. Afterward THF (5.0mL) was added. The flask was sealed and heated at 70C for 3h. After that time, the mixture was cooled to room temperature, the THF was carefully removed in vacuum and the residue was dissolved in diethylether and filtered trough a short plug of silica. The products were confirmed by GC-MS (n-dodecane was added as internal standard) and NMR analysis. The analytical properties of the products are in agreement with literature data. |
With ammonium formate; In toluene; at 90℃; for 12h; | General procedure: The round bottom flask containing a,b-unsaturated carbonyl (1 mmol), HCOONH4 (3 mmol) and ImmPd-IL (2 mol %) was added toluene (10 ml) and reaction mixture heated at 90 C for 12 h. The progress of the reaction was monitored by using TLC and GC analysis. After completion,the reaction mixture was cooled to room temperature and then filtered to separate catalyst. The filtrate was then evaporated under high vacuum and obtained residue waspurified by column chromatography using silica gel (100-200 mesh size) with pet ether and ethyl acetate (95:5) to give the desired pure product. | |
With 5%-palladium/activated carbon; hydrogen; In ethyl acetate; at 30℃; under 760.051 Torr; for 1h; | General procedure: t-BuOK (5.66 g, 50.0 mmol) was added to a stirred solution of anhydrousTHF containing an appropriate benzaldehyde derivative (7a-l)(5.00 g, 42.0 mmol) and 2-diethoxyphosphorylacetonitrile (8.10 g, 46.0 mmol) at 0 C for 30 min. Then, the reaction was maintained at25 C for a further 30 min. The mixture was extracted with ethyl acetateand the combined organics were washed with brine, dried over sodiumsulfate, and concentrated to give compounds 8a-l. To a solution of 8a-lin ethyl acetate, 5% Pd/C (0.2 equiv.) was added. The suspension wasfiltered and evaporated. Then, the mixture was maintained at 30 Cunder 1 atm of hydrogen for 1 h. Removal of the solvent by rotaryevaporation gave 9a-l. Under nitrogen protection, BH3·THF (2 mol/L,20.7 mL, 41.4 mmol) was added slowly to a solution of 9a-l (4.12 g,27.6 mmol) in anhydrous THF at room temperature. Then, the reactionwas refluxed at 60 C for 2 h. The mixture was extracted with ethylacetate and the combined organics were washed with brine and driedover sodium sulfate, and concentrated to give compounds 10a-l. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With allyl bromide; 1,1'-carbonyldiimidazole In acetonitrile 1.) 0.5 h, RT; 2.) 5 h, reflux; | |
89% | With pyridine; oxalyl dichloride; N,N-dimethyl-formamide In acetonitrile | |
85% | With triethylamine; trifluoroacetyl chloride In dichloromethane |
85% | With 2-(trifluoroacetyloxy)pyridine In acetonitrile for 5h; Heating; | |
85% | With trimethylsilyl methanesulfonate; phosphorus pentoxide at 70 - 75℃; for 3h; further reagents; | |
69% | With trimethylsilylphosphate for 2.33333h; Heating; | |
With phosphorus pentachloride | ||
With ethyl phosphate In chloroform at 80℃; Yield given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With tin(II) chloride dihdyrate; hydroxylamine hydrochloride; sodium hydrogencarbonate; In acetonitrile; at 80℃; for 12h; | General procedure: A solution of aldehyde (1.0 mmol), NH2OH.HCl (1.1 mmol, 1.1 equiv.), NaHCO3 (1.0mmol, 1.0 equiv.) and SnCl2.2H2O (0.1 mmol, 10 mol %) in dry MeCN (2 mL) wasstirred at 80 C under open air and monitored by TLC. After completion of the reaction,the mixture was purified by flash chromatography. |
98% | With trifluorormethanesulfonic acid; trimethylsilylazide; In acetonitrile; at 25℃; for 0.00138889h;Flow reactor; | General procedure: General procedure for synthesis of nitriles from aldehydes incontinuous ow is as follows. Take benzaldehyde as an example,benzaldehyde (0.6 mmol) and TfOH (0.9 mmol) were dissolved in3 mL MeCN and pumped into inlet A. TMSN 3 (0.6 mmol) wasdissolved in 3 mL MeCN and pumped into inlet B (ow rate A:B = 54 m L/min:65 m L/min for 5 s residence time). The whole systemwas maintained at 25C. The ow system was equilibrated (about5 min), then the product stream was quenched and collected in aglass vessel with saturated aqueous NaClO in it. The ow systemwas stopped after the inlet A reduced 0.5 mL. The crude mixturewas dissolved in ethyl acetate and washed with saline solution. Thecombined organic layers were dried over magnesium sulfate,ltered, and concentrated under reduced pressure. The resultingcrude product was puried by ash chromatography on silica gelwith hexane and EtOAc as eluent to afford the product |
93% | With bismuth(lll) trifluoromethanesulfonate; acetylhydroxamic acid; In acetonitrile; for 18h;Reflux; | General procedure: 4-Isopropylbenzaldehyde 1a (0.50 g, 3.37 mmol), acetohydroxamic acid (0.30 g, 4.05 mmol), acetonitrile (5 ml), and Bi(OTf)3 (0.11 g, 0.17 mmol) were taken into a 25 ml round-bottomed flask fitted with a condenser and calcium chloride guard tube. The mixture was refluxed for 14 h and after completion of the reaction (GC, 10% SE-30 on Chromosorb, 10' × 1/8 column), the reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. The crude product obtained was purified by normal column chromatography(silica gel 100-200 mesh, ethyl acetate/hexane = 1:20) to obtain 4-isopropylbenzonitrile 3a (0.47 g, 97%). |
91% | With hydroxylamine hydrochloride; zinc trifluoromethanesulfonate; In toluene; at 100℃; for 24h; | General procedure for the synthesis of nitriles: A pressure tube was charged with an appropriate amount of Zn(OTf)2 (0.036 mmol, 5.0 mol %), the corresponding aldehyde (0.72 mmol) and hydroxylamine hydrochloride (1.2 equiv, 0.86 mmol). After the addition of toluene (2.0 mL) the reaction mixture was stirred in a preheated oil bath at 100 C for 24 h. The mixture was cooled in an ice bath and biphenyl (internal standard) was added. The solution was diluted with dichloromethane and an aliquot was taken for GC-analysis (30 m Rxi-5 ms column, 40-300 C). The solvent was carefully removed and the residue was purified by column chromatography (n-hexane/ethyl acetate). The analytical properties of the corresponding nitriles are in agreement with the literature. |
91% | With hydroxylamine hydrochloride; In N,N-dimethyl-formamide; for 2h;Reflux; | General procedure: Aldehyde (0.5 mmol) and hydroxylamine hydrochloride (0.75 mmol) were added successively to a solution of Fe3O4-CTAB NPs (5.7 mg) i.e Fe3O4 (1.8 mol%) in 5 ml dry DMF. The mixture was refluxed for appropriate time (table 3). The progress of the reaction was monitored by TLC. After completion of the reaction, the solution was poured into 100 ml water and extract with ethyl acetate, washed several times with water. The combined organic mixture was dried over anhydrous Na2SO4, concentrated and the residue was purified by column chromatography on silica gel 60-120 mesh using petroleum ether/ethyl acetate (95:5) as eluent to afford the pure nitrile. All the products were characterized by IR, 1H NMR and 13C NMR. |
91% | With hydroxylamine hydrochloride; In methanol; water; at 20℃; for 17h;Irradiation; | General procedure: A round bottom flask was charged with a mixture of benzaldehyde 1(1.0 mmol), NH2OH.HCl 2 (1.5 mmol), Cog-C3N4 (20 mg) in H2O/MeOH (1:1, 5 mL) and stirred under the visible light condition at roomtemperature for 14-20 h. After completion of the reaction (monitored by TLC), the catalyst was filtered and added EtOAc (10 mL). Remaining organic layer was washed with brine (2×5 mL) and distilled water(1×10 mL) and dried over anhydrous sodium sulfate. Solvent was evaporated under reduced pressure to afford the crude residue, which was further purified by flash chromatography, EtOAc/n-hexane: 10:90 to obtain the analytically pure product 3 |
89% | With hexamethylene bis(N-methylimidazolium)bis(dichloroiodate); ammonia; In water; acetonitrile; at 20℃; for 0.5h; | General procedure: The mixture of HMBMIBDCI (0.5 mmol, 322 mg) in CH3CN (5 ml) was added into a solution of p-chlorobenzaldehyde (0.5 mmol, 70 mg) in NH3(aq) (1.5 ml) and the resulting dark mixture was stirred for the specified time designated in Table 2 at room temperature. The progress of the reaction was followed by TLC and the dark heterogeneous solution gradually changed to a red solution. To the mixture was added CHCl3 (30 ml) and then the organic phase was washed with an aqueous solution of NaHSO3 (5%, 20 ml). The organic layer was dried over MgSO4 and evaporated under reduced pressure. The crude material obtained was practically pure in most cases with no need for further purification. Otherwise, the crude products were purified by recrystallization or preparative TLC. All the nitrile products were identified by comparing melting point, 1H, and 13C NMR with those of authentic samples reported in the literature. Cinnamonitrile (Table 2, entry 13). Oil [24]; 1H NMR (400 MHz, CDCl3): delta (ppm) = 7.49-7.43 (m, 5 H), 7.43 (d, J = 16.6 Hz, 1 H), 5.91 (d, J = 16.6 Hz, 1 H). 13C NMR (100 MHz, CDCl3): delta (ppm) = 150.63, 133.52, 131.25, 129.14, 127.38, 118.19, 96.35. |
84% | With ammonium acetate; acetic acid; 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate; at 70℃; for 12h;Inert atmosphere; | General procedure: A 15 mm flame-dried test tube, which was equipped with a magnetic stir bar and charged with aldehyde (0.3 mmol, in case of solid), 4-AcNH-TEMPO+BF4- (2.0 equiv, 0.6 mmol), and NH4OAc (4.0 equiv, 1.2 mmol), was evacuated and backfilled with nitrogen (this process was repeated 3 times). After 0.3 mL of AcOH was added, aldehyde (0.3 mmol, in case of liquid), and AcOH (0.3 mL) were added in sequence. The reaction mixture was stirred for 12 h at 70 oC under N2 balloon, and then cooled to room temperature. The reaction was diluted by adding EtOAc and washed 4 M HCl aqueous solution. Two layers were separated, and the aqueous layer was extracted with EtOAc. The combined organic layers were washed with Na2CO3 aqueous solution. The organic layer was dried over MgSO4, filtered, and concentrated to a volume of approximately 20 mL by evaporator. To eliminate remaining aldehyde, aqueous 2 M Na2S2O5 aqueous solution (20 mL) was added to the organic layer and stirred for 2 hours. Two layers were separated, and the organic layer was dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by column chromatography to give nitrile products. |
68% | With potassium hexafluorophosphate; tert.-butylnitrite; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; 1,1,1,3,3,3-hexamethyl-disilazane; In acetonitrile; at 30℃; for 8h;Sealed tube; | In a 100-ml flask, 30 mL of acetonitrile, 10 mmol of HMDS, 0.4 mmol of TEMPO, 0.4 mmol of KPF6 and 0.6 mmol of TBN were added. The inside of the bottle was replaced with oxygen. After sealing the bottle with a rubber stopper, an oxygen balloon was inserted, Heated to 30 C in a preheated water bath, and 4 mmol of 1-cinnamaldehyde (as in formula (1-5)) was added slowly and reacted for 7 h. The reaction mixture was stirred with sodium thiosulfate solution and extracted with ether. The organic layer was separated, the solvent was distilled off under reduced pressure, and the residue was subjected to column chromatography. The mixture was stirred at a volume ratio of ethyl acetate / petroleum ether of 1: 100 Eluting solvent containing the target compound was collected, and the solvent was distilled off to give cinnamonitrile, and the isolation yield was 60%; The reaction steps described in Example 13, except that the amount of acetonitrile to 50mL, reaction 8h, Cinnamonitrile isolated yield of 68%. |
64% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium perchlorate; acetic acid; lithium hexamethyldisilazane; In acetonitrile; for 15h;Electrochemical reaction; | General procedure: Preparative electrolysis experiments were performed using 263 APotentiostat/Galvanostat (Princeton Applied Research, USA). 0.1 MNaClO4-CH3CN solution (10 mL) containing aldehydes (1 mmol),TEMPO (0.1 mmol), HMDS (2.5mmol) and AcOH (2.5mmol) was electrolyzedwith stirring in an undivided cell (30 mL) equipped with twoplatinum sheets as anode (1.5 cm2) and cathode (3.0 cm2) respectivelyat a constant potential of 1.5 V vs Ag/Ag+ (0.1MAgNO3 in acetonitrile).The electrode separation was 1 cm. When the reaction was finished,10mL of saturatedNa2SO3 solution was added into the reactionmixtureand stirred for 15 min. Then the mixture was extracted with CH2Cl2(20 mL × 3). The organic layer was dried with anhydrous Na2SO4 andconcentrated in a rotary evaporator. The productswere obtained via purificationof column chromatography and their structures were confirmedby 1H NMR, 13C NMR and MS. NMR was performed on a BrukerAvance III spectrometer. GC-MS was performed on the Thermo TraceISQ instrument with TG 5MS capillary column. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium amide 1.) Et2O, -5 deg C, 2.) a) Et2O, -5 deg C, 3 h, b) 15 deg C, 3 h; Yield given. Multistep reaction. Yields of byproduct given. Title compound not separated from byproducts; | ||
With sodium amide 1.) Et2O, -5 deg C, 2.) a) Et2O, -5 deg C, 3 h, b) 15 deg C, 3 h; Yield given. Multistep reaction. Yields of byproduct given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45.5% | With sodium amide In diethyl ether at 5 - 10℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With hydrogenchloride In 1,4-dioxane Ambient temperature; overnight; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With sodium amide In diethyl ether at 30℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With sodium hydroxide; dihydrogen peroxide In dichloromethane for 1.5h; Ambient temperature; | |
77% | With manganese(IV) oxide; silica gel In cyclohexane for 4h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98.3% | With 1,4-diaza-bicyclo[2.2.2]octane; trichlorophosphate In dichloromethane at 20℃; for 0.75h; | |
98% | With acetonitrile for 1.5h; Reflux; Green chemistry; | |
96% | With 1,2,3-Benzotriazole; thionyl chloride In dichloromethane for 0.416667h; Ambient temperature; |
96% | With thionyl chloride; sodium carbonate In dichloromethane at 0 - 20℃; for 0.25h; | |
96% | With 1,1,3,3-tetraphenyl-2-oxa-1,3-phoshpinobenzene bis(trifluoromethanesulfonate); triethylamine In dichloromethane at 20℃; for 0.333333h; | |
95% | With N-trifluoroacetylimidazole In tetrahydrofuran for 3.5h; Heating; | |
95% | With thionyl chloride; polyvinylpyrrolidone In dichloromethane at 20℃; for 0.25h; | |
94% | With carbon disulfide; Amberlyst A-26 for 0.666667h; Heating; | |
93% | With zinc trifluoromethanesulfonate In acetonitrile for 4h; Heating; | |
93% | With gallium(III) trichloride In acetonitrile at 80℃; for 4h; Inert atmosphere; | Synthesis of Nitriles from Oximes (Method 1A and 1B)A General procedure: A solution of oxime (0.5 mmol) and SnCl2.2H2O (Method 1A, under open air) or GaCl3 (Method 1B, under argon) (0.05 mmol) in dry MeCN (1 mL) was stirred at 80 °C and monitored by TLC. After completion of the reaction, the mixture was purified by flash chromatography. |
92% | With thionyl chloride; silica gel In dichloromethane at 0℃; for 0.0833333h; | |
91% | With 2-(trifluoroacetyloxy)pyridine In tetrahydrofuran Heating; | |
91% | With thionyl chloride; sodium sulfite at 0℃; for 0.05h; | |
91% | With bromethyl methyl ether; triethylamine In tetrahydrofuran for 0.583333h; Reflux; | General procedure for the preparation of Nitriles (Entry 1-13) General procedure: For the preparation of nitrile from aldoxime using amethoxymethyl bromide as the dehydration agent, Et3N(1.5 mmol) was added to a stirred mixture of aldoxime(1.0 mmol) and 10 mL of THF, followed by methoxymethylbromide (1.5 mmol). The resulting mixture was refluxed for aspecified period (Table 1). The reaction was monitored byTLC (ethyl acetate: petroleum ether, 1:1). After completion ofreaction, the contents were poured into water and neutralizedwith NaHCO3 solution (20 mL, 10%), and then extractedwith ethylacetate (10 mL x 3). The combined organic mixturewas dried over anhydrous Na2SO4, concentrated and theresidue was purified by column chromatography on silica gel(60-120 mesh) using ethyl acetate, and then the solvent wasremoved at reduced pressure to give products in 79%-96%yields (Entry 1-13). The nitriles characterized by LC-MS, 1HNMR and 13C NMR analysis. |
91% | With bromethyl methyl ether; triethylamine In tetrahydrofuran for 0.583333h; Reflux; | General procedure for the preparation of Nitriles (Entry 1-13) General procedure: For the preparation of nitrile from aldoxime using a methoxymethyl bromide as the dehydration agent, Et3N (1.5 mmol) was added to a stirred mixture of aldoxime(1.0 mmol) and 10 mL of THF, followed by methoxymethyl bromide (1.5 mmol). The resulting mixture was refluxed for aspecified period (Table 1). The reaction was monitored byTLC (ethyl acetate: petroleum ether, 1:1). After completion ofreaction, the contents were poured into water and neutralized with NaHCO3 solution (20 mL, 10%), and then extracted with ethyl acetate (10 mL x 3). The combined organic mixture was dried over anhydrous Na2SO4, concentrated and theresidue was purified by column chromatography on silica gel(60-120 mesh) using ethyl acetate, and then the solvent was removed at reduced pressure to give products in 79%-96%yields (Entry 1-13). The nitriles characterized by LC-MS, 1H NMR and 13C NMR analysis. |
90% | With dmap; thionyl chloride In dichloromethane for 0.416667h; Ambient temperature; | |
90% | With aluminium trichloride; sodium iodide In acetonitrile for 2h; Heating; | |
90% | With diethyl phosphorylchloridite In chloroform at -40℃; for 0.5h; | |
90% | With trifluoromethylsulfonic anhydride; triethylamine; triphenylphosphine In dichloromethane at 0℃; for 0.166667h; | |
90% | With oxalyl dichloride; Triphenylphosphine oxide In chloroform at 20℃; for 1h; | 4.3.2. Method b General procedure: To a solution of triphenylphosphine oxide (14 mg, 0.050 mmol) in either CHCl3, CDCl3 or EtOAc (3.0 mL) was added oxalyl chloride (102 μL, 1.21 mmol) and the reaction mixture was stirred for 5 min. The appropriate oxime (1.00 equiv) was then added in one portion and the reaction mixture was stirred for 1.0 h at room temperature after which the solvent was removed in vacuo. Purification by flash chromatography (silica, 10-100% Et2O/pet. ether) gave the pure nitriles. |
90% | With 8-bromocaffeine; 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide for 0.0194444h; Microwave irradiation; chemoselective reaction; | |
90% | With N,N,N’,N’-tetrabromobenzene-1,3-disulfonamide; triphenylphosphine In acetonitrile at 20℃; for 0.166667h; | 1 2.2 Typical procedure for the conversion of 4-nitrobenzaldehyde oxime to 4-nitrobenzonitrile with TBBDA and PPh3 To the mixture of PPh3 (0.525 g, 2 mmol) and TBBDA (0.287 g, 0.53 mmol) in dry acetonitrile (5 mL), 4-nitrobenzaldehyde oxime (0.166 g, 1 mmol) was added. The mixture was stirred at room temperature. The progress of the reaction was monitored by TLC. After completion of the reaction (Table 1), the solvent was evaporated. The crude products were purified by short-column chromatography (packed with silica gel, using n-hexane/ethyl acetate (8:2) as eluent) to achieve the desired 4-nitrobenzonitrile with 0.13 g, 92% yield. |
89% | With di-2-pyridyl sulfite In toluene for 0.5h; Heating; | |
89% | With phosphoric acid diethyl ester 2-phenylbenzimidazol-1-yl ester; triethylamine In acetonitrile at 20℃; for 0.916667h; | |
89% | With oxalyl dichloride; Tropone; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 50℃; for 0.166667h; Schlenk technique; Inert atmosphere; | |
88% | With fluorosulfonylchloride; triethylamine In dichloromethane for 8h; Ambient temperature; | |
88% | With trichloromethyl chloroformate In acetonitrile for 0.0833333h; | |
88% | With 1,4-diaza-bicyclo[2.2.2]octane; thionyl chloride In dichloromethane at 20℃; for 0.666667h; | |
88% | Stage #1: cinnamaldoxime With 2-chloro-1-methyl-pyridinium iodide In dichloromethane at 20℃; for 0.166667h; Stage #2: With triethylamine In dichloromethane at 20℃; for 1.5h; | |
88% | With 1,8-diazabicyclo[5.4.0]undec-7-ene; N-tosylimidazole In N,N-dimethyl-formamide for 0.583333h; Reflux; | |
87% | With bismuth(lll) trifluoromethanesulfonate In acetonitrile for 8h; Reflux; | 15 A typical method for preparation of a nitrile from an aldoxime using Bi(OTf)3 as the catalyst: 4-Isopropylbenzaldoxime 2a (0.5 g, 3 mmol), Bi(OTf)3 (60 mg, 0.09 mmol) and acetonitrile (5 ml) were taken into a 25 ml round bottomed flask fitted with a condenser and CaCl2 guard tube. The mixture was refluxed and when reaction was complete (GC), the reaction mixture was cooled to room temperature, concentrated under reduced pressure and the crude product was purified by normal column chromatography (silica gel 100-200 mesh, EtOAc/hexane = 1:20) to obtain 4-isopropylbenzonitrile 3a (0.43 g, 97%), which gave the spectral data identical to that given above. |
87% | With copper(II)-modified 4Å molecular sieve In acetonitrile at 80℃; for 8h; | |
87% | Stage #1: cinnamaldoxime With Bromotrichloromethane; triphenylphosphine In dichloromethane for 0.416667h; Reflux; Stage #2: With triethylamine In dichloromethane for 8h; Reflux; | Typical procedure B to preparebenzonitriles from benzaldoximes General procedure: BrCCl3 (940 mg, 4.8 mmol) was added to PPh3 (1.26 g, 4.8 mmol) in dry CH2Cl2 (14 mL). The resulting mixture was stirred at room temperature for 20 min, during which time the solution turned from yellow to red-brownish in colour. Thereafter,3,4-dimethoxybenzaldoxime (4i, 800 mg, 4.4 mmol) was added. The reaction mixture was heated under reflux for 25 min. Then, dry Et3N (485 mg, 4.8 mmol) was added dropwise with a syringe over 1 min. The reaction mixture was heated under reflux for 8 h. Thereafter, it was cooled to room temperature and added to cold water (50 mL). The mixture was extracted with dichloromethane (2 × 30 mL) and chloroform (30 mL). The combined organic phases were dried over anhydrous MgSO4, concentrated under reduced pressure and subjected to column chromatography on silica gel (CH2Cl2/hexane 4 : 1) to give 3,4-dimethoxybenzonitrile (2q, 665 mg, 92%) as a colourless solid. |
86% | With phthalic anhydride In acetonitrile for 0.0833333h; microwave irradiation; | |
86% | With iodine; triphenylphosphine In dichloromethane at 20℃; for 5h; | |
86% | With (E)-ethyl 2-cyano-2-(2-nitrophenylsulfonyloxyimino)acetate; 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 20℃; Inert atmosphere; | Representative procedure for nitrile synthesis General procedure: In an oven-dried two-necked 50 mLround-bottomed flask, equipped with a stirring bar, a solution of the oxime(1.0 mmol) and 2-NO2-C6H4-SO3XY(1.5 mmol) dissolved in anhydrous CH2Cl2 (5.0 mL) wasplaced under the atmosphere of nitrogen. The reaction mixture was stirred atroom temperature for 5 min, then DBU (2.5 mmol) was added drop wise over 2 min.The reaction mixture became a clear homogeneous solution after addition of DBU.The reaction was monitored by TLC. The reaction mixture was diluted with EtOAcand washed with water (2×5 mL) followed by brine (2×5 mL) upon completeconsumption of the starting material. Product was purified by columnchromatography.Furthermore, the by-product Oxymacould be readily recovered by acidifying the aqueous layer, and then extractingwith ethyl acetate. The Oxyma thus recovered can then be reused to regeneratethe sulfonate ester of Oxyma, which can be further used for a separate batch ofreaction. |
85% | With iodine; zinc In acetonitrile at 20℃; for 1h; | |
85% | With pyridinium chlorochromate In chloroform for 3h; Reflux; | Representative Experimental Procedure for Dehydration ofAldoximes: Conversion of Benzaldoxime to Benzonitrile (Table 1,Entry 1) General procedure: A mixture of benzaldoxime (121 mg, 1 mmol) and PCC (237 mg, 1.1 mmol) in CHCl3 was heated to reflux for 2 h (monitored by TLC). After the reaction was over, the black reaction mixture was filtered through a Celite pad and washed with EtOAc. Evaporation of the solvent left the crude product, which was purified by column chromatography over silica gel (hexane=EtOAc, 95:5) to afford pure benzonitrile (89 mg, 86%). The infrared (IR) and 1H and 13C NMR data of this compound are in good agreement with the reported data .[4d] Compounds 1-12 and 15 are known and were identified by comparison of their spectroscopic data (IR, 1H NMR, and 13C NMR) with those reported (see references in Table 1). Compounds 13, 14, 16, and 17 were characterized by their spectroscopic data, which are in agreement with the proposed structures. Representative spectroscopic characterization data (IR, 1H NMR, and 13CNMR) for the compounds are provided (compounds 13, 14, 16, and 17). |
85% | With Polyethylene glycol supported phosphorus chloride In dichloromethane for 0.583333h; Reflux; Molecular sieve; | Preparation of nitriles (4a-4r): General procedure General procedure: To a stirred solution of aldoxime 3 (1.0 mmol) in CH2Cl2 (5 mL)was added PEG-OPCl2 (0.20 mmol, 220 mg) and molecularsieves 4 A (2 wt equiv to aldoxime), the reaction mixture stirred at reuxing temperature for the given time in Table 2. Aftercompletion of the reaction (TLC), diethyl ether (100 mL) wasadded to the reaction mixture with vigorous stirring and thencooled to 0 °C. The recovered white precipitate, along withmolecular sieves 4 A was collected by fltration, washed with cold diethyl ether (2 × 20 mL) for reuse. The combined fltratewas concentrated in a rotary evaporator, and the residue waspurifed by through a pad of silica gel column (10-20% ethylacetate in hexane) to give pure product, which was characterized by comparison of its IR and 1H NMR spectra or meltingpoint with published13,14,16,18,26,28,30 values. The analytical datafor the obtained products 4a-4r are together with their 1H and13C NMR spectra are presented in the Supplemental Materials(Figures S1- S36). |
84% | With oxalyl dichloride; 2,3-bis(4-methoxyphenyl)cyclopropenone; 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane for 5.5h; Reflux; | |
84% | With triethylamine; ethanaminium,N-(difluoro-λ4-sulfanylidene)-N-ethyl-,tetrafluoroborate In ethyl acetate at 20℃; for 1h; Inert atmosphere; | Dehydration of Oximes and Amides to Nitriles; General Procedure General procedure: To a solution of the aldoxime or the amide (1.0 mmol) and Et3N (1.5mmol) in EtOAc (1 mL, 1 M) at r.t. was added XtalFluor-E8 (1.1 mmol)portionwise over ca. 2 min. The resulting solution was stirred at r.t.for 1 h. The reaction mixture was quenched with sat. aq Na2CO3 and extracted with CH2Cl2 (2 × 10 mL). The combined organic layers were washed with H2O and brine, dried (MgSO4), and concentrated under vacuum to afford the crude nitrile, which was purified by flash chromatography, if required. |
83% | With N,N-dimethyl-formamide; trichlorophosphate at 0 - 5℃; for 1h; | |
83% | With eosin; carbon tetrabromide; N,N-dimethyl-formamide In acetonitrile at 25℃; for 14h; Irradiation; Inert atmosphere; | |
80% | With 4,6-diphenyl-2-methylthio-pyrylium tetrafluoroborate; triethylamine In dichloromethane for 24h; | |
80% | With iodine In acetonitrile at 20℃; for 1.5h; | |
80% | With diethyl cyanophosphonate; triethylamine In dichloromethane at 20℃; for 20h; Inert atmosphere; | |
75% | With aluminium trichloride; potassium iodide In water; acetonitrile at 80℃; for 7h; | |
75% | With 2,4-Dinitrophenol; cobalt(II) diacetate tetrahydrate In water; acetonitrile at 80℃; for 24h; | 2.2. Typical procedures for the synthesis of nitriles from aldoximes General procedure: Aldoxime (0.25 mmol), cobalt acetate(II) tetrahydrate (6.2 mg, 0.025 mmol), 2,4-dinitrophenol (9.2 mg, 0.05 mmol) and acetonitrile/H2O (0.49 + 0.01 mL, 2 v/v% of water in acetonitrile) were added to an oven-dried vial. The mixture was vigorously stirred at 80 °C for 24 h and then diluted with ethyl acetate. Solvent was removed invacuo, and the desired product was purified and isolated by silica gel column chromatography (ethyl acetate/n-hexane). |
Multi-step reaction with 2 steps 1: triethylamine; silica gel / CHCl3 / 20 °C 2: 0 h / microwave irradiation | ||
75 %Chromat. | With chloro-trimethyl-silane at 90℃; for 4h; | |
With gallium anchored on polystyrene sulfonate polymer brushes In acetonitrile at 90℃; for 0.216667h; | Kinetic study The dehydration of cinnamaldehyde oxime (1, 10-25 μM) wascarried out in acetonitrile at 90 °C under 5 atm pressure. Cinnamaldehyde oxime (1) and cinnamonitrile (2) exhibit theabsorption maximum in acetonitrile at 286 nm and 271 nm, respectively.The conversion of cinnamaldehyde oxime (1) to cinnamonitrile (2) was calculated based on the decrease in theabsorption at 286 nm using the formula: [2] = (ε286 (1) · [1]0 -Aobserved) / (ε286 (1) - ε286 (2)) (Aobserved = absorbancemeasured experimentally, while carrying out the reaction). Themolar absorptivities (ε) of cinnamaldehyde oxime (1) and cinnamonitrile (2) in acetonitrile at 286 nm are 35640 and17800 L·mol-1·cm-1, respectively. The kobs values were calculatedby fitting the experimental data with the following equation:[2] = [1]0 · (1 - exp (-kobs·t)) using least-squares fit. Theexperimental errors in these measurements are ±4%. | |
With cobalt supported graphitic carbon nitride In methanol; water at 20℃; Irradiation; | ||
With fluorosulfonyl fluoride; triethylamine In acetonitrile at 20℃; for 0.25h; Schlenk technique; | 2. General procedure of converting aldoximes 2 to corresponding nitriles inacetonitriles 3 General procedure: Aldoximes 2 (1.0 mmol), CH3CN (2.0 mL) and Et3N (278 uL, 2.0 mmol) were added into a25 mL Schlenk flask equipped with magnetic stirrer and rubber stopper. Then the SO2F2 gaswas introduced into the stirring reaction mixture by slow bubbling through a SO2F2 balloon,and the reaction mixture was stirred at room temperature for 15 or 30 min. After the reaction,the mixture diluted with water and extracted with ethyl acetate (3×10 mL). And then thecombined organic layers were washed with brine, dried over anhydrous Na2SO4 andconcentrated to dryness. The residue was purified by column chromatography on silica gel(300-400 mesh) with hexane and ethyl acetate to give the corresponding nitriles 3. | |
With Escherichia coli BL21 expressing aldoxime dehydratase OxdBr1 In aq. buffer at 28℃; for 1h; Microbiological reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | With triethylamine In dichloromethane for 1h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 34% 2: 13% 3: 4% 4: 4% | With indium In N,N-dimethyl-formamide for 2h; Ambient temperature; ultrasonication; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With Triethoxysilane; [(2,5-F2C6H2-CH=N-C10H6)Co(III)(H)(PMe3)2]; In tetrahydrofuran; at 60℃; for 24h;Schlenk technique; | General procedure: To a 25 mL Schlenk tube containing a solution of 2 in 2 mL of THF was added amide (1.0 mmol) and (EtO)3SiH (0.50 g, 3.0 mmol). The reaction mixture was stirred at 60 C until there was no amide left (monitored by TLC and GC-MS). The product was purified according to literature procedures by Beller |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With iron pentacarbonyl; Bromotrichloromethane In benzene at 60℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With ammonium hydroxide; oxygen In tert-Amyl alcohol for 18h; Green chemistry; | 13 3-Phenylacryl alcohol was converted to 3-phenylacrylonitrile Followed by meso-Co-N / C (800) (35 mg, 0.5 mol% Co)3-phenylpropene alcohol (67 mg,0.5 mL), 28% aqueous ammonia (140 [mu] L) was added to a 10 ml reaction flask and then added1ml tert-amyl alcohol as solvent, placed in the reactor, oxygen to 0.5Mpa, placed in 130 oil bath,The degree of reaction was then measured by GC-MS. After the reaction, the internal standard biphenyl was added and analyzed by GC Product 3-phenylacrylonitrile yield. Reaction 18h, 3-phenylacrylonitrile yield of 89%, selectivity of 97%. |
Multi-step reaction with 2 steps 1: NH3(g), ethyl polyphosphate / CHCl3 / 1.) 0 - 5 deg C, 30 min, 2.) room temp., 1.5h 2: ethyl polyphosphate / CHCl3 / 80 °C | ||
Multi-step reaction with 2 steps 1.1: potassium carbonate; 18-crown-6 ether / tetrahydrofuran / 21 h / Inert atmosphere; Reflux 2.1: sodium diisobutyl-tert-butoxyaluminium hydride / tetrahydrofuran / 0 °C / Inert atmosphere 2.2: 2 h / 0 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With ammonia; oxygen In tert-Amyl alcohol; water at 100℃; for 5h; Autoclave; High pressure; | |
98% | With 2,3'-bipyridine; ammonium hydroxide; copper(l) iodide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen In ethanol at 20℃; for 24h; | |
98% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; ammonia; oxygen; copper(II) nitrate In water; dimethyl sulfoxide at 80℃; for 5h; |
95% | With potassium phosphate; ammonium formate In acetonitrile at 115℃; for 16h; Sealed tube; Green chemistry; | |
93% | With ammonia; oxygen In tert-Amyl alcohol; water at 130℃; for 24h; | |
92% | With ammonium hydroxide; copper(l) iodide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; N-Phenylglycine; sodium hydroxide In methanol at 50℃; for 24h; Cooling with ice; | 12 General procedure: Benzyl alcohol was added in a 2L round-bottomed flask (108.02g, 1000mmol, i.e., of formula (I) wherein R is H, X = C, n = 1, m = 0),cuprous iodide (9.50g, 50mmol) , of N- phenylglycine (7.51g, 50mmol), TEMPO ( 7.80g, 50mmol),sodium carbonate (10.60g, 100mmol), aqueous ammonia (300mL, 25 ~ 28%) ,800mL methanol, under ice-cooling, with the oxygen round bottom flask was evacuated of air ventilation 3 times, and then the system was stirred at 50 at 12h, after completion of the reaction, the reaction solution was cooled to room temperature, the solvent was distilled off under reduced pressure and dried to give the product benzonitrile 95.79g, yield 93%. The reaction was used as cinnamyl alcohol (134.00g, 1000mmol, i.e., of formula (I) wherein R is H, X = C, n = 1, m = 1), experimental methods and procedures were the same as in Example 1, except that : cuprous iodide (9.50g, 50mmol), N- phenylglycine (7.51g, 50mmol), TEMPO ( 7.80g, 50mmol), sodium hydroxide (4.00g, 50mmol), aqueous ammonia (300mL, 25 ~ 28% ), 800mL methanol, stirred at at 50 24h, to give the final product 118.68g, yield 92%. |
91% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [bis(acetoxy)iodo]benzene; ammonium acetate In water; acetonitrile at 20℃; for 3h; | Oxidative Conversion of Alcohols into Nitriles; GeneralProcedure: General procedure: To a solution of alcohol (1 mmol) in MeCN-H2O (9:1, 3 mL) were successively added TEMPO (7.8 mg,5 mol%), NH4OAc (0.308 g, 4 equiv), and PhI(OAc)2 (0.708g, 2.2 equiv). The suspension was stirred at roomtemperature (progress of the reaction was monitored byTLC) for the reaction time indicated in Table 2. The resultantclear two-phase reaction mixture was concentrated, dilutedwith H2O and Et2O, and the organic layer was dried (Na2SO4), filtered, and evaporated under reduced pressure.The residue was purified by flash column chromatography(PE-Et2O or PE-CH2Cl2) to give 2. |
90% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [hydroxy(tosyloxy)iodo]benzene; ammonium acetate In water; acetonitrile at 80℃; for 4h; | |
90% | With ammonium hydroxide; copper(l) iodide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In water for 24h; Reflux; Green chemistry; | |
89% | With ammonium hydroxide In <i>tert</i>-butyl alcohol at 120℃; for 24h; Sealed tube; Autoclave; | S7. Procedure for the synthesis of nitriles General procedure: The magnetic stirring bar and corresponding alcohol were transferred to 8 mL glass vial then 2 mL t-butanolsolvent was added. Then, 35 mg catalyst was added followed by the addition of aq. NH3. Then the vial wasf itted with septum, cap, and needle. The reaction vials were placed into a 300 mL autoclave (8 vials containingdif ferent substrates were placed at a time in the autoclave) and the autoclave was pressurized with 10 bar air.The autoclave was placed into an aluminium block and the temperature of the aluminum block was set in orderobtain 120 °C inside the autoclave. Temperature of the aluminum block was set to 130 oC to attain 120 oCinside the autoclave, which was considered as the reaction temperature. The reactions were allowed toprogress under continuous stirring for the required time at 120 °C. Af ter completion of the reaction, the autoclave was cooled down to room temperature and the remaining air was gradually discharged. Then, thecatalyst was f iltered-off, and washed with ethyl acetate. The solvent f rom the f iltrate containing the reactionproducts was purif ied by column chromatography. Products were analyzed by GC, GC-MS, and NMRspectroscopy. In the case of yields determined the by GC, 100 μL n-hexadecane was added to the reactionvial containing the products and diluted with ethyl acetate. Then the reaction mixture containing catalyst andproducts was filtered through a plug of silica and the filtrate containing product was analyzed by GC. |
85% | With ammonium hydroxide; dihydrogen peroxide In water; acetonitrile at 30℃; for 3h; | General procedure for the catalytic oxidation General procedure: In a typical experiment, alcohol (10 mmol), aqueous NH3*H2O (30 mmol), FeCl4-IL-SiO2 (0.5 g), and CH3CN (10 mL) were added to a round-bottomed flask. Then, aqueous 30 % H2O2 (21 mmol) was gradually added into the reactor at room temperature. The obtained mixture was stirred at 30 °C for appropriate time (Table 4). The reaction was monitored by TLC and GC. After completion of the reaction, the catalyst was recovered by filtration. Evaporation of the solvent under reduced pressure gave the crude product. Further purification was achieved by flash column chromatography on a silica gel (petroleum ether/ethyl acetate, 5:1) to give the desired product. Fresh substrates were then recharged to the recovered catalyst and then recycled under identical reaction conditions. |
81% | With copper(I) oxide; 1,10-Phenanthroline; oxygen; potassium ferrocyanide In dimethyl sulfoxide at 140℃; for 40h; Autoclave; | |
80% | With Iron(III) nitrate nonahydrate; ammonium hydroxide; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In acetonitrile at 20℃; for 12h; | |
76% | With ammonium bicarbonate In 1,3,5-trimethyl-benzene at 140℃; for 4h; | |
76% | With 1,4-diaza-bicyclo[2.2.2]octane; TEMPOL; ammonia; copper(l) chloride In water; acetonitrile at 20℃; for 24h; | General procedure for the synthesis nitriles in Table 2 General procedure: To a 25-mL Schlenk tube equipped with a magnetic stirrer, CuCl (0.05 mol, 5 mol%), DABCO (0.10 mol, 10 mol%), 4-HO-TEMPO (0.05 mmol, 5 mol%) were added. Substrates 1 (1 mmol) and NH3 (aq, 25-28%, 3 mmol, 3.0 equiv) in CH3CN (2 mL) were added subsequently. Then the reaction mixture was stirred at room temperature for 24 h in the presence of an air balloon. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was dried over anhydrous MgSO4. Subsequently, the combined organic layer was concentrated under reduced pressure and the crude product was purified by column chromatography to afford the corresponding products. |
With ammonia; oxygen In tetrahydrofuran at 120℃; for 5h; | ||
80 %Chromat. | With manganese(IV) oxide; ammonia; oxygen In toluene at 100℃; for 2h; Autoclave; | |
With copper(II) perchlorate hexahydrate; trimethylsilylazide; 2,3-dicyano-5,6-dichloro-p-benzoquinone In 1,2-dichloro-ethane at 60℃; | ||
90 %Chromat. | With ammonium hydroxide; oxygen In tert-Amyl alcohol at 130℃; for 18h; | |
70 %Chromat. | With ammonium hydroxide; oxygen at 50℃; for 12h; Sealed tube; Green chemistry; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: magnesium / N,N-dimethyl-formamide / -15 °C 1.2: 1 h / -15 °C 1.3: 36 h / Reflux 2.1: sulfuric acid / 5 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tert.-butylnitrite; boron trifluoride diethyl etherate at 25℃; for 14h; Sealed tube; | |
76% | With tert.-butylnitrite; saccharin at 20℃; for 6h; Green chemistry; | Typical procedure for the synthesis of 4-amidocinnolines General procedure: 2-(Phenylethynyl)aniline (1a, 193 mg, 1.0 mmol) was added and stirred slowly to 36 mg Sac-H (0.2 mmol) in1.0 cm3 dry nitrile for 5 min at room temperature. Then 0.20 cm3 t-butyl nitrite (* 1.5 mmol) was added through a micropipette over 2 min and the flask was stoppered and stirring was continued at room temperature for 6 h. After the completion, 5 cm3 10% aq. solution of NaHCO3 was added to the reaction mixture and the resulting solution was extracted with EtOAc (5 9 5 cm3). The combined ethylacetate extractions were washed with water (2 9 5 cm3)and brine (2 9 5 cm3), dried over anhydrous Na2SO4, and concentrated using vacuum rotary. The purification was carried out by column chromatography on silica gel (hexane/ethyl acetate = 8/2-4/6) to afford the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With trifluorormethanesulfonic acid; water; In dichloromethane; at -40℃; for 3h;Inert atmosphere; | To a stirring suspension of ynamide (0.15 mmol, 1.0 equiv), nitriles (0.3 mmol, 2.0 equiv) and H2O (0.3 mmol, 2.0 equiv) in dry dichloromethane (2.00 mL) was added TfOH dropwise (26.0 μL, 0.3 mmol, 2.0 equiv) via a syringe pump at -40 C under nitrogen atmosphere. The reaction was monitored by TLC. When progress appeared to be completed after about 3 h at the same temperature, the saturated sodium bicarbonate solution was added to the mixture and the resulting mixture was extracted with EtOAc. The organic layers were washed with sat aq NaCl and dried over Na2SO4. Filtration and concentration of the mixture in vacuo afforded the crude product that was purified by flash silica gel column chromatography [gradient eluent: EtOAc/petroleum ether] to obtain corresponding products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With palladium diacetate; copper(II) trifluoroacetate In N,N-dimethyl-formamide at 120℃; for 24h; Sealed tube; | General Procedure for the Synthesis of cyanate product General procedure: Aryl halide (0.5 mmol), α-Iminonitrile (0.6 mmol), Cu(TFA)2 (1.0 mmol), Pd(OAc)2(0.1 mmol) and 2ml DMF were added into a 15 ml sealed tube with a magneticstirring bar. Stirred under air at 120°C for 24 h. Monitor the reaction by TLC. Themixture was poured into water (10 ml) and extracted by ethyl acetate (3×10 ml).Dried by Na2SO4 and evaporated. Finally, pure the mixture by silica gel column. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With aluminum (III) chloride; at 80℃; for 1h; | Cinnamonitrile (100 mg, 0.78 mmol) was added to the mixture of AlX3 (X= Cl, Br) (5 mmol) and arene (5 mL). Reaction mixture was stirred at room temperature for 1 h.The mixture was poured into water (50 mL), extracted with chloroform (3×30 mL). The combined extracts were washed with water, a saturated aqueous solution of NaHCO3, wateragain, and dried over Na2SO4. The solvent was distilled off under reduced pressure, and theresidue was subjected to chromatographic separation on silica gel using hexanes - ethyl acetateas an eluent. Yields of the product 1a was determined after chromatographic isolation. The yields of the compounds 1a-i and 2a-g are given in Table 1. 3. Characterization of compounds 1a-i and 2a-d. 3,3-Diphenylpropanenitrile (1a) [2]. Colorless solid, m.p. 88-90 C. 1 NMR (CDCl3, 500 Hz): 3.04 d (2, 2, J = 7.7 Hz), 4.38 t (1, , J = 7.7 Hz),7.23-7.28 m (6arom.), 7.33-7.36 m (4arom.). 13 NMR (CDCl3, 125 Hz):24.2, 47.1, 118.4, 127.4, 127.5, 128.9, 141.2. GC-MS, m/z (Irel., %): 207 + (7), 167 (100), 152(18), 82 (8). IR, upsilon, cm-1: 3061, 3028, 2921, 2918, 2246 (C?N), 1600, 1496, 1452, 1425, 1084,784, 753, 740, 699, 632, 590, 504. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95.3% | With dmap at 115 - 125℃; for 3h; | 1; 2; 3; 4 Elimination of reaction in a 100ml with a thermometer, magnetic stirring rotor,In a three-necked flask of the condenser, cinnamaldehyde oxime was added: 41.5 g (98.3%, 0.2775 mol), acetic anhydride: 32.2 g (99.0%, 0.3125 mol), and N,N-dimethylaminopyridine: 0.25 g. The three-necked flask was heated with an electric heating jacket and refluxed at an internal temperature of 115 to 125 ° C for 3 hours.After the reflux is completed, the apparatus is changed from the reflux state to the recovery state, and the pressure is recovered. The acetic acid was recovered under reduced pressure at a vacuum of ≥0.08 MPa and an internal temperature of ≤110 °C.After the acetic acid is recovered, it is recovered by a high-vacuum vane pump, and the absolute pressure is ≤200Pa.Reduced by temperature ≤80 °CPressure recoveryCinnamonitrileFinished product: 34.5g (content 98.9%, yield: 95.3%) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With fluorescein sodium salt In acetonitrile at 20℃; for 10h; Irradiation; |
Tags: 4360-47-8 synthesis path| 4360-47-8 SDS| 4360-47-8 COA| 4360-47-8 purity| 4360-47-8 application| 4360-47-8 NMR| 4360-47-8 COA| 4360-47-8 structure
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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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