* 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.
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9
[ 586-39-0 ]
[ 7369-50-8 ]
[ 587-02-0 ]
Yield
Reaction Conditions
Operation in experiment
75%
With hydrogen In ethanol at 20℃; for 3 h;
General procedure: In a typical reaction, 0.015 g of catalyst and 2 mmol of the reactant were taken in 10 mL of ethanol under hydrogen atmosphere. The reaction was monitored by thin-layer chromatography (TLC). After complete disappearance of the starting material, the catalyst was separated by simple filtration and the solvent was removed under reduced pressure to obtain the pure product.
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[6] Chemical Communications, 2017, vol. 53, # 23, p. 3377 - 3380
[7] Journal of the American Chemical Society, 2018, vol. 140, # 11, p. 3940 - 3951
[8] Journal of Catalysis, 2018, vol. 364, p. 297 - 307
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[ 586-39-0 ]
[ 7369-50-8 ]
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[4] Chemistry - A European Journal, 2015, vol. 21, # 11, p. 4368 - 4376
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[6] Tetrahedron Letters, 1987, vol. 28, # 12, p. 1321 - 1322
[7] Journal of Organic Chemistry, 2000, vol. 65, # 26, p. 8933 - 8939
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[ 586-39-0 ]
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[ 15411-43-5 ]
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[2] Green Chemistry, 2016, vol. 18, # 5, p. 1332 - 1338
12
[ 586-39-0 ]
[ 241147-96-6 ]
[ 98-54-4 ]
[ 7369-50-8 ]
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[1] European Journal of Organic Chemistry, 2015, vol. 2015, # 33, p. 7253 - 7257
13
[ 586-39-0 ]
[ 7369-50-8 ]
[ 15411-43-5 ]
[ 587-02-0 ]
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[2] Journal of the American Chemical Society, 2008, vol. 130, # 27, p. 8748 - 8753
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[8] Journal of Molecular Catalysis A: Chemical, 2014, vol. 393, p. 257 - 262
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[10] Green Chemistry, 2016, vol. 18, # 5, p. 1332 - 1338
[11] Chemical Communications, 2017, vol. 53, # 12, p. 1969 - 1972
[12] Chemical Communications, 2017, vol. 53, # 23, p. 3377 - 3380
[13] Chemical Communications, 2017, vol. 53, # 23, p. 3377 - 3380
[14] Journal of the American Chemical Society, 2018, vol. 140, # 11, p. 3940 - 3951
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[1] Journal of Organic Chemistry, 1989, vol. 54, # 6, p. 1354 - 1359
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17
[ 67-56-1 ]
[ 586-39-0 ]
[ 52022-77-2 ]
[ 110435-89-7 ]
Reference:
[1] Canadian Journal of Chemistry, 1988, vol. 66, p. 2412 - 2421
With hydrazine hydrate; In ethanol; at 59.84℃; under 760.051 Torr;Inert atmosphere;
General procedure: Liquid-phase CTH reactions were carried out in a commer-cial semi-batch stainless steel stirred reactor (150 cm3, Buechi AG,Uster, Switzerland) equipped with 4 wall baffles. The reactiontemperature was controlled using an oil heating bath Ministat125 (Huber Kaeltemaschinenbau GmbH, Germany) connected to areactor jacket. A 6-blade disk turbine impeller ensured intensivemixing. The catalyst was fixed on four wire-mesh blades attacheddirectly to the stirrer shaft. The stirrer was driven by a magneticdrive and equipped with a speed controller (cyclone 075/cc 075,Buechi AG, Uster, Switzerland). The reactor temperature, pressureand stirring speed were monitored via a control unit (bpc 6002/bdsmc, Buechi AG, Uster, Switzerland). Prior to each experiment thereactor was charged with 0.3 g of the catalyst and 100 cm3of anethanol solution of nitroarenes (0.12 M) and 1 g of m-xylene (inter-nal standard for GC analyses). After flushing (4 times) with N2underagitation (?2000 rpm) to remove air, the reactor was heated up333 K and equilibrated for 5 min. Injection of 1.8 mL of the reduc-ing agent (3 equivalents), i.e. hydrazine monohydrate, defined thereaction start. A typical reaction was performed at T = 333 K, underatmospheric pressure with an agitation speed of 2000 rpm. Theinitial substrate to metal molar ratio of 50 was used by adjustingthe mass of catalyst introduced in the reactor. A non-invasive liq-uid sampling system allowed the controlled withdrawal of smallaliquots (?0.2 cm3) from the reactor during the reaction. In a seriesof blank experiments, no conversion of the substrates was detectedin the absence of the catalyst or in the presence of the ACF supportonly.
98%
With hydrogen; silver; In dodecane; at 110℃; under 4500.45 Torr; for 24h;
Catalyst A for Example obtained in Production Example 1 was treated with a catalyst amount of 27 mg (the amount of silver as metal was 12 mg) and 0.5 mmol of substrate 3-nitrostyrene, 5 ml of solvent dodecane, 0.6 MPa of hydrogen pressure, Hydrogenation reduction treatment was carried out under the conditions of a reaction temperature of 110 C. The reaction time was 10 hours in Example 1 and 24 hours in Example 2, and the yield and selectivity were measured using a gas chromatograph, respectively. The results are shown in Table 1.
88%
With hydrazine hydrate; at 80℃; under 4137.29 Torr; for 0.166667h;Microwave irradiation;
A mixture of 1c (100 mg, 0.81 mmol), hydrazine hydrate (121.5mg, 2.43 mmol), and SS-Rh (370 mg, 2 mol% Rh) were taken in an oven dried reaction tube equipped with screw cap. 0.5 ml of PEG-400 was added into the reaction mixture. The reaction was then irradiated in a microwave apparatus at 80C , 80 W for 10 min with a pressure of 80 Psi. After cooling to ambient temperature in the microwave cavity the reaction mixture was extracted with ethyl acetate (3x2 ml) and water (1ml). The combined organic layer wasdried over anhydrous Na2SO4 and the solvent was removed under reduced pressure and after purificationwith silica gel column chromatography (hexane: EtOAc::95:5) 2c as yellowish liquid (70 mg, 88%). 1Hand 13C NMR spectra has been compared with our previously reportedstudy.3 ESI-MS: m/z calc. for (M+H)+ C8H9N120.1712 and obsd. 120.0605. GCMS: m/z 119.
85%
With hydrazine hydrate; In ethanol; at 70℃; for 4h;
General procedure: In a typical reaction, 5.0 mg of Pd-gCN (5.0 wt% of Pd) catalyst was added to the solution of 1.0 mM of nitroarene in ethanol (2 mL)and 2 mM (1.2 equiv. 0.07 mL) of 60% of hydrazine hydrate. The mixture was placed into a 10 mL round-bottom flask at the reflux temperature (70 C) for the 4 h and then allowed to cool at room temperature. The resultant material was filtered and the filtrate was subjected to column chromatography over silica gel to obtain the corresponding products. For di-nitroarenes substrates 4.0 mM(2.4 equiv. 0.14 mL) of 60% of hydrazine hydrate solution was used.
81%
With hydrogen; triethylamine; In ethanol; water; at 110℃; under 30003 Torr; for 17h;Autoclave;
General procedure: In a 4 ml_ reaction glass vial fitted with a septum cap containing a magnetic stirring bar, Co-Co3O4Chit-700 (10 mg, 3.4 mol% Co), the nitroarenes (0.5 mmol, 1 .0 equiv.) and triethylamine (35 muIota_, 0.25 mmol, 0.5 equiv.) were added to a solvent mixture of EtOH/H20 (3/1 , 2 ml_). The reaction vial was then placed into a 300 ml_ autoclave, flashed with hydrogen five times and finally pressurized to 40 bar. The reaction mixture was stirred for appropriate time at 1 10 C. After cooling the reaction mixture to room temperature, the autoclave was slowly depressurized. The crude reaction mixture was filtered through a pipette fitted with a cotton bed and the solvent was evaporated under reduced pressure. The crude products were purified by passing through a silica plug (eluent: ethyl acetate) to give pure aniline derivatives after removal of solvent. The following compounds may be prepared from the respective nitroarenes using the catalyst of the invention:
63%
With hydrazine hydrate; In methanol; water; at 80℃; for 0.66h;
General procedure: To a mixture of nitroarene (1 mmol), SS-Pd (2 mol% Pd) and 2 ml of MeOH:H2O (3:7) in a 25 ml round bottom flask N2H4. H2O (3 mmol) was added in stirring condition. The mixture was then heated at 80 oC. Progress of the reaction was monitored by TLC. On completion, the reaction mixture was extracted with ethylacetate and dried over anhydrous Na2SO4. Evaporation of combined organic layer and followed by purification over silica gel (60-120 mesh) column chromatography gave desired corresponding amines.
With oxalic acid; titanium(IV) oxide; In water; acetonitrile; at 24.84℃; under 760.051 Torr; for 6h;Inert atmosphere; UV-irradiation; Sealed tube;
General procedure: Three kinds of commercial TiO2 samples were used as photocatalyst, i.e., P 25 (Degussa), ST-01 (Ishihara), and MT-150A (Tayca). Bare TiO2 powder (50mg) was suspended in a mixture of acetonitrile (Wako Pure Chemical Industries, Osaka) and water (5cm3) containing NS (50mumol, Sigma-Aldrich Japan, Tokyo) and oxalic acid (200mumol, Wako Pure Chemical Industries, Osaka) in a test tube. The tube was sealed with a rubber septum and then photoirradiated at a wavelength >300nm by a high-pressure mercury arc (Eiko-sha, 400W) under argon (Ar) with magnetic stirring at 298K. After the reaction, the gas phase was analyzed by a gas chromatograph (Shimadzu, GC-8A equipped with MS-5A columns). After the suspension had been filtered to remove the particles, the amounts of NS and product(s) were determined by high-performance liquid chromatography (Jasco, UV-2075Plus detector, PU-2089Plus pump, equipped with an Inertsil ODS-3 column, eluent: aqueous sodium borate buffer/acetonitrile=50:50, flow rate: 0.5cm3min-1 at room temperature) and GC-MS (GC-17A, GCMS-QP5050 (Shimadzu); column: DB-1, 0.25mm, 30m (J&W)).
With hydrogen; In toluene; at 50℃; under 2250.23 Torr; for 1.16667h;Autoclave;
General procedure: The catalytic testing for the chemoselective hydrogenationof nitroarenes was conducted in an autoclave equipped with apressure gauge, magnetic stirring system, and water bath. Amixture of nitroarene substrate, solvent, and an internal standardof o-xylene with a total volume of 5 mL was put into theautoclave. Then, the autoclave was flushed with 103 kPa hydrogen5 times. After sealing, the autoclave was charged withH2 to 300 kPa, then heated to 50 C in a water bath with stirringto initiate the reaction. After reaction, the product was analyzedby GC-MS.
With hydrogen; In toluene; at 120℃; under 5250.53 Torr;Catalytic behavior;
The chemoselective hydrogenation of nitroarenes was performed in batch reactors. The reactant, internal standard (dodecane), solvent (toluene or THF), and powder catalyst, as well as a magnetic bar, were added into the batch reactor. After the reactor was sealed, air was purged by flushing two times with 10 bar of hydrogen. Then the autoclave was pressurized with H2 to the corresponding pressure. The stirring speed was kept at 800 rpm and the size of the catalyst powder was below 0.02 mm to avoid either external or internal diffusion limitation. Finally, the batch reactor was heated to the target temperature. For the kinetic studies, 50 muL of the mixture was taken out for GC analysis at different reaction times. For the scope studies, 100 muL of the mixture wastaken out for GC analysis. The products were also analyzed byGC-MS.
With hydrogen; In toluene; at 50℃; under 2250.23 Torr; for 1.16667h;Catalytic behavior;
The catalyst before use of pure H2 reduction, the reducing conditions 1h to 550 C, reduction 1h rear, purging He for 30 min, rapid removal of a poured into 5 ml of the reaction liquid in the reaction tube, the reaction liquid is 0.1M the 3-nitrostyrolene reaction solution (toluene as the solvent, the O-xylene), the reaction condition is the 3bar PH 2, 50 C.
With 0.17percentPt/FeOx; In toluene; at 25℃; under 2250.23 Torr; for 150h;pH 2.0;Catalytic behavior;
General procedure: The catalyst was reduced to 10 C / min at 10 C / min and reduced to 250 C. After 30 min reduction, it was purged with He for 30 min and rapidly removed and weighed 0.1 g into the reaction tube , 5 ml of 0.1 M 3-nitrostyrene reaction solution (toluene as solvent, o-xylene as internal standard) was added to the pipettes. The reaction conditions were 3 bar P H2, 40 C.
With hydrogen; In water; at 50℃; under 30003 Torr; for 4.33h;Autoclave;
In a 30 mL autoclave equipped with a polytetrafluoroethylene liner, 6 mL of H 2 O, 0.16 g of 3-nitrostyrene, 0.1 g of reduced catalyst Pt-Sb / TiO 2 was added, the mass content of Pt was 0.5% The molar ratio of Sb to Pt was 7.2: 1, Pt was supported by ultrasonic impregnation, and the catalyst was reduced at 450 C for 2 h in H 2. Tighten the reaction kettle, at room temperature with high purity N2 blowing 5min, remove the air inside the reactor. Reactor in the 50 C constant temperature water bath preheat 20min, filled with 4MPa H 2, open stirring, reaction 4h. The reaction vessel was cooled and cooled, and the reaction product was extracted with toluene and analyzed by gas chromatography. The conversion of nitrostyrene was 97.3% and the selectivity of aminostyrene was 98.2%.
With hydrogen; In water; at 250℃; for 2h;Autoclave;
In a 50 mL autoclave, 5 mL of H2O was added,0.25 g of 3-nitrostyrene,0.15 g of the reduced catalyst Pt / SnO2-Sb2O3,The mass content of Pt is 0.5%The molar ratio of Sb to Sn is 0.1: 1,The Pt was supported by equal volume impregnation,The catalyst was reduced in H2 at 250 C for 2 h.Tighten the reactor,At room temperature with high purity N2 purge 5min,Remove the air from the reactor.The reactor was preheated at 50 constant temperature water bath for 15min,Filled with 4MPa H2,Open the stir,Reaction for 3 h.The reactor cooling cooling,The reaction product was extracted with toluene,Analysis by gas chromatography.The conversion of nitrostyrene was 96.7%The selectivity of aminostyrene was 98.1%.
With hydrogen; In toluene; at 100℃; under 15001.5 - 30003 Torr; for 24h;Autoclave;
The catalytic performance of Pt catalysts on raw and surfacemodifiedcarbon supports were tested for the selective hydrogenationof 3nitrostyrene using a 50 mL stainless steel autoclave withan inner Teflon coating. For a typical catalytic reaction, 0.5 mmol3-nitrostyrene and 10-40 mg catalyst were mixed in 5 mL toluene.The reactor was purged with 2 MPa H2 three times and it wassealed. The reaction was conducted at 4 MPa H2 at 100 C. The productswere analyzed by gas chromatography (Shimadzu, 2010)equipped with a capillary column (Restek-5 30 m x 0.25 mm x 0.25 mum) and a flame ionization detector (FID). Conversion wasdetermined by dividing the amount of NS consumed by the initialamount of NS; product selectivity was calculated by dividing theamount of a certain product by the amount of NS consumed.Site-time-yield was calculated by dividing the amount a certainproduct by the amount of exposed Pt atoms and reaction time.
With hydrogen; In 1,4-dioxane; at 149.84℃; under 22502.3 Torr; for 12h;Autoclave;Catalytic behavior;
General procedure: Commercially available organicchemicals were of analytical grade and used as purchasedwithout further purification. All the catalytic hydrogenationswere conducted in a high-pressure autoclave with a pressuregauge, a magnetic stirrer, and an oil bath. Typically, 0.10 gcatalysts, 0.10mmol nitroarenes (substrate/Ni molar ratio =1.4), 3.0mmol n-dodecane as an internal standard, and 5.0mL1,4-dioxane solvent were placed into a glass reaction tube andstirred at room temperature for a selected time. After the autoclavewas sealed, pure H2 gas was introduced to remove airfrom the system and kept at 3.0 MPa, and then the reactionsystem was heated to 423 K. After the reaction, the reactionmixture was taken out of the reaction system and analyzedby gas chromatography. The products were identified by gaschromatography (GC-8A, Shimadzu, using a flame ionizationdetector) equipped with a flexible quartz capillary columncoated with Silicon OV-17. The conversion and yields of theproducts were calculated using an internal standard method
With hydrogen; In toluene; at 125℃; under 22502.3 Torr;Flow reactor;Catalytic behavior;
The investigation of the catalytic properties was performed using continuous flow device H-Cube Pro (Thalesnano, Hungary) equipped with stainless-steel CatCart30 reactors of 30 mm in length and 4.0 mmin inner diameter.7,8 Before catalytic run, toluene was fed to the reactor loaded with catalyst (162-195 mg) until the required reaction parameterswere reached. Afterwards, the inlet was switched to the flask filled with a 0.025 m solution of 3-nitrostyrene in toluene. This point in time was chosen as the starting point of the reaction. The catalytic tests were carried out within the 80-125 C range with a hydrogen pressure of 3.0 MPa, where liquid and hydrogen feed rates were set to 0.5 and 60 ml min-1, respectively. We found earlier that there was no influence of external or internal mass transfer limitations under the conditions used.7 The performance of catalyst was evaluated by analysis of the samples taken 30-34 min after the start of the experiment. The reaction products were analyzed by GC (Agilent 6890N instrument with a capillary HP 5-MS column 60 m × 0.32 mm, 0.25 mum) using n-decane as the internal standard. Identification of the products was performed by GC-MS (Agilent 7000B Triple Quad System).
With hydrogen; In methanol; water; at 79.84℃; under 37503.8 Torr; for 12.0h;
Unless specified otherwise, all hydrogenation reactions were carried out at 353 K in small glass vials placed inside a 200-mL autoclave with vigorous magnetic stirring (P900 RPM). Conversions and selectivities were measured by 1H NMR and gas chromatographic techniques. All hydrogenated products were initially identified by using authentic commercial samples of the expected products. The recycling experiments with 1 and 2 were carried out at 353 K under 50 and 40 bar H2 pressure, respectively, with a substrate-to-Ru molar ratio of 283 and 625 in 5 mL of methanol and water, respectively. Recycling experiments with 2 covering five successive batches were also carried out with styrene as the substrate, with a styrene-to-Ru molar ratio of 625 in 5 mL of methanol. Catalyst 1 was filtered off, washed several times with methanol, and used for the second batch. For the reaction with 2, the product was separated from the aqueous solution by ethyl acetate extraction(2 x 10 mL). The aqueous solution of 2 was then reused. A few recycling experiments were also carried out, where 2 was precipitated from the water solution by the addition of acetone and reused. The results obtained by both these methods of catalyst recovery were comparable.
With hydrogen; In toluene; at 100℃; under 15001.5 - 30003 Torr; for 0.08333330000000001h;Autoclave;
The catalytic performance of Pt catalysts on raw and surfacemodifiedcarbon supports were tested for the selective hydrogenationof 3nitrostyrene using a 50 mL stainless steel autoclave withan inner Teflon coating. For a typical catalytic reaction, 0.5 mmol3-nitrostyrene and 10-40 mg catalyst were mixed in 5 mL toluene.The reactor was purged with 2 MPa H2 three times and it wassealed. The reaction was conducted at 4 MPa H2 at 100 C. The productswere analyzed by gas chromatography (Shimadzu, 2010)equipped with a capillary column (Restek-5 30 m x 0.25 mm x 0.25 mum) and a flame ionization detector (FID). Conversion wasdetermined by dividing the amount of NS consumed by the initialamount of NS; product selectivity was calculated by dividing theamount of a certain product by the amount of NS consumed.Site-time-yield was calculated by dividing the amount a certainproduct by the amount of exposed Pt atoms and reaction time.
Stage #1: Methyltriphenylphosphonium bromide With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane for 0.5h; Reflux;
Stage #2: 3-nitro-benzaldehyde In dichloromethane for 3h; Reflux;
88%
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In toluene at 70℃; for 0.5h; Inert atmosphere;
Stage #2: 3-nitro-benzaldehyde In toluene at 110℃; for 2h; Inert atmosphere;
6
According to route (D), methyl-triphenylphosphonium bromide (3.6 g, 10 mmoles, 2 eq.) was placed in dry toluene (17 mL) with potassium tert-butoxide (1.1 g, 10 mmoles, 2 eq.). The reaction mixture was heated at 70°C and stirred for 30 minutes under an inert atmosphere of argon. 3-Nitrobenzaldehyde (756 mg, 5 mmoles, 1 eq.) was then added. The reaction mixture was heated at 110°C and stirred for 2 hours under an inert atmosphere of argon. Upon cooling to room temperature, the reaction mixture was diluted with water and the resulting solution was extracted with ethyl acetate. The organic phase was dried over MgSO4, filtered and concentrated under reduced pressure. The resulting residue was purified by column chromatography on silica gel to afford 1-nitro-3-vinylbenzene (661 mg, 88%). 1H NMR (300 MHz, CDCl3) δ 8.20 (s, 1H), 8.06 (s, 1H), 7.68 (s, 1H), 7.46 (s, 1H), 6.83 - 6.66 (m, 1H), 5.87 (d, J = 17.5 Hz, 1H), 5.41 (d, J = 10.7 Hz, 1H).
80%
With Amberlite IR-400 In N,N-dimethyl-formamide at 95℃; for 10h; Inert atmosphere;
General method for wittig olefination
General procedure: A round-bottom flask was charged with the suspension of ylide (1.5 mmol) in DMF (4 mL) and then Amberlite IR-400 (OH-) (1.2 g) was added to it. The content was stirred for the next 20 min at 95 °C under inert atmosphere, then appropriate aldehyde (1 mmol) was added to the reaction mixture and heating was continued for next 10 h. On completion of the reaction (TLC [thin layer chromatography]), the resin was filtered off and the crude reaction mixture was evaporated to dryness. Isolation of the product was performed by flash chromatography (CombiFlash Rf 200i with UV/VIS and ELSD, Isco Teledyne Inc., USA) using RediSep column (SiO2). All the products were identified on the basis of their spectral data.
55%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 0 - 20℃; for 24h;
55%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 20℃; for 24h;
35%
Stage #1: Methyltriphenylphosphonium bromide With potassium carbonate In 1,4-dioxane at 20℃; for 4h; Inert atmosphere;
Stage #2: 3-nitro-benzaldehyde at 100℃; for 24h; Inert atmosphere;
1.2.2. Method B: Wittig olefination
General procedure: To a 2-necked round bottom flask (previously dried) equipped with a magnetic stirrer, a solution of 1.2 mmol of methyl triphenylphosphonium bromide and 1.6 mmol of previously grinded potassium carbonate in 30 mL of 1,4-dioxane were added. The system was purged with nitrogen and stirred at room temperature for 4 hours. Then, 1.0 mmol of the corresponding aldehyde was added dropwise. The reaction was then stirred at 100 °C for 24 hours. After reaction completion, the flask was cooled to room temperature and 50 mL of water were poured. The crude product was extracted with dichloromethane (3 x 20 mL). The combined organic layers were dried over anhydrous MgSO4 and the solvent removed in vacuo. The styrene product was then purified by flash chromatography employing SiO2 and n-hexane as eluent.
With n-butyllithium 1.) THF, hexane, RT, 1.5 h, 2.) a) RT, 1 h, b) 65 deg C, 5 h; Yield given. Multistep reaction;
With n-butyllithium In hexane
9.a 5-Ethenyl-4-oxo-1,4-dihydroquinoline-2-carboxylic acid
a) Treatment of 3-nitrobenzaldehyde (20 g) with methyltriphenylphosphonium bromide (61.5g) and n-butyllithium in hexane (172 mmol), as described in Example 1a, gave 3-ethenylnitrobenzene (10.3 g), δ (360 MHz, CDCl3), 5.44 and 5.59 (2H, 2d, CH2), 6.75 (1H, dd, CH), 7.49 (1H, t, 5-H), 7.70 (1H, dd, 4-H), 8.09 (1H, dd, 6-H) and 8.24 (1H, d, 2-H).
With potassium carbonate; In 1,4-dioxane; at 20 - 110℃; for 17h;Inert atmosphere;
Methyltriphenylphosphonium iodide (64.2 g, 158.8 mmol, 1.2 eq) was dissolved in 1,4-dioxane (500 mL) and potassium carbonate (27.4 g, 198.5 mmol, 1.5 eq) Stir at room temperature for 1 hour.3-nitrobenzaldehyde (20g,132.3 mmol, 1.0 eq) was added to the reaction system.Stir at 110 C for 16 hours under nitrogen.The solvent was removed under reduced pressure, and ethyl acetate (200 mL) was evaporated.The organic phase was dried over anhydrous sodium sulfate, filtered and evaporated.The residue was purified by column chromatography (hexane)A yellow oily liquid (17.8 g, yield 90%) was obtained.
2-(3-nitro-phenyl)-aziridine-1-sulfonic acid 2,2,2-trichloro-ethyl ester[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
95%
Stage #1: 1-nitro-3-vinyl-benzene; 2,2,2-trichloroethyl sulfamate With tetra(trifluoroacetamidato)dirhodium(II); magnesium oxide In benzene at 0℃;
Stage #2: With [bis(acetoxy)iodo]benzene In benzene at 0 - 25℃; for 8h; Further stages.;
With [bis(acetoxy)iodo]benzene; magnesium oxide In chlorobenzene at -10 - 23℃; for 8h;
3-[(E)-2-(6-acetamido-pyridin-3-yl)vinyl]nitrobenzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium hydrogencarbonate;palladium diacetate; In N,N-dimethyl-formamide;
PREPARATION 1 A mixture of 3-nitrostyrene (7.0 g), <strong>[7169-97-3]2-acetamido-5-bromopyridine</strong> (10.1 g), tetra-n-butylammonium chloride (13.1 g), palladium(II) acetate (0.08 g) and sodium bicarbonate (9.87 g) in N,N-dimethylformamide (70 ml) was stirred at 110pbC. for 6 hours. The reaction mixture was poured into ice-water and precipitated crystals were collected, washed with water and dried to give 3-[(E)-2-(6-acetamido-3-pyridyl)vinyl]nitrobenzene (12.0 g). NMR (DMSO-d6, delta): 2.11 (3H, s), 7.44 (1H, d, J=16Hz), 7.50 (1H, d, J=16Hz), 7.68 (1H, dd, J=8, 8Hz), 8.04 (1H, d, J=8Hz), 8.11 (3H, m), 8.43 (1H, m or dd, J=1, 1Hz), 8.55 (1H, s, or d, J=1Hz).
With sodium hydroxide; In acetic acid; ethyl acetate;
To a solution of the above 3-ethenylnitrobenzene (10 g) in acetic acid (30 ml) was added zinc powder (10 g) and the mixture heated to 70 C. with stirring for two hours, then cooled to room temperature and filtered. Ethyl acetate (300 ml) was added to the filtrate, followed by 1M sodium hydroxide until pH 10. The organic layer was separated, washed with water (100 ml), brine (100 ml) and dried over magnesium sulphate. The solvent was removed under reduced pressure to give the crude product, which was purified by column chromatography to give 3-ethenylaniline (4.9 g), delta (60 MHz, CDCl3) 3.60 (2H, bs, NH2), 5.1, 5.2, 5.5 and 5.8 (3H, 4d, CH2 and CH) and 6.3 to 7.3 (4H, m, ArH).
With hydrogen; silver; In dodecane; at 110℃; under 4500.45 Torr; for 6h;
Catalyst A for Example obtained in Production Example 1 was treated with a catalyst amount of 27 mg (the amount of silver as metal was 12 mg) and 0.5 mmol of substrate 3-nitrostyrene, 5 ml of solvent dodecane, 0.6 MPa of hydrogen pressure, Hydrogenation reduction treatment was carried out under the conditions of a reaction temperature of 110 C. The reaction time was 10 hours in Example 1 and 24 hours in Example 2, and the yield and selectivity were measured using a gas chromatograph, respectively. The results are shown in Table 1. Hydrogenation reduction treatment was carried out under the same conditions as in Example 1 except that 159 mg of the catalyst B for the comparative example was used in place of the catalyst A (the amount of silver as the metal was 12 mg) to obtain the yield and selectivity It was measured. The results are shown in Table 1.
With hydrogen; In toluene; at 100℃; under 15001.5 - 30003 Torr; for 8h;Autoclave;
The catalytic performance of Pt catalysts on raw and surfacemodifiedcarbon supports were tested for the selective hydrogenationof 3nitrostyrene using a 50 mL stainless steel autoclave withan inner Teflon coating. For a typical catalytic reaction, 0.5 mmol3-nitrostyrene and 10-40 mg catalyst were mixed in 5 mL toluene.The reactor was purged with 2 MPa H2 three times and it wassealed. The reaction was conducted at 4 MPa H2 at 100 C. The productswere analyzed by gas chromatography (Shimadzu, 2010)equipped with a capillary column (Restek-5 30 m x 0.25 mm x 0.25 mum) and a flame ionization detector (FID). Conversion wasdetermined by dividing the amount of NS consumed by the initialamount of NS; product selectivity was calculated by dividing theamount of a certain product by the amount of NS consumed.Site-time-yield was calculated by dividing the amount a certainproduct by the amount of exposed Pt atoms and reaction time.
With hydrogen; In toluene; at 125℃; under 22502.3 Torr;Flow reactor;
The investigation of the catalytic properties was performed using continuous flow device H-Cube Pro (Thalesnano, Hungary) equipped with stainless-steel CatCart30 reactors of 30 mm in length and 4.0 mmin inner diameter.7,8 Before catalytic run, toluene was fed to the reactor loaded with catalyst (162-195 mg) until the required reaction parameterswere reached. Afterwards, the inlet was switched to the flask filled with a 0.025 m solution of 3-nitrostyrene in toluene. This point in time was chosen as the starting point of the reaction. The catalytic tests were carried out within the 80-125 C range with a hydrogen pressure of 3.0 MPa, where liquid and hydrogen feed rates were set to 0.5 and 60 ml min-1, respectively. We found earlier that there was no influence of external or internal mass transfer limitations under the conditions used.7 The performance of catalyst was evaluated by analysis of the samples taken 30-34 min after the start of the experiment. The reaction products were analyzed by GC (Agilent 6890N instrument with a capillary HP 5-MS column 60 m × 0.32 mm, 0.25 mum) using n-decane as the internal standard. Identification of the products was performed by GC-MS (Agilent 7000B Triple Quad System).
With water; hydrazine; at 100℃; for 0.166667h;Inert atmosphere;
General procedure: The catalytic performance of several carbon materials prepared was tested in liquid-phase reduction of nitrobenzene, styrene, and 3-nitrostyrene by hydrazine. The Teflon-coated reactor was loaded with carbon catalyst, substrate, and hydrazine hydrate, purged by 0.2 MPa N2, and heated to a reaction temperature of 100 C on a heating place. The reaction mixture was stirred by a magnetic stirrer at 100 C for a certain period of time. The multiphase reaction mixture was so mixed at a stirring rate of >400 rpm that the influence of agitation was negligible. Then, the reactor was cooled by ice water and the liquid phase was separated by filtration. The liquid mixture was analyzed by gas chromatography (GL Science 390B) using decane as an internal standard. The conversion was determined from the amounts of substrate before and after reaction and the selectivity from the amount of a product divided by the total amount of all products detected.
With pyrographite; hydrazine; at 100℃; for 2h;Inert atmosphere;
General procedure: The catalytic performance of several carbon materials prepared was tested in liquid-phase reduction of nitrobenzene, styrene, and 3-nitrostyrene by hydrazine. The Teflon-coated reactor was loaded with carbon catalyst, substrate, and hydrazine hydrate, purged by 0.2 MPa N2, and heated to a reaction temperature of 100 C on a heating place. The reaction mixture was stirred by a magnetic stirrer at 100 C for a certain period of time. The multiphase reaction mixture was so mixed at a stirring rate of >400 rpm that the influence of agitation was negligible. Then, the reactor was cooled by ice water and the liquid phase was separated by filtration. The liquid mixture was analyzed by gas chromatography (GL Science 390B) using decane as an internal standard. The conversion was determined from the amounts of substrate before and after reaction and the selectivity from the amount of a product divided by the total amount of all products detected.
With hydrazine; at 100℃; for 2h;Inert atmosphere;
General procedure: The catalytic performance of several carbon materials prepared was tested in liquid-phase reduction of nitrobenzene, styrene, and 3-nitrostyrene by hydrazine. The Teflon-coated reactor was loaded with carbon catalyst, substrate, and hydrazine hydrate, purged by 0.2 MPa N2, and heated to a reaction temperature of 100 C on a heating place. The reaction mixture was stirred by a magnetic stirrer at 100 C for a certain period of time. The multiphase reaction mixture was so mixed at a stirring rate of >400 rpm that the influence of agitation was negligible. Then, the reactor was cooled by ice water and the liquid phase was separated by filtration. The liquid mixture was analyzed by gas chromatography (GL Science 390B) using decane as an internal standard. The conversion was determined from the amounts of substrate before and after reaction and the selectivity from the amount of a product divided by the total amount of all products detected.
With hydrazine; at 100℃; for 0.166667h;Inert atmosphere;
General procedure: The catalytic performance of several carbon materials prepared was tested in liquid-phase reduction of nitrobenzene, styrene, and 3-nitrostyrene by hydrazine. The Teflon-coated reactor was loaded with carbon catalyst, substrate, and hydrazine hydrate, purged by 0.2 MPa N2, and heated to a reaction temperature of 100 C on a heating place. The reaction mixture was stirred by a magnetic stirrer at 100 C for a certain period of time. The multiphase reaction mixture was so mixed at a stirring rate of >400 rpm that the influence of agitation was negligible. Then, the reactor was cooled by ice water and the liquid phase was separated by filtration. The liquid mixture was analyzed by gas chromatography (GL Science 390B) using decane as an internal standard. The conversion was determined from the amounts of substrate before and after reaction and the selectivity from the amount of a product divided by the total amount of all products detected.
With hydrazine; at 100℃; for 2h;Inert atmosphere;
General procedure: The catalytic performance of several carbon materials prepared was tested in liquid-phase reduction of nitrobenzene, styrene, and 3-nitrostyrene by hydrazine. The Teflon-coated reactor was loaded with carbon catalyst, substrate, and hydrazine hydrate, purged by 0.2 MPa N2, and heated to a reaction temperature of 100 C on a heating place. The reaction mixture was stirred by a magnetic stirrer at 100 C for a certain period of time. The multiphase reaction mixture was so mixed at a stirring rate of >400 rpm that the influence of agitation was negligible. Then, the reactor was cooled by ice water and the liquid phase was separated by filtration. The liquid mixture was analyzed by gas chromatography (GL Science 390B) using decane as an internal standard. The conversion was determined from the amounts of substrate before and after reaction and the selectivity from the amount of a product divided by the total amount of all products detected.
With hydrogen; at 49.84℃; under 30003 Torr;Catalytic behavior;
Prior to the catalytic tests, the catalysts were reduced under H2 flow (50cm3/min) at the desired reduction temperature (200 or 500C) for 3h. The hydrogenation of NS was carried out in a 50cm3 autoclave. The reactor was loaded with approximately 10mg of catalyst and 0.5cm3 of nitrostyrene (3.6mmol), purged with hydrogen to remove the air for three times. The reaction was carried out isothermally at 323K at 4MPa of H2 with a high-pressure liquid pump. Prior to the experiments the reaction mixture was stirred with a magnetic stirrer. After the reaction, the reactor was cooled below room temperature by ice-water and carefully depressurized. The obtained-products were then analyzed by a gas chromatograph attached with a flame ionization detector using decane as an internal standard.
With hydrogen; In ethanol; at 20.0℃; under 760.051 Torr; for 3h;
General procedure: In a typical reaction, 0.015 g of catalyst and 2 mmol of the reactant were taken in 10 mL of ethanol under hydrogen atmosphere. The reaction was monitored by thin-layer chromatography (TLC). After complete disappearance of the starting material, the catalyst was separated by simple filtration and the solvent was removed under reduced pressure to obtain the pure product.
With hydrogen; In toluene; at 100.0℃; under 15001.5 - 30003 Torr; for 0.0833333h;Autoclave;
The catalytic performance of Pt catalysts on raw and surfacemodifiedcarbon supports were tested for the selective hydrogenationof 3nitrostyrene using a 50 mL stainless steel autoclave withan inner Teflon coating. For a typical catalytic reaction, 0.5 mmol<strong>[586-39-0]3-nitrostyrene</strong> and 10-40 mg catalyst were mixed in 5 mL toluene.The reactor was purged with 2 MPa H2 three times and it wassealed. The reaction was conducted at 4 MPa H2 at 100 C. The productswere analyzed by gas chromatography (Shimadzu, 2010)equipped with a capillary column (Restek-5 30 m x 0.25 mm x 0.25 mum) and a flame ionization detector (FID). Conversion wasdetermined by dividing the amount of NS consumed by the initialamount of NS; product selectivity was calculated by dividing theamount of a certain product by the amount of NS consumed.Site-time-yield was calculated by dividing the amount a certainproduct by the amount of exposed Pt atoms and reaction time.
With sodium acetate;palladium diacetate; triphenylphosphine; In N,N-dimethyl-formamide; at 135℃; for 10h;Inert atmosphere;
According to route (B), 1-nitro-3-vinylbenzene (661 mg, 4.4 mmoles, 1.1 eq.) was placed in dimethylformamide (4 mL) with 1-bromo-3 (trifluoromethoxy)benzene (600 muL, 4 mmoles, 1 eq.), NaOAc (661 mg, 8 mmoles, 2 eq.), Pd(OAc)2 (45 mg, 0.2 mmole, 5 mol%), PPh3 (105 mg, 0.4 mmole, 10 mol%). The reaction mixture was heated at 135C and stirred for 10 hours under an inert atmosphere of argon. Upon cooling to room temperature, the reaction mixture was concentrated under reduced pressure and the resulting residue was partitioned between ethyl acetate and water. Upon decantation, the aqueous phase was further extracted with dichloromethane. The organic phases were gathered, dried over MgSO4, filtered and concentrated under reduced pressure. The resulting residue was purified by column chromatography on silica gel to afford (E)-1-nitro-3-(4-(methoxy)styryl)benzene (355 mg, 28%). 1H NMR (300 MHz, CDCl3) delta 8.37 (s, 1H), 8.13 (d, J = 8.4 Hz, 1H), 7.81 (d, J = 7.7 Hz, 1H), 7.54 (t, J = 7.9 Hz, 1H), 7.49 - 7.34 (m, 3H), 7.20 - 7.00 (m, 3H).
With bis(η3-allyl-μ-chloropalladium(II)); oxygen; copper(l) chloride In acetonitrile at 70℃; for 5h; Schlenk technique; Molecular sieve; regioselective reaction;
With 1 wt.%Ir/ZrO2; hydrogen; In ethanol; at 24.84℃; under 15001.5 Torr;Autoclave;Kinetics;
General procedure: Catalytic evaluation was carried out in liquid phase in a Parrstainless steel batch reactor at 298 K using 50.0 mg of catalyst and0.1 mol L-1 of the model molecule (nitrobenzene) and the otherssubstrates, under 20 bar hydrogen pressure. All the components(catalyst, solvent and substrate) were fed to the reactor and stirredat 700 rpm. Liquid samples were taken periodically from thereactor and analyzed in a GC-MS Shimadzu GCMS-QP5050 witha capillary column -Dex 225 (Supelco). The compounds are:m-chloronitrobenzene, m-nitrotoluene, m-nitrobenzaldehyde,m-nitrostyrene, m-nitrobenzonitrile, m-nitroanisole and mdinitrobenzeneand the effect on the activity and selectivityin function of the effects conferred by the substituents wasstudied
General procedure: Into a 2 dram vial was placed 4-nitroacetophenone (55 mg, 0.33 mmol), Ru/PS nanoparticle catalyst (8.0 mg, 0.477 mmol Ru/gram catalyst, 1 mol%), and hydrazine monohydrate (42 muL, 2.5 equiv) in 4 ml of chloroform. The reaction mixture was stirred for 1.25 h, at which point the solvent was removed under reduced pressure. The product was extracted from the solid mixture with 3x 2 ml EtOH. The combined ethanol extracts were then passed through a short silica plug in a pipet and the silica plug was washed 2 times with 1 ml ethanol. The EtOH was then removed on a rotary evaporator under reduced pressure. The product 4-(hydroxyamino)acetophenone was isolated as a pale yellow solid (44.3 mg, 0.29 mmol, 88% yield) as a >20:1 mixture of hydroxylamine to aniline.
With sodium acetate; palladium diacetate; tris-(o-tolyl)phosphine; In N,N-dimethyl-formamide; at 130℃; for 25h;Inert atmosphere;
(E)-5-(3-Nitrostyryl)nicotinamide (ID21) A mixture of <strong>[28733-43-9]5-bromonicotinamide</strong> (ID20, 1.61 g, 8.01 mmol), Pd(OAc)2 (36 mg, 0.16 mmol), P(O-tolyl)3 (146 mg, 0.48 mmol) and NaOAc (1.32 g, 16.1 mmol) in anhydrous DMF (16 mL) was evacuated and back-filled with argon and 1-nitro-3-vinylbenzene (ID19, 1.35 mL, 9.68 mmol) was added. The resulting mixture was heated at 130° C. for 25 h, cooled to rt, and then poured to ice-water (250 mL). The solid formed was filtered, washed with water, and dried to give compound ID21 as a pale solid (1.71 g, 79percent). 1H NMR (DMSO-d6, 600 MHz) delta 8.93 (s, 1H), 8.92 (s, 1H), 8.52 (s, 1H), 8.48 (s, 1H), 8.20 (s, 1H), 8.15 (d, J=7.2 Hz, 1H), 8.10 (d, J=7.2 Hz, 1H), 7.76-7.55 (m, 4H). HRMS (ESI+) calcd for C14H12N3O3 (M+H)+ 270.0873, found 270.0876.
Stage #1: 1-nitro-3-vinyl-benzene With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione In water at 60℃; for 1h;
Stage #2: thiourea In ethanol for 1h; Reflux;
11 Example 11Synthesis of 2-amino-4-(m-nitrophenyl)thiazole
Add 3mL of water and 30μL of Tween in sequence in a 25mL reaction flask, 0.5mmol of nitrostyrene and 0.75mmol of DBH reacted at 60°C for 1h.After the reaction was completed, the water was swirled, 3 mL of ethanol was added, and 0.75 mmol of thiourea was added. The reaction was refluxed for 1 h. After the reaction was completed, ethanol was spin-dried, and ethyl acetate was added to dissolve the solution.The mixture was extracted with saturated brine, and the organic layer was concentrated. Column chromatography afforded 93.5 mg of a white solid with a yield of 85%.
3,3'-((1E,1'E)-(2,5-dimethyl-1,4-phenylene)bis(ethene-2,1-diyl))bis(nitrobenzene)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70%
With triphenyl phosphite; triethylamine; bis(dibenzylideneacetone)-palladium(0); In N,N-dimethyl-formamide; at 110℃; for 24h;Inert atmosphere; Sealed tube;
General procedure: To a 10 mL headspace crimp vial equipped with a magnetic stirrer the corresponding styrene (2.0 mmol), aryl 1,4-dihalide precursor (1.0 mmol), bis(dibenzilidene)acetone palladium (0) (2.0 mol%) and triphenylphosphite (9.0 mol%) were added. The vial was then sealed with a PTFE septum and an aluminum cap followed by purge-saturation with argon. Dry DMF (3 mL) and triethylamine (2.0 mmol) were subsequently added via syringe. The reaction mixture was stirred at 110C for 24 hours. After reaction is complete, the crude was filtered over celite and precipitation of the product was induced by addition of cold water (75 mL). Recrystallization from a 2:1 DMF:1,4-dioxane afforded the desired OPVs.