| 99% |
With hydrogen; In methanol; at 50℃; under 15001.5 Torr; for 2h;Autoclave; |
2-(2,4-Dimethylphenylsulphanyl)nitrobenzene of formula X (25.9 g; 100 mmol) is placed into an autoclave, 250 ml of methanol and 3.9 g of Raney-Ni are added. The mixture is hydrogenated at pressure of 2000 kPa and 50C for 2 hours. The reaction mixture is cooled down to 20C, the catalyst is filtered off, and the filtration cake is washed in 20 ml ofmethanol. Methanol is evaporated and an oily product is obtained with the yield of 99%;HPLC99.2%. |
| 98% |
With hydrogen; In methanol; at 45 - 50℃; under 5250.53 Torr; for 5h; |
A mixture of formula-V (60g, 0.2313 mol), Raney nickel (9.0 g), and methanol (480mL)was prepared in a hydrogenated vessel. Hydrogen gas was then introduced to the vessel up to 7 kg/Cm2. The reaction suspension was heated to 4S-S0 C for S hours. After completion of the reaction, the reaction mass was filtered. The filtrate was concentrated under vacuum at 4S-S0C to yield formula-VI (S2 g, 98%yield).The obtained formula-VI was dissolved in toluene (S2OmL) and hydrobromic acid (38 mL) was slowly added. The reaction mix was stined the reaction mass for 60-90 minutes then filtered to obtain a product which was washed with toluene. The hydrobromic acid salt of formula-VI was converted into free base by using an aqueous sodium hydroxide solution(20%, 55 mL) to yield formula-VI as liquid. |
| 98% |
With palladium on activated charcoal; hydrogen; In methanol; at 25 - 30℃; under 760.051 Torr; |
In an oven-dried 3-necked round-bottomed flask,a mixture of (2, 4-dimethylphenyl) (2-nitrophenyl) sulfane(4, 15 g, 58 mmol) and Pd/C (wet, 0.75 g, 5%) in methanol(75 mL) was stirred for 6h at 25-30 C under H2 atmosphere(1 atm). Reactionmonitored onTLCwith hexane/ethylacetate 9:1. After completion, reaction mixture was filteredthrough a celite pad and filter cake washed with methanol(15 mL). The combined filtrate was evaporated in vacuo tofurnish compound 5. Brown semi solid; yield:13 g, 98%;M.p.: 34-36 C; IR (Neat) upsilon: 750 (o-substituted Ar), 807(o, p-substituted Ar), 1608 (C=C), 3369 (-NH2) and 3446(-NH2) cm-1; 1H NMR (CDCl3): delta 2.26 (s, CH3), 2.39 (s,CH3), 4.22 (s, NH2), 6.69 (d, J = 8.0 Hz, Ar-H), 6.73-6.80(m, Ar-2H), 6.85 (d, J = 8.0 Hz, Ar-H), 7.00 (s, Ar-H),7.19-7.23 (m, Ar-H) and 7.36 (dd, J = 7.0 Hz, Ar-H)ppm; 13C NMR (CDCl3): delta 19.98, 20.73, 115.01, 115.24,118.78, 126.49, 127.26, 130.41, 131.13, 131.68, 135.28,135.71, 136.55 and 148.13 ppm; MS (EI): m/z calculated forC14H15NS [M+H]+: 230.1; found 230.0. |
| 96.1% |
With hydrogen; In isopropyl alcohol; at 30 - 35℃;Autoclave; Large scale; |
2,4-dimethyl-1-[(2-nitrophenyl)thio]benzene (100 g; 0.3856 moles) in IPA (500 mL) was reduced using RaJNi (10 g) at 30-35 C in autoclave under 5-7 kg of hydrogen pressure, catalyst was filtered through celite bed, filtrate was concentrated to obtaIn oil of 2-[(2,4-dimethylphenyl)thiojaniline (V).[Yield: 85.0 g (96.1%); Purity (HPLC) 99.0%] |
| 96.8% |
With iron; ammonium chloride; In tetrahydrofuran; methanol; water; at 60℃; for 5.5h;Inert atmosphere; |
To a three-necked flask, 360 g of 2- (2,4-dimethylphenylsulfanyl) nitrobenzene (III), 233 g of iron powder,297.5 g ammonium chloride, 1.44 L methanol, 1.44 L tetrahydrofuran, 0.576 L water. Nitrogen substitution, 60 C for 5.5 h. Stop the reaction, let stand 18h, centrifuge, and then suction filtration, the filtrate was distilled to remove the solvent.Add 2 L of ethyl acetate, dissolve in water and wash twice with water, add 1 L each time, wash with 1 L saturated brine, add 500 g of anhydrous sodium sulfate and dry for 1 hour, evaporate the ethyl acetate to obtain 2- (2,4 -dimethylphenylsulfanyl) aniline (IV) was obtained in an amount of 96.8% and a purity of 96.9%. |
| 95.9% |
With iron(III) chloride; hydrazine hydrate; pyrographite; In methanol; for 3h;Reflux; |
In a 1 L reaction flask, intermediate (III) IV (79 g, 0.305 mol) and methanol (200 mL) were added. Add activated carbon (1 g, 0.62 mol) and ferric chloride (8 g, 0.030 mol). Heated to reflux. To the solution was added hydrazine hydrate (250 ml) dropwise. After completion of the addition, the reaction was continued for 3 hours. The reaction was stopped. Cooled to room temperature. Diatomaceous earth filtration. Rotary evaporated methanol. Extraction with ethyl acetate (400 ml x 3). The organic layers were combined. Washed with a saturated saline solution. Anhydrous sodium sulfate drying 20min. Filtration. The solvent was evaporated to give 67 g of a pale yellow oil (VI) in a yield of 95.9%. Analysis by liquid and NMR spectroscopy showed little to no other impurities. |
| 95.2% |
With palladium 10% on activated carbon; ammonium formate; In methanol; at 25℃; for 1h; |
In a 250 ml reaction flask,The compound (4) (13.0 g, 50 mmol),Was dissolved in 150 mL of methanol,Another 1.0 g of 10% Pd / C,Ammonium formate (12.6 g, 200 mmol),25 , continue stirring reaction 1 h,Filtration, the filtrate vacuum concentration,The residue was added with 150 mL of water,Extraction with dichloromethane (150 mL x 3)The organic layers were combined,Dried over anhydrous sodium sulfate,And concentrated to give the compound (5) (10.8 g) in a yield of 95.2%. |
| 93% |
With molybdenum(IV) oxide; hydrazine hydrate; pyrographite; In ethanol; at 20℃; for 6h;Green chemistry; |
Example 10 Preparation of 2-(2,4-dimethylphenylthio)benzenamine 2.00 g (7.70 mmol) of 2-(2,4-dimethyl phenyl sulfide) nitrobenzene, 0.01 g (0.077 mmol) of MoO2, 0.05 g of activated carbon and 30 mL of ethyl alcohol were added into a 50 mL flask. Then 0.92 g (15.0 mmol) of hydrazine hydrate (80%) was added dropwise at room temperature and reacted at room temperature for 6 hours until TLC analysis showed the raw materials were reacted completely and then filtered, concentrated filtrate, extracted with 20 mL of ethyl acetate and 10 mL of water, the obtained organic phase was washed and concentrated, finally, get 1.64 g of white solid, the molar yield was 93%, HPLC purity was 99.5%. 1HNMR data: 1HNMR (400 MHz, CDCl3) delta: 7.15-7.20 (m, 2H), 7.02 (s, 6.81-6.85 (m, 2H), 6.58-6.65 (m, 2H), 5.28 (s, 2H), 2.31 (s, 3H), 2.20 (s, 3H). |
| 93% |
With molybdenum(IV) oxide; pyrographite; hydrazine hydrate; In ethanol; at 20℃; for 6h; |
A 50 ml three-necked flask was charged with 2.00 g (7.70 mmol) of 2-(2,4-dimethylphenylthio)nitrobenzene, 0.01 g (0.077 mmol) of molybdenum dioxide, and 0.05 g of activated carbon. 30 ml of absolute ethanol and 0.92 g (15.0 mmol) of hydrazine hydrate (80%) were added dropwise at room temperature. After the reaction was carried out for 6 h at room temperature, TLC monitoring showed that the reaction was completed, filtered, and the residue was collected. After the filtrate was concentrated, 20 mL of ethyl acetate and 10 ml of water were added and extracted. The organic phase was washed with water and concentrated to afford 1.64g the desired product as a white solid, yield 93%, HPLC purity 99.5%. |
| 92.2% |
With iron; ammonium chloride; In ethanol; water; at 50 - 60℃; |
Example 7 Synthesis of 2-(2,4-dimethylphenylsulfanyl)aniline The reaction flask was added 250mL 2-(2,4-dimethylphenylsulfanyl)nitrobenzene (20.7g, 0.08mol), ammonium chloride (34.2g, 0.64mol) in water 70mL, iron powder (17.9g, 0.32mol), ethanol 130mL, warmed to 50-60C, the reaction 4-5 hours, filter, the solvent was evaporated, the residue was recrystallized from isopropyl ether to give an off-white solid 2- (2,4-dimethyl-phenylthio) aniline 16.9g, yield 92.2%, 99.1% purity |
| 90% |
With carbon monoxide; triethylamine; In tetrahydrofuran; water; at 125℃; for 24h;Autoclave; |
General procedure: An 8 mL glass vial (: 14 mm, height 50 mm) equipped with a Tefloncoated oval magnetic stirring bar (8 5 mm) and a plastic screw cap was charged with the corresponding nitroarene 1 (0.5 mmol, 1.0 equiv), Fe2O3/NGr(at)C catalyst (50 mg, 4.0 mol% Fe), Et3N (70 muL, 0.5 mmol, 1.0 equiv), THF (2 mL), and deionized H2O (0.2 mL). The silicone septum was punctured with a 26 gauge syringe needle (0.45 12 mm) and the vial was placed in an aluminum plate, which was then transferred into the 300 mL autoclave. Once sealed, the autoclave was placed into an aluminum block and purged 3 times with CO (at 5-10 bar). Then it was pressurized with CO to 30 bar, followed by additional 20 bar of N2. The aluminum block was heated up to 125 C under thorough stirring (700 rpm). After 24 h, the autoclave was removed from the aluminum block and cooled to r.t. in a water bath. The remaining gases were discharged and the vials containing reaction products were removed from the autoclave. The reaction mixture was filtered through a Celite pad (~1 cm), concentrated, and analyzed by GC and NMR spectroscoopy (Table 2). |
| 85% |
With iron; acetic acid; In water; acetonitrile; at 70 - 90℃;pH 3 - 4; |
Add 10g of reducing iron powder, 70mL of water to a 250mL three-necked flask, add 0.6mL of glacial acetic acid while stirring at room temperature to adjust the pH to 3-4, heat to 100, keep incubating and stir for 1h, cool to 70, add 2-( 2,4-Dimethylphenylsulfanyl)nitrobenzene 6g, acetonitrile 70mL, heated to 90C, kept stirring for 5-6h.Reduce to room temperature, adjust the pH to 7-8 with saturated sodium carbonate aqueous solution, add 100 mL of dichloromethane, stir for 1 hour, filter with a Buchner funnel pad with diatomaceous earth, separate the liquids, keep the organic phase, and use dichloride for the water phase Methane 50mL extraction.The organic phases were combined, dried over anhydrous magnesium sulfate, and spin-dried under vacuum to obtain 4.51 g of an orange oily substance with a yield of 85.0%. |
| 45.87 g |
With palladium 10% on activated carbon; hydrogen; In ethanol; at 80℃; for 6h;Autoclave; |
A solution of 51.9 g (0.2 mole) of 2,4-dimethyl-1-[(2-nitro-phenyl)-sulfanyll-benzene (IV) and 200 ml ethanol is placed in a hydrogenating autoclave whereupon 5.2 g of a 10 % palladium /charcoal catalyst are added. The closed autoclave is rinsed, placed under a hydrogen pressure of 10 bar and stirred in a 80C oil bath for 6 hours (if the internal pressure decreases to 0 bar, the autoclave is put again under a hydrogen pressure of 10 bar). The heating is stopped and the autoclave is allowed to stand at room temperature overnight. The catalyst is filtered, washed with ethanol and the filtrate is evaporated. Thus 45.87 g (theoretical yield 45.85 g) of a yellow-brown oily product are obtained (HPLC purity 96 %). The product is used in the next step without purification.Elementary analysis C14H15NS (229.35) calculated for the Formula:Caic [%] C: 73.32 H: 6.59 N: 6.11Found[%] C:73.02 H:6.56 N:6.14JR (film): 3473, 3374, 1609, 1479, 751 cm1.?H-NMR (CDC13, 500 MHz): 8 7.34 (m, 1H), 7.19 (m, IH), 6.98 (s, lH), 6.83 (d, J8.1 Hz, 1H), 6.74 (m, 1H), 6.72 (m, 1H), 6.70 (d, J=7.9 Hz, 1H), 4.19 (b, 2H), 2.37 (s, 3H), 2.25 (s, 3H) ppm. |
|
With iron; ammonium chloride; In water; at 30 - 85℃; |
,4-dimethyl-1-[(2-nitrophenyl)sulfanyl]benzene (52.5 g)), iron powder (52.5 g), ammonium chloride (10.5 g) and water (1050 ml) was added into round bottom flask at 30±5 C. The reaction mixture was heated to 85±5 C. for about 3-4 hrs. After completion of reaction, the reaction mixture was cooled to room temperature, filtered to remove metal catalyst and the compound was extracted with toluene (2×1050 ml). Toluene was distilled out under vacuum to give the desired compound. Residual mass was dissolved in dichloromethane and into this resulting solution, Methanolic HCl (128 ml, Assay=7.7%, 1.25 eq) was added at 30±5 C. The reaction mixture was stirred for 40 C. for 15-30 minutes then, Dichloromethane and methanol was distilled out under vacuum at 55 C. Cyclohexane was added into resulting solid mass and stirred it for 1 hr at 30±5 C. Resulting mixture was filtered and then solid mass was dissolved in acetone at reflux temperature for 1 hr then reaction mixture was cooled to 30±5 C. Resulting reaction mixture was filtered and it was dissolved in dichloromethane, into this solution 10% NaOH solution was added (pH >10). Organic layer was separated out and was distilled out to collect 2-[(2,4-dimethylphenyl)sulfanyl]aniline |
| 73 g |
With iron; ammonium chloride; In water; at 80℃; for 3h; |
Take 100 g of the 2-(2,4-dimethylphenylsulfanyl)nitrobenzene obtained in Example 1 and add it to 2L of water to add catalytic amount.Ammonium chloride, and iron powder 50g, heated to 80 C for 3 hours, cooling, filtration of iron powder, the filtrate was transferred to 30% aqueous potassium carbonate, after stirring, ethyl acetate was added for extraction, the organic phase was concentrated to give 73g 2- (2,4-Dimethylphenylthio)aniline; |
|
With ammonium formate; In ethanol; at 40 - 80℃; for 2h; |
The W/PdAl-Si prepared by the method of the first embodiment of the present invention is used as a catalyst to further optimize the solvent, hydrogen donor, amount and catalyst dosage of the catalytic hydrogen conversion reaction. The substrate was charged with the substrate 2-(2,4-dimethylphenylthio)nitrobenzene (10 mmol, 2.60 g), solvent 20 ml, catalyst W/PdAl-Si (0.052 g-0.39 g, 2.0- 15% wt), the hydrogen donor is stirred at room temperature and then heated to 60-80 C toThe equilibrium of the reaction was determined by HPLC (the substrate conversion was determined to be equilibrium within 2 h), and the conversion rate of each substrate of the catalytic system and the time required for the reaction were recorded; |
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