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CAS No. : | 138113-08-3 | MDL No. : | MFCD08704309 |
Formula : | C13H11NO | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | PYJMGUQHJINLLD-UHFFFAOYSA-N |
M.W : | 197.23 | Pubchem ID : | 11264068 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302 | Packing Group: | |
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 |
---|---|---|
91% | With trichlorophosphate; In dichloromethane; N,N-dimethyl-formamide; at 85℃; for 2h; | A mixture of 2-(7-methoxy-1 -naphthyl) acetic acid (100g), Dichloro methane(500 ml). Dimethyl formamide(l ml), thionyl chloride 65.98 g was stirred and heated to 35 to 40 C 1 hr. The solvent was distilled out completely under vacuum. Toluene (800 ml) was added to the residue, ammonia gas was purged at 0-5 C till pH 10-1 1. After the completion of reaction, reaction mixture was heated at 45-50C. Cooled the reaction mass, filtered the solid, washed with toluene. The materials so obtained, Phosphorous oxychloride (85.08 g) and toluene (500 ml) was stirred and heated at 85 C for 2 hrs. The mixture was partitioned between water and toluene. Organic phase was washed with aq. NaHCO3 solution. The solvent was distilled out completely under vacuum. Toluene (50 ml), methanol (200 ml) was added to the residue and cooled 5- 10 C. Filtered the solid and washed with methanol and dried to obtained 2-(7-methoxynaphthyl) acetonitrile (Yield 91 %, HPLC purity 99.5%). |
80% | With triethylamine; trifluoroacetic anhydride; In tetrahydrofuran; at 20℃;Cooling with ice; | Reference example 5: The preparation of 7-methoxy-1-naphthaleneacetonitrile 30g 7-methoxy-1-naphthaleneacetamide, 120ml THF and 35.7g triethylamine were added into reaction flask. The mixture was stirred and cooled with external ice saline bath. Trifluoroacetic anhydride was slowly added in drops. After completion of addition, it was stirred for further 15main. Then, the ice bath was removed and stirring was carried out for 2h at room temperature. After completion of the reaction, the reaction solution was evaporated. Subsequently, 200ml water was added and the solution was filtered and dried after stirring for 0.5 hours, to obtain 28g crude product. Recrystallization was carried out using 280ml isopropyl ether and 1.4g activated carbon to obtain 22g refined product with the mp of 82- 84C. The yield is 80%. |
With trifluoroacetic anhydride; In tetrahydrofuran; at 0 - 20℃; | Step 6 (7-Methoxy-naphthalen-1-yl)acetonitrile: At about 0 C., trifluoroacetic anhydride (9.29 g; 44.2 mmol) was added dropwise to a suspension of 2-(7-methoxy-naphthalen-1-yl)acetamide (2.38 g; 11.1 mmol) in anhydrous tetrahydrofuran (30 mL). Under continuous stirring, the mixture was maintained at about 0 C. until 2-(7-methoxy-naphthalen-1-yl)acetamide was no longer detected by TLC. After warming to ambient temperature, the reaction mixture was concentrated and purified by flash column chromatography on silica gel (4*16 cm, ethyl acetate/petrol ether=1:30 elution) to give the title product as a white solid (1.6 g, yield 73% over three steps). 1H NMR (300 MHz, CDCl3) delta 3.98 (s, 3H), 4.09 (s, 2H), 7.09 (d, J=2.1 Hz, 1H), 7.22 (dd, J=9.0, 2.4 Hz, 1H), 7.34 (dd, J=7.8, 7.5 Hz, 1H), 7.55 (d, J=6.9 Hz, 1H), 7.81 (dd, J=8.7, 6.9 Hz, 2H). GC-MS: 197 (M)+. |
5.2 kg | With phosphorus pentoxide; In toluene;Reflux; | 6.0Kg of the compound of the formula (III), 6.5Kg of phosphorus pentoxide and 180L of toluene were added to the reaction vessel, and the reaction was refluxed for 9 to 10 hours, and the temperature was lowered. The reaction solution was washed with 150 L of water, 150 L of sodium hydrogencarbonate solution and 150 L of brine. Dry sodium sulfateDry, filter, and concentrate the filtrate to dryness under reduced pressure. The obtained oil was added 3 L of isopropyl ether, stirred at room temperature for 15 to 20 minutes, filtered, and the filter cake was blast dried for 6 to 8 h to give the compound of formula (IV): 5.2 Kg. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With hydrogen; sodium hydroxide; In methanol; water; at 30℃; under 3000.3 Torr; | In a 10L reactor compound of formula II (230 g), methanol (3,7 L), NaOH solution ((123,3) g NaOH is diluted in 460mL water) and Raney Nickel (41 ,193 g) is charged. Reaction mixture is stirred at 30C and 4 bar hb and monitored with HPLC. After reaction is done, it is filtered and solvent is evaporated. To concentrate is added toluene (4,25 L) and water (2,13 L), mixed and separated. To organic phase water is added (2,13 L), pH is adjusted to 2 with 37 % HCI, and phases are separated. To water phase fe/f-butyl methyl ether (2,13 L) is added and pH is adjusted to 10 with 40 % NaOH. Further organic phase is concentrated, ethanol (230 mL) is added, heated to 50C then 4 M HCI in ie/f-butyl methyl ether (355 mL) and ie/f- butyl methyl ether (920 mL). White precipitate started to obtain. Suspension is cooled to room temperature, filtered, washed with ie/f-butyl methyl ether and dried. Product is white solid (256,2, yield 92%). |
90% | A mixture of 2-(7-methoxynaphthyl) acetonitrile (100g), methanol (800 ml), aq. sodium hydroxide (30.42 g sodium hydroxide in 100 ml water), 20 g of Raney Ni stirred in hydrogen atmosphere (apply H2 gas up to 10 kg) at 25 to 30 C for 2-3 hrs. Filtered the reaction mixture, distilled out solvent completely under vacuum. IPA is added to the residue and heated at 50 to 55 C, IPA HCI added at 50 to 55 C and stirred for one hour. Cooled the reaction mixture at 10-15C, filtered the solid, washed with IPA and dried. There was thus obtained 2-(7-methoxynanphthyl)ethanamine hydrochloride (Yield 90%, HPLC purity 99.5 to 99.9 %) | |
83% | Example 2: Preparation of 2-(7-methoxy-l-naphthyi)ethanamine hydrochloride of Formula (D) Methanol (500 ml) was added to an autoclave with 1 Kg/cm2 pressure of Ammonia gas at 10C to 15C and stirred for 1 hour followed by addition of (7-methoxy-l- naphthyl)acetonitrile of Formula (C) (70 g). Raney Nickel (14 g) was added and 5.0 Kg/cm2 pressure of Hydrogen gas was applied at 15C to 25C. The reaction was heated to 50C to 55C. The reaction mass was filtered and treated with ethyl acetate (500 ml) at 25C to 35C and cooled to 0C to 5C followed by addition of Con. HCI acid and maintained for 1 hour. The reaction mass was filtered and washed with chilled ethyl acetate (2 X 50 ml) afforded 2-(7-methoxy- l-naphthyl)ethanamine hydrochloride of formula (D) Yield - 83% |
32% | A solution of (7-methoxynaphthalen-l-yl)acetonitrile (30 g) in methanol (150 mL) and aqueous ammonia (15 mL) was treated with hydrogen gas (3 Kg) in the presence of Raney nickel (45 g) at 40C. After completion of the reaction, the reaction mixture was filtered through a Hyflo. The filtrate was concentrated under vacuum (200-220 mbar) at 45C to 50C to obtain a residue. The residue in ethyl acetate (60 mL) was acidified (pH 2) with concentrated hydrochloric acid (10 mL to 15 mL) at 10C to 15C to obtain a solid. The solid was dried under vacuum (5-10 mbar) at 45C to 50C over 10 to 15 hours to get the title product.Yield (w/w): 32% | |
32% | A solution of <strong>[138113-08-3](7-methoxynaphthalen-1-yl)acetonitrile</strong> (30 g) in methanol (150 mL) and aqueous ammonia (15 mL) was treated with hydrogen gas (3 Kg) in the presence of Raney nickel (45 g) at 40 C. After completion of the reaction, the reaction mixture was filtered through a Hyflo. The filtrate was concentrated under vacuum (200-220 mbar) at 45 C. to 50 C. to obtain a residue. The residue in ethyl acetate (60 mL) was acidified (pH 2) with concentrated hydrochloric acid (10 mL to 15 mL) at 10 C. to 15 C. to obtain a solid. The solid was dried under vacuum (5-10 mbar) at 45 C. to 50 C. over 10 to 15 hours to get the title product. Yield (w/w): 32% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(7-Methoxy-naphth-1-yl)acetonitrile (20 g) is dissolved in 150 ml of anhydrous tetrahydrofuran. Sodium hydride (202.8 mmol) is added at ambient temperature, and the mixture is refluxed for 30 minutes. Dimethyl carbonate (12 ml) is added with caution, and the reaction mixture is refluxed for 30 minutes. The mixture is poured into ice-cold water, and the aqueous phase is acidified with 21 ml of 37% hydrochloric acid solution and then extracted twice with 100 ml of ether. The organic phase is washed with water, dried, decoloured and evaporated. The oil obtained is precipitated from ether, and the precipitate formed is filtered off under suction and then recrystallized to yield the title compound in the form of a white solid. Melting Point: 80-82 C. | ||
Methyl cyano(7-methoxy-1-naphthyl)acetate (7-Methoxy-naphth-1-yl)acetonitrile (20 g) is dissolved in 150 ml of anhydrous tetrahydrofuran. Sodium hydride (202.8 mmol) is added at ambient temperature, and the mixture is refluxed for 30 minutes. Dimethyl carbonate (12 ml) is added with caution, and the reaction mixture is refluxed for 30 minutes. The mixture is poured into ice-cold water, and the aqueous phase is acidified with 21 ml of 37% hydrochloric acid solution and then extracted twice with 100 ml of ether. The organic phase is washed with water, dried, decoloured and evaporated. The oil obtained is precipitated from ether, and the precipitate formed is filtered off under suction and then recrystallized to yield the title product in the form of a white solid. Melting point: 80-82 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With ammonia; hydrogen; In ethanol; water; at 60℃; under 228015 Torr; for 12h;Autoclave; | Reference example 6: The preparation of 2-(7-methoxy-1-naphthyl)ethylamine 56g 7-methoxy-1-naphthaleneacetonitrile, 120ml ammonia water, 332ml 95% ethanol, 20g Raney-Ni were added into autoclave. H2 was introduced after vacuuming it. The operation was repeated for 3 times. The reaction was stirred for 12 hours while H2 was introduced and the condition of 300 atm and 60C was maintained. After completion of the reaction, the reaction was kept overnight at room temperature. On the next day, it was vacuumed and N2 gas was introduced. The autoclave was opened up, and the reaction solution was filtered to remove the catalyst. The filtrate was vacuum evaporated until dry to obtain 56g light green oil. The content is measured as 96.95% by HPLC, and the yield is 95%. |
92% | With hydrogen; ammonium hydroxide;nickel; In methanol; at 20℃; under 3102.97 Torr; for 20h; | Step 7 2-(7-Methoxy-naphthalen-1-yl)-ethylamine: At ambient temperature and under a pressurized hydrogen atmosphere (60 psi), a mixture of (7-methoxy-naphthalen-1-yl)acetonitrile (1.6 g; 8.1 mmol), Raney nickel (0.5 g) in methanol (80 mL), and ammonium hydroxide (5 mL) was continuously stirred for about 20 hours. The catalyst was then removed by filtration and the filtrate was concentrated to give the title product as a yellow oil, which was used directly in the next step without further purification (1.5 g, yield 92%). 1H NMR (300 MHz, CD3OD): delta 3.00 (br. s, 2H), 3.20 (br. s, 2H), 3.93 (s, 3H), 7.12 (d, J=8.7 Hz, 1H), 7.24 (m, 3H), 7.63 (d, J=7.8 Hz, 1H), 7.73 (d, J=8.7 Hz, 1H). LC-MS: 202 (M+H)+. |
71.2% | With ammonia; hydrogen; In ethanol; at 45℃; under 15001.5 Torr;Green chemistry; | A hydrogenation reaction vessel was charged with <strong>[138113-08-3](7-methoxy-1-naphthyl)acetonitrile</strong> (10.0 g, 50.7 mmol), added to a 500 ml hydrogenreaction vessel, dissolved in 200 ml of anhydrous ethanol, and 0.95 g of Raney nickel wasadded to thehydrogenation reaction. kettle introducing gaseous ammonia, ammonia gas stream flatstable holding 0.1-5h; 1-5 times and then replaced by hydrogen, a sealed reactor; hydrogenation reactor was placed 45 C, 2.0MPa bar hydrogen pressureand stirred overnight under member; the reaction was monitored by TLC until complete; the reaction solution was decanted, suction filtered, rinsed with a little 95% ethanol; filtrate concentratedsolution has a pH, and dissolved in ethyl acetate, hydrochloric acid gas was introduced, the control of the mother liquor is 8.0 to 9.0, a large number of white precipitate heavyprecipitate Suction suspension was filtered off, the filter cake was washed with ethyl acetate, and the filter cake was dried at 50 C. to obtain an off-white solid, ie compound (II) 8.7 g, yield 71.2%, product properties: white powder.Purity: 99.52%. |
With ammonia; hydrogen;nickel; In ethanol; water; at 40℃; under 22502.3 Torr; | There are introduced into a 1100 litre reactor 80.0 kg of the compound obtained in Step B, 24.0 kg of Raney nickel in ethanol and 170 l of ammonium hydroxide. The mixture is stirred under a hydrogen pressure of 30 bars, then brought to 40 C. When all the starting substrate has disappeared, the solvent is evaporated off, the resulting residue is redissolved in ethyl acetate, and 41.5 l of an 11N hydrochloric acid solution are added. After filtration, the precipitate obtained is washed with ethyl acetate and then dried in an oven to give the title product in a yield of 95.3% and with a chemical purity exceeding 99.5%. Melting point: 243 C. | |
With sodium tetrahydroborate; di-tert-butyl dicarbonate; nickel dichloride; In methanol; for 12h; | A mixture of 2-(7-methoxynaphthalen-1-yl) acetonitrile (compound 2,1.99 g, 10.0 mmol), sodiumborohydride (417mg, 11.0 mmol), nickelchloride(475 mg, 5.0 mmol) and dibutyldicarbonate (0.2 mL) in 20 mL methanol were stirred at room temperature for 12 h, then the reaction was suspended with 20 mL water. The resulting mixture was concentrated under reduced pressure, then 20 mL water was added, extracted with ethyl acetate(20 mL×3), the combined organic layer were concentrated under reduced pressure. After that 10 mL trifluoroacetic acid and 10 mL dichloromethane were added, stirred at room temperature for 4 h and adjust to pH=12, then washed with water (20 mL×3) and compound 3 was obtained after concentrated under reduced pressure. | |
With ammonia; hydrogen; In ethanol; at 30 - 40℃; under 2250.23 - 3000.3 Torr; for 24h;Autoclave; | To the autoclave was charged 30 g of (7-methoxy-1-naphthyl) acetonitrile prepared in Example 19, 7.5 g of Raney nickel,95% ethanol 200ml, ammonia 60ml, autoclave sealed, nitrogen replacement, access to hydrogen,Control the pressure of 0.3-0.4Mpa, temperature 30-40 , holding pressure after 24 hours, cooling, remove the reaction solution, filter recovery Raney nickel, the filtrate evaporated under vacuum (7-methoxy-1-naphthyl) Ethylamine oil;To the oil was added 120 ml of toluene, 25 ml of triethylamine was stirred and dissolved,Control temperature below 30 add acetic anhydride 17ml, and 0-10 incubation reaction 30min,Then, 120 ml of water was added dropwise and cooled to 0-5 C for 2 h. The mixture was filtered and dried to give 31 g of aggamatine, the yield was 83.8% and the HPLC purity was 99.9%. |