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[ CAS No. 14097-35-9 ] {[proInfo.proName]}

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Chemical Structure| 14097-35-9
Chemical Structure| 14097-35-9
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CAS No. :14097-35-9 MDL No. :MFCD17019397
Formula : C10H12N2O2 Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W : 192.21 Pubchem ID :-
Synonyms :

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* 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.

  • Downstream synthetic route of [ 14097-35-9 ]

[ 14097-35-9 ] Synthesis Path-Downstream   1~5

  • 1
  • [ 50-00-0 ]
  • [ 42923-79-5 ]
  • [ 14097-35-9 ]
YieldReaction ConditionsOperation in experiment
84% In acetic acid; at 100℃; for 4h; PREPARATION 212-methyl-1 ,2,3,4-tetrahydro-7-isoquinolinamineStep 1. 2-methyl-7-nitro-1 ,2,3,4-tetrahydroisoquinolineTo a mixture of formaldehyde (26 mL, 944 mmol) and HC02H (15 mL), was added 7- nitro-1 ,2,3,4-tetrahydroisoquinoline (6.32 g, 29.4 mmol). The mixture was heated at 100 C for 4 h. The reaction was then cooled to rt, poured into ice, and basified to pH 1 1 with aq. ammonia. The gummy residue which precipitated was extracted with CH2CI2 (2 x 150 mL). The combined organic extracts were dried over MgS04, filtered, and concentrated in vacuo. The compound was loaded onto florisil and purified via flash column chromatography (ISCO, 120 g silica, 0-5% HCI/ CH2CI2) to give 2-methyl-7-nitro-1 , 2,3,4- tetrahydroisoquinoline (5 g, 84%) as an orange solid. 1 H NMR (400 MHz, DMSO-d6) delta 7.95 - 8.00 (m, 2H), 7.39 (d, J = 8.81 Hz, 1 H), 3.58 (s, 2H), 2.93 (t, J = 5.79 Hz, 2H), 2.62 (t, J = 5.92 Hz, 2H), 2.36 (s, 3H); MS (m/z) 193.1 (M+H)+.
67% Step A: 2-Methyl-<strong>[42923-79-5]7-nitro-1,2,3,4-tetrahydroisoquinoline</strong> 7-Nitro-1,2,3,4-tetrahydroisoquinoline (4.15 g, 23.3 mmol) was combined with paraformaldehyde (3.7 g, 116 mmol), HOAc (6.7 mL, 116 mmol), sodium cyanoborohydride (7.3 g, 116 mmol) in DCE (300 mL) and heated at reflux for 15 h. The reaction was cooled and quenched by stirring with saturated aqueous NaHCO3. The organic layer was dried with MgSO4. The solvent was removed under vacuum and the crude oil was purified by silica gel flash column chromatography (40-100% EtOAc/hexanes). Purification yielded 3.0 g (67%) of the title compound as an oil. 1H NMR (400 MHz, DMSO-d6) delta 8.14 (s, 1H), 8.09 (dd, J=8.5, 2.4 Hz, 1H), 7.52 (d, J=8.2 Hz, 1H), 4.22 (s, 2H), 3.29-3.23 (m, 2H), 3.16-3.08 (m, 2H), 2.67 (s, 3H).
With water; sodium tris(acetoxy)borohydride; In 1,2-dichloro-ethane; at 20℃; for 24h; To a stirring solution of 7-nitro- 1,2,3, 4-tetrahydro-isoquinoline (5.00 g, 23.3 mmol) in dry 1,2-dichloroethane (200 mL) add formalin (37% aq. formaldehyde) (1.91 mL, 25.6 mmol) followed by sodium triacetoxyborohydride (23.4 g, 104.8 mmol). Stir the reaction vigorously at rt for 24 h. TLC (10% MeOH/DCM) indicates formation of desired product (Rf = 0.35) and absence of starting material. Concentrate the reaction in vacuo and dilute the residue with EtOAc (400 mL). Quench this with portionwise addition of sat. NaHCC^ (400 mL) and vigorous stirring (delayed onset of vigorous bubbling). Extract the aqueous with more EtOAc (400 mL), dry the combined organics (Na2S04), and concentrate in vacuo to give a brown oil. Purify the crude product by silica gel chromatography eluting with a gradient of 0% to 2.5% MeOH/DCM to afford an oil. This crystallizes to a solid overnight in vacuo to give the desired product 2-methyl-7-nitro- 1,2,3, 4-tetrahydro- isoquinoline as a solid (3.43 g, 17.3 mmol).
1.5 g With sodium cyanoborohydride; In water; 1,2-dichloro-ethane; at 20℃; for 24h; To a stifled solution of 7-nitro-i,2,3,4-tetrahydroisoquinoline (10 g, 56.18 mmol) in dry i,2-dichloroethane (200 mL) was added formalin (2.3 mL, 61.80 mmol, 37% aq. formaldehyde) followed by NaCNBH3 (52 g, 245.35 mmol). The reaction was stifled vigorously at RT for 24 h. The solvent was removed in vacuo, and the mixture was diluted with EA (200 mL). Sat. NaHCO3 (200 mL) was added with vigorous stifling. The layers were separated, and the water layer was extracted with ethyl acetate (2 x 100 mL). The combined organic layers were dried (Na2504) and concentrated in vacuo to give a brown oil. The crude product was purified by chromatography (5i02, MeOH/DCM) to afford mixture of 3-regio isomers (5 g, 26.04 1 mmol). The mixture of regioisomers (4 g) was purified by SFCPrep (Lux Amylose-2, (4.6 x 250 mm), 90% C02: 10% 0.5% DEA in ethanol) to afford 2- methyl-7-nitro- 1,2,3 ,4-tetrahydroisoquinoline (1.5 g). MS (ESI) m/z 193.0 [M+H] .

  • 2
  • [ 13058-73-6 ]
  • [ 14097-35-9 ]
YieldReaction ConditionsOperation in experiment
With formaldehyd In formic acid 3.a (a) (a) 7-nitro-2-methyl-1,2,3,4-tetrahydroisoquinoline hydrochloride A solution of 4.00 g (18.7 mmol) of 7-nitroisoquinoline in 10 ml of formic acid and 17 ml of 38% aqueous formaldehyde was heated at reflux for 1 h. The reaction mixture was cooled, poured onto ice and basified with aqueous ammonia. The gummy residue which precipitated was extracted twice with methylene chloride. The dried (magnesium sulfate) organic phase was concentrated to give crude 7-nitro-2-methyl-1,2,3,4-tetrahydroisoquinoline as a thick oil.
  • 3
  • [ 42923-79-5 ]
  • [ 14097-35-9 ]
YieldReaction ConditionsOperation in experiment
85% 2-Methyl-<strong>[42923-79-5]7-nitro-1,2,3,4-tetrahydroisoquinoline</strong> (252). Formic acid (9.4 mL, 250 mmol) was added dropwise to Ac2O (19 mL, 202 mmol) at 0 0C. The solution was stirred at 50 0C for 45 min, then cooled to -18 0C, diluted with THF (100 mL) and a solution of 7-nitro- 1 ,2,3,4-tetrahydroisoquinoline [(a) Tercel, M.; et al., J. Med. Chem. 1996, 39, 1084-1094; (b) Zhu, Z., et al., J. Med. Chem. 2003, 46, 831-837] (251) (13.8 g, 5.0 mmol) in THF (100 mL) was added and stirred at -15 to -18 0C for 30 min. The solution was warmed to 20 0C, the solvent evaporated and the residue partitioned between saturated aqueous NaHCO3 solution (250 mL) and EtOAc (250 mL). The aqueous fraction was extracted with EtOAc (3 x 250 mL), dried and the solvent evaporated. The residue was dissolved in THF (200 mL), EPO <DP n="159"/>cooled to 10 0C and BH3 DMS solution (10 M, 19.4 mL, 194 mmol) was added. The solution was stirred at 20 0C for 1 h, diluted with MeOH (30 mL) and acidified with HCI solution (1 M, 45 mL). The solution was stirred at 40 0C for 15 min, the solvent evaporated and the residue partitioned between saturated aqueous NaHCO3 solution (250 mL) and EtOAc (250 mL). The aqueous fraction was extracted with EtOAc (3 x 250 mL), dried and the solvent evaporated. The residue was purified by chromatography, eluting with a gradient (2-5%) of MeOH/DCM, to give isoquinoline 252 (12.6 g, 85%) as an orange solid: 1H NMR delta 8.09 (dd, J = 8.4, 2.3 Hz, 1 H, H-6), 7.95 (d, J = 2.3 Hz, 1 H, H-8), 7.37 (d, J = 8.4 Hz, 1 H, H-5), 4.27 (d, J = 16.1 Hz1 1 H, H-1), 3.94 (d, J = 16.1 Hz, 1 H, H-1), 3.23-3.34 (m, 2 H, CH2), 2.99-3.18 (m, 2 H, CH2), 2.17 (s, 3 H, NCH3); MS (APCI) m/z 193 (MH+, 100%).
  • 4
  • [ 64-18-6 ]
  • [ 42923-79-5 ]
  • [ 14097-35-9 ]
  • 5
  • [ 50-00-0 ]
  • [ 99365-69-2 ]
  • [ 14097-35-9 ]
YieldReaction ConditionsOperation in experiment
With sodium cyanoborohydride; acetic acid; In methanol; water; at 50℃; for 15h; 2) Production of 2-methyl-7-nitro-1,2,3,4-tetrahydroisoquinoline: 5.9 g of sodium cyanoborohydride was added to a methanol (450 mL) solution of 10 g of the compound obtained in the above reaction 1), 10.4 mL of aqueous 37 percent formaldehyde solution and 4 mL of acetic acid, and stirred at 50°C for 15 hours. The precipitated solid was taken out through filtration and washed with methanol. The resulting crude product was purified through basic silica gel column chromatography (hexane/ethyl acetate) to obtain 8.7 g of the entitled compound as a colorless solid. 1H-NMR (CDCl3) delta: 7.99 (1H, dd, J=8.5, 2.0 Hz), 7.92 (1H, d, J=2.0 Hz), 7.26 (1H, d, J=8.5 Hz), 3.65 (2H, s), 3.01 (2H, t, J=5.9 Hz), 2.73 (2H, t, J=5.9 Hz), 2.49 (3H, s) ESI-MS Found: m/z [M+H] 193
With sodium cyanoborohydride; acetic acid; In methanol; water; at 50℃; for 15h; Sodium cyanoborohydride (5.9 g) was added to a methanol (450 mL) solution of the compound (10 g) obtained in the above reaction 1), aqueous 37 percent formaldehyde solution (10.4 mL) and acetic acid (4 mL), and stirred at 50°C for 15 hours. The precipitated solid was collected through filtration, and washed with methanol. The resulting crude product was purified through basic silica gel column chromatography (hexane/ethyl acetate) to give the entitled compound as a colorless solid (8.7 g). 1H-NMR (CDCl3) delta: 7.99 (1H, dd, J = 8.5, 2.0 Hz), 7.92 (1H, d, J = 2.0 Hz), 7.26 (1H, d, J = 8.5 Hz), 3.65 (2H, s), 3.01 (2H, t, J = 5.9 Hz), 2.73 (2H, t, J = 5.9 Hz), 2.49 (3H, s). ESI-MS Found: m/z[M+H] 193.
Into a 500 mL erlenmeyer flask was charged 7-nitro-l,2,3,4-tetrahydroisoquinoline hydrochloride (5 g, 23.30 mmol) and 1,2-dichloroethane (250 mL). The solution was treated with 1 N NaOH (~50 mL) and stirred 10 minutes. The layers were separated and the organic layer was treated with paraformaldehyde (3.50 g, 116 mmol), acetic acid (6.67 mL, 24.48 mmol) and sodium cyanoborohydride (5.42 g, 86 mmol). The reaction was heated at 90 °C for 16 hours. The reaction was cooled to ambient temperature and saturated sodium bicarbonate (60 mL) was added. The bilayer was stirred for 1 hour and charged to a separatory funnel. The organic layer was dried ( a2S04) and concentrated. The concentrate was purified by flash chromatography on a 130 g silica gel column with a gradient of from 0percent to 1percent methanol in CH2C12 to provide the title compound. MS (DCI(+)) m/e 193.0 (M+H)+.
Into a 125 niL Erlenmeyer flask was charged 7-nitro- 1,2,3,4- tetrahydroisoquinoline, hydrochloric acid (3.17 g, 14.77 mmol) in dichloroethane (148 ml). The solution was stirred 10 minutes with 1 N NaOH, and the layers were separated. Paraformaldehyde (2.217 g, 73.8 mmol), acetic acid (4.23 ml, 73.8 mmol) and sodium cyanoborohydride (4.64 g, 73.8 mmol) were added. The reaction was heated at 90 0C overnight. The reaction was cooled to room temperature, and quenched with saturated aqueous sodium bicarbonate. The layers were separated, and the organic layer was dried over MgSO4, filtered, and concentrated onto silica gel. The reaction was purified by flash chromatography (50percent ethyl acetate:hexanes for 20 minutes, then to 100percent ethyl acetate:hexanes over 30 minutes) to provide the title compound. MS (DCI) m/e 193 (M+H)+.

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