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Chemical Structure| 4424-20-8 Chemical Structure| 4424-20-8

Structure of 4424-20-8

Chemical Structure| 4424-20-8

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Product Details of [ 4424-20-8 ]

CAS No. :4424-20-8
Formula : C10H13N
M.W : 147.22
SMILES Code : C12=CC=CC=C1CCNCC2
MDL No. :MFCD04012620
InChI Key :MWVMYAWMFTVYED-UHFFFAOYSA-N
Pubchem ID :1400243

Safety of [ 4424-20-8 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H314
Precautionary Statements:P260-P264-P280-P301+P330+P331-P303+P361+P353-P304+P340-P305+P351+P338-P310-P321-P363-P405-P501
Class:8
UN#:2735
Packing Group:

Application In Synthesis of [ 4424-20-8 ]

* 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 [ 4424-20-8 ]

[ 4424-20-8 ] Synthesis Path-Downstream   1~4

  • 1
  • [ 613-73-0 ]
  • [ 4424-20-8 ]
YieldReaction ConditionsOperation in experiment
47% With ammonia; hydrogen;Raney Nickel; In methanol; at 70℃; under 36201.3 Torr; for 48h; A mixture of 1 ,2-phenylenediacetonitrile (2Og, 0.128mol) and Raney Nickel (2g) in 20% methanolic ammonia (120ml) and methanol (400ml) were charged with hydrogen (700 psi). The mixture was then heated at 700C for 2 days. After cooling the mixture was filtered through celite and evaporated in vacuo. The resultant crude material was purified by dry flash column chromatography (eluting with 10% MeOH in DCM and 1% triethylamine) to yield 2,3,4,5-tetrahydro-1 H-3-benzazepine as a brown oil (15A) (9g, 47%). 1H NMR (CDCI3) 8.08-7.15 (4H, m, ArH), 2.96-2.86 (8H, m, 8H) ppm.2,3,4,5-tetrahydro-1 H-3-benzazepine (15A) (18.34g, 0.124mol) was cooled to 00C and cone. H2SO4 (70ml) added. The mixture was stirred for 30mins before cone. HNO3 (4.55ml, 0.099moi) was added dropwise. The mixture was stirred for 2 hours at 00C before being poured onto ice/water (500ml). The mixture was basified with solid NaOH and organics extracted with ethyl acetate (3 x 50ml). The solvent was evaporated in vacuo to yield 7-nitro- 2,3,4, 5-tetrahydro-1 H-3-benzazepine as a brown oil (15B) (6.07g, 25%). This crude material was used directly in the next step. A small amount of material <n="41"/>was purified by flash column chromatography (eiuting with 1-10% MeOH/NH3 in DCM) for characterisation.1H NMR (CDCI3) 7.95-7.90 (2H, m, ArH), 7.25 (1 H, m, ArH), 3.0-2.9 (8H, m) ppm.LCMS [M+H]+ 193.To a stirred mixture of 7-nitro-2,3,4,5-tetrahydro-1 H-3-benzazepine (15B) (6.26g, 32.5mmoi) and triethylamine (6.5ml, 48.8mmo.) in DCM (100ml) at 0C was added benzyl chloroformate (5.6ml, 39.1 mmol). The mixture was allowed to warm to room temperature and stirred overnight. Water (80ml) was then added and after stirring for 15 mins the organic layer was separated, dried (MgSO4) and evaporated in vacuo. The resultant oil was purified by flash column chromatography (eiuting with 4:1 hexane:ethyi acetate) to yield benzyl 7-nitro-1 ,2,4,5-tetrahydro-3H-3-benzazepine-3-carboxy.ate (15C) as a white solid (5.42 g, 43%).1H NMR (CDCI3) 8.0 (2H, d, ArH), 7.4- 7.35 (6H1 m, ArH), 5.2 (2H, s, CH2), 3.65 (4H, br s, 2 x CH2), 3.0 (4H, br s, 2 x CH2) ppm. LCMS [M+H]+ 327.Zinc dust (12.67g, 13.85mmo.) was added to a mixture of benzyl 7-nitro- 1 ,2,4,5-tetrahydro-3H-3-benzazepine-3-carboxylate (15C) (4.52g, 13.85mmol) and ammonium chloride (1.48g, 27.70mmoi) in methanol (125ml). The mixture was refluxed for 2 hours until tic indicated no starting materia. was present. The mixture was cooled, filtered through celite and solvent evaporated in vacuo to yield benzyl 7-amino-1 ,2,4,5-tetrahydro-3H-3-benzazepine-3- carboxylate (15D) as an off-yellow solid (4.12, 100%). 1H NMR (DMSO-d6) 7.38 - 7.28 (5H, m, ArH), 6.75 (1 H, d, ArH), 6.32 (1 H, d, ArH)1 6.28 (1 H, dd, ArH), 5.1 (2H, s, CH2), 4.82 (2H, s, NH2), 3,45 (4H, br s, 2 x CH2), 2.64 (4H, br s, 2 x CH2) ppm. LCMS [M+H]+ 297.HBr in AcOH (50ml) was added to benzyl 7-atnino-1 ,2,4,5-tetrahydro-3H-3- benzazepine-3-carboxylate (15D) (4.12g, 0.013mol) and the mixture stirred for 3 hours at room temperature. The resultant yellow solid was washed with diethyl ether and dried to yield 2,3,4,5-tetrahydro-1 H-3-benzazepin-7-amine 2HBr salt (15E) as an off-yellow solid (4.25 g, 94%).1H NMR (DMSO-de) 8.9 (2H, br s, NH2), 7.26 (1 H, m, ArH), 7.15 (2H, m, ArH), 3.1 (4H, br s, 2 x CH2), 3.05 (4H, br s, 2 x CH2) ppm. LCMS [M+H]+ 163.2,3,4,5-Tetrahydro-i H-3-benzazepin-7-amine 2HBr salt (15E) (1 OOmg, 0.308mmol) was stirred in DCM (10ml) and 2M NaOH (2ml) was added. After stirring for I Omins the DCM layer was separated and evaporated in vacuo. The free base was re-suspended in THF (8m.) and p-toluenesuifonyl isocyanate was then added. After 2 hours stirring at room temperature, diethyl ether (~ 15ml) was added dropwise. The resultant solid was filtered, washed with small volumes of ether and dried to yield the title compound N-[(4- methylphenyl)sulfonyl]-7-([(4-methylphenyl)sulfonyl]carbamoyl}amino)- 1 ,2,4,5-tetrahydro-3H-3-benzazepine-3-carboxamide as a white solid (276 mg, 80%). <n="42"/>1H NMR (DMSO-Ci6) 10.8 (1 H1 br s, NH), 8.65 (1 H, s, NH), 8.8- 7.7 (4H, m, ArH)1 7.4- 7.32 (4H, m, ArH), 7.1- 6.95 (3H1 m, ArH), 3.35 (4H, br s, 2 x CH2), 2.65 (4H, br s, 2 x CH2), 2.36 (3H, S1 CH3), 3.34 (3H, s, CH3) ppm. LCMS [M+H]+ 557.
35% In ethanol; dichloromethane; 2,3,4,5-Tetrahydro-1H-3-benzazepine 1,2-Phenylenediacetonitrile (7.5 g, 48 mmol) dissolved in ethanol (150 ml) was added to Raney Ni (2 g) which had been previously washed with ethanol (3*20 ml). The mixture was then hydrogenated at 50 C. at 50 psi pressure with shaking for 24 h. The reaction mixture was then cooled to room temperature and filtered through a pad of kieselguhr and washed through with ethanol (100 ml). The filtrate was evaporated in vacuo to give a brown oil which was chromatographed on silica gel (10 g), eluding with 2-10% methanol in CH2Cl2 to give the title compound as a brown oil (2.45 g, 35%). Mass spectrum (API+) Found: 148 (MH+). C10H13N requires 147.
35% With hydrogen; nickel; In ethanol; at 50℃; under 2585.81 Torr; for 24h; 1, 2-Phenylenediacetonitrile (7.5g, 48 mmol) dissolved in ethanol (150ml) was added to Raney Ni (2g) which had been previously washed with ethanol (3x20ml). The mixture was then hydrogenated at 50C at 50psi pressure with shaking for 24h. The reaction mixture was then cooled to room temperature and filtered through a pad of kieselguhr and washed through with ethanol (100ml). The filtrate was evaporated in vacuo to give a brown oil which was chromatographed on silica gel (100g), eluting with 2-10% methanol in CH2CI2 to give the title compound as a brown oil (2.45g, 35%). Mass spectrum (API+) Found: 148 (MH+). C10H13N requires 147.
  • 2
  • [ 613-73-0 ]
  • [ 4424-20-8 ]
  • [ 42988-81-8 ]
  • 3
  • [ 64-17-5 ]
  • [ 7664-41-7 ]
  • [ 613-73-0 ]
  • nickel [ No CAS ]
  • [ 4424-20-8 ]
  • [ 42988-81-8 ]
  • 4
  • [ 4424-20-8 ]
  • [ 32315-10-9 ]
  • [ 127294-75-1 ]
  • [ 7087-68-5 ]
  • [ 535960-93-1 ]
YieldReaction ConditionsOperation in experiment
0.165 g (66%) With sodium hydrogencarbonate; EXAMPLE 17 N-Piperidin-3-yl-1,2,4,5-tetrahydro-3H-3-benzazepine-3-carboxamide To a solution of 2,3,4,5-tetrahydro-1H-3-benzazepine (0.122 g, 0.825 mmol) and Hunig's base (0.17 mL, 0.128 g, 0.99 mmol) was added triphosgene (0.135 g, 0.454 mmol) at 0 C. The mixture was stirred at 0 C. for 1 hour and then at room temperature for 2 h. The mixture was again cooled to 0 C. and another portion of Hunig's base (0.78 mL, 0.576 g, 4.46 mmol) and <strong>[127294-75-1]3-aminopiperidine dihydrochloride</strong> (0.0.25 g, 1.44 mmol) were added and the mixture was stirred at room temperature for 16 h. Sodium bicarbonate solution was added and the mixture was extracted twice with CH2Cl2. The combined organic layers was dried over MgSO4 and filtered. The filtrate was concentrated in vacuo to dryness and the residue was subjected to column chromatography (CH2Cl2:MeOH:NH4Cl, 90:10:1) to give 0.165 g (66%) of colorless solid as the desired product: mp 214-216 C.; IR (diffuse reflectance) 3105, 3059, 3030, 3017, 2999, 2988, 2978, 2941, 2910, 2901, 2841, 1635, 1592, 1511, 1470, 1451, 1420, 1387, 1378, 1303, 1254, 1223, 947, 905, 740 cm-1; 1H NMR (400 MHz, DMSO-d6) delta7.15-7.10 (m, 4H), 3.63 (m, 1H), 3.34-3.31 (m, 5H), 3.20-3.10 (m, 1H), 2.92-2.77 (m, 6H), 2.05-1.97 (m, 1H), 1.76-1.72 (m, 1H), 1.56-1.46 (m, 2H); 13C NMR (100 MHz, DMSO-d6) delta163.4, 140.8, 129.1, 126.1, 48.9, 48.4, 47.3, 46.2, 36.4, 28.0, 22.4; MS (EI) m/z 273 (MH+); HRMS (FAB) calcd for C16H23N3O+H 274.1919, found 274.1923; Anal. calcd. for Cl16H23N3O+HCl: C, 62.02; H, 7.81; N, 13.56. Found: C, 61.80; H, 7.75; N, 13.44.
 

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