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Product Details of (R)-α-Methyl-4-nitrobenzylamine HCl

CAS No. :57233-86-0
Formula : C8H11ClN2O2
M.W : 202.64
SMILES Code : N[C@H](C)C1=CC=C([N+]([O-])=O)C=C1.[H]Cl
MDL No. :MFCD00066311
InChI Key :CZQQGVFHLSBEDV-FYZOBXCZSA-N
Pubchem ID :16212177

Safety of (R)-α-Methyl-4-nitrobenzylamine HCl

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of (R)-α-Methyl-4-nitrobenzylamine HCl

* 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 [ 57233-86-0 ]

[ 57233-86-0 ] Synthesis Path-Downstream   1~30

  • 1
  • [ 50-00-0 ]
  • [ 57233-86-0 ]
  • [ 542-92-7 ]
  • (+)-(1S,1'R)-2-<1'-(4''-Nitrophenyl)ethyl>-2-azabicyclo<2.2.1>hept-5-ene [ No CAS ]
  • (-)-(1R,1'R)-2-<1'-(4''-Nitrophenyl)ethyl>-2-azabicyclo<2.2.1>hept-5-ene [ No CAS ]
  • 2
  • [ 57233-86-0 ]
  • 1-tert-Butyl-8-chloro-6-(2-fluoro-phenyl)-4H-2,5,10b-triaza-benzo[e]azulene-3-carbonyl chloride [ No CAS ]
  • <R>-(-)-(R)-8-chloro-1-(1,1-dimethylethyl)-6-(2-fluorophenyl)-N-(4-nitro-1-phenylethyl)-4H-imidazo<1,5-a><1,4>benzodiazepine-3-carboxamide [ No CAS ]
  • 3
  • [ 57233-86-0 ]
  • [ 159596-55-1 ]
  • 4-{2-[(R)-1-(4-Nitro-phenyl)-ethylamino]-3,4-dioxo-cyclobut-1-enylamino}-benzonitrile [ No CAS ]
  • 4
  • [ 24424-99-5 ]
  • [ 57233-86-0 ]
  • [ 694529-38-9 ]
YieldReaction ConditionsOperation in experiment
94.38% With sodium hydrogencarbonate; In dichloromethane; water; for 3h; Step 1 : Synthesis of (i?)-[l-(4-Nitrophenyl)ethyl]carbamic acid t-butyl ester; (Ri3= Me)(i?)-methyl-4-nitrobenzylaminehydrochloride (50mg, 0.25mmol) was put into 25ml of flask and dissolved in the saturated solution (NaHCO3 : CH2Cl2 = 1:1). To the solution was added di-t-butyl dicarbonate (135mg, 0.60mmol), followed by stirring for 3 hours. The reacting mixture was diluted with methylene chloride, washed with water and brine, dried over Na2SO4 and concentrated under reduced pressure. The obtained liquid was purified by column chromatography (n-hexane/ethyl acetate = 10/1) to yield EPO <DP n="61"/>pale yellow liquid (62.0 mg, 94.38%).[alpha]D22: -43.66(C LSS3 CHCl3);IR (NaCl, neat, cm"1): 3403, 3332, 2977, 2932, 1697, 1522, 1347; 1H NMR (400MHz, CDCl3): 8.20 (d, 2H, J=8.8Hz), 7.47 (d, 2H, J = 8.8 Hz), 4.91 (s, IH), 4.85 (s, IH), 1.46 (d, 3H, J= 6.8 Hz), 1.42 (s, 9H)
92% With sodium hydrogencarbonate; In dichloromethane; at 25℃; for 24h; Step 1: Preparation of (R)-tert-butyl 1-(4-nitrophenyl)ethylcarbamate (C1) (R)-1-(4-nitrophenyl)ethanamine hydrochloride salt (1.0 g, 4.9 mmol), tert-butoxycarbonyl (BOC) anhydride (1.18 g, 5.43 mmol), and 10.0 mL of 1M sodium bicarbonate solution were dissolved in DCM (15 mL) and allowed to stir at 25 C. for 24 h. The organic layer was collected, and the aqueous layer was washed with DCM. The combined organic layers were then washed with water and 0.1N HCl, dried over MgSO4, filtered, and concentrated to provide C1 as a white solid. Yield: 1.2 g, 92%. GC-MS=266. 1H NMR (500 MHz, d6-DMSO) delta: 8.15 (d, 2H), 7.56 (d, 1H), 7.52 (d, 2H), 4.68 (m, 1H), 1.32 (s, 9H), 1.27 (d, 3H).
  • 5
  • [ 878548-90-4 ]
  • [ 13094-51-4 ]
  • [ 57233-86-0 ]
  • (S)-(-)-α-methyl-4-nitrobenzylamine hydrochloride [ No CAS ]
  • di-tert-butyl 4-aminobutylphosphonateN1-tert-butoxycarbonyltryptamine [ No CAS ]
  • C84H109N17O26P2S [ No CAS ]
  • 6
  • [ 31088-81-0 ]
  • [ 57233-86-0 ]
  • [ 694529-13-0 ]
YieldReaction ConditionsOperation in experiment
98% With triethylamine; In dichloromethane; at 20℃; To a stirred solution of (R or S)-alpha-METHYL-4-NITROBENZYL amine hydrochloride (203 mg, 1 mmol) in anhydrous CH2C12 (10 mL) was added triethylamine (0.28 mL, 2 mmol) at room temperature. When the reaction mixture became clear, isothiocyanate (1 mmol) was added and stirred OVERNIGNT at room temperature. The mixture was evaporated by rotary evaporator and the residue was purified by flash column chromatography on silica gel with EtOAc: hexanes as eluant to N-(4-T-BUTYLBENZYL)-N -F (1R)-1- [4- (methylsulfonylamino) phenyl] ethyl} thiourea (16-5, SU-388). 98% yield, a sticky colorless oil IH NMR (CDC13) 6 8.12 (d, 2 H, J= 8.76 Hz), 7.34 (bd, 4 H), 7.14 (d, 2 H, J= 8.0 Hz), 6.21 (bs, 2 H), 5.37 (bs, 1 H), 4.54 (M, 2 H), 1.47 (d, 3 H, J= 7. 05 HZ), 1.30 (s, 9 H)
  • 10
  • [ 57233-86-0 ]
  • [ 694529-72-1 ]
  • 11
  • [ 57233-86-0 ]
  • [ 694529-76-5 ]
  • 12
  • [ 57233-86-0 ]
  • [ 910534-76-8 ]
  • 15
  • [ 57233-86-0 ]
  • <i>N</i>-(4-{1-[3-(4-<i>tert</i>-butyl-benzyl)-thioureido]-ethyl}-phenyl)-acetamide [ No CAS ]
  • 16
  • [ 32315-10-9 ]
  • [ 57233-86-0 ]
  • N-{4-[(6,7-Dimethoxy-4-quinolyl)oxy]phenyl}-N'-[(1R)-1-(4-nitrophenyl)ethyl]urea [ No CAS ]
YieldReaction ConditionsOperation in experiment
13% Example 36: N-{4-[(6,7-Dimethoxy-4-quinolyl)oxy]phenyl}-N'-[(1R)-1-(4-nitrophenyl)ethyl]urea 4-[(6,7-Dimethoxy-4-quinolyl)oxy]aniline (70 mg) was dissolved in chloroform (1 ml) and triethylamine (0.14 ml) to prepare a solution. A solution of triphosgene (33 mg) in chloroform (0.2 ml) was then added to the solution, and the mixture was stirred at room temperature for 75 min. Next, a solution of (1R)-1-(4-nitrophenyl)ethylamine hydrochloride (47 mg) in chloroform (0.2 ml) was added thereto, and the mixture was stirred at room temperature for 10 hr. The stirred mixture was purified by chromatography on silica gel using chloroform/methanol for development to give the title compound (16 mg, yield 13%). 1H-NMR (CDCl3): 1.52 (3H, d, J = 7.07 Hz), 4.03 (3H, s), 4.04 (3H, s), 5.11 (1H, m), 5.24 (1H, d, J = 6.83 Hz), 6.43 (1H, d, J = 5.36 Hz), 6.76 (1H, s), 7.12 (2H, d, J = 8.78 Hz), 7.40 (2H, d, J = 8.78 Hz), 7.41 (1H, s), 7.51 (2H, d, J = 8.78 Hz), 7.55 (1H, s), 8.19 (2H, d, J = 8.78 Hz), 8.46 (1H, d, J = 5.36 Hz)
  • 17
  • [ 31088-81-0 ]
  • [ 57233-86-0 ]
  • [ 824937-61-3 ]
YieldReaction ConditionsOperation in experiment
81% With triethylamine; In dichloromethane; at 20℃; To a stirred solution of (R or S)-OE-METHYL-4-NITROBENZYL amine hydrochloride (1.1 mmol) in CH2CL2 (8 mL) was added Et3N (1.1 mmol) at room temperature. The mixture was stirred for 10 minutes. When the reaction mixture became clear, isothiocyanate (1 mmol) in CH2CL2 (2 mL) was added. The mixture was stirred overnight at room temperature and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel with EtOAc: hexanes (1: 2 to 1: 1). 81% yield, yellow oil IH NMR (CDC13) 8 8.15 (d, 2 H, J= 8.5 Hz), 7.45 (d, 2 H, J= 8.5 Hz), 7. 15-7. 35 (M, 5 H), 6.60 (bs, 1 H), 6.08 (bs, 1 H), 5.22 (bs, 1 H), 4.47 (bs, 1 H), 4.13 (dd, 1 H, J= 3, 11. 8 Hz), 3.86 (dd, 2 H, J= 5.6, 11. 8 Hz), 2.96 (dd, 1 H, J= 5.85, 13.5 Hz), 2.80 (dd, 1 H, J= 7. 3,13. 5 HZ), 1.49 (d, 3 H, J= 7. 1 Hz), 1.16 (s, 9 H)
  • 18
  • [ 57233-86-0 ]
  • [ 3919-76-4 ]
  • C19H15Cl2N3O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; triethylamine; In N,N-dimethyl-formamide; at 0℃; for 2h; EXAMPLE 50 3-(2,6-dichlorophenyl)-N-{(1R)-1-[4-(diethylamino)phenyl]ethyl}-5-methylisoxazole-4-carboxamide To 3-(2,6-dichloro-phenyl)-5-methyl-isoxazole-4-carboxylic acid (272 mg, 1.0 mmol) in DMF (1.5 mL) was added (+)-(R)-1-(4-Nitro-phenyl)-ethylamine hydrochloride (202 mg, 1.0 mmol), Et3N (202 mg, 2.0 mmol), and TBTU (321 mg, 1.0 mmol) at 0 C. After 2 hours ice chips and 50 mL ethyl acetate were added. Organic layer was washed with water (3*30 mL), dried over MgSO4, and then concentrated under reduced pressure. The crude material was dissolved in ethanol (15 mL) and water (1 mL) followed by addition of NH4Cl (107 mg, 2.0 mmol) and Fe (1.12 g, 20 mmol). The insoluble material was filtered off after 16 hours and the filtrate was dried over MgSO4 and concentrated under reduced pressure. The crude material was dissolved in methanol buffer (1 M, pH4, 7.5 mL) followed by addition of acetaldehyde (132 mg, 3.0 mmol) and sodium cyanoborohydride (124 mg, 2.0 mmol). The volatiles were removed under reduced pressure after 3 hour and the residue was purified by reversed phase HPLC (5-100% 1% TFA in acetonitrile) to provide the titled compound (60 mg, 13% over 3 steps). 1H NMR (300 MHz, DMSO-d6) delta 8.15 (d, J=8.1 Hz, 1H), 7.60 (d, J=9.6 Hz, 1H), 7.59 (d, J=6.0 Hz, 1H), 7.52 (dd, J=6.0, 9.6 Hz, 1H), 7.04 (d, J=8.7 Hz, 2H), 6.57 (d, J=8.7 Hz, 2H), 4.84 (quintet, J=7.2 Hz, 1H), 3.29 (q, J=7.2 Hz, 4H), 2.64 (s, 3H), 1.32 (d, J=7.2 Hz, 3H), and 1.06 (t, J=7.2 Hz, 6H). MS (ESI) positive ion 446 (M+H)+, 448 (M+H)+; negative ion 444 (M-H)-, 446 (M-H)-.
  • 19
  • [ 57233-86-0 ]
  • [ 159596-55-1 ]
  • (R)-4-{2-[1-(4-Nitro-phenyl)-ethylamino]-3.4-dioxo-cyclobut-1-enylamino}-benzonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
0.70 g (78%) With N-ethyl-N,N-diisopropylamine; In ethanol; EXAMPLE 7 (R)-4-{2-[1-(4-Nitro-phenyl)-ethylamino]-3.4-dioxo-cyclobut-1-enylamino}-benzonitrile To the squarate of Example 1, step 1 (0.598 g, 2.47 mmol) in ethanol (50 mL) was added (R)-alpha-methyl-4-nitrobenzylamine hydrochloride (0.50 g, 2.5 mmol) and N,N-diisopropylethylamine (0.43 g, 2.5 mmol). The mixture was heated at reflux for 16 hours. After cooling the precipitate was filtered off to afford 0.70 g (78%) of product as an orange solid: mp 290-295 C.; [alpha]25D -100.52 (DMSO); 1 H NMR (DMSO-d6): delta9.98 (s, 1H), 8.32 (d, 1H), 8.25 (d, 2H), 7.79 (d, 2H), 7.68 (d, 2H), 7.57 (d, 2H), 5.42 (m, 1H), 1.61 (d, 3H). IR (KBr): 3200, 2220, 1790, 1670, 1600 cm-1; MS (m/z) 362 (M+). Elemental analysis for C19 H14 N4 O 4 Calc'd: C, 62.98; H, 3.89; N, 15.46. Found: C, 62.38; H, 3.73; N, 14.95.
YieldReaction ConditionsOperation in experiment
44.8 g (91.4%) EXAMPLE 4 65.7 g (0.122 mole) of the bis R-(+)-alpha-methyl-p-nitrobenzylamine salt of (+)-threo-epoxyaconitic acid (98-99% optical purity) and 73 ml of 0.5 N HCl (0.365 mole) were heated at reflux for 16 hrs. The solution was cooled and extracted with EtOAc (2 * 100 ml). The organic layers were backwashed in turn with water (50 ml) and the combined aqueous layers were evaporated to dryness under reduced pressure. The residue was triturated with EtOAc (3 * 100 ml) and the solids were recovered by filtration to give 44.8 g (91.4%) of recovered R(+)-alpha-methyl-p-nitrobenzylamine hydrochloride (m.p. 246-7). The filtrate was dried over MgSO4, evaporated in vacuo and the residue was heated at 75-80 in vacuo for 1/2 hr. to ensure lactonization. Crystallization of the residue (21 g) from EtOAc-CCl4 furnished the gamma-lactone of (-)-threo-hydroxycitric acid in two crops: 6.0 g [m.p. 174-6; [alpha ]D25 +105.6] and 3.2 g [168-173;[alpha]D25 +100.5].
  • 21
  • [ 1943-83-5 ]
  • [ 57233-86-0 ]
  • (R)-2-(1-(4-nitrophenyl))ethylaminooxazoline [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% (R)-alphamethyl-4-nitrobenzylamine hydrochloride (645 mg, 0.32 mmole) was suspended in 5 ml tetrahydrofuran and stirred with triethylamine (330 mg) for 1 hour. 2-chloroethylisocyanate (360 mg, 95%) was added in 5 ml tetrahydrofuran with stirring and the mixture stirred for 4 hours. 6 ml of water was then added followed by 2 ml 10 molar sodium hydroxide and the mixture heated to reflux for 24 hours. The mixture was then diluted with 50 ml ethyl acetate and shaken. The aqueous phase was discarded and the organic layer washed with 5 ml water, then extracted twice with 5 ml 1 molar hydrochloric acid. The extracts were combined and basified with 10 molar sodium hydroxide. The precipitated product was extracted with 25 ml ethyl acetate, washed with water and then reduced to dryness in vacuo. The product forms pale yellow crystals on drying, mp. 112-116 C. Yield 0.62 g (83%). Proton nmr in CDCl3 shows 7.8 (4H dd, J=9 and 42 Hz), 4.8 (1Hq, J=7 Hz), 3.9 (4Hm) 1.4(3H d, J=7 Hz).
  • 22
  • (-)-p-nitro-α-methylbenzylamine hydrochloride [ No CAS ]
  • [ 57233-86-0 ]
  • (S)-(-)-α-methyl-4-nitrobenzylamine hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
With chiral stationary phase including isopropyl-functionalized CF6; In methanol; acetic acid; triethylamine; acetonitrile; at 20℃;Purification / work up; In addition to the foregoing, numerous other chromatographic separations using a column bonded with a CSP including a derivatized cyclofructan residue were carried out. Tables 5-9 list some additional examples of chromatographic separations using a column bonded with a CSP of the present invention. AU examples of chromatographic separations using columns bonded with CSPs of the present invention were carried out using the following experimental conditions and procedures.|0132| The high performance liquid chromatography (HPLC) column packing system was composed of an air driven fluid pump (HASKEL, DSTV- 122), an air compressor, a pressure regulator, a low pressure gauge, two high-pressure gauges (10,000 and 6,000 psi), a slurry chamber, check valves, and tubings. The CSPs were slurry packed into a 25 cm x 0.46 cm (inner diameter, I. D.) stainless steel column.|0133| The HPLC system was an Agilent 1 100 system (Agilent Technologies, Palo Alto,CA), which consisted of a diode array detector, an autosampler, a binary pump, a temperature- controlled column chamber, and Chemstation software. All chiral analytes were dissolved in ethanol, methanol, or other appropriate mobile phases, as indicated. For the LC analysis, the injection volume and flow rate were 5 muL and 1 mL/min, respectively. Separations were carried out at room temperature (~20 0C) if not specified otherwise. The wavelengths of UV detection were 195, 200, 210, and 254 nm. The mobile phase was degassed by ultrasonication under vacuum for 5 min. Each sample was analyzed in duplicate. Three operation modes (the normal phase mode, polar organic mode, and reversed phase mode) were tested, unless indicated otherwise. In the normal phase mode, heptane with ethanol or isopropanol was used as the mobile phase. In some cases, trifluoroacetic acid (TFA) was used as an additive, as indicated. The mobile phase of the polar organic mode was composed of acetonitrile/methanol and small amounts of acetic acid and triethylamine. Water/acetonitrile or acetonitrile/acetate buffer (20 mM, pH = 4.1 ) was used as the mobile phase in the reversed-phase mode.|0134| Two different supercritical fluid chromatographic instruments were used. One was a Berger SFC unit with an FCM 1200 flow control module, a TCM 2100 thermal column module, a dual pump control module, and a column selection valve. The flow rate was 4 mL/min. The cosolvent was composed of methanol/ethanol/isopropanol = 1 : 1 : 1 and 0.2% diethylamine (DEA). The gradient mobile phase composition was 5% cosolvent hold during 0- 0.6 min, 5-60% during 0.6-4.3 min, 60% hold during 4.3-6.3 min, 60%-5% during 6.3-6.9 min, and 5% hold during 6.9-8.0 min. The other SFC system was a Jasco (MD, USA) system comprised of an autosampler unit (AS-2059-SF Plus), a dual pump module (PU-2086 Plus), a column thermostat module (CO-2060 Plus), a UV/Vis detector (UV-2075 Plus), and a back pressure regulator module (SCH-Vch-BP). Unless otherwise specified, the mobile phase was composed of CCVmethanol (0.1 % TFA or 0.1% diethylamine). The flow rate was 3 mL/min.|0135| For the calculations of chromatographic data, the "dead time" to was determined by the peak of the refractive index change due to the sample solvent or determined by injecting l ,3,5-tri-/e/-/-butylbenzene in the normal phase mode.
  • 23
  • [ 24424-99-5 ]
  • [ 57233-86-0 ]
  • [ 177947-88-5 ]
YieldReaction ConditionsOperation in experiment
With sodium hydroxide; In tetrahydrofuran; water; at 20℃; for 2h; To a solution of in di-ferf-butyldicarbonate (4.9 g, 22.45 mmol, 1.5 eq.) in 30 ml THF at rt was added (R)-alpha-methyl-4-nitrobenzylamine hydrochloride (3.0 g, 14.81 mmol) followed by 30 ml of 1 N aq. NaOH solution. The mixture was stirred vigorously for 2 hr, diluted with water and extracted 3x with ether. The combined organic layer was washed with brine, dried over MgSO4, filtered andconcentrated to provide 5.50 g (S)-tert-butyl 1 -(4-nitrophenyl)ethylcarbamate.
  • 24
  • [ 24424-99-5 ]
  • [ 57233-86-0 ]
  • [ 255060-77-6 ]
  • 25
  • [ 1210-39-5 ]
  • [ 57233-86-0 ]
  • [ 1569819-30-2 ]
YieldReaction ConditionsOperation in experiment
Example 45: (R)-4-(1-((3,3-diphenylallyl)nitro)ethyl)aniline (Compound 47)To a RB flask under a nitrogen atmosphere was added 3 -phenyl-cinnamaldehyde (0.483 g, 2.319 mmol), 8 mL DCE, <strong>[57233-86-0](R)-1-(4-nitrophenyl) ethanamine hydrochloride</strong> (0.517 g,2.55 mmol) and phosphotungstic acid hydrate (33 mg). The reaction was stirred at rt for 5 minutes before addition of NaBH(OAc)3 (1.081 g, 5.1025 mmol). The reaction was then stirred at rt overnight and worked up by addition of 10% NaOH solution and EtOAc extraction. The EtOAc layer was washed with brine, dried over MgSO4 and rotary evaporated under reduced pressure to give a jade colored crude oil. The crude oil was furtherpurified by flash column chromatography on 200 g of silica gel (3 0-70% EtOAc/hexanes) to afford Compound 47.?H NMR (CD3C1, 400 MHz): oe 8.102 (d, J=8.8 Hz, 2H), 7.38 (d, J=8.8 Hz, 2H), 7.18- 7.29 (m, 14H), 7.05-7.08 (m, 2H), 6.14 (t, J=7.2 Hz, 1H), 3.86 (q, J=6.4 Hz, 1H), 3.10-3.19 (m, 2H), 1.31 (d, J= 6.4 Hz, 3H)ESI(MS) of [C23H22N202+H] calculated is 359.17, found 359.2
  • 26
  • [ 381-97-5 ]
  • [ 57233-86-0 ]
  • C4H5F3O2*C8H10N2O2 [ No CAS ]
  • C4H5F3O2*C8H10N2O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In isopropyl alcohol; at 20 - 70℃; General procedure: To a solution of racemic acid 1 (5.68 mg, 0.04 mmol, 1 equiv) in IPA (0.2 mL, 0.2 M) was added the chiral base (0.04 mmol, 1 equiv as a 0.2 M stock solution in IPA). The resulting mixture was heated at 70 C for 15 min to solubilize all the solids, and then allowed to cool naturally to ambient temperature with stirring overnight. Overall, 23 precipitates were obtained from the 80 combinations. The enantiomeric excess of the solid precipitate and the liquor for each reaction was analyzed by SFC.
  • 27
  • [ 50777-76-9 ]
  • [ 57233-86-0 ]
  • C27H23N2O2P [ No CAS ]
  • 28
  • [ 57233-86-0 ]
  • SU-692 [ No CAS ]
  • 29
  • [ 57233-86-0 ]
  • [ 824937-62-4 ]
  • 30
  • [ 4422-95-1 ]
  • [ 57233-86-0 ]
  • N<SUP>1</SUP>,N<SUP>3</SUP>,N<SUP>5</SUP>-tris((R)-1-(4-nitrophenyl)ethyl)benzene-1,3,5-tricarboxamide [ No CAS ]
 

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