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Chemical Structure| 191480-61-2 Chemical Structure| 191480-61-2

Structure of 191480-61-2

Chemical Structure| 191480-61-2

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Product Details of [ 191480-61-2 ]

CAS No. :191480-61-2
Formula : C20H26N2
M.W : 294.43
SMILES Code : [C@@H]1(NCC2=CC=CC=C2)[C@@H](NCC3=CC=CC=C3)CCCC1
English Name :(1S,2S)-N1,N2-Dibenzylcyclohexane-1,2-diamine
MDL No. :MFCD29067259
InChI Key :SJBYIGXWWGSEES-PMACEKPBSA-N
Pubchem ID :11119970

Safety of [ 191480-61-2 ]

Application In Synthesis of [ 191480-61-2 ]

* 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 [ 191480-61-2 ]

[ 191480-61-2 ] Synthesis Path-Downstream   1~6

  • 1
  • [ 147127-11-5 ]
  • [ 191480-61-2 ]
YieldReaction ConditionsOperation in experiment
With sodium tetrahydroborate
With sodium tetrahydroborate In methanol at 0 - 20℃; for 12h; Inert atmosphere; (1S,2S)-N1,N2-dibenzylcyclohexane-1,2-diamine (2). To a solution of (1S,2S)-cyclohexane-1,2-diamine (1.14 g, 10.0 mmol) in dry methanol was added benzaldehyde (2.03 mL, 20.0 mmol, 2.0 equiv). The solution was refluxed for 4 h and then cooled via an ice bath. Addition of NaBH4 (1.62 g, 43.0 mmol, 4.3 equiv) was performed slowly and in small portions to prevent boiling, and the reaction mixture was stirred for 12 h until completion. The solvent was evaporated in vacuo, and then saturated NaHCO3 (50 mL), water (50 mL) and EtOAc (200 mL) were added and the aqueous layer was extracted with EtOAc. The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo to afford a waxy, yellow solid. Product was purified by silica column chromatography to afford 2 as yellow oil. Yield 90%. 1H NMR (500 MHz, CDCl3): δ ppm 7.25-7.37 (m, 10H), 3.92 (d, J = 13.3 Hz, 2H), 3.69 (d, J = 13.3 Hz, 2H), 2.17-2.32 (m, 6H), 1.76-1.77 (m, 2H), 1.07-1.29 (m, 4H). 13C NMR (126 MHz, CDCl3): δ ppm 141.1, 128.4, 128.1, 126.8, 60.9, 50.9, 31.5, 25.1. ESIMS (m/z) 295 [M+H]+, 317 [M+Na]+, 293 [M-H]-.
  • 2
  • [ 21436-03-3 ]
  • [ 100-52-7 ]
  • [ 191480-61-2 ]
YieldReaction ConditionsOperation in experiment
69% Stage #1: (S,S)-1,2-diaminocyclohexane; benzaldehyde In methanol for 4h; Reflux; Stage #2: With sodium tetrahydroborate In methanol for 12h; 1S,2S)-N1,N2-dibenzylcyclohexane-1,2-diamine (7) To a solution of (1 S,2S)-cyclohexane-1 ,2-diamine (1.14 g, 10.0 mmol) in dry methanol was added benzaldehyde (2.03 ml_, 20.0 mmol, 2 equiv). The solution was refluxed for 4 h and then cooled via an ice bath. Addition of NaBH4 (1.62 g, 43.0 mmol, 4.3 equiv) was performed slowly and in small portions to prevent boiling, and the reaction mixture was stirred for 12 h until completion. The solvent was evaporated in vacuo, and then saturated NaHC03 (50 mL), water (50 mL) and dichloromethane (200 mL) were added. The aqueous layer was extracted twice more with dichloromethane (100 mL). The combined organic layers were dried over MgS04, filtered, and concentrated in vacuo to afford a waxy, yellow solid. Product was purified by silica column chromatography to afford 7 as yellow oil. Yield 69%. 1H NMR (500 MHz, CDCI3 ):δ ppm 7.29-7.40 (m, 8H), 7.23-7.29 (m, 2H), 3.92 (d, J= 10.0 Hz, 2H), 3.69 (d, J= 10.0 Hz, 2H), 2.28-2.35 (m, 2H), 2.14-2.26 (m, 4H), 1.76 (m, 2H), 1.21-1.33 (m, 2H), 1.03-1.14 (m, 2H), 13C NMR (126 MHz, CDCI3): δ ppm 141.15, 128.40, 128.15, 126.84, 60.92, 50.92, 31.58, 25.18. ESIMS (m/z) 295 [M+H]+, 317 [M+Na]+, 293 [M-H]-
Stage #1: (S,S)-1,2-diaminocyclohexane; benzaldehyde In methanol for 0.5h; Reflux; Stage #2: With sodium cyanoborohydride In methanol at 20℃; Reflux; 109 Benzaldehyde (6.36 g, 60 mmol) was added dropwise over a period of 2 minutes to a solution of (S,S)-cyclohexane-1,2-diamine (3.42 g, 30 mmol) in 50 mL of anhydrous MeOH at refluxing temperature. After stirring for 30 min, the solution was allowed to cool to room temperature and NaBH3CN (2.4 g, 63 mmol) was added in portions. After the vigorous effervescence subsided down, the mixture was brought to refluxing and stirred for 20 min. The reaction was quenched by water and extracted with dichloromethane. The organic phase was dried and concentrated to give 8.5 g of crude product (yield 95%) which was used in the next step reaction without further purification.
In toluene at 70℃; for 12h; Molecular sieve;
Stage #1: (S,S)-1,2-diaminocyclohexane; benzaldehyde In methanol Reflux; Stage #2: With sodium tetrahydroborate In methanol at 0 - 20℃;
Stage #1: (S,S)-1,2-diaminocyclohexane; benzaldehyde In methanol for 0.5h; Reflux; Stage #2: With sodium cyanoborohydride at 20℃; for 0.333333h; Reflux;

  • 3
  • [ 191480-61-2 ]
  • [ 146432-43-1 ]
  • [ 2029195-64-8 ]
YieldReaction ConditionsOperation in experiment
88% With sodium carbonate In acetonitrile at 60℃; for 24h; Inert atmosphere; tetra-tert-Butyl 2,2',2'',2'''-(((((1S,2S)-cyclohexane-1,2-diyl)bis(benzylazanediyl))bis(ethane-2,1-diyl))bis(azanetriyl))tetraacetate (3). To a solution of 2 (294 mg, 1.0 mmol) and di-tert-butyl 2,2'-((2-bromoethyl)azanediyl)diacetate (S2) (739 mg, 2.1 mmol, 2.1 equiv) in MeCN was added sodium carbonate (318 mg, 3.0 mmol, 3.0 equiv). The solution was heated for 24 h at 60 °C. Sodium carbonate was removed by filtration. The filtrate was washed with H2O and aqueous phase extracted with EtOAc. The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. Product was purified by silica column chromatography to afford 3 as yellow oil. Yield 88%. 1H NMR (500 MHz, CDCl3): δ ppm 7.07-7.28 (m, 10H), 3.73 (d, J = 13.5 Hz, 2H), 3.37 (d, J = 13.5 Hz, 2H), 3.26 (s, 8H), 2.53-2.73 (m, 8H), 1.91-1.95 (m, 4H), 1.63-1.64 (m, 2H), 1.35 (s, 36H), 1.02-1.11 (m, 4H). 13C NMR (126 MHz, CDCl3): δ ppm 170.5, 141.1, 128.8, 127.8, 126.3, 80.4, 61.0, 60.2, 55.9, 54.8, 53.8, 48.4, 28.0, 26.6, 26.0, 20.9, 14.1. ESIMS (m/z) 837 [M+H]+, 859 [M+Na]+, 835 [M-H]-.
88% With sodium carbonate In N,N-dimethyl-formamide at 60℃; for 24h; Inert atmosphere; tert-butyl 2,2 2, 2'"-(2,2,-(1S,2S)-cyclohexane-1,2-diylbis(benzylazanediyl)b^^, 1-diyl))bis(azanetriyl)tetraacetate (8) To a solution of compound 7 (294 mg, 1.0 mmol) and compound S2 (739 mg, 2.1 mmol, 2.1 equiv) in DMF was added sodium carbonate (317 mg, 3 mmol, 3 equiv). The solution was heated for 24 h at 60°C under N2. Sodium carbonate was removed by filtration. The filtrate was washed with H20 and aqueous phase extracted twice with EtOAc. The combined organic layers were dried over MgS04, filtered, and concentrated in vacuo. Product was purified by silica column chromatography to afford 8 as yellow oil. Yield 88%. 1H NMR (500 MHz, CDCI3):5 ppm 7.07-7.28 (m, 10H), 3.73 (d, J= 10.0 Hz, 2H), 3.37 (d, J= 10.0 Hz, 2H), 3.26 (s, 8H), 2.53-2.71 (m, 10H), 1.35-1.63 (m, 43H). 13C NMR (126 MHz, CDCIs): δ ppm 170.54, 141.1 1 , 128.84, 127.80, 126.36, 80.46, 61.02, 60.23, 55.96, 54.82, 53.86, 48.49, 28.08, 26.61 , 26.04, 20.92, 14.17. ESIMS (m/z) 837 [M+H]+, 859 [M+Na]+, 835 [M-H]-
With sodium carbonate In acetonitrile at 60℃;
  • 4
  • [ 5292-43-3 ]
  • [ 191480-61-2 ]
  • [ 2029195-84-2 ]
YieldReaction ConditionsOperation in experiment
89% With sodium carbonate In acetonitrile at 20℃; for 24h; Inert atmosphere; tert-Butyl N-benzyl-N-((1S,2S)-2-(benzylamino)cyclohexyl)glycinate (14). To a solution 2 (1.76 g, 6.0 mmol) and sodium carbonate (636 mg, 6.0 mmol, 1.0 equiv) in dry MeCN was added dropwise a solution of tert-butyl bromoacetate (219 mL, 1.5 mmol, 0.25 equiv). The reaction mixture was stirred at 24 h at room temperature. Sodium carbonate was filtered and the filtrate concentrated in vacuo to dryness. EtOAc and water were added and aqueous layer were extracted with EtOAc. The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. Product was purified by silica column chromatography. Yield 89%. 1H NMR (400 MHz, CD3OD): δ ppm 7.23-7.40 (m, 10H), 3.70-3.80 (m, 2H), 3.54-3.61 (m, 2H), 3.18 (d, J = 12.8 Hz, 1H), 3.03 (d, J = 12.8 Hz, 1H), 2.40-2.42 (m, 2H), 2.14-2.16 (m, 2H), 1.95-1.97 (m, 1H), 1.60-1.78 (m, 2H), 1.37 (s, 9H), 1.07-1.21 (m, 4H). 13C NMR (100 MHz, CD3OD): δ ppm 172.2, 139.5, 139.4, 129.2, 128.8, 128.5, 128.4, 127.3, 80.9, 64.7, 57.8, 50.8, 30.6, 29.8, 27.4, 25.6, 24.5, 24.0. ESIMS (m/z) 409 [M+H]+, 431 [M+Na]+, 407 [M-H]-.
  • 5
  • [ 100-39-0 ]
  • [ 180683-64-1 ]
  • [ 191480-61-2 ]
YieldReaction ConditionsOperation in experiment
36.9% Stage #1: tert-butyl ((1S,2S)-2-aminocyclohexyl)carbamate With potassium carbonate In acetonitrile at 20℃; for 0.166667h; Stage #2: benzyl bromide In acetonitrile at 20℃; 1.1 1. Synthesis of compound of formula (I) Weigh (1S,2S)-1-(Boc-amino)-2-aminocyclohexane (CAS No.: 180683-64-1) (5.0 g, 23.3 mmol) in a round-bottom flask, add K2CO3(6.7 g, 69.9 mmol) and 50 mL of acetonitrile, stir at room temperature for 10 min, then slowly drop benzyl bromide (4.0 g, 171.0 mmol), after the addition is complete, stir at room temperature overnight. After the reaction is completed by TLC and LC-MS monitoring, filter, concentrate the filtrate, and purify the residue by silica gel flash column chromatography (dichloromethane/methanol 50:1, v/v) to obtain a transparent oil (2.6 g, yield 36.9%).
  • 6
  • [ 191480-61-2 ]
  • [ 207450-11-1 ]
YieldReaction ConditionsOperation in experiment
95% With hydrogenchloride In ethyl acetate at 20℃; 1.2 2. Synthesis of formula (II.) compounds The transparent oil (2.6g, 8.54mmol) was dissolved in HCl/EA mixed solvent (30mL), and the concentration of hydrochloric acid in the mixed solvent was 5M, and then stirred and mixed overnight at room temperature. After the TLC and LC-MS monitoring reactions were completed, the mixed products were concentrated to obtain oily crude products (1.6g, 95%).
 

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