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Product Details of [ 60835-71-4 ]

CAS No. :60835-71-4 MDL No. :MFCD00068686
Formula : C14H21NO5 Boiling Point : -
Linear Structure Formula :- InChI Key :CQNGAZMLFIMLQN-UHFFFAOYSA-N
M.W : 283.32 Pubchem ID :2724797
Synonyms :

Safety of [ 60835-71-4 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 60835-71-4 ]

* 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 [ 60835-71-4 ]

[ 60835-71-4 ] Synthesis Path-Downstream   1~60

  • 1
  • [ 75-15-0 ]
  • [ 60835-71-4 ]
  • [ 128093-18-5 ]
YieldReaction ConditionsOperation in experiment
74% With sodium hydroxide In ethanol at 0 - 5℃; for 2 - 3h; III To a cold solution of 4'-aminobenzo-15-crown-5 (0.283 g, 1.0 mmol) and sodium hydroxide (0.04 g, 1.0 mmol) in 5 mL of ethanol was added carbon disulfide (0.076 g, 1.0 mmol) dropwise. The resulting mixture was stirred at 0-5 °C for another 2-3 h. Upon addition of 20 mL of diethyl ether with vigorous stirring, a grey precipitate was formed, which was isolated by filtration, washed twice with ether (2 x 10 mL) and dried under vacuum to give the product as a grey solid (0. 28 g, yield 74%). 1H NMR (D20, chemical shift 6 in ppm): 6.73 (d, 1 H, J = 8.5 Hz), 6.38 (d, 1 H, J = 2.5 Hz), 6.25 (dd, 1 H, J = 8.5 and 2.5 Hz), 3.95 (m, 4H), 3.70 (m, 4H), and 3.60-3. 55 (m, 8H).
45% With sodium hydroxide In water at 0℃; for 6h;
  • 2
  • [ 112-16-3 ]
  • [ 60835-71-4 ]
  • [ 109065-13-6 ]
YieldReaction ConditionsOperation in experiment
67% With triethylamine In tetrahydrofuran for 3h; Ambient temperature;
  • 4
  • [ 60835-69-0 ]
  • [ 60835-71-4 ]
YieldReaction ConditionsOperation in experiment
100% With hydrazine hydrate monohydrate In 1,4-dioxane
100% With palladium on activated charcoal; hydrazine hydrate monohydrate In ethanol for 5h; Reflux;
99% With palladium 10% on activated carbon; hydrogen In methanol at 20℃; for 5h; 4 Synthesis of amino benz-15-crown-5-ether A suspension of nitro-benz-15-crown-5-ether (5g, 16 mmol) and the catalyst (10% Pd/C, 0.5g) in methanol (150 mL) was subjected to hydrogenation under atmospheric pressure at RT for 5h. The catalyst was filtered off and the solvent was removed under reduced pressure to give a slightly reddish viscous oil. Yield 4.6g (99%) . 1H NMR (CDCI3) , 5 6.73 (d, 1H, J = 8.4 Hz) , 6.27 (d, 1H, J = 2.4 Hz) , 6.21 (dd, 1H, J = 8.4 Hz, J = 2.4 Hz) , 4.08 - 4.04 (m, 4H) , 3.90 - 3.85 (m, 4H) , 3.74 (s, 8H) , 3.46 (brs, 2H) ppm.
93% With hydrazine hydrate monohydrate In 1,4-dioxane at 100℃; for 3h;
86% With hydrazine hydrate monohydrate In ethanol for 1.5h; Heating;
70% With hydrazine hydrate monohydrate In ethanol for 2h;
70% With hydrazine hydrate monohydrate at 500℃; 4-Aminobenzo-15-crown-5(AB15C5) production For the purpose of 4-nitrobenzo-15-crown-5reducition we chose the method of reduction byhydrazine hydrate over skeleton Raney nickel catalystin the alcohol media as the most convenient andeffective one. Contrary to other methods, a reductionby hydrazine hydrate over nickel catalyst takes placeat normal pressure and without autoclave.5 g Raney nickel was added to 34 g (0.108mole) 4-nitrobenzo-15-crown-5 with in 200-ml ethylalcohol and heated to 500 0C, followed by dripping34 ml hydrazine hydrate. In one hour’s time it wasfltered off the catalyst, with solution boiled out andresidue recrystallized from 30-ml ethyl alcohol. Theyield of AB15C5 was 70%, with its melting point of79.5-80.5 0C.Infrared spectrum (KBr, ν, cm-1): 497(weak), 581 (weak), 631 (weak), 712 (weak), 766(weak), 793 (weak) (NH2), 847 (medium) (NH2),917 (weak), 940 (medium), 987 (medium), 1060(medium) (C-O-C), 1079 (medium), 1127 (strong)(C-O-C), 1181 (medium), 1217 (medium) (C-N),1251 (medium), 1294 (medium), 1332 (weak),1355 (weak), 1452 (medium), 1511 (strong) (CH2),1589 (weak) (aromatic C-C), 1610 (medium) (NH2),2878 (medium) (C-H), 2921 (medium) (C-H), 2957(medium) (C-H), 3056 (aromatic C-H), 3346 (strong)(NH2), 3396 (strong) (NH2).1HNuclear magnetic resonance(DMSO-d6, 300 MHz): 3.60 (broad singlet, 8H,CH2+CH2+CH2+CH2), 3.68-3.77 (multiplet, 4H,CH2+CH2), 3.85-3.97 (multiplet, 4H, CH2+CH2), 4.67(broad singlet, 2H, NH2), 6.05 (double doublet, 1H,J=8.4, J=2.5, CH), 6.22 (doublet, 1H, J=2.5, CH),6.63 (doublet, 1H, J=8.4, CH).13C Nuclear magnetic resonance (DMSOd6, 75 MHz): 67.77, 68.84, 69.27, 69.71, 70.09,70.16, 70.30, 100.96, 105.53, 117.49, 139.35,143.95, 149.92.
42% With hydrazine hydrate monohydrate In methanol at 35℃; for 1.75h; Reflux; 4-Aminobenzo-15-crown-5 (1) A mixture of 15.65 g(0.05 mol) of 4-nitrobenzo-15-crown-5, 150 mL ofmethanol, and 10 mL of hydrazine hydrate was heated to 35°C, 3 g of Raney nickel was added, and themixture was kept for 45 min and was then heated for 1h under reflux. The mixture was cooled, the catalystwas filtered off, and the filtrate was treated withcharcoal on heating under reflux and filtered. Aftercooling to room temperature, the precipitate wasfiltered off, recrystallized from 3-methylbutan-1-ol,and dried. Yield 42%, mp 95-96°C, purity 97% (GC/MS). IR spectrum, ν, cm-1: 497 w, 581 w, 631 w, 712w, 766 w, 793 w, 847 m, 917 w, 940 m, 987 m, 1060m, 1079 m, 1127 s, 1181 m, 1217 m, 1251 m, 1294 m,1332 w, 1355 w, 1452 m, 1511 s, 1589 w, 1610 m,2878 m, 2921 m, 2957 m, 3056, 3346 s, 3396 s. 1HNMR spectrum, δ, ppm: 3.60 br.s (8H), 3.68-3.77 m(4H), 3.85-3.97 m (4H), 4.67 br.s (2H), 6.05 d.d (1H,J = 8.4, 2.5 Hz), 6.22 d (1H, J = 2.5 Hz), 6.63 d (1H,J = 8.4 Hz). 13C NMR spectrum, δC, ppm: 67.77,68.84, 69.27, 69.71, 70.09, 70.16, 70.30, 100.96,105.53, 117.49, 139.35, 143.95, 149.92. Found, %: C59.31; H 7.41; N 4.94. C14H21NO5. Calculated, %: C59.62; H 7.63; N 4.71.
With hydrogen
1.0 g With hydrogen In N,N-dimethyl-formamide for 1.5h;
With hydrogen In methanol; water monomer
With hydrogen In ethanol
With hydrazine hydrate monohydrate
With hydrazine hydrate monohydrate
With hydrogen Yield given;
With hydrogen In ethanol
With hydrogen In 1,4-dioxane at 18℃; other catalyst: palladium black;
With hydrogen In N,N-dimethyl-formamide Ambient temperature;
With hydrogen In 1,4-dioxane at 18℃;
With hydrogenchloride; zinc powder at 40℃; for 2h;
With palladium on activated charcoal; hydrazine
With platinum; hydrazine
With palladium on activated charcoal
With hydrazine monohydrate; palladium on activated charcoal In diethylene glycol dimethyl ether
With palladium 10% on activated carbon; hydrogen In tetrahydrofuran; methanol at 20℃; for 12h;
With palladium 10% on activated carbon; hydrogen In tetrahydrofuran; methanol at 20℃; for 12h;
With palladium 10% on activated carbon; hydrogen In tetrahydrofuran; methanol at 20℃; Compound M1 To a degassed solution of 4-nitrobenzo-15-crown-5 ether (1.10 g, 3.51mmol) in 40 mL of a THF:MeOH mixture (1:4) 20 mg of 10% Pd/C was added. The reactionmixture was kept under a H2 atmosphere (balloon pressure) at room temperature overnight.The catalyst was removed by filtration through a pad of Celite and washed withMeOH. The filtrate was concentrated under reduced pressure to give the crude productin a near-quantitative yield (0.98 g). The obtained 4-aminobenzo-15-crown-5 ether wasused in the next step without further purification.To the solution of 4-aminobenzo-18-crown-6 ether (0.98 g 3.46 mmol) in methanol (20mL), 3,4-dimethoxy-3-cyclobutene-1,2-dione (0.49 g, 3.45 mmol) was added. The reactionmixture was stirred at room temperature overnight. The resulting precipitate was isolatedby filtration and obtained solid material was washed several times with methanol. Theobtained white solid was dried in vacuo to give the desired product (1.18 g, 3.00 mmol,87% yield).HRMS (ESI): calcd for C13H7F6NO3Na [M + Na]+: 416.1321, found: 416.1333. 1H NMR(300 MHz, DMSO-d6) δ 10.64 (s, 1H), 7.17-6.95 (m, 1H), 6.95-6.90 (m, 1H), 6.87 6.77 (m, 1H)4.37 (s, 3H), 4.07-3.99 (m, 4H), 3.82-3.72 (m, 4H), 3.65-3.58 (m, 8H). 13C NMR (75 MHz,DMSO-d6) δ 189.1, 184.1, 178.7, 169.6, 149.3, 145.9, 132.1, 114.9, 112.23, 106.9, 70.9, 70.9, 70.3,70.2, 69.4, 69.4, 69.1, 68.7, 60.9.

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[2]Bunchuay, Thanthapatra; Docker, Andrew; Eiamprasert, Utt; Surawatanawong, Panida; Brown, Asha; Beer, Paul D. [Angewandte Chemie - International Edition, 2020, vol. 59, # 29, p. 12007 - 12012][Angew. Chem., 2020, vol. 132, # 29, p. 12105 - 12110,6]
[3]Current Patent Assignee: NWPT NANO WATER PURIFICATION TECHNOLOGY; N W P T NANO WATER PURIFICATION TECH - WO2022/44000, 2022, A1 Location in patent: Page/Page column 89
[4]Gorodnyuk, V. P.; Grigorash, R. Ya.; Chuprin, G. N.; Kotlyar, S. A. [Russian Journal of General Chemistry, 1998, vol. 68, # 6, p. 1001 - 1002][Zhurnal Obshchei Khimii, 1998, vol. 68, # 6, p. 1051 - 1052]
[5]Berezina; Kobrin; Kusov; Lubenets [Russian Journal of Organic Chemistry, 1998, vol. 34, # 10, p. 1517 - 1518]
[6]Kilic, Zeynel; Weber, Edwin; Guenduez, Necla; Kilic, Emine; Nazir, Hasan; et al. [Zeitschrift fur Naturforschung, B: Chemical Sciences, 1992, vol. 47, # 4, p. 547 - 552]
[7]Glushko, Valentina N.; Sadovskaya, Natalya Yu.; Kozhuhov, Vadim I.; Blokhina, Lidiya I.; Antropova, Irina A.; Petina, Ekaterina S.; Retiviov, Vasiliy M.; Melnikova, Ekaterina Yu. [Oriental Journal of Chemistry, 2017, vol. 33, # 4, p. 1689 - 1697]
[8]Sadovskaya, N. Yu.; Glushko; Retivov; Belus'; Grokhovskii [Russian Journal of General Chemistry, 2015, vol. 85, # 12, p. 2771 - 2777][Zh. Obshch. Khim., 2015, vol. 85, # 12, p. 2041 - 2048,8]
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[10]Keating, M. Y.; Rechnitz, G. A. [Analytical Chemistry, 1984, vol. 56, # 4, p. 801 - 806]
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  • 5
  • [ 14098-44-3 ]
  • [ 60835-71-4 ]
YieldReaction ConditionsOperation in experiment
Multistep reaction;
Multi-step reaction with 2 steps 1: 98 percent / aq. HNO3; CH3COOH / CHCl3 2: 100 percent / N2H4*nH2O / Pd/C / dioxane
Multi-step reaction with 2 steps 1: fuming nitric acid / CCl4 / 3.5 h / 20 - 45 °C 2: 86 percent / hydrazine hydrate / 4 percent Pd/C / ethanol / 1.5 h / Heating
Multi-step reaction with 2 steps 1: HNO3 / acetic acid 2: H2 / Pd/C
Multi-step reaction with 2 steps 1: HNO3 (d = 1.42, 70percent) / acetic acid / 0.5 h 2: 1.0 g / hydrogen / Raney Ni/H20 slurry / dimethylformamide / 1.5 h / 2068.6 Torr
Multi-step reaction with 2 steps 1: nitric acid; acetic acid 2: palladium on activated charcoal; hydrazine
Multi-step reaction with 2 steps 1: nitric acid; acetic acid 2: hydrazine; platinum
Multi-step reaction with 2 steps 1: acetic acid; nitric acid 2: palladium on activated charcoal
Multi-step reaction with 2 steps 1: nitric acid / acetonitrile / 0.33 h / 70 °C 2: hydrazine hydrate / methanol / 1.75 h / 35 °C / Reflux
Multi-step reaction with 2 steps 1: nitric acid; acetic acid / chloroform / 0 - 20 °C 2: palladium on activated charcoal; hydrazine hydrate / ethanol / 5 h / Reflux

  • 6
  • [ 60835-71-4 ]
  • [ 108-95-2 ]
  • [ 77100-96-0 ]
YieldReaction ConditionsOperation in experiment
89.3% Stage #1: 4'-aminobenzo-15-crown-5-ether With hydrogenchloride; sodium nitrite In water for 1h; cooling; Stage #2: phenol With sodium hydroxide In water for 0.166667h; Further stages.;
89.3% Stage #1: 4'-aminobenzo-15-crown-5-ether With hydrogenchloride; sodium nitrite In water Cooling with ice; Darkness; Stage #2: phenol With sodium hydroxide In water Cooling with ice; Darkness;
53% Stage #1: 4'-aminobenzo-15-crown-5-ether With hydrogenchloride; sodium nitrite In water at 0 - 2℃; for 1h; Stage #2: phenol With sodium hydroxide In water at 0 - 2℃; for 1h;
With hydrogenchloride; sodium hydroxide; sodium carbonate; sodium nitrite 2.) water, 3 h; Multistep reaction;
With hydrogenchloride; sodium nitrite 1.) H2O, 0 deg C; Multistep reaction;

  • 7
  • [ 60835-71-4 ]
  • [ 1079-66-9 ]
  • [ 161868-41-3 ]
YieldReaction ConditionsOperation in experiment
90% With triethylamine In dichloromethane for 1h; Ambient temperature;
86% With triethylamine In tetrahydrofuran for 3h; Inert atmosphere;
  • 8
  • [ 60835-71-4 ]
  • [ 103-71-9 ]
  • 4-phenylurea-benzo-15-crown-5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% In dichloromethane for 2h; Inert atmosphere; General synthesis General procedure: 4′-Aminobenzo-15-crown-5 (5 mmol) was dissolvedin dry dichloromethane (50 ml) and the appropriateisocyanate or isothiocyanate (5 mmol) dissolved indry dichloromethane (10 ml) was added with vigorousstirring under N2. The reaction mixture wasstirred for a further 2 h to ensure complete formationof the corresponding urea or thiourea derivativebefore the solvent was removed under vacuum.The products were recrystallised from acetonitrile,isolated by filtration and air dried. 1a was obtained as a white powder. Yield: 330 mg(96%); 1H NMR (CDCl3) δ: 7.31 (s, 1H, NH), 7.29 (s, 1H,NH), 7.25 (m, 3H, Ar), 7.15 (q, 2H, J = 8.4 Hz, Ar), 6.99 (s,1H, Ar), 6.68 (s, 2H Ar), 4.03 (s, 2H, crown), 3.94, (s, 2H,crown), 3.87 (s, 2H, crown), 3.80 (s, 2H, crown), 3.75 (m,8H, crown), 2.23 (s, 2H, NH); 13C NMR (CDCl3) δ: 153.0,149.5, 144.2, 139.6, 134.0, 128.7. 122.0, 118.5, 115.5,111.0, 106.2, 70.8, 70.7, 70.4, 70.2, 69.9, 69.6, 69.2,68.7; m. p. 168-169°C; IR (cm-1): 3300 (N-H), 1640 (C =O); m.p. 168-169°C, ESI HRMS m/z found: 425.1747,calculated: 425.1616 [M + Na]+.
93% In acetonitrile for 5h; Heating;
91% In chloroform for 5h; Heating;
  • 9
  • [ 60835-71-4 ]
  • [ 24801-88-5 ]
  • 4-[3-(triethoxysilyl)propyl]ureidobenzo-15-crown-5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% In chloroform at 20℃; for 48h; 27.2 g of 97% 4'-aminobenzo-15-crown-5 (Aldrich reference 39,342-8, MR=283.33), i.e. 96 mmol, are dissolved in 345 ml of chloroform. 26.12 g of 3-(triethoxysilyl)propylisocyanate (Aldrich reference 41,336-4, MR=247.37), i.e. 105.6 mmol, corresponding to 10% excess with respect to the crown ether, are added and the reaction medium is stirred at ambient temperature for 48 hours. The yellow solution obtained is brought to dryness by evaporation on a water bath at 40° C. under vacuum to constant weight. 53.32 g of compound (XX) are obtained. The yield is greater than 100% as the silane is used in excess.
90% In acetonitrile for 5h; Heating;
  • 10
  • [ 60835-71-4 ]
  • [ 64709-55-3 ]
  • N-(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecin-15-yl)-1-pyreneacetamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
16% With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 0 - 25℃;
  • 11
  • [ 60835-71-4 ]
  • [ 4986-89-4 ]
  • C73H104N4O28 [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With triethylamine In methanol at 50℃; for 144h;
  • 12
  • [ 60835-71-4 ]
  • [ 15625-89-5 ]
  • 3-(6,7,9,10,12,13,15,16-octahydro-5,8,11,14,17-pentaoxa-benzocyclopentadecen-2-ylamino)-propionic acid 2,2-bis-[3-(6,7,9,10,12,13,15,16-octahydro-5,8,11,14,17-pentaoxa-benzocyclopentadecen-2-ylamino)-propionyloxymethyl]-butyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
73.3% With triethylamine In methanol at 50℃; for 144h;
  • 13
  • [ 60835-71-4 ]
  • [ 38588-64-6 ]
  • [ 304682-07-3 ]
YieldReaction ConditionsOperation in experiment
59% Stage #1: 3,5-bis(methoxycarbonyl)benzoic acid With dmap; 1-hydroxy-7-aza-benzotriazole; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In acetonitrile at 0 - 5℃; for 0.5h; Stage #2: 4'-aminobenzo-15-crown-5-ether In acetonitrile at 20℃; for 6h; Further stages.;
  • 14
  • [ 60835-71-4 ]
  • [ 5736-88-9 ]
  • (4-butoxy-benzylidene)-(6,7,9,10,12,13,15,16-octahydro-5,8,11,14,17-pentaoxa-benzocyclopentadecen-2-yl)-amine [ No CAS ]
  • 15
  • [ 60835-71-4 ]
  • [ 130296-37-6 ]
  • N-(1-hexyl-heptyl)-N'-(4'-benzo-15-crown-5)-perylene-3,4:9,10-bis(dicarboximide) [ No CAS ]
YieldReaction ConditionsOperation in experiment
50% Example 7: N-(1-Hexyl-heptyl)-N'-(4'-benzo-15-crown-5)-perylene-3,4:9,10-bis(dicarboximide); 0.70 g (1.22 mmol) of N-(1-hexyl-heptyl)-perylene-3,4:9,10-tetracarboxylic acid 3,4-anhydride 9,10-imide and 0.43 g (1.52 mmol) of 4'-aminobenzo-15-crown-5 are heated for 4 hours at 140C, under a protecting gas, with 0.08 g (0.36 mmol) of zinc acetate dihydrate in 10 g of imidazole. Before solidifying, the mixture is introduced with a total of 100 ml of ethanol into 300 ml of 2N hydrochloric acid and stirred for 2 hours at room temperature. The resulting precipitate is filtered off with suction over a D4 frit, washed with water and dried. The filtrate is extracted with a total of 800 ml of chloroform, the solvent is removed and the two crude products are combined. The colourant so obtained is worked up by column chromatography on aluminium oxide in chloroform/ethanol (20 + 1) (50.4 cm column), the product N-(1-hexyl-heptyl)-N'-(4'-benzo-15-crown-5)-perylene-3,4:9,10-bis(dicarboximide) being obtained as the first red, non-fluorescent band. The dye fraction obtained is filtered through a D4 frit and the solvent is then removed; the fraction is washed with methanol/water and then dried for 24 hours under an oil-pump vacuum (80C/0.13 mbar). Yield 0.51 g (50 %), m.p. 288-290C. - RF (silica gel/CHCl3 + ethanol (10 + 1)) = 0.25. IR (KBr): nu = 2955 cm-1 (m), 2927 (s), 2858 (m), 1698 (s), 1660 (s), 1594 (s), 1579 (m), 1512 (s), 1455 (w), 1433 (w), 1405 (m), 1354 (m), 1345 (s br.), 1308 (w), 1264 (m), 1254 (s br.), 1176 (w), 1130 (s br.), 980 (w), 855 (w), 811 (s), 795 (m), 746 (m).- Fluorescence (CHCl3): lambdamax(epsilon) = 535 nm, 575. C51H54N2O9 (838.4): calc. C 73.01, H 6.49, N 3.34; found C 73.12, H 6.46, N 3.14.
  • 16
  • [ 60835-71-4 ]
  • [ 128-69-8 ]
  • N,N'-bis(4'-benzo-15-crown-5)-perylene-3,4:9,10-bis(dicarboximide) [ No CAS ]
YieldReaction ConditionsOperation in experiment
22% Stage #1: 4'-aminobenzo-15-crown-5-ether; perylene-3,4,9,10-tetracarboxylic acid 3,4:9,10-dianhydride With 1H-imidazole; zinc(II) acetate at 140℃; for 3h; Stage #2: With hydrogenchloride In etrhanol; water for 1h; 10 Example 10: N,N'-Bis(4'-benzo-15-crown-5)-perylene-3,4:9,10-bis(dicarboximide) Example 10: N,N'-Bis(4'-benzo-15-crown-5)-perylene-3,4:9,10-bis(dicarboximide); 0.39 g (1.27 mmol) of perylene-3,4:9,10-tetracarboxylic acid bisanhydride, 0.76 g (2.67 mmol) of 4-aminobenzo-15-crown-5, 0.08 g of zinc acetate dihydrate and 7 g of imidazole are stirred for 3 hours at 140°C. The reaction mixture is suspended while still warm in 50 ml of ethanol and is then transferred into 300 ml of 2N hydrochloric acid. After one hour, the resulting precipitate is filtered off with suction and dried. 0.5 g of the crude product is boiled a total of three times with 200 ml of 10 % potassium carbonate solution each time and the insoluble product is isolated using a D4 frit. The filtrate is discarded. The precipitate is washed several times with hot water and then dried at 100°C. The powdered product N,N'-bis(4'-benzo-15-crown-5)-perylene-3,4:9,10-bis(dicarboximide) is transferred to an extraction thimble and extracted in succession with methylene chloride, acetone and ethanol for in each case from one to two days. The insoluble product N,N'-bis(4'-benzo-15-crown-5)-perylene-3,4:9,10-bis(dicarboximide) is in the extraction thimble. Yield 0.11 g (22 %), based on 0.5 g of the crude product treated in that manner. - IR (KBr) : ν = 2920 cm-1 (m), 2870 (m), 1702 (s), 1662 (s), 1594 (s), 1578 (m), 1514 (s), 1453 (m), 1431 (m), 1404 (m), 1362 (s), 1331 (m), 1268 (s br.), 1256 (s br.), 1197 (m), 1179 (m), 1133 (m br.), 1122 (s br.), 1050 (m), 970 (w), 940 (m), 856 (m), 811 (m), 798 (m), 768 (m), 760 (m), 630 (m). - UV (H2SO4): λmax(ε) = 603 nm (79 000), 558 (46 200), 522 sh (16 600), 400 (6500). - C52H46N2O14 (922.9): calc. C 67.67, H 5.02, N 3.03; found C 62.97, H 4.59, N 2.91.
  • 17
  • [ 13669-05-1 ]
  • [ 60835-71-4 ]
  • [ 1036369-48-8 ]
  • 18
  • [ 60835-71-4 ]
  • [ 1116463-43-4 ]
  • [ 1116463-31-0 ]
YieldReaction ConditionsOperation in experiment
68% With dmap; dicyclohexyl-carbodiimide In dichloromethane for 24h; Inert atmosphere;
  • 19
  • [ 60835-71-4 ]
  • C14H21NNaO5(1+)*ClO4(1-) [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium perchlorate In acetonitrile 4.3. Synthesis of 1:1 and 1:2 complexes of M-AM3 and 1:1 complex with AB15C5 with sodium cations A 0.07 mol dm-3 solution of 1:1 complex of AB15C5 with sodium cation was obtained by adding equimolar amount of NaClO4 dissolved in acetonitrile to acetonitrile solution of AB15C5.
  • 20
  • [ 60835-71-4 ]
  • [ 17090-79-8 ]
  • [ 1269615-71-5 ]
YieldReaction ConditionsOperation in experiment
71% With benzotriazol-1-ol; dicyclohexyl-carbodiimide In tetrahydrofuran; dichloromethane at -10 - 20℃; for 48h; 4.2. Preparation of monensin A amide with AB15C5 amine Monensin A sodium salt (MON-Na) was dissolved in dichloromethane (CH2Cl2) and stirred vigorously with a layer of aqueous sulfuric acid (H2SO4; pH=1.5). The organic layer containing MONA was washed with distilled water, and dichloromethane was then evaporated under reduced pressure to dryness. A solution of MONA (1000 mg, 1.49 mmol), 1,3-dicyclohexylcarbodiimide (DCC-515 mg, 2.50 mmol) and 4-aminobenzo-15-crown-5 (AB15C5-1133 mg, 4.00 mmol) all dissolved in dichloromethane and 1-hydroxybenzotriazole (HOBt-330 mg, 2.44 mmol) dissolved in tetrahydrofuran was mixed together and stirred at a temperature between 0 and -10 °C for 24 h. After this time the reaction mixture was stirred at room temperature for the next 24 h, diluted with H2O and extracted with CH2Cl2. The organic phase was evaporated under reduced pressure to dryness. The residue was suspended in hexane and filtered off to remove 1,3-dicyclohexylurea (DCU) as a by-product. The filtrate was evaporated under reduced pressure and purified by chromatography on silica gel (Fluka type 60) to give M-AM3 (988 mg, 71% yield) as an amorphous, brown solid.Elemental analysis for M-AM3 (C50H81NO15): Calculated: C 64.15%, H 8.72%, N 1.50%. Found: C 64.05%, H 8.78%, N 1.61%.Furthermore, M-AM3 and its 1:1 and 1:2 complexes with sodium perchlorate were fully characterised by ESIMS, 1H, 13C NMR and FTIR spectroscopy.
  • 21
  • [ 60835-71-4 ]
  • [ 607-42-1 ]
  • [ 1314228-22-2 ]
YieldReaction ConditionsOperation in experiment
65% With benzotriazol-1-ol; dicyclohexyl-carbodiimide In N,N-dimethyl-formamide at 0℃; for 24h; 4.1. Syntheses of 4'-(1-anthracene- and 2-anthracenecarboxamido)benzo-15-crown-5 (1AC and 2AC) General procedure: 1- or 2-Anthracenecarboxylic acid (2.22 g, 0.01 mol) and HOBt (1.53 g, 0.01 mol) were dissolved in 50 mL of DMF; then 4'-aminobenzo-15-crown-5 (5.1 g, 0.018 mol) was added. The solution was treated using dicyclohexylcarbodiimide (3.4 g, 0.018 mol) under stirring for 1 day at 0 °C. The solvent was evaporated under reduced pressure. Thereby, a crude compound was obtained. Compound 1AC and 2AC was recrystallized from acetic acid. Model compounds xA were also synthesized in the above method from 9-, 1- or 2-anthracenecarboxylic acid (1.11 g, 0.005 mol) and 1-propylamine (0.29 g, 0.005 mol).
  • 22
  • [ 60835-71-4 ]
  • [ 613-08-1 ]
  • [ 1314228-23-3 ]
YieldReaction ConditionsOperation in experiment
70% With benzotriazol-1-ol; dicyclohexyl-carbodiimide; In N,N-dimethyl-formamide; at 0℃; for 24h; General procedure: 1- or 2-Anthracenecarboxylic acid (2.22 g, 0.01 mol) and HOBt (1.53 g, 0.01 mol) were dissolved in 50 mL of DMF; then 4'-aminobenzo-15-crown-5 (5.1 g, 0.018 mol) was added. The solution was treated using dicyclohexylcarbodiimide (3.4 g, 0.018 mol) under stirring for 1 day at 0 C. The solvent was evaporated under reduced pressure. Thereby, a crude compound was obtained. Compound 1AC and 2AC was recrystallized from acetic acid. Model compounds xA were also synthesized in the above method from 9-, 1- or <strong>[613-08-1]2-anthracenecarboxylic acid</strong> (1.11 g, 0.005 mol) and 1-propylamine (0.29 g, 0.005 mol).
  • 23
  • [ 60835-71-4 ]
  • [ 141-75-3 ]
  • [ 1314228-27-7 ]
YieldReaction ConditionsOperation in experiment
67% In tetrahydrofuran at 20℃; for 24h; 4.1. Syntheses of 4'-(1-anthracene- and 2-anthracenecarboxamido)benzo-15-crown-5 (1AC and 2AC) Compound C was prepared as follows: 4'-aminobenzo-15-crown-5 (2.84 g 0.01 mol) and 1-butanoyl chloride (0.53 g, 0.005 mol) dissolved in 50 mL of THF solvent under stirring for 1 day at rt. After filtrated the precipitation, the filtrate was evaporated under reduced pressure. The obtained crude compound was recrystallized from EtOH.
  • 24
  • [ 60835-71-4 ]
  • [ 628-36-4 ]
  • [ 1255774-64-1 ]
  • 25
  • [ 60835-71-4 ]
  • [ 824945-97-3 ]
  • [ 1352612-71-5 ]
YieldReaction ConditionsOperation in experiment
64% In methanol for 3h; Reflux;
  • 26
  • [ 60835-71-4 ]
  • [ 824945-97-3 ]
  • [ 1352612-76-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: methanol / 3 h / Reflux 2: sodium perchlorate / methanol / 1 h
  • 27
  • [ 60835-71-4 ]
  • [ 1379115-40-8 ]
  • 3-benzothiazol-2-yl-4-[4-chloro-6-(6,7,9,10,12,13,15,16-octahydro-5,8,11,14,17-pentaoxa-benzocyclopentadecen-2-yl-amino)-[1,3,5]triazin-2-yl-amino]-benzenesulphonic acid potassium salt [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate In water at 20℃; for 3h; 1 Example 1Preparation and testing of compounds of formula (I) wherein Rx is a group of formula (d)540 mg (1.10 mmoles) of 3-benzotriazoi-2-yl-4-(4,6-dichloro-[1 ,3,5]tnazin-2- yl-amino)-benzenesulphonic acid potassium salt were dissolved in 50 ml of water, and the pH of the solution was adjusted to 7 with solid potassium carbonate. Thereafter 311 mg ( 1.10. mmoles) of 6,7, 9, 10, 12, 13, 15, 16-octahydro-5, 8, 11 ,14,17-penta- oxa-benzocyclopentadecen-2-yl-amine were added to the solution, and the reaction mixture was stirred at room temperature for 3 hours. The solution was then evaporated, and the residue was crystallized from methanol 510 mg of 3-benzothi;, az0i«2"yl-4-»|4-chloro-6-(6,7,9,-10, 12, 3,15, 6-octahydro~5,8, 1 ,14, 17 -pentaoxa-. ^ benzocyclopentadecen-2-yl-amino)-[1 ,3,5jtriazin-2-y.-amino]-benzenesulphonic acid potassium salt were obtained as a white powder
  • 28
  • [ 60835-71-4 ]
  • [ 71190-35-7 ]
  • N-(4'-benzo-15-crown-5)-4-pyridylpyridinium hexafluorophosphate [ No CAS ]
YieldReaction ConditionsOperation in experiment
26.6% Stage #1: 4'-aminobenzo-15-crown-5-ether; 1-(2,4-dinitrophenyl)-4,4'-bipyridinium chloride In ethanol; water at 20 - 40℃; for 74h; Stage #2: With ammonium hexafluorophosphate In water 4.1 4.4.1. N-(4'-Benzo-15-crown-5)-4-pyridyl-pyridinium hexafluorophosphate (1). A 40 ml aqueous ethanol solution of N-(2,4-dinitrophenyl)-4-pyridyl-pyridinium chloride (1.0 g, 2.8 mmol) was added over 2 h to a 40 ml aqueous ethanol solution of 4'-aminobenzo-15-crown-5 (1.04 g, 3.67 mmol) at 40 °C. The reaction mixture was stirred at room temperature for 3 days. After removing the solvent, the crude solid was washed with diethyl ether several times and recrystallized three times from methanol and diethyl ether. The solid was dissolved in water and saturated aqueous solution containing ammonium hexafluorophosphate salt was added. The precipitate was filtered and washed with water. The product was obtained as a white solid (1.07 g, 26.6%). Compound 1: mp: 167-168 °C. 1H NMR (400 MHz; CD3CN): δ 9.03 (d, 2H, J=7.1 Hz), 8.94 (d, 2H, J=6.1 Hz), 8.50 (d, 2H, J=7.1 Hz), 7.92 (d, 2H, J=6.1 Hz), 7.34-7.31 (m, 2H), 7.22 (t, 1H), 4.26-4.23 (m, 4H), 3.91-3.89 (m, 4H), 3.74-3.71 (m, 4H), 3.69-3.67 (m, 4H) ppm. 13C NMR (400 MHz; CD3CN): δ=153.81, 150.78, 150.44, 149.04, 144.51, 141.19, 135.15, 125.51, 121.81, 116.71, 112.94, 109.12, 69.85, 69.80, 68.89, 68.44, 68.19, 67.88 ppm. Anal. Calcd for C24H27N2O5PF6: C 50.71, H 4.79, N 4.93%. Found: C 50.61, H 4.63, N 5.01%.
  • 29
  • [ 75-15-0 ]
  • [ 60835-71-4 ]
  • [ 606-25-7 ]
  • C25H28N2O7S2 [ No CAS ]
  • 30
  • [ 75175-77-8 ]
  • [ 60835-71-4 ]
  • C23H26FNO6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
71% In acetonitrile; at 20℃; for 1.5h; General procedure: A mixture of substituted 3 -(dimethylamino) -1-phenylprop-2-en-1-one compounds 1 (1 mmol), amino benzo crown ether 3/6/7 (1 mmol) and acetonitrile (5 ml) were charged in 25 ml round bottom flask. The reaction mixture was stirred at RT up to completion of reaction as monitored by TLC (Chloroform: Methanol, 9.5:0.5). After completion of reaction, a thick precipitated was obtained. The generated solid was filtered off and wash with cold acetonitrile to afford pure product. In those cases, where a solid was not formed after cooling, the solvent was evaporated by rotary evaporation and the crude product obtained was purified by column chromatography on silica gel (Chloroform: Methanol, 9.5: 0.5) to get pure benzo crown ether enamine (Table 1, entries 3,4,5,7,8).
  • 31
  • [ 68760-11-2 ]
  • [ 60835-71-4 ]
  • C23H26N2O8 [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% In acetonitrile at 20℃; for 1.5h; General procedure for the synthesis of benzo crown ether enamine derivatives (8a-8b, 9a-9d, 10a-10b) General procedure: A mixture of substituted 3 -(dimethylamino) -1-phenylprop-2-en-1-one compounds 1 (1 mmol), amino benzo crown ether 3/6/7 (1 mmol) and acetonitrile (5 ml) were charged in 25 ml round bottom flask. The reaction mixture was stirred at RT up to completion of reaction as monitored by TLC (Chloroform: Methanol, 9.5:0.5). After completion of reaction, a thick precipitated was obtained. The generated solid was filtered off and wash with cold acetonitrile to afford pure product. In those cases, where a solid was not formed after cooling, the solvent was evaporated by rotary evaporation and the crude product obtained was purified by column chromatography on silica gel (Chloroform: Methanol, 9.5: 0.5) to get pure benzo crown ether enamine (Table 1, entries 3,4,5,7,8).
  • 32
  • [ 60835-71-4 ]
  • (η5-cyclopentadienyl carboxaldehyde)rhenium tricarbonyl [ No CAS ]
  • C23H24NO8Re [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% In toluene for 12h; Reflux; Molecular sieve; Inert atmosphere; Schlenk technique; Synthesis of [(η5-C5H4-CH=N-4′-benzo-15-crown-5)Re(CO)3] (3a) 4′-Aminobenzo-15-crown-5 (78 mg, 0.276 mmol) was added to a solution of (η5-C5H4CHO)Re(CO)3 (100 mg, 0.276 mmol) in dry toluene (15 mL). The reaction mixture was refluxed for 12 h with a 4 molecular sieve. Following this procedure, the IR spectrum of the solution was measured and showed the disappearance of the starting material (i.e., 2033s, 1940, 1694w cm-1 disappeared) and the appearance of the new CO absorptions bands attributed to 3a. The reaction mixture was filtered through Celite and the solvent was concentrated under reduced pressure. Compound 3a was obtained as a yellow oily liquid. (yield: 150 mg, 0.239 mmol, 87%). IR [CH2Cl2, cm-1] ν(CO): 2026 (s) 1937 (s) ν(C=N): 1636 (w). 1H NMR (CDCl3) δ: 3.76 (m, 8H, CH2); 3.91 (m, 4H, CH2); 4.15 (m, 4H, CH2); 5,41 (t, 2H, JHH=2.2Hz, C5H4); 5.95 (t, 2H, JHH=2.2Hz, C5H4); 6.68 (dd, 1H, JHH=2.4; 8.4Hz, C6H3O2); 6.71 (d, 1H, JHH=2.4Hz, C6H3O2); 6.85 (d, 1H, JHH=8.4Hz, C6H3O2); 8.07 (s, 1H, CH=N). 13C NMR (CDCl3): 69.4; 69.8; 69.9; 70.0; 70.9; 71.0; 71.5; 71.6 (8s, CH2); 85.3 (s, C5H4); 86.1 (s, C5H4); 100.6 (s, Cipso, C5H4); 108.1 (s, C6H3O2); 113.2 (s, C6H3O2); 114.9 (s, C6H3O2); 145.2 (s, C6H3O2); 148.5 (s, C6H3O2); 150.0 (s, C6H3O2); 150.8 (s, CH=N); 193.2 (s, CO). Mass spectrum (based on 187Re) m/z: 629 [M+].
  • 33
  • [ 60835-71-4 ]
  • [ 100-52-7 ]
  • 4-(benzylideneamino)benzo-15-crown-5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% In methanol at 20℃; for 2h; (4-Benzylideneamino)benzo-15-crown-5 (2) Benzaldehyde,0.5 mL (0.005 mol), was added dropwise to a solution of 1.41 g (0.005 mol) of 4-aminobenzo-15-crown-5 in 20 mL of methanol. The mixture was kept for 2 h at room temperature, and the precipitate was filtered off and dried. Yield 94%, off-white powder, mp 64.5-65.0°C. IR spectrum, ν, cm-1: 500 w, 554 w,595 w, 697 m, 796 w, 801 w, 847 w, 894 w, 943 w, 986m, 1053 m, 1107 m, 1131 s, 1234 , 1263 s, 1294 m,1354 w, 1426 w, 1454 m, 1509 s, 1575 w, 1591 w,1624 m, 1646 w, 2862 m, 2898 m, 2929 m, 3030 w, 3055 w, 3068 w. 1H NMR spectrum, δ, ppm: 3.63 br.s(8H), 3.74-3.82 m (4H), 4.03-4.15 m (4H), 6.87 d.d(1H, J = 2.3, 8.4 Hz), 6.94-7.02 m (2H), 7.46-7.55 m(3H), 7.87-7.95 m (2H), 8.66 s (1H). Found, %: C65.12; H 7.21; N 3.48. C21H25NO5. Calculated, %: C65.32; H 7.43; N 3.71.
  • 34
  • [ 60835-71-4 ]
  • [ 123-11-5 ]
  • 4-(4-methoxybenzylideneamino)benzo-15-crown-5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% In ethanol at 42℃; for 3h; (4-Benzylideneamino)benzo-15-crown-5 (2) General procedure: Benzaldehyde,0.5 mL (0.005 mol), was added dropwise to a solution of 1.41 g (0.005 mol) of 4-aminobenzo-15-crown-5 in 20 mL of methanol. The mixture was kept for 2 h at room temperature, and the precipitate was filtered off and dried. Yield 94%
  • 35
  • [ 872-85-5 ]
  • [ 60835-71-4 ]
  • 4-[(pyridin-4-ylmethylidene)amino]benzo-15-crown-5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% In ethanol at 41℃; for 3h; (4-Benzylideneamino)benzo-15-crown-5 (2) General procedure: Benzaldehyde,0.5 mL (0.005 mol), was added dropwise to a solution of 1.41 g (0.005 mol) of 4-aminobenzo-15-crown-5 in 20 mL of methanol. The mixture was kept for 2 h at room temperature, and the precipitate was filtered off and dried. Yield 94%
86% In ethanol at 40℃; for 3h; Synthesis of the Schiff’s bases General procedure: 0.012 mol of the corresponding aldehyde 5 or 4 was added dropwise to a solution of 0.01 mol of aniline 3 or crown ether 1 or2 in 10 mL of ethanol. The obtained mixture was keptat 40° for 3 h and then evaporated off. The precipitate was filtered off and dried in air at room temperature. N-(Pyridin-4-ylmethylenamino)benzo-15-crown-5(1a). Yield 86%, light-green powder, mp 75.1-76.0°.IR spectrum, ν, cm-1: 627 w, 814 w, 851 w, 934 w,989 w, 1050 m, 1091 m, 1131 s (C-O-C), 1230 s,1266 s, 1316 m, 1363 w, 1414 w, 1453 m, 1513 s,1555 w, 1588 m, 1598 m, 1626 w (C=N), 2868-2922 br. s (C-H), 3030-3060 br. w (-Ar). 1 NMRspectrum, δ, ppm: 3.62 br. s (8, 2), 3.75-3.82 m(4, 2), 4.05-4.16 m (4, 2), 6.96 d. d (1, ,J = 8.5, 2.2 Hz), 7.01 d (1H, CH, J = 8.5 Hz), 7.08 d(1H, CH, J = 2.2 Hz), 7.79-7.85 m (2H, CH), 8.68-8.77 m (3, + HC=N). Found, %: 64.69; 6.57;N 7.58. C20H24N2O5. Calculated, %: 64.50; 6.53;N 7.52.
  • 36
  • [ 52661-56-0 ]
  • [ 60835-71-4 ]
  • 4-[3-(5-nitrofuran-2-yl)prop-2-en-1-ylideneamino]benzo-15-crown-5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
86% In methanol; at 35℃; for 1.0h; General procedure: Benzaldehyde,0.5 mL (0.005 mol), was added dropwise to a solution of 1.41 g (0.005 mol) of 4-aminobenzo-15-crown-5 in 20 mL of methanol. The mixture was kept for 2 h at room temperature, and the precipitate was filtered off and dried. Yield 94%
  • 37
  • [ 60835-71-4 ]
  • [ 3218-36-8 ]
  • 4-[(biphenyl-4-ylmethylidene)amino]benzo-15-crown-5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% In methanol at 35℃; for 1.5h; (4-Benzylideneamino)benzo-15-crown-5 (2) General procedure: Benzaldehyde,0.5 mL (0.005 mol), was added dropwise to a solution of 1.41 g (0.005 mol) of 4-aminobenzo-15-crown-5 in 20 mL of methanol. The mixture was kept for 2 h at room temperature, and the precipitate was filtered off and dried. Yield 94%
  • 38
  • [ 60835-71-4 ]
  • C20H16FeO2 [ No CAS ]
  • C34H35FeNO6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% In toluene for 5h; Inert atmosphere; Reflux; Schlenk technique; General procedure: 4'-aminobenzo-15-crown-5 (IId) was added to a solution of the corresponding organometallic chalcone 3a-b in dry toluene (15mL). The reaction mixture was refluxed for 5h with stirring and under nitrogen. After this time, the solvent was concentrated under reduced pressure to obtain 4. The compounds were isolated as crystalline solids after crystallization from hexane/CH2Cl2 mixture. 4.3.1 (η5-C5H4C(O)CH=CH-C6H4CH=N-benzo-15-crown-5)Fe(η5-C5H5) (4a) 4'-aminobenzo-15-crown-5 (IId) (50mg, 0.17mmol) and (η5-C5H4C(O)CH=CH-C6H4CHO)Fe(η5-C5H5) (3a) (61mg, 0.17mmol). Red solid, yield: 88% (95mg, 0.15mmol). IR (KBr, cm-1), νCO 1650, νC=C 1589, νC=N 1620. 1H NMR ((CD3)2SO) δ: 3.63 (s, 8H, OCH2), 3.79 (m, 4H, OCH2); 4.08 (m, 2H, OCH2); 4.13 (m, 2H, OCH2); 4.25 (s, 5H, C5H5); 4.70 (t, 2H, J=1.8Hz, C5H4); 5.09 (t, 2H, J=1.8Hz, C5H4); 6.93 (dd, 1H, J=8.4; 2.2Hz, C6H3O2); 7.00 (d, 1H, J=8.4Hz, C6H3O2); 7.04 (d, 1H, J=2.2Hz, C6H3O2); 7.54 (d, 1H, J=15.7Hz, CH=CH); 7.68 (d, 1H, J=15.7Hz, CH=CH); 8.00 (dd overlap, 4H, C6H4); 8.73 (s, 1H, CH=N). 13C NMR ((CD3)2SO) δ: 68.4, 68.7, 68.8, 68.9, 69.7 (5s, OCH2); 69.8 (s, C5H4); 69.9 (s, C5H5); 70.5, 70.5 (2s, OCH2); 72.9 (s, C5H4); 80.7 (s, Cipso, C5H4); 106.9, 113.9, 114.2 (3s, C6H3O2); 124.8 (s, CH=CH); 128.8, 129.1 (2s, C6H4); 137.4, 137.6 (2s, C6H4); 138.9 (s, CH=CH); 144.4, 147.5, 149.0 (3s, C6H3O2); 157.8 (s, CH=N); 191.9 (s, CO). Mass spectrum HR-MS (C34H35NO6Fe) m/z: 610.1863 [M+]. Anal (%) Cal. for C34H35NO6Fe: C 67.00, H 5.78; Found: C 64.53, H 5.53. UV-Vis. λ=317nm; extinction coefficient ε=26600M-1cm-1 and λ=371nm; extinction coefficient ε=24000M-1cm-1 in CH3CN.
  • 39
  • [ 60835-71-4 ]
  • C18H11O5Re [ No CAS ]
  • C32H30NO9Re [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% In toluene for 5h; Inert atmosphere; Reflux; Schlenk technique; General procedure: General procedure: 4'-aminobenzo-15-crown-5 (IId) was added to a solution of the corresponding organometallic chalcone 3a-b in dry toluene (15mL). The reaction mixture was refluxed for 5h with stirring and under nitrogen. After this time, the solvent was concentrated under reduced pressure to obtain 4. The compounds were isolated as crystalline solids after crystallization from hexane/CH2Cl2 mixture.
  • 40
  • [ 60835-71-4 ]
  • [ 35737-10-1 ]
  • C32H36N2O8 [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% Stage #1: N-Fmoc-β-alanine With 1,1'-carbonyldiimidazole In dichloromethane for 3h; Reflux; Stage #2: 4'-aminobenzo-15-crown-5-ether In dichloromethane at 20℃; for 24.5h; Reflux;
  • 41
  • [ 60835-71-4 ]
  • [ 1614-94-4 ]
  • C28H41NO6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% In ethanol for 0.5h; Reflux; Synthesis and analytical data for 2-hydroxy-8-methyl-tricyclo[7.3.1.02.7]tridec-13-N-4'(benzo-15-crown-5)-imine (HL) and complexes For HL to 1 mmol of 2-hydroxy-8-methyl-tricyclo[7,3,1,02,7]-13-one-tridecane dissolved in 8 mL ethanol was added 1 mmol of 4'-aminobenzo-15-crown-5-ether. The mixture was stirred and refluxed for 30 min and afterword was stirred at room temperature overnight. The reaction was stopped, and the solvent was removed under reduced pressure. A solid was formed with 93 % yield. The purity of the obtained product was checked with thin layer chromatography using CH2Cl2: MeOH (5:0.5, v/v) as eluent. The β-cycloketol derivative was obtained by a Michael reaction by using a modified Tilicenko-Barbulescu method [31, 32]. Yield 93 %. Analysis found: C, 68.91, H, 8.44, N, 2.83, C28H41NO6 calculate: C, 68.97, H, 8.48, N, 2.87 %; m. p. 72-73 °C; ESI-MS (positive mode, CH3CN:CH3OH) m/z: [M-3H]+, 484.2; [C27H34NO6]+, 468.4; [C25H32NO6]+, 442.1; [C24H30NO6]+, 428.1; [C18H34NO5]+, 344.3; [C15H27NO5]+, 301.4; [C15H28NO]+, 226.3; [C11H16O]+, 164.0; [C7H8N]+, 106.6; [C6H11]+, 83.4; [C6H11]+, 83.4; 1H-NMR (400 MHz, CDCl3, 303 K, δ (ppm), J (Hz)): 6.72 (d, 1H, H-5, 8.4); 6.27 (d, 1H, H-2,2.5); 6.20 (dd, 1H, H-6, 2.5, 8.4); 4.02-4.10 (m, 4H, H-20, H-27, syst. A2B2); 3.84-3.92 (m, 4H, H-21, H-26, syst. A2B2); 3.75 (s, 8H, H-22 ÷ H-25); 3.50 (bs, 1H, OH); 2.29 ÷ 2.17 (m, 4H, H-8, H-9, H-10, H-12); 2.11 ÷ 1.57 (m, 4H, H-aliph.); 1.52 ÷ 1.20 (m, 10H, H-aliph.); 1.02 (d, 3H, H-9', 7.0); 13C-NMR (CDCl3, 303 K, δ ppm): 219.59 (C-7); 150.55 (C-3); 141.95 (C-1); 141.62 (C-4); 117.51 (C-5); 107.29 (C-6); 102.70 (C-2); 78.09 (C-11); 70.99 (CH2-CE); 70.91 (CH2-CE); 70.85 (C-23, C-24); 70.54 (CH2-CE); 69.99 (CH2-CE); 69.65 (CH2-CE); 68.74 (CH2-CE); 59.89 (CH); 52.75 (CH); 45.89 (CH); 37.56 (CH); 36.47 (CH2); 29.30 (CH2); 28.88 (CH2); 26.19 (CH2); 25.51 (CH2); 21.24 (CH2); 20.18 (CH2); 15.86 (C-9') (CE, crown ether moiety) (The atom numbering is presented in Figure 1S).
  • 42
  • [ 60835-71-4 ]
  • 5,15-biphenyl-10-(4-nitrophenyl)-20-(4-bromophenyl)porphyrin [ No CAS ]
  • 5,15-biphenyl-10-(4-nitrophenyl)-20-(4-aminophenyl-benzo-15-crown-5)porphyrin [ No CAS ]
YieldReaction ConditionsOperation in experiment
52% With tris-(dibenzylideneacetone)dipalladium(0); sodium t-butanolate; XPhos In toluene at 70 - 100℃; 2.3. Synthesis of 5,15-biphenyl-10-(4-nitrophenyl)-20-(4-aminophenyl-benzo-15-crown-5)Porphyrin To 50 mL three-neck flask was added Pd (3-1-PhC3H4(5-C5H5) or Pd2dba3 (0.5-4 mol%), XPhos (1-8 mol%, Pd: L = 1 2) and degassed toluene (2 mL) followed by airreplacementwith argon.Then themixturewas stirred at 70 Cfor 15 min. Then 5,15-biphenyl-10-( 4-nitrophenyl)-20-(4bromophenyl)porphyrin (1 mmol), 3amine15crown5(1.1 mmol) and NaOt Bu (1.4 mmol) were added successivelyand the reaction mixture was kept at 70 100 C.After completion of reactionmonitored by TLC, the mixturewas cooled and filtered, the precipitate was purified by columnchromatography (silica gel,Hexanes/EtOAc:1/3 v/v) togive 223mg(52%) 5,15-biphenyl-10-(4-nitrophenyl)-20-(4-aminophenylbenzo15crown5)porphyrin.mp > 300 C.1HNMR (500 MHz, DMSO) : = 375 (t, J = 6 Hz, 8H),3.92 (t, J = 7 Hz ,4H), 4.15 (t, J = 6 Hz ,4H), 6.89 (d, J =7 Hz, 3H), 7.82 (d, J = 7 Hz, 8H), 8.21 (d, J = 6 Hz, 5H),8.33 (d, J = 9 Hz, 3H), 8.35 (d, J = 9 Hz, 2H), 8.83 (s, 8H).
  • 43
  • [ 60835-71-4 ]
  • [ 3158-26-7 ]
  • 1-(benzo-15-crown-5-15-yl)-3-octylurea [ No CAS ]
YieldReaction ConditionsOperation in experiment
80% In acetonitrile for 24h; Inert atmosphere; Reflux; Synthesis of alkyl-ureido-benzo-15-crown-5-ethers n-Octyl-benzoureido-15-crown-5-ether (15C5n8) wasprepared by refluxing for 24 h 50 mg (0.1766 mmol) ofamino-benzo-15-crown-5-ether with 1.1 equivalents ofn-octyl-isocyanate (0.195 mmol, 30 mg, 36.8 μL) in 2 mLacetonitrile, under nitrogen atmosphere. The resulting mixturewas cooled for 24 h at -20 °C and then filtered under thevacuum to collect the precipitate, yield: 80%.ESI-MS: m/z (%): [M+Na]+ = 461.61. 1H-NMR: ((CD3)2S=O,ppm) δ = 0.86 (t, 3H, CH3), 1.26 (m, 10H, CH2), 1.40 (m, 2H,CH2), 3.05 (m, 2H, CH2), 3.60 (m, 8H, -O-CH2-CH2 -Ocrownether), 3.74 (m, 4H, -O-CH2-CH2-O- crown ether), 3.97(m, 4H, -O-CH2-CH2-O- crown ether), 6.00 (t, 1H, NHAlkyl),6.79 (m, 2H, H-Ar), 7.13 (d, 1H, H-Ar), 8.18 (s, 1H,NH -Ar).
In chloroform Reflux;
  • 44
  • [ 60835-71-4 ]
  • [ 745783-87-3 ]
  • C23H38N2O6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
82% In acetonitrile for 24h; Inert atmosphere; Reflux; Synthesis of alkyl-ureido-benzo-15-crown-5-ethers General procedure: n-Octyl-benzoureido-15-crown-5-ether (15C5n8) wasprepared by refluxing for 24 h 50 mg (0.1766 mmol) ofamino-benzo-15-crown-5-ether with 1.1 equivalents ofn-octyl-isocyanate (0.195 mmol, 30 mg, 36.8 μL) in 2 mLacetonitrile, under nitrogen atmosphere. The resulting mixturewas cooled for 24 h at -20 °C and then filtered under thevacuum to collect the precipitate
  • 45
  • [ 60835-71-4 ]
  • [ 745783-86-2 ]
  • C23H38N2O6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% In acetonitrile for 24h; Inert atmosphere; Reflux; Synthesis of alkyl-ureido-benzo-15-crown-5-ethers General procedure: n-Octyl-benzoureido-15-crown-5-ether (15C5n8) wasprepared by refluxing for 24 h 50 mg (0.1766 mmol) ofamino-benzo-15-crown-5-ether with 1.1 equivalents ofn-octyl-isocyanate (0.195 mmol, 30 mg, 36.8 μL) in 2 mLacetonitrile, under nitrogen atmosphere. The resulting mixturewas cooled for 24 h at -20 °C and then filtered under thevacuum to collect the precipitate
  • 46
  • [ 60835-71-4 ]
  • 2,3,4-trichloro-1-phenoxy-9,10-anthraquionone [ No CAS ]
  • 4'-(1-hydroxy-2,3,4-trichloro-9,10-anthraquinone-9-imino)benzo-15-crown-5-ether [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% In toluene Irradiation; Photochemical synthesis of compounds 4- (general procedure). General procedure: The solution of corresponding derivative 2- (0.5 mmol)and 4-aminobenzo-15-crown-5-ether (0.6 mmol) in 150 mL of toluene was exposed to sunshine for 5-6 h. Control over the course of the reaction was carried out by TLC. The photolysate was evaporated to 10-15 mL and chromatographed ona column with SiO2 (eluent was benzene). During gradient elution with increasing polarity of the eluent (addition ofethyl alcohol), the main fraction of red-brown color containing target product was isolated. The fraction was evaporated to 5-10 mL and hexane was added. The precipitated crystals were fi ltered off , washed with hexane, and dried at room temperature. The product was recrystallized from ethanol-benzene.4-(1-Hydroxy-2,3,4-trichloro-9,10-anthraquinone-9-imino)benzo-15-crown-5-ether (4). Yield 0.22 g (74%), m.p.170-171 . IR, /cm1: 3078, 3042 (=C-H); 2949, 2915, 2857(C-H); 1672 (C=O); 1618 (C=N); 1592 (C=Cr); 957 (C-Cl).1H NMR (CDCl3), : 16.63 (s, 1 H, OH); 8.12 (m, 1 H, H(5));7.53 (m, 1 H, (6)); 7.45 (m, 1 , (8)); 7.29 (m, 1 H, (7));6.87 (m, 1 H, (6)); 6.62 (d, 1 H, (5), J = 8.5 Hz); 6.0(m, 1 H, (2)); 4.16-3.72 (m, 16 , -2-). Found (%):C, 56.25; H, 3.96; Cl, 17.82; N, 2.16. C28H24Cl3NO7. Calculated(%): C, 56.71; H, 4.05; Cl, 17.97; N, 2.36.
  • 47
  • [ 60835-71-4 ]
  • [ 68256-54-2 ]
  • 4'-(2-amino-1-hydroxy-9,10-anthraquionone-9-imino)benzo-15-crown-5-ether [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% In toluene Irradiation; Photochemical synthesis of compounds 4- (general procedure). General procedure: The solution of corresponding derivative 2- (0.5 mmol)and 4-aminobenzo-15-crown-5-ether (0.6 mmol) in 150 mL of toluene was exposed to sunshine for 5-6 h. Control over the course of the reaction was carried out by TLC. The photolysate was evaporated to 10-15 mL and chromatographed ona column with SiO2 (eluent was benzene). During gradient elution with increasing polarity of the eluent (addition ofethyl alcohol), the main fraction of red-brown color containing target product was isolated. The fraction was evaporated to 5-10 mL and hexane was added. The precipitated crystals were fi ltered off , washed with hexane, and dried at room temperature. The product was recrystallized from ethanol-benzene.
  • 48
  • [ 1121-60-4 ]
  • [ 60835-71-4 ]
  • C20H24N2O5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With acetic acid In ethanol at 25℃; for 12h; Imine synthesis sample procedure. General procedure: The aniline (10 mmol) was combined with the aldehyde (10 mmol) in 20 mL of absolute ethanol. To this solution was added glacial acetic acid (ca. 0.1 mL) and the mixture is stirred at room temperature for 12 h. The solvent was then removed and the crude product was dried under high vacuum for overnight to give pure imine product with quantitative yield.
  • 49
  • [ 500-22-1 ]
  • [ 60835-71-4 ]
  • 4'-(pyridin-3-ylmethylenamino)benzo-15-crown-5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% In ethanol at 40℃; for 3h; Synthesis of the Schiff’s bases General procedure: 0.012 mol of the corresponding aldehyde 5 or 4 was added dropwise to a solution of 0.01 mol of aniline 3 or crown ether 1 or2 in 10 mL of ethanol. The obtained mixture was keptat 40° for 3 h and then evaporated off. The precipitate was filtered off and dried in air at room temperature
  • 50
  • [ 60835-71-4 ]
  • [ 103-72-0 ]
  • C21H26N2O5S [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% In dichloromethane for 2h; Inert atmosphere; General synthesis General procedure: 4′-Aminobenzo-15-crown-5 (5 mmol) was dissolvedin dry dichloromethane (50 ml) and the appropriateisocyanate or isothiocyanate (5 mmol) dissolved indry dichloromethane (10 ml) was added with vigorousstirring under N2. The reaction mixture wasstirred for a further 2 h to ensure complete formationof the corresponding urea or thiourea derivativebefore the solvent was removed under vacuum.The products were recrystallised from acetonitrile,isolated by filtration and air dried.
  • 51
  • [ 60835-71-4 ]
  • [ 100-28-7 ]
  • C21H25N3O8 [ No CAS ]
YieldReaction ConditionsOperation in experiment
98% In dichloromethane for 2h; Inert atmosphere; General synthesis General procedure: 4′-Aminobenzo-15-crown-5 (5 mmol) was dissolvedin dry dichloromethane (50 ml) and the appropriateisocyanate or isothiocyanate (5 mmol) dissolved indry dichloromethane (10 ml) was added with vigorousstirring under N2. The reaction mixture wasstirred for a further 2 h to ensure complete formationof the corresponding urea or thiourea derivativebefore the solvent was removed under vacuum.The products were recrystallised from acetonitrile,isolated by filtration and air dried.
  • 52
  • [ 60835-71-4 ]
  • [ 2131-61-5 ]
  • C21H25N3O7S [ No CAS ]
YieldReaction ConditionsOperation in experiment
88% In dichloromethane for 2h; Inert atmosphere; General synthesis General procedure: 4′-Aminobenzo-15-crown-5 (5 mmol) was dissolvedin dry dichloromethane (50 ml) and the appropriateisocyanate or isothiocyanate (5 mmol) dissolved indry dichloromethane (10 ml) was added with vigorousstirring under N2. The reaction mixture wasstirred for a further 2 h to ensure complete formationof the corresponding urea or thiourea derivativebefore the solvent was removed under vacuum.The products were recrystallised from acetonitrile,isolated by filtration and air dried.
  • 53
  • [ 60835-71-4 ]
  • [ 471-25-0 ]
  • N-(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecyn-15-yl)prop-2-ynamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
62% Stage #1: 4'-aminobenzo-15-crown-5-ether; Propiolic acid In dichloromethane at 0℃; for 0.5h; Stage #2: With dicyclohexyl-carbodiimide In dichloromethane at 20℃; for 4h; N-(2,3,5,6,8,9,11,12-Octahydro-1,4,7,10,13-benzopentaoxacyclopentadecyn-15-yl)prop-2-ynamide (3) Propiolic acid, 350 mg (5 mmol), was added to a solution of 1.41g (5 mmol) of 4-aminobenzo-15-crown-5 in 10 mL of CH2Cl2. After slow agitation at 0°C for 30 min, 1.28 g of DCC (6.25 mmol) in CH2Cl2 (10 mL) was added. The mixture was stirred at room temperature for 4 h and then cooled in ice water, filtered through celite, and washed with 20 mL of 1M HCl, 20 mL of saturated aqueous NaHCO3, and 20 mL of water. After drying over MgSO4 and evaporation of the solvent under vacuum, alkyne 3 was purified by column chromatography in heptane-EtOAc, 13 : 7. Yield 1.03 g (62%), beige solid, mp 146°C. IR spectrum, ν, cm-1: 3375 (NH), 3186 (CH), 2895-2857 (CH2), 2093 (CC), 1650 (C=O). 1H NMR spectrum (CDCl3), δ, ppm: 2.99 s (1H, CCH), 3.73 s (8H, 4CH2), 3.86-3.87 m (4H, 2CH2), 4.07 m (4H, 2CH2), 6.72 d (1H), 7.01 d.d (1H), 7.29 d (1H), 8.67 s (1H, NH). 13C NMR spectrum (CDCl3), δ, ppm: 68.75, 69.31, 69.50, 70.35, 70.39, 70.84, 74.46, 77.78, 107.19, 112.96, 114.36, 131.46, 146.16, 149.05, 149.95. Found, %: C 60.821; H 6.290; N 4.170; O 28.113. C17H21NO6. Calculated, %: C 60.886; H 6.311; N 4.177; O 28.625. Mass spectrum: m/z 358 [M + Na]+.
  • 54
  • [ 60835-71-4 ]
  • [ 35661-40-6 ]
  • C38H40N2O8 [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In dichloromethane; N,N-dimethyl-formamide at 20℃; for 18h;
  • 55
  • [ 60835-71-4 ]
  • [ 4053-08-1 ]
  • 6-chloro-2-(2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,7,10,13]pentaoxacyclopentadecin-15-yl)-1H-benzo[de]isoquinoline-1,3(2H)-dione [ No CAS ]
YieldReaction ConditionsOperation in experiment
62% In 2-methoxy-ethanol at 110℃; for 20h;
  • 56
  • [ 41507-35-1 ]
  • [ 60835-71-4 ]
  • 4'-(N-3-thiophenecarboxamido)benzo-15-crown-5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
64% With triethylamine In dichloromethane at 23℃; for 12h; 2.1. Synthesis 4 -( N -3-thiophenecarboxamido)benzo-15-crown-5 (TH3CA4AB15C5) ( Fig. 1 A), used as a monomer for electro- chemical polymerization, was synthesized at the Department of Organic Chemistry, UCT Prague via the following procedure: Dichloromethane (5 mL) and triethylamine (0.28 mL, 2.0 mmol) were added to a mixture of thiophene-3-carbonyl chloride (176 mg, 1.20 mmol) and 4 -aminobenzo-15-crown-5 ( 283 mg, 1.0 mmol). The resultant mixture was stirred at 23 °C for 12 h. Then the reaction mixture was diluted with dichloromethane (50 mL) and the organic layer was washed with Milli-Q water (2 ×30 mL). The organic layer was dried over MgSO 4 , the solvent was removed under reduced pressure, and column chromatography (silica gel, CHCl 3 /MeOH 9:1, R f 0.15)gave250 mg(64%)oftheamide1 as a white solid, mp = 160.9 -163.9 °C. 1 H NMR ( 400 MHz, CDCl 3 ) δ 8.16 (br s, 1H), 7.97 -7.96 (m, 1H), 7.48 -7.46 (m, 1H), 7.38 (s, 1H), 7.32 -7.30 (m, 1H), 6.98 -6.95 (m, 1H), 6.77 -6.75 (m, 1H), 4.09 -4.03 (m, 4H), 3.88 -3.81 (m, 4H), 3.74 -3.72 (m, 8H). 13 C NMR ( 101 MHz, CDCl 3 ) δ 161.3, 149.3, 145.9, 137.7, 132.0, 128.7, 126.7, 126.3, 114.7, 113.0, 107.5, 77.1, 71.0, 71.0, 70.6, 70.4, 69.7, 69.6, 69.4, 68.7. HRMS (APCI) m/z : [ M + H ] + calcd for C 19 H 23 NO 6 S, 394.1319; found, 394.1323. The data on structure confirmation of newly synthesized compound are in “Supplementary materials ”.
  • 57
  • 2-chloromethyl-2,3-dihydrothieno[3,4-b][1,4]dioxine [ No CAS ]
  • [ 60835-71-4 ]
  • C21H27NO7S [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With anhydrous sodium carbonate In acetonitrile at 70℃; for 48h; Inert atmosphere; 1 In a 100 mL three-necked flask, under an inert atmosphere, chloro-methyl-EDOT (0.3436 g; 1.71 mmol; 1 eq.), 4′-aminobenzo-15-crown-5 (0.5 g; 1.71 mmol; 1 eq.) and sodium carbonate (0.561 g; 5.29 mmol; 3 eq.) have been successively added. The whole has been dissolved in dry acetonitrile (40 mL) using a magnetic stirrer and heated under reflux (70° C.) for 48 h under an inert atmosphere. After return to room temperature, the solvent has been evaporated under vacuum and the obtained raw product has been dissolved in 30 mL of dichloromethane. Its purification has been carried out by liquid-liquid extraction with water (3×10 mL). Afterwards, the organic phase has been dried with magnesium sulfate. After filtration and evaporation of the solvent and drying under vacuum at 45° C. for 24 hours, the pure monomer 6 has been obtained in the form of a brown viscous oil (0.703 g, Rdt=90%). 1H-RMN (400 MHz; CDCl3; 298K): ppm 6.71 (d, 1H); 6.35 (m, 2H); 6.27 (d, 1H); 6.20 (dd, 1H); 4.48 (s, 16H); 4.35 (m, 1H); 4.28-4.12 (m, 2H); 4.05 (m, 4H); 3.87 (m, 4H); 3.74 (s, 8H); 3.71-3.63 (m, 2H). 13C-NMR (75 MHz; CDCl3; 298K): δ/ppm: 150.7; 142.10; 141.34; 141.24; 140.79; 117.49; 107.49; 102.79; 100.24; 72.95; 70.92-68.73; 65.68; 41.45.
  • 58
  • [ 60835-71-4 ]
  • [ 2633-67-2 ]
  • C22H27NO7S [ No CAS ]
YieldReaction ConditionsOperation in experiment
54% Stage #1: 2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,7,10,13]pentaoxacyclopentadecin-15-amine With triethylamine In acetonitrile for 1h; Stage #2: 4-vinylbenzenesulfonyl chloride In acetonitrile at 0 - 20℃; for 16h; 1.2 Step 2-Synthesis of 4-vinylbenzyl(sulfonyl)-4′-(benzo-15-crown-5)-ylamine (Sph15cr5SI) In a three-necked flask, dried and flamed beforehand, anhydrous acetonitrile (V=50 mL), triethylamine (4.29 g; 30.2 mmol; 3 eq.) and 4′-aminobenzo-15-crown-5 (3.00 g; 10.1 mmol; 1 eq.) have been added. This mixture has been stirred for one hour. Meanwhile, the 4-styrene sulfonyl chloride solution (of step 1) has been cooled down to 0° C. Afterwards, the 4′-aminobenzo-15-crown-5 solution has been added under vacuum to the latter. After the addition, the reactive mixture has been stirred at room temperature for 16 hours. The solvent of the reactive medium has been evaporated under reduced pressure and the obtained residue has been solubilised in dichloromethane, and then successive extractions with potassium carbonate have been carried out followed by washing with a 1M solution of hydrochloric acid. Finally, the organic solvent has been evaporated and the obtained residue dried under vacuum for 16 h at 45° C. The product has been obtained in the form of a brown-coloured viscous solid (yield (Rdt)=54%). 1H-NMR (400 MHz; CDCl3; 298K): ppm 7.73 (d, 2H); 7.57 (d, 2H); 6.79 (q, 1H); 6.71 (d, 1H); 6.29 (s, 1H); 6.21 (d, 1H); 5.95 (d, 1H); 5.38 (d, 1H); 3.85 (m, 4H); 3.74 (dt, 4H); 3.67-3.63 (m, 8H); 13C-NMR (75 MHz; DMSO-d6; 298K): ppm 144.21; 139.55; 135.57; 126.43; 125.87; 126.36-122.06-117.77-113.47 (q CF3); 116.55; FTIR (ATR cm-1): =1400, 1329, 1281, 1195, 1172, 1159, 1140, 1090, 1058, 844, 776, 735, 655; m/z (ESI-HRMS) 313.9779 ([M-] C9H7F3NO4S2 corresponds to 313.9769).
  • 59
  • [ 540-80-7 ]
  • [ 60835-71-4 ]
  • [ 76427-67-3 ]
  • C28H37N2O11(1-)*Cs(1+) [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: tert.-butylnitrite; 2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,7,10,13]pentaoxacyclopentadecin-15-amine With hydrogenchloride In methanol; water monomer at -10 - 10℃; for 0.5h; Stage #2: 4′-hydroxybenzo-15-crown-5 With Cs2CO3 In methanol; water monomer at 0℃; for 1h; 1 Synthesis of bisazocrownether cesium salt Solution A: concentrated aqueous HC1 (4.1 mL, 45 mmol) was added dropwise to a stirred solution of amino benz-15-crown-5- ether from Example 2 (2.3g, 8.1 mmol) in methanol (80 mL) at 10 °C. Then tert-butyl nitrite (2.2 mL, 18.4 mmol) was added dropwise to the mixture at -10 °C. The reaction mixture was stirred at -10 °C for 30 min. (0338) Solution B: in another reactor phenol from Preparation 7 (3g, 10.6 mmol) was added to a stirred solution of cesium carbonate (18.4g, 56.5 mmol) in water (92 mL) and the mixture was stirred at RT for 20 min. (0339) Solution A was added dropwise to a stirred solution B at 0 °C. The reaction mixture was stirred at 0 °C for Ih causing precipitation of an orange solid of the cesium salt that was involved in the next reaction step without further purification .
  • 60
  • [ 60835-71-4 ]
  • [ 96840-72-1 ]
YieldReaction ConditionsOperation in experiment
29% With potassium permanganate In dichloromethane at 20℃; 9 Synthesis of bisazocrownether by oxidation KMnCh (1.23g) was added to a solution of commercially available aminobenzocrown ether (350 mg) in DCM 20 ml at RT and stirred overnight. The precipitate was filtered off, the solution was evaporated and treated with ether, the product was filtered. Yield of 15 - 200 mg (29%) MW = 562 (LCMS) . NMR (CDC13) , 5 7.54 (dd, 1H, J = 8.4 Hz, J = 2.4 Hz) , 7.48 (s, 1H, ) , 6.95 (d, 1H, J = 8.4 Hz) , 4.23 (t, 4H) , 3.94 (t, 4H) , 3.78 (m, 8H) ppm.
Same Skeleton Products
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