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CAS No. : | 80262-44-8 | MDL No. : | MFCD05664716 |
Formula : | C36H36N24O12 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MSBXTPRURXJCPF-UHFFFAOYSA-N |
M.W : | 996.82 | Pubchem ID : | 196163 |
Synonyms : |
|
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: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 42 %Spectr. | With methanesulfonic acid In neat (no solvent) at 80 - 100℃; for 18 h; | Synthesis of cucurbit[n]urils in methanesulphonic acid using Diethoxymethane(Ethylal)Unsubstituted glycoluril (19.94 g) and methane sulphonic acid (neat, 82 mL) were placed in a reaction flask and heated to 80 °C. Ethylal (35.21 mL) was added in drop-wise and the reaction mixture was then heated to 100 °C (internal temp) for 18 hours. The reaction mixture was cooled and added to acetone (410 ml) to produce a brown powder which was analysed by1H NMR.Approximate Yields b1H NMR (percent of recovered product) cucurbii[5]urii 8percent, cucurbit[6]uri 42percent, cucurbit[7]uril 43percent, cucurbit[8]uril 7percent, cucurbit[9]uril 0percent, cucurbit[10]uril 0percent, cucurbit[ 13uril 0percent.Residual formaldehyde by HPLC method was 34 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 44 %Spectr. | With hydrogenchloride In water at 90 - 100℃; for 18 h; | Synthesis of cucurbit[n]urils in hydrochloric acid using paraformaldehyde Unsubstituted glycoluril (20 g) and hydrochloric acid (37 percent w/v, 30 mL) were placed in a reaction flask and heated to 90°C. Paraformaldehyde (8.87 g) was added in portion-wise and the reaction mixture was then heated to 100 °C (internal) for 18 hours. The reaction mixture was cooled and added to methanol (150 mL) to produce a beige powder which was analysed by1H NMR.Approximate Yields by1H NMR (percent of recovered product) cucurbit[5]uril 8percent, cucurbit[6]uril 44percent, cucurbit[7]uril 28percent, cucurbit[8]uril 18percent, cucurbit[9]uril 0percent, cucurbit[10]uril 0percent cucurbit[11]uril 0percent.Residual formaldehyde by HPLC method was 682 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 58 %Spectr. | at 80 - 100℃; for 18 h; | Synthesis of cucurbit[n]urils in methanesulphonic acid usingTetramethoxymethylglycoluril (TMMG)Unsubstituted glycoluril (19.94 g) and methane sulphonic acid (neat, 82 ml_) were placed in a reaction flask and heated to 80 °C. TMMG (44.66 g) was added in drop-wise and the reaction mixture was then heated to 100 °C (internal temp) for 18 hours. The reaction mixture was cooled and added to methanol (410 ml) to produce a beige powder which was analysed by1H NMR. Approximate Yields b1H NMR (percent of recovered product) cucurbit[5]uri 5percent, cucurbit[6]uri 58percent, cucurbit[7]uril 28percent, cucurbit[8]uril 9percent, cucurbit[9]uril 0percent, cucurbit[10]uril 0percent, cucurbit[11]uril 0percent |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | In water at 20℃; for 3h; | |
In water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | In water at 20℃; for 3h; | |
In water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid; In water; at 75 - 100℃; for 24h; | After melting glycouryl (5.7 g, 40mmol) in 20 ml_ of sulfuric acid (9M), an aqueou s formaldehyde solution (7.0 mL, 91 mmol) was added. The resultant reaction mixture was stirred at 75 0C for 24 hours. The temperature was raised to 95-1000C, and the r eaction was further performed. 200 mL of water was quickly poured into the reaction mixture, and 1L of acetone was further added to obtain a precipitate. The precipitate was filtered under reduced pressure and washed with a 1 :4 mixed solution of water and acetone. The solid filtrate was dissolved in 200 mL of a 1 :1 mixed solution of water a nd acetone and filtered under reduced pressure to remove a precipitate (cucurbit[6]uril). 800 mL of acetone was added to the filtrate to precipitate a mixture of cucurbit[7 ]uril and cucurbit[5]uril. The precipitated mixture of cucurbit[7]uril and cucurbit[5]uril wa s dissolved in 40 mL of water, and 25 mL of methanol was added to precipitate only cue urbit[7]uril. The precipitated cucurbit[7]uril was filtered under reduced pressure and dri ed in a vacuum. The results of an analysis are as follows.1H NMR (500 MHz, D2O): delta = 5.56 (d, 14H), 5.35 (s, 14H), 4.11 (d, 14H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 12% 2: 46% 3: 24% 4: 8% | With hydrogenchloride at 100℃; for 18h; Further byproducts.; | |
1: 35 % Spectr. 2: 52 % Spectr. 3: 9 % Spectr. 4: 4 % Spectr. | With hydrogenchloride at 100℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | In water at 20℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45% | With dipotassium peroxodisulfate at 85℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With sulfuric acid; at 20 - 75℃; | To a mixture of <strong>[496-46-8]glycoluril</strong> 5 g (35 mmol) and paraformaldehyde2.11 g (70 mmol) was slowly added 25 mL of concentrated H2SO4(9 M) under constant stirring at room temperature. The solidsdissolve and the reaction mass becomes pale yellow colored homogenoussolution within 5-10 min. Further, on constant stirringat room temperature, the reaction mass suddenly sets into unstirrableviscous white colored gel. Next, the reaction mass was heatedat 75 C for 18 h. As the heating ensures the viscous gel dissolvesand the reaction mass again becomes homogenous solution. After18 h the reaction mass was cooled down to room temperature andto it was added 500mL of water when a white solid precipitate ofCB[n]s mixture falls out. The mixture consists of major amount ofCB[6]. The solution was filtered and washed with copious amountof water. Next, the solid was stirred in hot water at 90-95 C and hot filtered to remove water-soluble analogues CB[5] and CB[7]present if any. The process was repeated thrice to yield 4.8 g of pureCB[6] in 60% yield.CB[6] 1H NMR (850 MHz, D2O): delta 5.71 (d, 1H), 5.61 (s, 2H), 4.33(d, 1H). MALDI-MS (m/z): calcd. for [CB[6]Na±]: 1019.2842, found:1019.062. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With sulfuric acid at 160℃; for 36h; Dean-Stark; | |
50% | With sulfuric acid In water at 70 - 75℃; for 24.5h; | |
50% | With hydrogenchloride; sulfuric acid In water at 70 - 80℃; |
50% | With hydrogenchloride; sulfuric acid In water at 80 - 115℃; | |
0.103 g | With [1-(3-sulfonic acid)]propyl-3-methylimidazolium hydrogen sulfate In water at 160℃; for 0.5h; Microwave irradiation; | 15 Example 15 Glycoluril (0.214 g),Paraformaldehyde (0.095 g),L-methyl-3- (3-sulfo) propylimidazole bisulfate ([C3SO3Hmim] HS04) ionic liquid (1000g)And water (2.000 g) were mixed and the microwave (800 W) was heated to 160 ° C for 30 min. The reaction solution was allowed to stand for 1-2 days, cucurbit[6]uril product crystallization (0.103g),The ionic liquid can be recycled. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
30% | With sulfuric acid; at 90℃; for 24h; | EXAMPLE 2; AFFINITYPURIFICATION OFDIMETHYLCYCLOPENTANO-CB; Dimethylcyclopentano-CB (Figure 4, Compound 3) was synthesized according to the procedures described by Day et al. (J. Org. Chem. 2001, 66, 8094) and Isobe et al. (ORG. Lett. 2002, 4, 1287), by heating at 90 C for 24 hours, a 5 : 1 mixture of <strong>[496-46-8]glycoluril</strong> (Compound 2) and dimethylcyclopentano-<strong>[496-46-8]glycoluril</strong> (Figure 4, Compound 3), and formaldehyde in the presence of concentrated sulfuric acid (Figure 4), so as to give the desired cucurbituril product in 30 % yield. The water-soluble fraction (740 mg) of the crude, heterogeneous mixture (1.3 gram) was dissolved in neutral water (50 ml) and passed through a column loaded with the protonated aminated resin prepared as described above, at a flow rate of 0.5 ml/minute (of the heterogeneous mixture in water). The column was then washed sequentially with water, methanol, CH2C12, and again with methanol. Removal of the solvent from the combined eluent afforded a solid residue (510 mg). This residue was used for collecting a second harvest of CB [6] using the same column, as is detailed hereinbelow. A sample of the resin was dried under reduce pressure overnight and was analyzed by FTIR. The obtained spectrum, presented in Figure 13, indicated that the resin is indeed loaded with the CB [6]. The resin-bound CB [6] was released from the column by elution with a 1: 2 mixture of TRIETHYLAMINE-DMF (100 ml) at a flow rate of 2 ml/minute. The column was thereafter washed with water (200 ml), and the combined eluent was concentrated under reduced pressure. Methanol was then added and the precipitate was collected and dried. The resultant white powder (195 mg) was analyzed BY H NMR and ESI- MS and the analyses are presented in Figures 14 and 15, respectively. As is shown in Figures 14 and 15, the resin-bound CB [6], obtained as a powder upon elution from the column, contained mainly a mixture of Compound 4 (Figure 4) and Compound 1 (Figure 2), with a small amount of di (dimethylcyclopentano) -CB [6]. Regeneration of the column was performed by washing it with 10 % (v/v) trifluoroacetic acid in CH2C12. The regenerated column was used again to harvest additional amounts of CB [6] from the CB-depleted remnants obtained in the first harvest (510 mg). That residue was dissolved in neutral water and loaded on the column as described above. Unloading the column with triethylamine-DMF yielded a second crop of pure CB [6] (165 mg). The performance of the column over multiple cycles of affinity chromatography was evaluated by loading and unloading a sample of purified CB [6] (150 mg) four times. The sample was trapped and released quantitatively in all eight operations with no apparent loss of the column capacity. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45%; 15%; 20%; 15% | With sulfuric acid; In water; for 0.0125h;Microwave irradiation; | Example 2: Synthesis of cucurbituril homologues; [27] 3 g of paraformaldehyde was added to 5.68g of <strong>[496-46-8]glycoluril</strong>s of formula 9 and 20 mL of a 9M sulfuric acid was added thereto. Then, a 800W microwave was irradiated to the reaction mixture for 45 seconds. [28] The reaction solution was recrystallized with acetone and methanol to thereby synthesize and separate four cucurbituril homologues, CB[5], CB[6], CB[7], and CB[8 ], as represented by formula 1 where X is 0, Rand R are H, and n is 5,6, 7, and 8, respectively. The yields of CB[5], CB[6], CB[7], and CB[8] were 15%, 45%, 20%, and 15%, respectively. [29] CB [5]:¹ H (500 MHz, D 2O/CF CO DID SO 4 (1:1:0.15)): No. 4.43 (d, J = 15.5 Hz, 10H), 5.65 (s, 10H), 5.85 (d, J =15.5 Hz, lOH). [30] CB [6]:¹ H (500 MHz, D 2 O/CF 3CO2 DID 2 SO 4 (1: 1:0.15)): No. 4.35 (d, J = 15.5 Hz, 12H), 5.61 (s, 12H), 5.69 (d, J =15.5 Hz, 12H). [31] CB [7]:¹ H (500 MHz, D 2 O/CF 3CO2 DID 2 SO 4 (1: 1:0.15)): No. 4.29 (d, J = 15.5 Hz, 14H), 5.60 (s, 14H), 5.91 (d, J =15.5 Hz, 14H). [32] CB [8]:¹ H (500 MHz, D 2 O/CF 3CO2 DID 2 SO 4 (1: 1:0.15)): No. 4.28 (d, J = 15.5 Hz, 16H), 5.60 (s, 16H), 5.93 (d, J =15.5 Hz, 16H). |
With sulfuric acid; In water; at 100℃; for 14h; | A mixture of cucurbiturils was prepared by preparing a solution of <strong>[496-46-8]glycoluril</strong> (111 g, 0.781 moles) in water (123 ml, 6.833 moles) under stirring. Sulphuric acid (125 mL, 2.34 moles) and formalin (116 mL, 1.56 moles) were added to the solution of <strong>[496-46-8]glycoluril</strong> and the mixture heated to 100C and held under stirring for 14 hours. The reaction mixture was then cooled to room temperature over a 3 hour time period and the cooled reaction mixture precipitated into methanol (1000 ml). The precipitate was filtered, slurried with methanol (1000 ml), filtered again and dried. (0047) The mixture was determined using nuclear magnetic resonance (1H NMR) imaging to be 20- 25 percent by weight CB[5], 45-55 percent by weight CB[6], 20-25 percent by weight of CB[7], 5-8 percent by weight of CB[8], and less than 1 percent by weight CB[9] and higher cucurbiturils, based on the total weight of cucurbituril in the mixture |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 41 %Spectr. 2: 30 %Spectr. 3: 26 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 42 %Spectr. 2: 42 %Spectr. 3: 11 %Spectr. 4: 5 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 48 %Spectr. 2: 36 %Spectr. 3: 13 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 75 %Spectr. 2: 17 %Spectr. 3: 8 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 43 %Spectr. 2: 33 %Spectr. 3: 20 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 53 %Spectr. 2: 17 %Spectr. 3: 10 %Spectr. 4: 7 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 41 %Spectr. 2: 35 %Spectr. 3: 24 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 68 %Spectr. 2: 17 %Spectr. 3: 12 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 52 %Spectr. 2: 31 %Spectr. 3: 14 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 57 %Spectr. 2: 21 %Spectr. 3: 15 %Spectr. 4: 7 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 40 %Spectr. 2: 33 %Spectr. 3: 22 %Spectr. 4: 5 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 44 %Spectr. 2: 35 %Spectr. 3: 18 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 84 %Spectr. 2: 10 %Spectr. 3: 6 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 67 %Spectr. 2: 27 %Spectr. 3: 6 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 90 %Spectr. 2: 7 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 53 %Spectr. 2: 30 %Spectr. 3: 15 %Spectr. | With hydrogen chloride In water-d2 at 50℃; for 18h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | In water-d2 at 90℃; for 2h; phosphate buffer; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With cucurbituril In water-d2 at 90℃; for 2h; phosphate buffer; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | In water-d2 at 25℃; phosphate buffer; |
Yield | Reaction Conditions | Operation in experiment |
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14%; 43% | With hydrogenchloride; In water; at 95℃; for 24h; | 3a-Methyl<strong>[496-46-8]glycoluril</strong> 1 (0.26 g, 1.67 mmol), <strong>[496-46-8]glycoluril</strong> 2 (1.42 g, 10 mmol) and paraformaldehyde (0.9 g, 30 mmol) were added to concentrated hydrochloric acid (5 ml), and the resultant mixture was heated at 95 C for 24 h. After evaporation of the solvent, the residue was added to water (300 ml) and heated under stirring. The white solid was filtered, and then added to a mixed solvent (30 ml) consisting of formic acid and acetic acid in a ratio of 2:1 (v/v). After thorough stirring, the insoluble material (CB[6]) was removed by filtration, and acetone was added to the acidic filtrate. The precipitates generated therein were collected to afford the desired product 4 in a yield of 14%. TOF mass: m/z 1033 (M+Na+). 1H NMR (500 MHz, in D2O with Na2SO4): delta 5.66 (d, Jin,out = 15.8 Hz, 11H, methylene Hout), 5.59 (d, Jin,out = 16 Hz, 1H, methylene Hout), 5.55 (s, 10H, methine H), 5.29 (s, 1H, methine H), 4.35 (d, Jin,out = 16 Hz, 1H, methylene Hin), 4.28 (d, Jin,out = 15.8 Hz, 11H, methylene Hin) and 1.75 ppm (s, 3H, methyl H). 13C NMR (125 MHz, in D2O with Na2SO4): delta 157.7 (C'O), 157.2 (CO), 77.1 (CH), 74.8 (C-CH3), 71.0 (CH), 52.1 (CH2), 48.1 (CH2) and 20.2 ppm (CH3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With magnesium chloride nonahydrate; triethylamine In water at 20 - 110℃; for 17h; Sealed tube; | Preparation of [Mg(H2O)6](bdc)CB[6]·14H2O (1). 0.013 g of cucurbit[6]uril decahydrate (CB[6], C36H36N24O12··10H2O, 0.011 mmol), 0.022 g MgCl2·9H2O (0,085 mmol), 0.016 g terephthalic acid (H2bdc, 0.096 mmol), 3 mL H2O and50 mkL NEt3 were placed in a 7 mL glass vial with a cap. The vial was heated according to the following schedule: (1)heating from room temperature to 110 ° for 5 h; (2) maintenance at 110 ° for 12 h; (3) slow cooling to room temperatureover 36 h. The colorless crystals of 1 shaped as rombohedrals were isolated after cooling. The yield was 0.014 g (82% inrelation to CB[6]).For C44H78MgN24O35 (1 - H2O) calculated, %: C 34.6, H 5.1, N 22.0. Found, %: C 34.5, H 5.0, N 22.2.IR spectrum (ν, cm-1): 3596 s, 3474 s, 3010 s, 2934 s, 1737 s, 1630 s, 1570 s, 1476 s, 1416 s, 1379 s, 1327 s, 1297 s,1284 s, 1258 s, 1236 s, 1191 s, 1148 s, 1014 s, 965 s, 802 s, 760 s, 673 s, 629 s, 566 s, 511 s, 456 s. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
158.47 mg | Stage #1: N-(p-nitrophenyl)-1,8-diaminooctane hydrochloride; cucurbituril; per-6-amino-6-deoxy-β-cyclodextrin heptahydrochloride In methanol; water at 20℃; for 0.0666667h; Irradiation; Stage #2: In deuteromethanol; water at 80℃; for 0.166667h; Microwave irradiation; | Preparation of the 1-3 complex The solid sample was obtained as follows: 112.85mg of Am7βCD (81.6mmol), 48.78mg of CUC[6] (48.8mmol) and 12.16mg of 3 (40.3 mmol) were suspended in 1mL of a 1:1 v/v water methanol mixture. The suspension was first subjected to ultrasound irradiation (200 W) at room temperature for 4 min; the sample was subsequently irradiated in an MW apparatus at 80 °C for 10 min. Then, the systemwas cooled with a stream of N2 at 220 °C, 2mL of water were added and the product was filtered off. Yield 158.47 mg. Elem. Anal. for C134H228Cl15N41O70 (i.e. for a formally 1:1 stoichiometry complex) calcd C 39.59%, H 5.65%, Cl 13.08%, N 14.13%; found C 39.55%, H 5.69%, Cl 13.07%, N 14.09%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: C61H87N3O14 With trifluoroacetic acid In dichloromethane at 20℃; for 24h; Inert atmosphere; Schlenk technique; Stage #2: cucurbituril In water for 24h; Inert atmosphere; Schlenk technique; Reflux; Stage #3: With ammonium hexafluorophosphate In water | Synthesis of pseudo[2]rotaxane 5: To a solution of compound 3 (0.22 g, 0.2 mmol) in dry DCM (10 mL), trifluoroacetic acid (0.37 mL, 6.0 mmol) was added and the mixture was stirred for 4 h at room temperature under nitrogen atmosphere, and then the solvent was removed under a vacuum. Then to a solution of the residue in H2O, cucurbit[6]uril (0.24 g, 0.24 mmol) was added and the mixture was refluxed for 24 h under nitrogen atmosphere. After cooling, the mixture was filtered and the filtrate was treated with saturated NH4PF6 (6 mL, aq.) to yield a white precipitate. The solid was collected by filtration, washed with water and dried under vacuum to give the title compound 5 in a yield of 87%. The compound 5: 1H NMR (400 MHz, CD3CN): δ 7.64 (s, 2H), 7.44 (s, 3H), 7.38 (d, 4H, J=8.0 Hz), 7.01 (d, 4H, J=8.0Hz), 6.70 (s, 2H), 6.55 (s, 1H), 5.74 (d, 12H, J=16.0 Hz), 5.40 (s, 12H), 4.26 (m, 12H), 4.18 (s, 4H), 4.11 (s, 8H), 4.02 (s, 4H), 3.78 (s, 8H), 3.64 (s, 8H), 3.20-2.98 (m, 4H), 0.91-0.76 (m, 4H), 0.76-0.51 (m, 4H). The 13C NMR spectrum was not collected due to the poor solubility of pseudo[2]rotaxane 5; MALDI-MS m/z 1782.7 [M-PF6--2HPF6], calculated 2220.2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | at 20℃; | CdCl2·2.5H2O (28.0mg 0.12mmol) and C8H19N-HCl (20.0mg 0.12mmol) were dissolved in 4.0mL 3.0mol/L HCl, and 3.0mL of 3.0mol/L HCl containing Q[6] (21.0mg, 0.02mmol) was then added with stirring. The solution was allowed to stand to allow slow evaporation in air at room temperature. Colorless crystals were obtained from the solution within one week (41% yield based on Q[6]·10H2O). Anal. Calcd. for C52H114N26O30Cd2Cl8 (%): C 29.85, H 5.49, N 17.41; found: C 29.76, H 5.54, N 17.32. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | 0.35 g (0.3 mmol) of Cucumber ring (Q [6]), 0.2 g (1.2 mmol) of CsCl, 0.5 g of H3BTB0.044 g (0.1 mmol).The Q [6] and CsCl were placed in a 250 mL beaker containing 90 mL of distilled water, shaken for 10 min. To disperse the Q [6] particles uniformly, heated to 50 C and stirred with a magnetic stirrer to give a white turbid solution. The H3BTB was then placed in a 50 mL beaker containing 10 mL of distilled water, stirred with a magnetic stirrer, and poured into 1 mL of concentrated aqueous ammonia. After stirring for 10 min, it was poured into the cloudy solution of Q [6] and stirring was continued for 5 h.The stirred solution was then transferred to a high pressure autoclave,The program temperature to 180 C, constant temperature 20h,And then cooled to 50 C,Constant temperature 10h;Close the program temperature oven,The autoclave was cooled to room temperature,After standing for 24h,(BTB3 - Q [6] -Cs +), the structural formula is {Cs6 (H20) 6 (0 [6]), which is an aromatic organic multidentate ligand - cucurbit - ring porous framework polymer. ) 3.2 (8 8) 1112 O} in a yield of 50-60%. |
Yield | Reaction Conditions | Operation in experiment |
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for 240h; | General procedure: iQ[6] (20.0 mg, 0.02 mmol) and ZnCl2 (13.9 mg,0.10 mmol) were dissolved in 1.0 mL of 6 M of HCl to prepare solution (V1), the guest 1 (18.9 mg, 0.14 mmol) was dissolved in deionized water to prepare solution (V2), which was then added with stirring to solution V1. X-ray quality crystals (compound A) could be obtained from the solution after a period of 10 days. iQ[6] (20.0 mg,0.02 mmol) was dissolved in 1.0 mL 6 M of HCl to prepare solution (V3), Zn(NO3)2 (35.4 mg, 0.12 mmol) and guest 3 (19.8 mg, 0.17 mmol) were dissolved in 1.0 mL of water to prepare solution (V4), which was then added with stirring to solution V3. X-ray quality crystals (compound B) could be obtained from the solution after a period of 10 days. Crystal data and structure refinement details for compounds A and B were given in table S1. Anal. calcd.for compound iQ[6][ZnCl4]0.51H3O17H2O (A), C37H77N25O30ZnCl4 (%): C, 28.50; H, 4.98; N, 22.46, found:C, 28.44; H, 5.01; N, 22.51. Anal. calcd for compound {3iQ[6][ZnCl4]2[Zn(H3O)Cl3]-18H2O (B), C42H92N26O31Zn2Cl7 (%): 27.47; H, 5.05; N, 19.83, found: C,27.44; H, 5.09; N, 19.86. |
Yield | Reaction Conditions | Operation in experiment |
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92% | In water at 40℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
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82% | In water at 40℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
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86% | In water at 40℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In water-d2 at 24.84℃; | Spectral measurements of inclusion complex General procedure: The spectral changes of the aromatic amines in the presence of CB[6] were monitored with a Hitachi U-3210 spectrophotometer (Tokyo, Japan). The pH conditions for measurements were selected with the base NaOH to avoid the protonation of amines: pH 8.0 for PDA and TD, 10.5 for XDA, and 7.0 for BV. The reaction temperature was controlled at 298 ± 0.1 K by circulating thermostated water. The typical solution concentrations were [PDA] = 9.0 × 10-5 M (M = mol dm-3) and [CB[6]] = 0 to12.8 × 10-5 M.The 1H NMR spectra were measured in D2O with a VarianMercury 300 (300 MHz) at room temperature. Chemicalshifts were recorded as δ values relative to HOD (δ4.79) as an internal standard [15]. | |
In methanol; formic acid; water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In water-d2 at 24.84℃; | Spectral measurements of inclusion complex General procedure: The spectral changes of the aromatic amines in the presence of CB[6] were monitored with a Hitachi U-3210 spectrophotometer (Tokyo, Japan). The pH conditions for measurements were selected with the base NaOH to avoid the protonation of amines: pH 8.0 for PDA and TD, 10.5 for XDA, and 7.0 for BV. The reaction temperature was controlled at 298 ± 0.1 K by circulating thermostated water. The typical solution concentrations were [PDA] = 9.0 × 10-5 M (M = mol dm-3) and [CB[6]] = 0 to12.8 × 10-5 M.The 1H NMR spectra were measured in D2O with a VarianMercury 300 (300 MHz) at room temperature. Chemicalshifts were recorded as δ values relative to HOD (δ4.79) as an internal standard [15]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In water-d2 at 24.84℃; | Spectral measurements of inclusion complex General procedure: The spectral changes of the aromatic amines in the presence of CB[6] were monitored with a Hitachi U-3210 spectrophotometer (Tokyo, Japan). The pH conditions for measurements were selected with the base NaOH to avoid the protonation of amines: pH 8.0 for PDA and TD, 10.5 for XDA, and 7.0 for BV. The reaction temperature was controlled at 298 ± 0.1 K by circulating thermostated water. The typical solution concentrations were [PDA] = 9.0 × 10-5 M (M = mol dm-3) and [CB[6]] = 0 to12.8 × 10-5 M.The 1H NMR spectra were measured in D2O with a VarianMercury 300 (300 MHz) at room temperature. Chemicalshifts were recorded as δ values relative to HOD (δ4.79) as an internal standard [15]. | |
In methanol; formic acid; water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide; In water-d2; at 24.84℃;pH 7.0; | General procedure: The spectral changes of the aromatic amines in the presence of CB[6] were monitored with a Hitachi U-3210 spectrophotometer (Tokyo, Japan). The pH conditions for measurements were selected with the base NaOH to avoid the protonation of amines: pH 8.0 for PDA and TD, 10.5 for XDA, and 7.0 for BV. The reaction temperature was controlled at 298 ± 0.1 K by circulating thermostated water. The typical solution concentrations were [PDA] = 9.0 × 10-5 M (M = mol dm-3) and [CB[6]] = 0 to12.8 × 10-5 M.The 1H NMR spectra were measured in D2O with a VarianMercury 300 (300 MHz) at room temperature. Chemicalshifts were recorded as delta values relative to HOD (delta4.79) as an internal standard [15]. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With barium chloride; triethylamine In water at 20 - 95℃; for 53h; | 2.2.1 [Ba2(bdc)CB[6](H2O)6]bdc·12H2O (1) A mixture of cucurbit[6]uril, C36H36N24O12·10H2O (0.012g, 0.01mmol), BaCl2·6H2O (0.016g, 0.05mmol), H2bdc (0.010g, 0.06mmol) and NEt3 (50µL, 3.57×10-4mmol) in 3ml H2O were placed in a 7mL glass vial with a cap. The vial was heated according to the following schedule: (1) heating from room temperature to 95°C for 5h; (2) maintenance at 95°C for 12h; (3) slow cooling to room temperature over 36h. Colorless crystals of 1 and 2 shaped as rhombohedrals and sticks, respectively, were isolated after cooling. The yields were 0.018g for 1 (93%) and 0.001g for 2 (5%, based on CB[6]). For C52H80Ba2N24O38(+3H2O) calculated, %: C, 31.57; H, 4.38; N, 16.99. Found, %: C, 31.3; H, 4.3; N, 17.1. IR (KBr, cm-1): 449 (m), 491 (m), 634 (m), 678 (m), 756 (s), 802 (s), 889 (w), 964 (s), 1145 (s), 1190 (s), 1238 (s), 1328 (s), 1379 (s), 1464 (m), 1485 (s), 1575 (s), 1668 (m), 1724 (s), 174 5 (s), 2059 (vw), 2137 (vw), 2399 (vw), 2480 (vw), 2675 (w), 2854 (m), 2927 (m), 3460 (s), 3535 (s), 3784 (w), 3884 (w), 3975 (w). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
4.9 mg | With hydrogenchloride; aqueous cadmium chloride In water at 60℃; for 0.0833333h; | Preparation of complex Q[6][at]HV+ Q[6] (15.8 mg, 0.013 mmol) was added to a solutionof 1-hexyl-4-(4-pyridyl)pyridinium bromide (18.9 mg,0.059 mmol) and CdCl2·2.5H2O (11.9 mg, 0.05 mmol) in3 M HCl solution (3 mL). The resulting reaction mixturewas stirred for 5 min at 60 °C and then filtered. After slowevaporation of the volatiles from the filtrate in air over about3 weeks, rhombic colorless crystals of the complex Q[6]HV+ were obtained (4.9 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 65%Spectr.; Ca. 35%Spectr. | With methanesulfonic acid; In neat (no solvent); at 85℃; for 18h; | Synthesis of cucurbit[n]urils in methanesulphonic acid usingDimethoxymethane (methylal)Methanesulphonic acid (neat, 82 ml) was added to the reaction vessel. To this methylal (24.83 ml) was added to the reaction. Unsubstituted <strong>[496-46-8]glycoluril</strong> (19.94 g) was added immediately afterwards in one portion and the reaction mixture was heated to 85 C (internal) for 18 hours. The reaction mixture was added to methanol (250 ml) to produce a dark brown gummy paste which was analysed by1H NMR.Approximate Yields by1H NMR (% of recovered product) cue urbit[5]uril 0%, cucurbit[6]uril 65%, cucurbit[7]uril 35%, cucurbit[8]uril 0%, cucurbit[9]uril 0%, cucurbit[10]uril 0%, cucurbit[1 1]uril 0%.Residual formaldehyde by HPLC method was 24 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 42%Spectr.; Ca. 7%Spectr.; Ca. 8%Spectr.; Ca. 43%Spectr. | With methanesulfonic acid; In neat (no solvent); at 80 - 100℃; for 18h; | Synthesis of cucurbit[n]urils in methanesulphonic acid using Diethoxymethane(Ethylal)Unsubstituted <strong>[496-46-8]glycoluril</strong> (19.94 g) and methane sulphonic acid (neat, 82 mL) were placed in a reaction flask and heated to 80 C. Ethylal (35.21 mL) was added in drop-wise and the reaction mixture was then heated to 100 C (internal temp) for 18 hours. The reaction mixture was cooled and added to acetone (410 ml) to produce a brown powder which was analysed by1H NMR.Approximate Yields b1H NMR (% of recovered product) cucurbii[5]urii 8%, cucurbit[6]uri 42%, cucurbit[7]uril 43%, cucurbit[8]uril 7%, cucurbit[9]uril 0%, cucurbit[10]uril 0%, cucurbit[ 13uril 0%.Residual formaldehyde by HPLC method was 34 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 58%Spectr.; Ca. 42%Spectr. | With methanesulfonic acid; at 80 - 100℃; for 18h; | Synthesis of cucurbit[n]urils in methanesulphonic acid usingDipropoxymethane (Propylal)Unsubstituted <strong>[496-46-8]glycoluril</strong> (19.94 g) and methane sulphonic acid (neat, 82 mL) were placed in a reaction flask and heated to 80 C. Propylal (45 mL) was added in drop-wise and the reaction mixture was then heated to 100 C (internal temp) for 18 hours. The reaction mixture was cooled and added to acetone (410 ml) to produce a beige powder which was analysed by1H NMR. Approximate Yields by1H NMR (% of recovered product) cucurbit[5]urii 0%, cucurbit[8]uril 58%, cucurbit[7]uril 42%, cucurbit[8]uril 0%, cucurbit[9]uril 0%, cucurbit[10]uril 0%, cucurbit[11]urii 0%. Residual formaldehyde by HPLC method was 5 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 58%Spectr.; Ca. 9%Spectr.; Ca. 28%Spectr. | With methanesulfonic acid; at 80 - 100℃; for 18.0h; | Synthesis of cucurbit[n]urils in methanesulphonic acid usingTetramethoxymethyl<strong>[496-46-8]glycoluril</strong> (TMMG)Unsubstituted <strong>[496-46-8]glycoluril</strong> (19.94 g) and methane sulphonic acid (neat, 82 ml_) were placed in a reaction flask and heated to 80 °C. TMMG (44.66 g) was added in drop-wise and the reaction mixture was then heated to 100 °C (internal temp) for 18 hours. The reaction mixture was cooled and added to methanol (410 ml) to produce a beige powder which was analysed by1H NMR. Approximate Yields b1H NMR (percent of recovered product) cucurbit[5]uri 5percent, cucurbit[6]uri 58percent, cucurbit[7]uril 28percent, cucurbit[8]uril 9percent, cucurbit[9]uril 0percent, cucurbit[10]uril 0percent, cucurbit[11]uril 0percent |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 63%Spectr.; Ca. 35%Spectr. | With methanesulfonic acid; In neat (no solvent); at 90 - 100℃; for 18h; | Synthesis of cucurbit[n]urils in methanesulphonic acid (MSA) using paraformaldehydeUnsubstituted <strong>[496-46-8]glycoluril</strong> (20 g) and methanesulphonic acid (neat, 82 mL) were placed in a reaction flask and heated to 90 C. Paraformaldehyde (8.45 g) was added in portion-wise and the reaction mixture was then heated to 100 C (internal) for 18 hours. The reaction mixture was cooled and added to methanol (410 ml) to produce a brown powder which was analysed by1H NMR.Approximate Yields by1H NMR (% of recovered product) cucurbit[5]uril 0%, cucurbit[6]uril 63%, cucurbit[7]uril 35%, cucurbit[8]uril 0%, cucurbit[9]uril 0%, cucurbit[10]uril 0% cucurbit[11]uril 0%.Residual formaldehyde by HPLC method was 1621 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ca. 44%Spectr.; Ca. 18%Spectr.; Ca. 8%Spectr.; Ca. 28%Spectr. | With hydrogenchloride; In water; at 90 - 100℃; for 18h; | Synthesis of cucurbit[n]urils in hydrochloric acid using paraformaldehyde Unsubstituted <strong>[496-46-8]glycoluril</strong> (20 g) and hydrochloric acid (37 % w/v, 30 mL) were placed in a reaction flask and heated to 90C. Paraformaldehyde (8.87 g) was added in portion-wise and the reaction mixture was then heated to 100 C (internal) for 18 hours. The reaction mixture was cooled and added to methanol (150 mL) to produce a beige powder which was analysed by1H NMR.Approximate Yields by1H NMR (% of recovered product) cucurbit[5]uril 8%, cucurbit[6]uril 44%, cucurbit[7]uril 28%, cucurbit[8]uril 18%, cucurbit[9]uril 0%, cucurbit[10]uril 0% cucurbit[11]uril 0%.Residual formaldehyde by HPLC method was 682 ppm. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.68% | In water Reflux; | |
In water | ||
In water |
In water at 100℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.76% | In water Reflux; | |
88.76% | In water at 100℃; | |
In water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89.5% | Stage #1: urea With perchloric acid on silica gel; bis(trichloromethyl) carbonate In ethanol at 20℃; for 1h; Stage #2: formaldehyd In ethanol at 45 - 50℃; for 4h; | 1-2 Example 2 Urea (0.1 mol) and triphosgene (30 mmol) were dissolved in ethanol (1.2L) at room temperature, Tf0HSi02 (4.0g) was added, stirred for 1.0 h, polymerised formaldehyde (2.0 mol, 60g) was added, and the temperature was raised to 45-50 ° C, and the reaction was further stirred for 4 h, the reaction solution was poured into ice water, filtered, and the cake was recrystallized to obtain pumpkin squash CB[6] (calculated molar yield was about 89.5%);the structure confirmation data is consistent with Example 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In water; N,N-dimethyl-formamide; at 120℃; for 48h;Autoclave; High pressure; | Na2NDS (0.031 g, 0.25 mmol), CB[6] (0.05 g, 0.05 mmol), DMF (1mL) and H2O (3 mL) in a sealed Teflon-lined stainless steel container(10 mL), which was heated at 120 C for 48 h, and then cooled to roomtemperature at 4 oC·h-1. After cooling down to room temperature,colorless crystals of 1 was collected by filtration and washed with H2Othree times. Anal. calcd for 1 (C46 H42 N24 O18 S2): C, 43.06; H, 3.30;N, 26.20%. Found: C, 42.98; H, 3.36; N, 26.23%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With formic acid In methanol at 40℃; for 48h; | Preparation of solid inclusion complexesand physical mixtures General procedure: ATZ, AME, and CBn stock solutions (1 mmol L-1) were prepared in methanol and 60% formic acid for guest and hosts, respectively. Inclusion complexes were obtained by mixing the stock solutions of the individual host with the respective CBn. Then the mixtures were incubated in a shaker-incubator (IKA KS 4000i Control Incubating Shaker,Cole-Parmer) for 48 h at 40 °C and the resultant solutions were subjected to freeze-drying (Lyo Quest, Telstar) for72 h. The physical mixtures were obtained by mixing the solid guest and host in a pestle-mortar until a homogenous solid mixture is obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | at 20 - 100℃; for 53h; | 2.2.4. (H3O)3[Hg2Cl7]·(C36H36N24O12)·6H2O (4) A mixture of mercury (I) nitrate (Hg2(NO3)22H2O, 30 mg, 0,05mmole) and cucurbit[6]uril ((C6H6N4O2)610H2O, 10 mg, 0,009mmole) in 10 ml 6M HCl was heating ording to the following schedule: (1) heating from room temperature to 100 °C for 5 h; (2)maintenance at 100 °C for 48 h; (3) slow cooling to room temperatureover 36 h. Large colorless crystals were collected after 3 daysand dried on air. Yield 12 mg (74% based on CB[6]).Anal. Calc. for C36Cl7H57Hg2N24O21 (1811), %: C, 23,9; H, 3.2; N,18,6. Found: C, 24.1; H, 3.2; N, 18.7%.IR (KBr, cm-1): 455 (m), 577 (m), 631 (m), 676 (s), 760 (s), 801(vs), 961 (vs), 1051 (w), 1147 (m), 1193 (s), 1238 (s), 1290 (m), 1325(vs), 1378 (s), 1415 (vs), 1481 (vs), 1614 (w), 1720 (vs), 2930 (w),3005 (w), 3202 (w), 3523 (w), 3582 (w). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | at 20 - 100℃; for 53h; | 2.2.5. (H3O)2[Hg2Cl6]·(C36H36N24O12)·4H2O (5) A mixture of mercury (II) nitrate (Hg(NO3)22H2O, 24 mg, 0,07mmole) and cucurbit[6]uril ((C6H6N4O2)610H2O, 10 mg, 0,009mmole) in 10 ml 3M HCl was heating ording to the following schedule: (1) heating from room temperature to 100 °C for 5 h; (2)maintenance at 100 °C for 48 h; (3) slow cooling to room temperature over 36 h. Large colorless crystals were collected after 3 dayson air. Yield 10 mg (64% based on CB[6]).Anal. Calc. for C36H50Cl6Hg2N24O18(1721), %: C, 25,1; H, 2.9; N,19,5. Found: C, 24.8; H, 3.1; N, 19.2%. IR (KBr, cm-1): 455 (m), 536 (m), 630 (m), 676 (s), 760 (m), 801(vs), 819 (s) 960 (vs), 985 (m) 1055 (w), 1146 (m), 1190 (vs), 1237(vs), 1259 (w), 1286 (m), 1327 (vs), 1377 (s), 1411 (s), 1478 (vs), 1650(sh), 1734 (vs), 2333 (vs), 2855 (w), 2932 (m), 3005 (m), 3424 (m),3526 (w). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | at 20 - 100℃; for 17h; | 2.2.1. (H3O)4[Bi2Cl10]·(C36H36N24O12)·14H2O (1) To a solution of bismuth chloride (BiCl3, 0,158 g, 0,5 mmole) in5ml 2M HCl and cucurbit[6]uril ((C6H6N4O2)610H2O, 0,010 g, 0,01mmole), (2H5)3N (200 ml, 2 mmole) was added. Amorphoussubstance was filtered out. The vial with pure solution was heatedaccording to the following schedule: (1) heating from room temperatureto 100°C for 5 h; (2) maintenance at 100 °C for 12 h; (3)slow cooling to room temperature over 36 h. A crop of large colorless crystals were collected and dried in air. Yield 10 mg (51%based on CB [6]).Anal. Calc. for Bi2C36Cl10H62N24O23 (-7 H2O, 1972), %: C, 21.9; H,3.2; N, 17.1. Found: C, 21.7; H, 3.2; N, 17.2%. IR (KBr, cm-1): 675 (s),759 (s), 800 (s), 883 (w), 962 (s), 1028 (m), 1143 (s), 1190 (s), 1236(s), 1375 (s), 1473 (s), 1633 (m), 1737 (s), 2036 (vw), 2121 (vw), 2276(vw), 2385 (vw), 2476 (vw), 2929 (w), 2999 (w), 3072 (w), 3174 (m),3246 (m), 3419 (m). Raman (ν, cm-1): 65, 104, 153 sh, 242 sh, 277. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | at 20 - 100℃; for 17h; | 2.2.2. (H3O)4[BiCl6]Cl·(C36H36N24O12)·8H2O (2) A solution of bismuth chloride (BiCl3, 0,080 g, 0,25 mmole) in5ml 2M HCl and solution of cucurbit[6]uril ((C6H6N4O2)610H2O,0,020 g, 0,02 mmole) in 2ml concentrated HCl were mixed. The vialwas heated according to the following schedule: (1) heating from room temperature to 100 °C for 5 h; (2) maintenance at 100 °C for12 h; (3) slow cooling to room temperature over 36 h. A crop oflarge colorless crystals were collected and dried in air. Yield 12 mg(39% based on CB[6]).Anal. Calc. for BiC36Cl7H52N24O18 (6 H2O, 1566), %: C, 27.6; H,3.3; N, 21.5. Found: C, 27.3; H, 3.1; N, 21.3%. IR (KBr, cm-1): 424 (w),455 (w), 522 (w), 630 (m), 675 (m), 759 (m), 800 (s), 962 (s), 1029(m),1147 (m), 1190 (s), 1236 (s), 1377 (s), 1477 (s), 1737 (s), 2123 (w),2927 (m), 2999 (m), 3444 (m). Raman (ν, cm-1): 59 (vw), 71 (vw),84 (vw), 119 (vw), 144 (vw), 169 (vw). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
50% | With hydrogenchloride; water; calcium chloride at 60℃; | 2.2.1. [Ca2(C36H36N24O12)(H2O)10]Cl6·14H2O2(H3O) (1) Q[6] (0.050 g, 0.05 mmol) and CaCl2 (0.011 g, 0.10 mmol) weredissolved in 6.0 ml 1.0M HCl solution with stirring at 60 °C. Slow solventevaporation of the filtrate at room temperature in an open beaker.After about a week colorless crystals of compound 1 were collected in50% yield based on Q[6]. Anal. Calcd. (Found) for 1: C, 27.37 (27.31),N, 21.28 (21.21), H, 4.47 (4.52). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With calcium(II) nitrate tetrahydrate; sulfuric acid; water at 60℃; | 2.2.2. [Ca2(C36H36N24O12)(H2O)8(SO4)2](SO4)2·4(H3O) (2) Q[6] (0.050 g, 0.05 mmol) and Ca(NO3)2·4H2O (0.024 g,0.10 mmol) were dissolved in 6.0 ml 1.0M H2SO4 solution with stirringat 60 °C. Slow solvent evaporation of the filtrate in air. colorless crystalsof compound 2 were collected in 55% yield based on Q[6]. Anal. Calcd.(Found) for 2: C, 25.78 (25.81), N, 20.04 (20.06), H, 3.61 (3.68). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With calcium(II) nitrate tetrahydrate; water; nitric acid at 60℃; | 2.2.3. [Ca2(C36H36N24O12)(H2O)10](NO3)8·4H2O4(H3O) (3) Ca(NO3)2·4H2O (0.024 g, 0.10 mmol) was added to a solution of Q[6] (5.0 ml, 0.02 mol·L-1) in HNO3 (1.0 mol·L-1) with stirring at 60 °C. The filtrate was kept at room temperature in an open beaker. X-rayquality colorless crystals of 3 separated after a week. The crystals of 3were collected in 55% yield. Anal. Calcd. (Found) for 3: C, 22.74(22.69), N, 23.57 (23.55), H, 4.03 (3.98). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With potassium hexafluorophosphate; water; calcium chloride at 60℃; | 2.2.4. [Ca(C36H36N24O12)(H2O)5](PF6)2·8H2O (4) Q[6] (0.050 g, 0.05 mmol), KPF6 (0.018 g, 0.10 mmol) and CaCl2(0.011 g, 0.10 mmol) were dissolved in 6.0 ml H2O with stirring at60 °C. Slow solvent evaporation of the filtrate at room temperature inan open beaker. After about a week colorless crystals of compound 4were collected in 40% yield based on Q[6]. Anal. Calcd. (Found) for 4:C, 27.70 (21.80), N, 21.53 (21.56), H, 4.00 (4.08). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | at 80℃; for 0.166667h; | 2.2.1. (C36H36N24O12)·{Cu[(SCN)4(H3O)]2·2(H3O)·35H2O (1) Q[6]·10H2O (0.06 g, 0.05 mmol) NH4SCN (0.0107 g, 0.15 mmol)and CuSO4 (0.016 g, 0.05 mmol) were dissolved in deionized water(10 mL). The mixture was heated at 80 °C for 10 min. After cooling toroom temperature, the mixture was filtered. One days later lamellaryellow crystals suitable for X-ray analysis separate in high yields. Yield:70% (based on Q[6]). Anal. Calcd for 1: C, 23.02; H, 5.18; N, 19.52.Found: C, 22.95; H, 5.55; N, 19.48. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | for 1h; | 2.2.2. [(C36H36N24O12)·(CuCl(H2O)3]2}·2Cl·10H2O (2) Q[6]·10H2O (0.06 g, 0.05 mmol) and CuCl2·2H2O (0.034 g,0.2 mmol) were distributed in deionized water (10 mL). The mixturewas magnetically stirred for 1 h and placed in a dust-free environment.Slow evaporation of the solvent over a period of a week provided greenlumpcrystals. Yield: 62% (based on Q[6]). Anal. Calcd for 2: C, 27.93;H, 4.03; N, 21.72. Found: C, 27.97; H, 4.05; N, 21.76. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With sulfuric acid In lithium hydroxide monohydrate at 20℃; for 24h; | Synthesis of phCB[6] A mixture of 6C (2.0 g, 2.1mmol) and phthalaldehyde (0.30 g, 2.5 mmol) were dissolved in 9.0 M aq. H2SO4 (20 mL) and stirred at RT for 24 h. The clear brown reaction solution was slowly poured into a stirred solution of MeOH (100 mL), which resulted in an off-white precipitate. After filtration, the filter cake was dried under vacuum, then dissolved in water (100 mL) and stirred for 30 min. A clear yellowy solution was obtained by filtration and then decolored with activated carbon (200 mg) at 60 for 2 h. After filtration, a colorless solution was gained and the water was removed by rotary evaporation, which resulted in a white solid. The white solid was washed with MeOH (40mL) twice, then dried under vacuum to give phCB[6] as a white solid (1.4 g, 1.3 mmol, 63%). 1H NMR (400 MHz, D2O, 1.0 equiv. PXDA2HCl was added): δ 7.61 (s, 4H), 7.39 (s, 2H, unbound probe), 6.77 (s, 2H), 6.43 (s, 4H, bound probe), 5.80 (d, J = 16 Hz, 2H), 5.63 (d, J = 8.8 Hz, 2H), 5.50 (m, 10H), 5.19 (d, J = 9.2 Hz, 2H), 5.10 (d, J = 8.8 Hz, 2H), 5.00 (d, J = 9.6 Hz, 2H), 4.81 (d, J = 9.6 Hz, 2H), 4.47 (d, J = 16 Hz, 2H), 4.30 (s, 4H,bound probe), 4.13 - 4.03 (m, 6H, including 2H of unbound probe), 3.89 (d, J = 15.2 Hz, 4H). |
50% | With sulfuric acid at 20℃; for 36h; |
Precautionary Statements-General | |
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P260 | Do not breathe dust/fume/gas/mist/vapours/spray. |
P261 | Avoid breathing dust/fume/gas/mist/vapours/spray. |
P262 | Do not get in eyes, on skin, or on clothing. |
P263 | Avoid contact during pregnancy/while nursing. |
P264 | Wash hands thoroughly after handling. |
P265 | Wash skin thouroughly after handling. |
P270 | Do not eat, drink or smoke when using this product. |
P271 | Use only outdoors or in a well-ventilated area. |
P272 | Contaminated work clothing should not be allowed out of the workplace. |
P273 | Avoid release to the environment. |
P280 | Wear protective gloves/protective clothing/eye protection/face protection. |
P281 | Use personal protective equipment as required. |
P282 | Wear cold insulating gloves/face shield/eye protection. |
P283 | Wear fire/flame resistant/retardant clothing. |
P284 | Wear respiratory protection. |
P285 | In case of inadequate ventilation wear respiratory protection. |
P231 + P232 | Handle under inert gas. Protect from moisture. |
P235 + P410 | Keep cool. Protect from sunlight. |
Response | |
Code | Phrase |
P301 | IF SWALLOWED: |
P304 | IF INHALED: |
P305 | IF IN EYES: |
P306 | IF ON CLOTHING: |
P307 | IF exposed: |
P308 | IF exposed or concerned: |
P309 | IF exposed or if you feel unwell: |
P310 | Immediately call a POISON CENTER or doctor/physician. |
P311 | Call a POISON CENTER or doctor/physician. |
P312 | Call a POISON CENTER or doctor/physician if you feel unwell. |
P313 | Get medical advice/attention. |
P314 | Get medical advice/attention if you feel unwell. |
P315 | Get immediate medical advice/attention. |
P320 | |
P302 + P352 | IF ON SKIN: wash with plenty of soap and water. |
P321 | |
P322 | |
P330 | Rinse mouth. |
P331 | Do NOT induce vomiting. |
P332 | IF SKIN irritation occurs: |
P333 | If skin irritation or rash occurs: |
P334 | Immerse in cool water/wrap n wet bandages. |
P335 | Brush off loose particles from skin. |
P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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